BSR MEngThesis PDF

Optical Characterisation of
Sputtered Silicon Thin Films

for Photovoltaic Applications
A thesis submitted as partial fulllment
of the requirement for the Degree of
Master of Engineering Science

by
Bryce Sydney Richards

at the
Photovoltaic Special Research Centre

School of Electrical Engineering
University of New South Wales
New South Wales 2052
Australia
February 1998
Certicate of Originality
I hereby declare that this submission is my own work and that, to the best of my
knowledge and belief, it contains no material previously published or written by
any other person nor material which to a substantial extent has been accepted for
the award of any other degree or diploma of a university or other institute of higher
learning, except where due acknowledgement is made in the text.
I also declare that the intellectual content of this thesis is the product of my own
work, even though I may have received assistance from others on style, presentation
and language expression.
Abstract
The modied envelope method, developed by the present author, is a very useful
tool for determining the optical constants and thickness of inhomogeneous thin lms
from transmission spectra. Implemented as a Mathematica computer program,
the modied envelope method has been dubbed NAKED since it determines the
refractive index nf , absorption coecient f , extinction coecient kf , the optical
bandgap Eg , and thickness d { essentially revealing a lm's bare optical essentials.
Based on the original method of Swanepoel (1984), the authors' modications permit, rstly, the optical characterisation of non-uniformly thick lms which are
absorbing over a wide wavelength range, such as amorphous and polycrystalline
silicon. The original method could only characterise lms which exhibited a transparent region (e. g. hydrogenated amorphous silicon or crystalline silicon). Secondly, substrate absorption is incorporated into the method, and a more accurate
version of an existing envelope curve tting algorithm, ENVELOPE, is developed
(McClain 1997).
A thin silicon-on-sapphire sample is used to test the method, as the optical properties of the lm is well documented. The results obtained using NAKED show that
nf values are accurate to within 1%, while f values are within 5% of published
results.
After successfully demonstrating the accuracy of the modied envelope method,
sputtered amorphous and polycrystalline silicon (both as-deposited and furnace
annealed) non-uniformly thick lms on Corning 1737 glass are optically characterised. Results obtained for the Eg of amorphous lms, determined from Tauc
plots, were found to be well within the range of published results, while nf and
f values were observed to decrease with increased substrate heating. Refractive
indices for the annealed polycrsytalline lms were found to be within 0.1 (absolute) of crystalline values over the whole wavelength range. The f values are
two to three times greater than crystalline silicon for energies greater than 1.4eV.
The increased absorption is attributed to the amorphous material fraction (i. e.
grain boundaries), and agreement with this model is obtained using Raman spectroscopy. Increased sub-bandgap absorption is attributed to dangling bond defects
in the material (Jackson et al. 1983). The Eg of the annealed material is found to
be in the range 0:93 ; 1:13eV.
Acknowledgements
Firstly, I would like to thank my supervisor Alistair Sproul, for keeping me on
track when frustrations ran high, and for the many lunchtime discussions. A big
thank you also goes out my partner in crime, Andreas Lambertz, whose energy
and devotion kept the whole thin lm group alive, and who sputtered more lms
than you could poke a stick at. I gratefully acknowledge the nancial support,
in the form of half-time contracting work, provided by Martin Green and Pacic
Solar. Thanks to Mark Keevers for doing an extremely thorough job, proof reading
80% of this thesis - it probably would've been 100% if the words 'time management'
meant anything to me! Thanks also to Mark for advice and discussions on all things
optical, as well as more down-to-earth topics, and for justifying the name NAKED.
Thanks to Mark Gross and Tom Puzzer for their on-line help, and many a cynical
chat. I am grateful to Stuart Wenham for delving deep into his memory banks and
retrieving the silicon-on-sapphire samples for me - they were better than Aralditing
wafers onto glass any day! Anatoli Chtanov provided great insight into the problems
faced with optical characterisation and Mathematica - I hope my program does you
justice, Anatoli. Thank you to Svetlana Chtanov for the spectroscopic ellipsometry
results, Rad Flossman in Applied Geology for polishing that damn hard sapphire,
and to Marjorie McClain for her willingness to accept and implement my changes
to ENVELOPE. A big cheer goes out to Varian Australia for turning me into a
cynic of SCary proportions! I would like to thank Steve Robbo for the limited time
we spent biking and talking together - you will always be special to me. Thanks to
Paulo Santos and the MPI-FKF crew who got me interested in PV a few years back.
Thanks also to John Russel, whom I've never met, but who compiled a CD of 20
NZ classic tunes, "Bliss", which I bought second hand for $2 and proved invaluable
company, passing many a long day in front of the computer together. I appreciate
all the eorts of my family and friends to remain in touch with me while I serve my
sentence on this small o-shore island. Finally, a big thank you to Andrea for her
understanding, support, and motivating inuence over the last few years.
Publications from this Work (to date)

1. Richards B, Lambertz A and Sproul A (1997), 'Optical characterisation of
sputtered silicon thin lms on glass for solar cell applications', Australia and
New Zealand Solar Energy Society(ANZSES): Solar '97 Conference Proceedings, Canberra, paper no. 113.
Contents
1 Introduction
2 Literature Review
2.1 Use of Determining Optical Constants . . . . . . . . .

2.2 Review of Methods for Determining Optical Constants
2.2.1 Overview . . . . . . . . . . . . . . . . . . . . .
2.2.2 The Envelope Method . . . . . . . . . . . . . .
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3 Materials and Methods
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3.1 Substrates . . . . . . . . . . . . . . . . . .
3.1.1 Glass . . . . . . . . . . . . . . . . .
3.1.2 Sapphire . . . . . . . . . . . . . . .
3.2 DC Magnetron Sputtering . . . . . . . . .
3.2.1 System Description . . . . . . . . .
3.2.2 Targets and Sputtered Films . . . .
3.3 Crystallisation . . . . . . . . . . . . . . . .
3.4 Spectrophotometry . . . . . . . . . . . . .
3.4.1 System Description . . . . . . . . .
3.4.2 SBW and Energy Level . . . . . . .
3.4.3 The Step! . . . . . . . . . . . . . .
3.4.4 Scattering Samples and Aperturing
3.4.5 Rotating Sample Holder . . . . . .
3.5 Other Characterisation Techniques Used .
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4 Optical Characterisation using the Modied Envelope Method

4.1 Overview of Procedure . . . . . . . . . . . . . . . . . . . . . . . . .
1
27
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46
4.2 ENVELOPE Fitting . . . . . . . . . . . . . . . . .

4.3 NAKED - The Modied Envelope Method . . . . .
4.3.1 Envelope Method Extensions . . . . . . . .
4.3.2 NAKED Operation . . . . . . . . . . . . . .
4.4 Modied Envelope Method Verication . . . . . . .
4.4.1 Theoretical a-Si:H Film on Glass . . . . . .
4.4.2 Theoretical c-Si Film on Corning 1737 Glass
4.4.3 Silicon-on-Sapphire . . . . . . . . . . . . . .
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5 Optical Characterisation of Sputtered Silicon Thin Films

5.1
5.2
5.3
5.4
Overview . . . . . . . . . . .
Sputtered a-Si Films . . . .
As-Deposited poly-Si Films
Annealed a-Si Films . . . .
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64
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6 Conclusions
78
A Thin Film Optical Theory
81
A.1
A.2
A.3
A.4
A.5
A.6
Introduction . . . . . . . . . . . . . . . . . . . . . .
Reectance and Transmittance at a Single Interface
Single Transparent Layer . . . . . . . . . . . . . . .
Single Absorbing Film . . . . . . . . . . . . . . . .
Single Film on a Semi-Innitely Thick Substrate . .
Thin Film on a Thick Substrate . . . . . . . . . . .
B NAKED: Program Listing2
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81
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The Mathematica (version 2.2.3) le NAKED.ma is included on a disk in the inside rearcover.
Chapter 1
Introduction
Polycrystalline silicon thin lms on foreign substrates are an active area of research
in the photovoltaics industry in an eort to reduce the cost of solar cells to levels
where photovoltaics can compete with existing utility-scale generation. Signicant
emphasis by the semiconductor industry has been placed on developing thin silicon
lms for thin lm transistors and at-panel displays, however these lms are too
thin for photovoltaic applications and the desirable properties of the lm are quite
dierent.
Various techniques for depositing thin amorphous and polycrystalline silicon lms
have been investigated, with chemical vapour based depositions currently proving
popular. However, silicon lms produced by direct current sputtering oer safety
advantages, avoiding the use of toxic gases, and can be better suited to industrialscale, large-area depositions. Sputtering also oers improved adhesion to the substrate as during the deopsition the atoms have much greater kinetic energy than
that of other processes (Materials Research Corporation 1975). A wide range of
substrates are also being investigated, including glass, plastic, ceramics and stainless steel. Transparent materials have the advantage that they can serve both as
a superstrate or a substrate. As a superstrate, the material provides mechanical
support and a protective front surface to the module, while still transmitting light
to the semiconducting lm deposited on the rear. For these reasons, this work has
focused on sputtered silicon lms on glass. The deposition of both amorphous and
polycrystalline silicon is investigated, and also the solid phase crystallisation of the
amorphous material in a conventional furnace.
The major aim of this work is to determine refractive index and absorption coecient as a function of wavelength, the optical bandgap, and average thickness and
thickness variation of the lms. The absorption coecient, especially, is a useful
tool for determining the the lm quality and the eect of additional absorption
mechanisms, such as free carrier and defect level absorption. Additionally, the
transition from amorphous to polycrystalline material can be observed via the large
changes in the optical properties of the material.
An improved version of the envelope method, originally presented by Swanepoel
(1984), was developed and implemented by the author as a Mathematica computer program, called NAKED, to speed up the lm characterisation. The envelope
3
4
method was chosen due to its ability to analyse non-uniformly thick lms, its elegance, and the unique solution of its output. The extensions to the method made
by the author, include:
the inclusion of substrate absorption, which is signicant at certain wave-
lengths. Swanepoel did not include this in his method, but even for glass and
especially sapphire the absorption can be large
improving the method so that material which is absorbing across the whole
wavelength range can be characterised. Previously, a lm was required to have
a transparent region, but both amorphous and polycrystalline silicon exhibit
some level of absorption over the whole measured wavelength range and,
the use of a highly accurate envelope-curve tting program called
ENVELOPE, written by McClain et al. (1991) with subsequent modications
made in collaboration with the author of this work (McClain 1997).
A commercially grown silicon-on-sapphire lm was used as a reference to establish

the accuracy of the optical properties determined by the method. This lm was
chosen because the optical properties of epitaxially grown silicon-on-sapphire are
very similar to bulk crystalline silicon, and are well documented. Having demonstrated the accuracy of the envelope method, amorphous and polycrystalline lms
on glass were analysed. Results for the refractive index, absorption coecient, and
optical bandgap are compared to other published polycrystalline data, and conclusions about the optical properties of the material reached. Raman spectra also oer
information relating to the level of defects and crystallinity of the lm.
The non-destructive nature of this method is essential to enable further characterisation and processing of the samples into solar cells. The method could be applied
to any absorbing lm on a transparent substrate that exhibits interference in the
ultra-violet, visible, and near-infrared wavelength ranges. Another example of this
in photovoltaics would be determining the optical properties of anti-reection coatings, although the thickness of the lms would have to be much thicker than is
currently standard, in the order of a few microns, to observe the necessary interference.
Chapter 2
Literature Review
2.1 Use of Determining Optical Constants
It is important to know the optical properties of a semiconducting material intended for photovoltaic (PV) applications in order to understand and predict the
photoelectric behaviour of working devices. A material is considered to have a complex refractive index n~f = nf ; ikf , where nf is called the refractive index and kf
the extinction coecient. All of these functions are wavelength dependent. The
absorption coecient f is related to the extinction coecient by:
f
f = 4k
.
(2.1)
For a light beam incident on a non-scattering, absorbing lm, the amounts of light
reected, absorbed, or transmitted by the lm are related by
1=R+A+T .
(2.2)
where R is reectance, A absorbance, and T transmittance. The denitions of these

terms are the ratios of reected, absorbed, and transmitted ux to the incident ux,
respectively (ASTM Standard 1992).
The refractive index largely determines how reective a lm will be, governed by
the Fresnel equations (see Appendix A) . This is important in solar cell design as
light reected from the front surface is lost and does not contribute to cell output.
Knowledge of the refractive index of the lm also assists in the design of suitable
anti-reection (AR) coatings to minimise such reection losses.
The absorption coecient is a measure of the extent to which photons of energy
hc = 1:24 (with in m)
(2.3)
Eph = q

are absorbed in the silicon (Si) lm, which is of primary importance to solar cell
operation. The photon energy Eph is given in electron-volts (eV), h is Planck's constant 6.62610;34 J. s, c is the velocity of light in a vacuum 3108 m s;1 , and q is
5
the charge on an electron 1.60210;19 J. eV. A photon absorbed in Si can generate

an electron-hole (e-h) pair, the resulting minority carrier can then be collected by
the pn junction, and a useful electric current extracted from the device. In practice, however, defects within the polycrystalline silicon (poly-Si), poorly passivated
surfaces, and grain boundaries (GB) between adjacent crystallites, act as recombination sites for minority carriers, which prevents them from being collected by the
pn junction. The presence of such defects also impacts upon the absorption coecient of the material, and therefore the determination of f is also a useful tool to
determine the degree of crystallinity in a given sample. The f can be compared to
that of bulk c-Si and the increased absorption at various photon energies attributed
to additional absorption mechanisms.
2.2 Review of Methods for Determining Optical

Constants
2.2.1 Overview
A wide range of techniques can be used and there have been many works published
on the determination of the optical constants of thin lms. For material with a
refractive index similar to that of silicon (nf 3.4) between 0.5 and 5 m thick,the
use of a spectrophotometer along with some spectrum analysis can provide a simple,
quick, and non-destructive method for determining a lm's optical constants. All
of the experimental data for the methods described below can be collected using
a spectrophotometer with a reectance accessory, to obtain transmission and/or
reectance data, except for ellipsometry, which naturally requires the use of an
ellipsometer.
In this section, popular methods that researchers have developed over the years are
described, and the advantages, disadvantages, and limitations of each assessed, with
the present application, the analysis of non-uniformly thick lms, in mind. These
techniques include:

reection and transmission at a single location

iterative tting methods
Kramers-Kronig analysis
matrix method
ellipsometry and,
interference methods, including:
{ angular rotation method

{ curve-tting methods and,
{ envelope methods.
While there is often considerable overlap between these methods, the categorisation
is useful for the following overview. Although mainly concerned with nding the
refractive indices of single and multilayer lms for lters, Chapter 3 of Palik (1991)
provides a good overview of methods that can be used for determining the optical
constants of thin lms.
The method used in this work for determining the thin lm optical constants is
based on the envelope method developed by Swanepoel (1984), and considerably
modied and improved to produce, what the present author refers to as, the modied
envelope method.
Transmission and Re ection at a Single Location

This method is one of the earliest used to analyse a transparent or weakly absorbing
thin lm of thickness d upon a thick transparent substrate. A lm which is weakly
absorbing has a refractive index much greater than its extinction coecient over
the spectral range in question. In this case, several absorbing terms drop out of the
analytical equations, and the expressions describing the reection and transmission
become greatly simplied (see Appendix A).
Determining the optical constants requires measuring the transmission, reection,
and thickness at exactly the same point. This requires special modications to the
spectrophotometer, and, unless the sample is optically at and parallel, it is vital
that each measurement illuminates exactly the same spot in order to avoid errors
being introduced from sample inhomogeneities (Lyashenko and Miloslavskii 1964).
Ward (1994) highlights several photometric techniques that were used in the 1950s
and 1960s. Although considerable simplications can be made if measurements are
made at normal incidence (Appendix A), there are often several pairs of nf , kf
values which satisfy the equations at any given . Therefore, it is generally not
possible to solve equations for nf and kf uniquely (Ward 1994).
Various other elaborate methods have been suggested for calculating the optical
constants. In 1964, Mal!e (Ward 1994) proposed a graphical method, which used
intersections of plotted curves to nd nf and kf , but it was a tedious process
and not necessarily very accurate. Earlier, in 1931, Murmann (Ward 1994) had
used a similar method, but found that additional knowledge was still required to
eliminate unwanted multiple solutions. Section 5.4 of Heavens (1955) presents an
excellent outline of other early (pre-1955) techniques implemented to obtain the
optical constants and thickness of thin lms.
Iterative Fitting Methods

There are an extremely large number of publications (see for example Minkov 1990,
Mrafko and Ozvold 1995, Romanov et al. 1996, Swanepoel 1989) which present
analytical expressions for the transmission or reection of thin lms on various substrates. The values for the optical constants and thickness are then determined by
simply iterating each parameter until agreement with the experimental transmission and/or reection data is achieved. The inherent problem is that a number of
solutions can accurately t the spectra, and it is often dicult to determine the correct answer (Ward 1994). This is in contrast with the envelope method, described
below, which retrieves more information from the spectra by the construction of
envelope curves. This provides two additional equations describing the extrema
that can instead be solved for a unique solution of nf , kf , average thickness d", and
thickness variation #d. To avoid the problems associated with multiple solutions
another method was sought for use in this thesis, hence the iterative methods were
not pursued at length.
Note that a Windows-based computer program, Optikan (Bader et al. 1995), which
simply iterates nf , kf , and d" to t experimental transmission and reection data was
occasionally used. This proved to be useful for determining the optical behaviour
of the substrates, which exhibit no interference fringes in the range of interest, as
well as theoretical sample structures. The capabilities of the software are somewhat
limited as it can only handle a maximum of 256 data points, and it is unable to
treat non-uniformly thick layers.
Kramers-Kronig Analysis
A good summary and application of the technique developed by Kramers, in 1929,
and improved two years later by Kronig, is provided in Chapter 3 of Ward (1994).
The Kramers-Kronig method uses the spectral distribution of measured or calculated optical data (reection, transmission, or phase change upon reection or
transmission) over a very wide range of frequencies to extract the unknown optical
information.
Regarded as one of the most powerful tools for calculating optical constants, the
analysis is based on the assumption that for the complex refractive index, if the
variation of the real part with wavelength is known then the imaginary component
can be determined, and vice versa. Due to this requirement of one predetermined
component, either nf or kf , over a very large range (tens of microns) the method
is not suitable for this current application, where it is desired to nd d, nf and kf
simultaneously in the ultraviolet (UV) to near-infrared (NIR) region, hence, it will
not be pursued further in this work.
Matrix Method
Another method used by researchers is the matrix method. The analysis is founded
on the relationship of electric eld vectors on either side of each optical interface,
which can be expressed in terms of matrices. By evaluating these matrices, equations describing the transmission and reection of a layer can be derived. The
elegance of this method only becomes apparent when multilayer lms are being
investigated, as the derived expressions can be simply multiplied by the matrix describing the next layer to solve the experimental reection and transmission data for
nf , kf , and d". The technique is popular for investigating AR and highly reective
coatings, and various optical lters. One major disadvantage of the matrix method
is its requirement for lms to be uniform over large areas (Arndt et al. 1984), and
for this reason its application to our problem is not covered in more detail here.
Ellipsometry
Ellipsometry is a commonly used and extremely accurate method for determining
thin lm optical constants. The technique involves measuring the change in polarisation of linearly polarised, monochromatic light due to reection from the lm
surface at at least three angles of incidence to yield a unique solution. This allows
the ratio of the complex Fresnel coecients, = r~k=r~? = tan exp;i, to be determined, where expresses the polarisation state of the reected wave, tan is the
dierential attenuation, and # represents a dierential phase retardation. Some
advantages of ellipsometry are (Arndt et al. 1984):
i. only measurements of polarisation angles are involved (no absolute or relative
photometric measurements), so it can be highly accurate
ii. lm thickness and the optical constants are determined simultaneously and,
iii. the substrate refractive index and absorption coecient (if signicant) can be
determined
while disadvantages include (Arndt et al. 1984):
i. the method is very sensitive to lm non-uniformities and,
ii. most ellipsometers use lasers as an illumination source, which limits the
amount of optical constant data available to a few single wavelengths. Spectroscopic ellipsometers, which have a monochromator built in, exist, however
the one we had access to was limited to the 300-800nm range, missing valuable information about the Si material which could be obtained in the infrared
(IR) region.
Since the disadvantages were critical to our application, and a spectrophotometer
with a 175 ; 3300nm wavelength range was available for use, ellipsometry was not
investigated further. A very complete description of the application of ellipsometry
for measuring the complex refractive indices of materials can be found in Chapter
3 of Palik (1985).
Interference Methods
Interference fringes occur when the amplitudes of beams reected from the front
and back surfaces of a lm add to produce various degrees of constructive or destructive interference. These are observed as maxima or minima in the reection
or transmission spectra. As the number of interference fringes observed is determined by the optical thickness nf d, lms with a lower refractive index will need to
be thicker to observe a useful number of interference fringes (within the operating
range of the spectrophotometer).
In 1964, Lyashenko and Miloslavskii (1964) proposed a simple method which could
be applied to weakly absorbing lms where nf kf . The necessary conditions for
the method were:
10
i. uniformly thick lms

ii. no scattering and,
iii. the spectral bandwidth (SBW) of the spectrophotometer (determined by the
grating dispersion and slit widths) should be less than the half-width of the
interference maximum.
The method was based on the observed thin lm interference in the transmission
spectrum. First of all, the chromatic order m was determined from two adjacent
extrema, m and m+1 , and then nf found using Eqn. A.35, which describes the
interference minima. This method resulted in errors for nf and d of around 2%.
For weakly absorbing lms, such as tin oxide, values for kf were iterated until a
sucient approximation was obtained.
At the same time, Valeev (1963) proposed an iterative method that was characterised by the use of nomograms. Importantly, Valeev included the use of an
envelope along the transmission minima, which provided additional information
about the optical system. The method was applied to cadmium telluride lms on
calcium ouride substrates, however the accuracy was not stated.
Michailovits et al. (1983) developed the work of Valeev further, including envelope
curves for both the interference minima and maxima. An iterative method was used
to extract the values for nf and kf for the vanadium oxide lms. The accuracy of
the method was estimated to be within 5% for nf , 1% for kf > 0:01, and as high
as 10% for kf values around 0.001. Thickness values were accurate to within 5%.
Angular Rotation Method

To avoid many of the problems inherent in thin lm optics, Swanepoel (1985) proposed a method based on the shift in interference extrema as the angle of incidence
is varied. The technique had the advantage in that it:
i.
ii.
iii.
iv.
could analyse inhomogeneous thin lms

was less sensitive to SBW variations
beam polarisation had no eect and,
it determined d and nf to better than 1% accuracy.
The method was successfully applied by another group of researchers (Corrales

et al. 1995) in determining the refractive index of arsenic selenide. Unfortunately,
no information about f is obtainable with this method, although it could play a
useful role in checking nf values determined with another method.
Direct Curve Fitting

Attempts by researchers to t parameter sets directly to the equation describing the
interference fringes observed in the transmission spectra (Kubinyi et al. 1996) are
11
related to the iterative tting methods. As presented in Appendix A, the equation

most commonly used to describe the transmission of a uniformly thick, weakly
absorbing (nf kf ), thin lm on a thick transparent substrate of refractive index
ns is (Swanepoel 1983)
Ax
T = B ; Cx
(2.4)
+ Dx2 ,
where
A
B
C
D

x
=
=
=
=
=
=
16nsn2f
;

2
(nf + 1);2 (nf + 1); nf + n
s ,
2 cos n2f ; 1 n2f ; n2s ,
;

(nf ; 1)2 (nf ; 1) nf ; n2s ,
4nf d ,

exp;f d .
Kubinyi et al. (1996) utilise Swanepoel's (1983) envelope method, described fully
below, to calculate the optical constants. It is claimed that while the envelope
method of Swanepoel is satisfactory for lms of 1m thickness, lms of greater
or lesser thickness produce less accurate results (Kubinyi et al. 1996). Kubinyi
et al. claim that results obtained from thinner lms will be less accurate with
this method since the number of observable interference fringes decrease, thereby
reducing the amount of data points extracted. However, this also depends on the
spectrophotometer employed, and Kubinyi et al. used a ultraviolet-visible (UV-Vis)
spectrophotometer, which had an upper wavelength limited of 900nm. A UV-VisNIR spectrophotometer, such as the Varian Cary 5G as used at the Photovoltaics
Special Research Centre (PVSRC) at the University of New South Wales (UNSW),
can reach wavelengths up to 3.3m. This yields many more interference fringes,
and silicon lms of thicknesses as thin as 400nm have been successfully analysed
using the envelope method of Swanepoel.
Why Kubinyi et al. reason that lms thicker than 1m were dicult to analyse remains unclear. It was claimed that the interference fringes were too close together,
and that the fringe order of interference m became dicult to determine. The author has not encountered this problem to date, and both amorphous silicon (a-Si)
and poly-Si lms of up to 3m thickness have been successfully analysed. One possible explanation for the claim of Kubinyi et al. is perhaps the spectrophotometer
used had poor wavelength resolution, rendering peak determination dicult.
As a result of the perceived limitations of the envelope method by Kubinyi et al.,
an alternate method is proposed, using a ve parameter set (a1 a2 a3 a4 d) to
describe the nf and f (see Equations 2.5 and 2.6). These coecients are then
tted to Eqn. 2.4, and the sum-of-squares errors for each parameter at every
minimised. This method is rst applied to the following theoretical model for an
hydrogenated amorphous silicon (a-Si:H) lm as used by (Swanepoel 1983):
nf () = a12 + a2
(2.5)
5
= 3:5 2 10 + 2:6 ( in nm) ,

log10 f () = a32 + a4
6
= 1:5 2 10 ; 8
12
(2.6)
( in nm;1, in nm) .
To compare Swanepoel's (1983) envelope method with the curve tting method,
Kubinyi et al. (1996) simulated and analysed 100 spectra, and the errors for each
parameter averaged. Kubinyi et al. claimed that the average mean square errors are
typically ten times less when curve tting over the whole spectrum, than when using
the envelope method. However, later in the paper a plot comparing the spectrum
generated from the now known parameters and the original measured transmission
spectrum suggests that there are substantial errors somewhere in the method. This
is presented here as Figure 2.1 and the poor agreement obtained using the curve
tting method of Kubinyi et al. (1996) is obvious.
Figure 2.1: Plot illustrating the poor t obtained with the direct curve
tting method of Kubinyi et al. (from Kubinyi et al. 1996)
It is claimed that the t in the 700-900nm wavelength range is very good, and
the reason for the large deviation below 700nm is due to the fact that nf () and
f () cannot be modelled with the simple empirical formulae, Eqns. 2.5 and 2.6,
as the absorption becomes signicant. The method is then limited by the fact that
a fairly good estimate of how the optical constants vary with must already be
known before the method will work successfully!
Thus, the method sounded promising, but results in the end can only be regarded
as unsatisfactory for the purposes of this thesis. Additionally, the analysis is limited to homogeneous thin lms, which excludes the possibility of characterising
non-uniformly thick lms. The latter is a necessity for the majority of thin lm
depositions.

$LU
G
13
Q
Q1
)LOP a
Q 1 LN 1
*ODVV Q Q8 8
Figure 2.2: The thin-lm on innitely thick substrate model used by Manifacier et al. (1976) to develop the envelope method.
2.2.2 The Envelope Method

Another group of researchers to take note of Valeev's (1963) envelope curve approach and develop the concept further were Manifacier et al. (1976). The work of
Manifacier et al. has resulted in the rst 'classic' paper in the area of determining
nf and kf from transmission interference fringes. Swanepoel (1983) made several
initial improvements and corrections to the work of Manifacier et al., and then
proceeded to develop a more complex method capable of analysing inhomogeneous
thin lms (Swanepoel 1984), which has been the starting point of this thesis. A
summary of these three key papers, and more recent work, is given in this section.
Manifacier et al. (1976)

For the sample structure shown in Figure 2.2, Manifacier et al. derive an equation
describing the transmission of light through a weakly absorbing, uniform thin lm
(kf2 n2f ) on an innitely thick substrate:
16n n n2 x
T = C 2 + C 2 x2 +0 2s Cf C x cos ,
1 2
1
2
(2.7)
where C1 = (nf + n0 )(ns + nf ), C2 = (nf ; n0 )(ns ; nf ), x = exp;f d and =

4nf d=. Outside the region of signicant absorption, the extrema of Eqn. 2.7
occur for
4nf d = m ,
(2.8)

where m is the order number. For the semiconductor on glass case, where nf > ns,
the envelopes surrounding the extrema are considered to be continuous functions
of (via nf () and f ()) and are given by
16n0nsn2f x
,
Tmax () =
(C1 + C2 x)2
16n0nsn2f x
Tmin() =
.
(C1 ; C2 x)2
(2.9)
(2.10)

Solving Eqns. 2.9 and 2.10 for x gives
14
C 1 ; (T =T )1=2
x = C1 $1 + (Tmax=Tmin)1=2 ] .
(2.11)
2
max min
The lm's refractive index can then be expressed by rearranging Eqn. 2.9 to yield:
nf = N + (N 2 ; n20 n2s )1=2

where
1=2
2
2
; Tmin .
N = n0 +2 ns + 2n0ns Tmax
Tmax Tmin
(2.12)
(2.13)
Once nf is known, x can found using Eqn. 2.11. The thickness of the lm is
determined using Eqn. 2.8 with two consecutive maxima or minima forcing m = 1:
d = 2 (n ( ) 1;2 n ( ) ) .
(2.14)
f 1 2
f 2 1
Finally, the absorption coecient f can be found using f = ; ln x=d. The error
in the refractive index values was determined to be about 2 ; 5%, and, at best, 4%
for the thickness d. No estimate of the accuracy was given for absorption coecient values. It was also noted that the SBW of the spectrophotometer should be
maintained at a value less than the half-width of the interference maximum to avoid
smearing out of the extrema as a result of poorer resolution. This, in fact, creates an
upper limit on the thickness that can be measured with the spectrophotometer. Although the method presented by Manifacier et al. (1976) has many advantages over
other previously described techniques, there are several disadvantages, for example:
i. the envelopes are required to be drawn by hand
ii. the substrate is assumed to be of innite thickness
iii. the substrate refractive index ns is assumed to be constant over the whole
wavelength range
iv. the sample must be homogeneous and parallel faced (i. e. uniformly thick)
and,
v. the variation of nf , kf with should be small, limiting the analysis to weakly
absorbing regions.
Swanepoel (1983)
In 1983, Swanepoel presented a very complete paper, making several improvements
and corrections to the original work of Manifacier et al. (1976). These will be more
fully discussed in the following pages, however, briey, these were:
i. modelling the substrate as nitely thick and,
15
ii. a more accurate method for determining the refractive index nf , absorption
coecient f , and thickness d. The accuracy of all calculated values, nf , f
and d, is determined to be within 1% (for f values > 100cm;1).
Swanepoel's (1983) analysis begins with considering the transmission of the bare
substrate, given by
Ts = n22n+s 1 ,
(2.15)
s
or for a known transmission the substrate refractive index, is given by

1=2
ns = T1 + T12 ; 1
s
s
(2.16)
The following equation determines the number and position, with respect to the
wavelength of the light, of the interference fringes, where the order m is an integer
for maxima and half-integer for minima:
2nf d = m .
(2.17)
The sample structure used in Swanepoel's (1983) model is depicted in Figure 2.3,
noting that the substrate is now of nite thickness.
$LU
G
Q
Q1
)LOP a
Q 1 LN 1
*ODVV Q Q8 8

7
$LU
Q
Figure 2.3: The thin-lm on nitely thick substrate model used by

Swanepoel (1983) to improve the envelope method.
The expression describing the transmission for such a sample, where nf kf , as

presented earlier is
Ax
T = B ; Cx cos
(2.18)
+ Dx2 ,
where
A = 16nsn2f ,
;

B = (n;f + 1)2(n; f + 1) n f + n2s ,
C = 2 n2f ; 1 n2f ; n2s ,
16
D = (nf ; 1)2 (nf ; 1) nf ; n2s ,

= 4nf d ,
x = exp;f d .
As the cosine term takes a value of +1 for a maximum and -1 for a minimum, the
extremes of the interference fringes can be written as
Tmax = B ; CAxx+ D x2 ,
(2.19)
(2.20)
Tmin = B + CAxx+ D x2 .
As can be see from Figure 2.4, this means that each extrema has a corresponding
value lying on the other envelope curve. Additionally, Swanepoel divides up the
transmission spectrum into three regions of absorption: transparent, weak and
medium, and strong.
100
Transmission (%)
80
Ts
Tmax
T
60
Ti
40
Tmin
20
Strong
0
500
Medium
600
Weak
700
Wavelength (nm)
Transparent
800
900
Figure 2.4: Simulated transmission for a 1m thick a-Si:H thin lm on a
nitely thick glass substrate. The curves drawn are described in the text
(from Swanepoel 1983).
In the transparent region the lm is non-absorbing and f = 0, and the maxima
are given by the transmission of the bare substrate Ts. Thus, the refractive indices
of the substrate and lm can be found now by substituting x = 1 into Eqns. 2.19
and 2.20, respectively. This yields an equation of the same form as Eqn. 2.16 for
the substrate refractive index

1=2
1
1
ns = T + T 2 ; 1
,
(2.21)
max
max

and the lm's refractive index can now be determined from

nf = M + (M 2 ; n2s )1=2 1=2 ,
17
(2.22)
2
M = ns 2+ 1 + 2ns T2ns .
(2.23)
min
The lm begins absorbing when the maxima depart from Ts, and f 6= 0. In this
region, Swanepoel derives the same expression for nf as (Manifacier et al. 1976) to
obtain

nf = N + (N 2 ; n2s )1=2 1=2 ,
(2.24)
where
2
; Tmin .
N = 1 +2 ns + 2ns Tmax
(2.25)
Tmax Tmin
Swanepoel suggests that the transmission of the bare substrate could initially be
measured and the refractive index ns() then obtained over the whole wavelength
range using Eqn. 2.21, although this was not implemented.
Now that nf () and ns (assumed to be constant) have been calculated, the coecients of Eqn. 2.18 are known. Solving either Eqn. 2.19 or Eqn. 2.20 quadratically
for x, and simplifying using Eqn. 2.18 produces (shown here for Eqn. 2.19)

2
2
Emax
; Emax
; (n2f ; 1)3(n2f ; n4s ) 1=2
x =
, (2.26)
(nf ; 1)3 (nf ; n2s )
8n2f ns
where
Emax = T + (n2f ; 1)(n2f ; n2s ) .
max
It should be noted that Eqn. 2.26 is not equivalent to Eqn. 2.11 as derived by
Manifacier et al., due to the dierence in substrate models.
In Figure 2.4, Ti is a curve passing through the inection points of the interference
fringes and is given by
Ti = T2 Tmax+TTmin ,
(2.27)
max
min
and T is the geometric mean, denoted by
p
T = Tmax Tmin .
(2.28)
where
In the region of strong absorption the interference fringes start to disappear, and
there is not enough information contained within the spectrum to calculate nf and
x independently. Therefore, Swanepoel recommends extrapolating nf () values
found in the other parts of the spectrum and then using Eqn. 2.26 again to nd x.
Alternatively, T can be used to determine f values, using the following equation
h
where
i1=2
G ; G2 ; (n2f ; 1)6 (n2f ; n4s )2 1=2

x =
,
(2.29)
(nf ; 1)3= (nf ; n2s )
128n4 n2
G = T 2f s + n2f (n2f ; 1)2 (n2s ; 1)2 + (n2f ; 1)2 (n2f ; n2s )2 .
18
Instead of calculating the thickness d from any two extrema, Swanepoel proposes a
more accurate, graphical method. Supposing that the order number from the rst
visible extrema is m1 , Eqn. 2.17 can be written as
l=2 = 2 d (nf =) ; m1 ,
(2.30)
where l = 0 1 2 3 : : :. If l=2 is plotted against nf = and a straight line tted to the

points, the line will have a slope 2d and a negative y-intercept of m1 . This method
determines the thickness to an accuracy of better than 1%. Once the thickness is
determined, the known m and d values can be fed back into Eqn. 2.17 and a more
accurate value for nf is obtained. The accuracy achieved for nf is also in the order
of 1%. Absorption coecient values were found to be accurate to within 1% in the
range of 100cm;1 to 5 104cm;1. Swanepoel notes that relative errors of 1% in ns
and nf lead to an absolute error of about 20cm;1 and 100cm;1 in f , respectively.
Swanepoel also demonstrated that the innite substrate approximation predicts a
4% larger transmission than the measured substrate alone. This is due to the fact
that the model presented by Manifacier et al. (1976) neglects transmission losses
arising from reections from the rear surface of the glass. A correction for a too
great a SBW is covered as well, which will shrink the amplitude of the interference
fringes if not accounted for.
In summary, this is a very accurate and relatively straight-forward method. It
improves greatly upon the work of Manifacier et al. and the accuracy of nf , f ,
and d are all 1%. Two major disadvantages still remained however:
i. the envelopes were still required to be drawn by hand and,
ii. the sample must be homogeneous and parallel faced.
The latter of these problems was addressed by Swanepoel the following year.
Swanepoel (1984)
The case now being considered is for analysing inhomogeneous samples, such as that
illustrated in Figure 2.5. The lm thickness is now expressed as d = d" #d, where d"
is the average thickness and #d is the thickness variation. It is assumed that there is
no variation in the optical properties throughout the lm, and that thickness varies
linearly over the illuminated area. The variation can be in the form of sinusoidal,
rectangular, or triangular surface roughnesses, and more random variations can be
approximated by the these (Swanepoel 1984).
The expression for the transmission through a non-uniformly thick sample is now
an integration of Eqn. 2.18 over dmax = d" + #d to dmin = d" ; #d. Substituting x
and into Eqn.2.18, the integral appears as
1
Td = d ; d
max
min
Z dmax
dmin
A exp;f d

dd0 .(2.31)
4nf d
;

d
;
2

d
f
f
B ; C cos exp
+D exp
0
$LUQR
G
/LJKW
G
)LOP a
Q I = Q I LN I
GDYJ
6XEVWUDWHQV
GV
$LUQR
19
7G
Figure 2.5: A non-uniformly thick, absorbing thin-lm on a transparent

substrate.
To illustrate the eect of the thickness variation, consider a transparent lm with
the following properties: #d = 1000nm40nm, nf = 3:5, ns = 1:51. Equation 2.31
was evaluated for the non-uniformly thick, transparent lm (above), as well as a
uniformly thick lm with the same optical properties. The compressive eect of
thickness variation on the transmission spectra can be seen in Figure 2.6.
Transmission (%)
100
80
60
40
d=0nm
20
0
d=40nm
Envelope curves for d=40nm

600
700
800
900
1000
Wavelength (nm)
1100
1200
Figure 2.6: Simulated transmission for a 1m thick transparent thin lm,
with and without a 40nm thickness variation (from Swanepoel 1984).
A slightly more complex comparison is plotted in Figure 4.4 in Section 4.3.1. The
transmission maxima of the uniformly thick lm meet the bare substrate transmission Ts, described by Eqn. 2.15. For the non-uniformly thick lm, the extrema
never reach Ts even though the modelled c-Si lm is transparent for > 1100nm.
Considering only the interference free absorption, given by the geometric mean T
and Eqn. 2.28, thickness variations in the lm, if not corrected for, can lead to the
false assumption that the lm is more strongly absorbing than the uniform lm and
20
has a higher absorption coecient.

As the integral Td is dicult to solve analytically, an approximation is to consider
x as having an average value over the integration range (Swanepoel 1984), of
x" = exp;f d .
(2.32)
This is an excellent approximation, provided that #d d" and that 0 < #d <
=4nf . The cosine term in Eqn. 2.31 has the dominant shrinking eect on the
spectra, as for each d0 the frequency of the fringes will be dierent, and integrating
over the range dmin to dmax will average out the extrema. This simplies the integral
to
"
Td = 4n #d p ax 2 arctan

1 ; bx
f
!
1 + bx tan 4nf dmax

p

1 ; b2x

!#
1
+
b
4
n
d
x
f
min
; arctan p 2 tan
,

1 ; bx
where
"
ax = B +AxD
x"2
and
" ,
bx = B +C xD
x"2
(2.33)
(2.34)
and the envelope expressions are then (M&arquez et al. 1995)
Tmax x
Tmin x

p a arctan p1 + b tan 2nf #d , (2.35)

=
2nf #d 1 ; b2

1 ; b2

a
1
;
b
2
n
#
d
f
= 2n #d p
. (2.36)
arctan p
tan

1 ; b2
1 ; b2
f
In the transparent region of the transmission spectra the coecients become

A
C .
a= B+
and
b
=
(2.37)
D
B+D
Thus we now have two independent equations to solve simultaneously for the two
unknowns #d and nf , yielding a unique solution (Swanepoel 1984). Where the lm
becomes absorbing, Eqns. 2.35 and 2.36 can be solved using the coecients ax and
bx, replacing the transparent region coecients a and b. As #d is now known, there
are again two equations to solve uniquely for two unknowns, nf and x.
The average thickness d" is found using the same method as described in the earlier
work of Swanepoel (1983) in the previous section. Once d" has been determined f
can be found easily from x, and kf can be calculated. If the calculated f values
near the strongly absorption region appear noisy, since they are calculated from
the dierence between the two envelope curves and can be aected by experimental
errors, these few points can be determined using the geometric mean T , or solely
Tmax using Eqn. 2.26 as Swanepoel recommends.
Swanepoel found that the average thickness, refractive index, and absorption coecient of the lms to be within 0.1%, 0.1%, and 5%, respectively. Although
21
the absorption coecient values are less accurate than that from the uniform lm
analysis, it is essential to be able to deal with lm inhomogeneities.
A variation in refractive index for a uniformly thick lm is also modelled by
Swanepoel. The optical pathlength nf d occurs as a product in the phase angles, and
therefore the eect of #nf d and nf #d are equivalent, with #nf = 0:14 corresponding to #d = 40nm for the curves in Figure 2.6. Thus, it is actually impossible to
determine whether #nf or #d is causing the shrinking of the transmission spectra
(Swanepoel 1984). Although Swanepoel does not mention it, the author believes
that no change in f should be observed. Referring to Eqns. 2.32 to 2.36 it can be
seen that x always uses the average thickness d", and that x would be the same for
a uniformly thick lm d with a non-uniform refractive index #nf .
Bah et al. (1993)

Bah et al. (1993) propose a simple, approximate method which is designed to model
the transmission of a non-uniformly thick, thin lm on a transparent substrate. The
analysis relies upon the following:
i. the transmission extrema values only change with optical thickness nf d" and,
ii. the magnitude of the transmission minima are less aected by thickness nonuniformities than those of the maxima.
Light transmission through a non-uniformly thick lm d = d" #d is given by (Bah
et al. 1993)
Z d+d
~T = 1
T (d ) dd ,
(2.38)
2#d d;d
yielding the following equations for the upper and lower envelopes around the extrema
T~max
1=2
= 2 (TmaxTmin ) arctan
T~min
1=2
= 2 (TmaxTmin ) arctan
"
"
Tmax
Tmin
1=2
tan 2 ,
(2.39)
Tmin
Tmax
1=2
tan 2 ,
(2.40)
where Tmax and Tmin are the transmission values for a plane-parallel lm of thickness
d", and = 4nf #d=. At normal incidence, Tmax and Tmin can be expressed as
(Bah et al. 1993)
; R23 )(1 ; R31) x

Tmax = (1 ; x (R (1R; )R1=122 ))(1
,
2 ; R ((R )1=2 ; x (R )1=2 )2
12 23
31
23
12
; R23)(1 ; R31 ) x
Tmin = (1 + x (R (1R; )R1=122))(1
,
2 ; R ((R )1=2 + x (R )1=2 )2
12 23
31
23
12
(2.41)
(2.42)
22
where R12 , R23 , and R31 are the reectances at the air-lm, lm-substrate, and
substrate-air interfaces, respectively, and x = exp;f d . Expanding the trigonometric functions in Eqns. 2.39 and 2.40 one obtains
#Tmax = Tmax ; T~max = x2 Tmax ; Tmin ,
Tmax
Tmax
3
Tmin
#Tmin = T~min ; Tmin = x2 Tmax ; Tmin ,
Tmin
Tmin
3
Tmax
and combining these
#Tmin = Tmin
#Tmax
Tmax
2
(2.43)
(2.44)
(2.45)
Using Eqns. 2.43, 2.44, and 2.45, Bah et al. (1993) derive the relation
Tmin = T~min ; #Tmax
T~min
Tmax
!2
(2.46)
for the region of negligible absorption where x = 1. In this case the expressions
describing the extrema then simplify from Eqns. 2.41 and 2.42 down to
Tmax = n22n+0 nns2 ,

0
s
4n n2 n
Tmin = (n2 + n20)(fn2 s+ n2 ) ,
0
s
f f
(2.47)
(2.48)
where n0, nf , and ns are the air, lm, and substrate refractive indices, respectively.
Since Tmax is independent of nf , its value can now be determined and subsequently
used in Eqn. 2.46 to nd Tmin and thus nf . However, Eqn. 2.46 is only strictly
true when Tmin = T~min (i.e. #Tmin = 0) so Bah et al. (1993) make the assumption
that there is no change in the magnitude of the minima due to thickness variations.
There is a denite change in the minima though, as shown in Figure 2.6, and
it is exactly this few percent change in transmission that contains the important
information to enable the optical constants to be correctly determined!
The absorption coecient of the lm is found assuming that the reectivity from
the substrate-air interface R31 is zero. This is not valid for a substrate of nite
thickness, and for glass this value would typically be around 4%.
Using Swanepoel's (1983) model for an a-Si:H lm of thickness d = d" #d and a
substrate refractive index of ns = 1:5 the lm's refractive index nf is found to be
accurate to 0:01 (absolute) (Bah et al. 1993). However, the discrepancy between
theoretical and calculated f values is around 30% at the shortest (600nm) calculated, while at the longest wavelength (1200nm) the error in f can exceed 100%.
Thus, the large number of approximations and the large error in f , which became
apparent after testing the method briey, did not encourage the present author to
investigate the method further.
23
More Recent Advances

Several research groups, working in conjunction with Swanepoel, have continued
to develop and apply the envelope method (M&arquez et al. 1995, Myburg and
Swanepoel 1987, Minkov and Swanepoel 1993). Myburg and Swanepoel (1987) investigated the parameter #d and found it to be an important quantity embodying
the eect of the following four factors:
i. the product of the average refractive index n" f and thickness variation #d over
the illuminated area
ii. the product of the average thickness d" and refractive index variation #nf over
the illuminated area
iii. eect of slit width and,
iv. eect of #nf with depth (perpendicular to the plane of the substrate).
It was recommended that the variation of refractive index nf be determined by
measuring the lm at several points on the sample, and that the slit width be
kept to a value of 1nm or less. The SBW, which depends on the slit width and
the dispersion angle of the grating (Oriel Corporation 1994), is actually the more
important parameter here, rather than the physical slit width alone. It is unclear
what SBW was used in the work of Myburg and Swanepoel. As a mathematical
correction for the last factor does not exist, Myburg and Swanepoel assumed that
there is no variation of nf along the optical axis.
In this work Myburg and Swanepoel monitored the stability of a-Si:H lms over
time, and reported a signicant increase in thickness and decreases in the values
of #d, nf , and f . Values of the optical bandgap Eg were determined by plotting
(f h )1=2 versus (vs.) energy, E or h , where = 1=, commonly referred to as a
Tauc plot. This is implies that
p
f h / h ; Eg ,
(2.49)
and assumes that the density of electron states near the edges of the conduction
and valence bands have a parabolic distribution. It has been shown that
p
3
f hnf / h ; Eg
(2.50)
gives a better t to experimental data for a-Si and a-Si:H than the Tauc plot
(Swanepoel et al. 1985, Klazes et al. 1982).
In 1992, Minkov, rstly, showed that using envelope curves to obtain the optical
constants guaranteed that the solution is always singular (Minkov 1992a). In a
second paper (Minkov 1992b), the eect of angle of incidence and polarisation of
the light was investigated. It was found that using s-polarised light incident at an
angle of 30 provides more accurate results. It was also noted that transmission can
usually be measured to a greater accuracy than reection by most spectrophotometers due to calibration problems. In the strong absorption region, the transmission
spectra yield more accurate kf values, although nf will be less accurate than could
24
Envelopes i () Polar- d (nm) #ns (%) #d (%) #nf (%) #nf (%)
isation
(strong) (weak)
True
0 Unpol. 1000
0.3
0.2
1.8
0.6
True
0 Unpol. 550
0.2
0.2
1.8
0.6
True
30
s
1000
0.2
0.1
1.8
0.6
True
30
s
550
0.2
0.2
1.8
0.6
Computer 0 Unpol. 1000
0
0
4.6
0.4
Computer 0 Unpol. 550
0.8
0.6
2.7
1.2
Computer 30
s
1000
0.1
0.1
5.8
0.3
Computer 30
s
550
0.9
0.8
4.6
1.2
Table 2.1: Comparison of errors in refractive index and thickness values
for both computer and hand-drawn envelopes, various angles of incidence,
light polarisations, and lm thicknesses.
be obtained using reection spectra. Minkov and Swanepoel (1993) developed the
envelope method further by implementing a computer program to t envelope curves
to the transmission and reection spectra. It was claimed that the ENVELOPEy
algorithm of (McClain et al. 1991), a modied form of which was employed by
the author of this work, was not suitable and an alternative method was developed. Minkov and Swanepoel's (1993) algorithm used a parabolic curve t in the
absorbing region of the spectra, and a linear t in the transparent region. A comparison between computer tted envelopes and the "true", which are assumed to
be hand-drawn, envelopes show agreement to within 2%. This algorithm is suitable
for a-Si:H lms but not for a-Si or poly-Si lms which can be absorbing across the
whole wavelength range, and do not necessarily have a at linear region in the NIR.
Additionally, lms that exhibit free carrier absorption in the NIR region could not
be analysed with this algorithm. Error analysis using the computerised algorithm
yielded the results shown in Table 2.1 from the transmission spectra (Minkov and
Swanepoel 1993).
Surprisingly, Minkov and Swanepoel found the error in absorption coecient values
to be less than 0.2% for all cases. Therefore, it was noted from Table 2.1 that the
error in the refractive index of the lm was signicantly greater than all other errors.
The errors in analysis of the thinner lm are higher due to the fewer extrema in the
spectra, which had an upper limit of = 900nm.
M&arquez et al. (1995) used Swanepoel's (1984) method to characterise wedge-shaped
amorphous arsenic trisulphide thin lms using a UV-Vis-NIR spectrophotometer
in the range 0:3 ; 2m. Diuse reectance measurements showed that negligible
amounts of light were scattered from the lms, removing any uncertainty in this
regard.
A second version of Swanepoel method was used by M&arquez et al. (1995) for
obtaining the optical constants (Swanepoel 1984). It is not described in the section
above, however it achieves exactly the same results. The dierence to the initial
y ENVELOPE, written in capitals, refers strictly to the computer program.
25
method is that eect of #d on the extrema is calculated and the output is a set
of extrema for a uniform lm of the same average thickness. The ENVELOPE
algorithm (McClain et al. 1991) was then used to t envelope curves to the corrected
extrema. The author noted that some of the corrected maxima lie above Ts, the
bare substrate transmission level, by up to 1.8% (absolute) which would introduce
serious errors in the analysis. M&arquez et al. found that the accuracy of d" values
for three samples were 1.5%, 2.4%, and 0.8% when compared with surface proler
(Dektak IIA) results, which is higher than expected from the method. The accuracy
of nf and kf results were not supplied.
Laaziz and Bennouna (1996) examined the experimental eect of #d and SBW
using 1 ; 2m thick a-Si lms. The method used models the inverse transmission,
instead of the transmission, of a uniformly thick lm, as an interference-free term
and an oscillatory term. For non-uniformly thick lms two correction terms are
added, and along with non-zero SBW corrections the equation used appears as
follows

1 = expd +R10 R2 exp;d $1 ; R2R3 A2 ] +
T
(1 ; R10 )(1 ; R2 )(1 ; R3 )A
p

2 R10 R2 $1 ; R2R3 A2 ] sin #
(1 ; R10 )(1 ; R2 )(1 ; R3 )A #
2
sin
4
4nf d
3
2
5 cos(1 + 2 ; )
4nf d
2
(2.51)
where = 4nf d=, and 1 and 2 are the phases of the Fresnel reection coecients.
The method nds nf , d", and #d, and the work conrms the work of other authors
in the eects that #d and non-zero SBW have on the interference fringes. It is of
concern to the author that envelope curves were simply tted using a high order
polynomial, as the envelopes do not seem to be a good t to the transmission
extrema in the gures of Laaziz and Bennouna (1996).
Rizk et al. (1996) published a paper investigating the optical properties of sputtered
amorphous and subsequently annealed silicon thin lms. Using Swanepoel's (1983)
method for uniformly thick lms, the optical bandgap Eg for a-Si was found to be
1.25eV, increasing to around 1.40eV for the microcrystalline silicon (c-Si) lms
formed upon annealing.
Finally, it should be noted that more varied uses for the envelope method have
been found. Bovard et al. (1985) used transmission measurements, performed in a
vacuum, to determine the optical constants and thickness of titanium dioxide while
the material is being deposited onto glass. This permits the study in variations of
the optical constants with changes in the deposition conditions, and also identies
any deposited layers that are unstable (e.g. oxygen decient).
After considering all of the above methods, the envelope method of (Swanepoel
1984) came the closest to being able to characterise lms for the present application.
The author decided to investigate this method further, and to try and implement
26
changes which would permit the envelope method to characterise a-Si and poly-Si
lms, which are absorbing across the whole wavelength range. The extensions to
the envelope method developed by the author are presented in Chapter 4.
Chapter 3
Materials and Methods
3.1 Substrates
There are a large range of materials that can be used as substrates for thin lm
solar cells. The most common of these is glass, although stainless steel, sapphire,
and ceramics are also popular. Glass and sapphire substrates were used in this
work, particularly because of their transparent nature, enabling them to become the
protective top surface of the module after encapsulation. In this section, the reasons
these substrates were chosen will be discussed, along with their most important
features, namely:
i.
ii.
iii.
iv.
transmission range
refractive index
structural characteristics - thermal, mechanical and chemical and,
cost.
The transmission range and refractive index determine the amount of light absorbed
or reected by the substrate, and therefore what fraction of the incident light can
be potentially utilised by the solar cell. The thermal characteristics of the substrate
are important when the material undergoes high temperature deposition processes.
In our case, a good match of the thermal expansion coecient will minimise the
number of silicon lms that peel or ake o the substrate. Signicant mechanical
characteristics are strength and resistance to shock, while chemical characteristics,
such as resistance to corrosion from gases and water vapour in the atmosphere,
aect the suitability of the material to harsh environments. Finally, in order to
produce a solar cell that can generate electricity for as few jc/kWh as possible, cost
naturally plays an important role.
3.1.1 Glass
Glass is formed from molten silicon dioxide (SiO2), which when cooled rapidly, forms
a transparent amorphous solid. The glass softens again gradually when heated,
27
3.1 Substrates
28
without exhibiting any sharp melting point. Ordinary glass has an approximate
composition of 76% SiO2 and the remainder being calcium and sodium oxides,
however several other oxides can be added to give the glass dierent properties.
For example, the addition of boron oxide produces borosilicate glass which expands
very little upon heating, while alumina improves the chemical resistance (Gillespie
et al. 1989).
Glass Properties
Most of the glass now used for photovoltaic research was originally developed as a
substrate for at panel displays. One original glass developed for this purpose is
Corning 7059 bariaborosilicate glass and this has been extensively used in thin lm
solar cell research. Bariaborosilicate glass is borosilicate glass with a baria content,
used instead of lime or lead to give the glass a higher refractive index. More recently,
Corning have developed a new boroaluminosilicate glass, coded 1737, which has
several advantages over 7059 (Lapp et al. 1994):
i. the boroaluminosilicate glass can be annealed at higher temperatures due to
a higher strain point, 666C for 1737 versus 600C for 7059
ii. for deposition temperatures up to 350C, commonly used for a-Si deposition,
1737 does not require pre-annealing to ensure minimal thermal shrinkage.
However for poly-Si depositions an annealing step is still needed to reduce
thermal shrinkage.
iii. 1737 has a thermal expansion coecient almost the same as that of silicon,
giving silicon lms deposited onto 1737 glass a greater resistance to thermal
shock
iv. the improved chemical durability of 1737 glass permits harsher cleaning methods to be used with no danger of damaging the surface and,
v. the lower density of 1737 glass still provides a sti front surface for PV modules
while reducing the weight
For the above reasons, the author purchased 250 50mm50mm1.1mm pieces of
1737 glass from Corning for our thin lm silicon depositions.
Optical Characterisation of 1737 Glass

Initially, it was necessary to optically characterise the glass to obtain the most accurate results from the envelope method analysis. Three dierent sets of data for
ns and ks were obtained and the results from each compared. Firstly, Corning supplied refractive index data for seven wavelength values between 436nm and 656nm
(Corning Inc. n.d.), and a more complete data set for both ns and s values was
obtained from Corning upon request (Corning Inc. 1997a). Secondly, transmission
and reection measurements were performed on the glass, and the optical constants
determined with Optikan (Bader et al. 1995). Finally, the ns of the glass in the
3.1 Substrates
29
range 300-800nm was measured using spectroscopic ellipsometry. A comparison

of the results is illustrated for the refractive index in Figure 3.1 and absorption
coecient in Figure 3.2.
-4
Refractive index ns
-6
n1737 = 1.65599 - 6.62248*10 + 1.36881*10
1.54
-9
- 1.59892*10 + 1.0667*10
1.52
+ 7.56102*10
-20
-12
- 5.62614*10
- 3.97249*10
-24
-16
1.50
Corning
Ellipsometry
Reflection and transmission
1.48
1.46
500
1000
1500
2000
Wavelength (nm)
2500
-1
Absorption coefficient s (cm )
Figure 3.1: Refractive index of Corning 1737 glass determined by various

techniques. The solid line is a polynomial t to the data acquired from
Corning (Corning Inc. 1997a), ellipsometry, and reection and transmission.
10
-6
10
-7
10
-8
10
-9
10
-10
10
-11
Corning
Reflection and transmission
500
1000
1500
Wavlength (nm)
2000
2500
Figure 3.2: Absorption coecient s : The solid line is an interpolated

t to the data acquired from Corning (Corning Inc. 1997a).
The results achieved with transmission and reection experiments, and subsequent
analysis using Optikan, are not quite consistent with the other results. This is
because the method is less sensitive than ellipsometry, and there are a wider range
of possible ns and ks values which provide good agreement with the experimental
3.1 Substrates
30
data. However, as the reection and transmission data for ns spanned the desired
wavelength range, a seventh-order polynomial was tted to all three data sets,
and this is displayed in Figure 3.1. Initially it was thought to be doubtful that
the long wavelength (> 2000nm) ns data dropped so far below 1.5, and all possible
experimental errors were considered. Upon further reading, it was found that a local
maximum in s at a certain wavelength is accompanied by a point of inection in
ns very close to the same wavelength, and at longer wavelengths ns can decrease
to values near, or even below, unity (Jenkins and White 1957). This is shown
in Figure 3.3, where a reduction in n for a transparent sample occurs near the
absorption band. Additionally, the limited validity of the Cauchy expression n =
n0 + n1=2 + n2 =4 is indicated in Figure 3.3, where n0, n1, and n2 are constants.
Since it was desirable to optically characterise the 1737 glass into the NIR, a higher
order polynomial, displayed in Figure 3.1, was required to model the dispersion in
the glass and this expression is used in the modied envelope method analysis.
Figure 3.3: Dispersion of a transparent material (similar to quartz),

showing a reduction in n in the NIR due to increased absorption (from
Jenkins and White 1957).
It is not stated how the s data from Corning was measured, but as the sample used
was 3mm thick (Corning Inc. 1997a) the results are likely to be more accurate than
those obtained by reection and transmission experiments. This is because there is
so little absorption in 1.1mm of 1737 glass, the determination of s by reection and
transmission is limited by the noise level. It is interesting to note that the reection
and transmission data follows the same trend as the Corning data, and while it
does not appear to be noisy, it is oset by a factor of 103. This cannot be explained
by the author. However, a thicker sample with increased absorption should result
in more accurate s values, regardless of the method used, and to model the glass
absorption, interpolated values from Corning's data are used, obtained using the
Mathematica function 'interpolation'. The properties of the glass in the IR were
3.1 Substrates
31
Transmission (%)
100
80
60
40
20
0
3
4
Wavelength (m)
Figure 3.4: Transmission of 1737 glass in the IR, showing several strong
absorption peaks beyond 2.6m.
also investigated using Fourier transform infrared (FTIR) spectroscopy after strong
absorption beyond 2.6m was observed with spectrophotometry. As illustrated in
Figure 3.4, no light is transmitted at > 5m, and there are several absorption
peaks between 2m and 5m. The peak at 2.8m is found in all silicate glasses
and is due to the hydroxyl stretch of the Si-OH group. Absorption at 3.7-3.8m
is attributed to an overtone of a boron lattice vibration (B-O stretch), however
overtones of the Si-O stretch are also found at these wavelengths (Corning Inc.
1997b).
Glass Cleaning
Various cleaning methods were tested for their eectiveness on the glass. Initially,
an ultrasound bath containing a beaker of soapy water with the samples mounted
upright was implemented. However, this was found to be unsatisfactory as several
visible spots remained on the sample after one hour of operation. A method used
since then involved cleaning the grease o the surfaces with a lint-free cloth and
liquid soap, rinsing in deionised (DI) water, placing the glass in a beaker of RCA1
(hydrogen peroxide : ammonium hydroxide : DI water in the ratio 1:1:4) and boiling
for 20 minutes. This removes any organic compounds on the surface of the glass.
This step is followed by another DI water rinse, and then blow-drying the plates
with a nitrogen gun. The glass has essentially no visible marks on it after this
procedure, as long as care was taking during the drying stage.
Later, an oxygen plasma etch was used instead to remove contaminants from the
front surface of the glass. Placing the glass in the plasma for 10 minutes proved
successful, and although only the surface which will have a Si lm deposited onto
it is cleaned by this technique it is much quicker and avoids the problem of stains
appearing during drying.
3.1 Substrates
32
3.1.2 Sapphire
Sapphire, crystalline aluminium oxide (Al2O3 ), was also used as a substrate in
this work. Commercially grown epitaxial silicon-on-sapphire (SOS) samples were
available and proved extremely useful as a \test sample" in determining the accuracy
of the envelope method. Thus, sapphire was not used for deposition purposes,
however its properties make it a very interesting substrate material due to (Griot
1995/1996):
i. it being an extremely hard and strong material. This means that substrates
need only to be a few hundred m thick to provide adequate mechanical
support
ii. it is chemically inert and insoluble in almost everything
iii. wide-range transmittance (between 150nm and 6000nm)
iv. it has a relatively good lattice constant match to silicon, and allows epitaxial
growth directly o the substrate (Schl(otterer 1976) and,
v. it has exceptional thermal conductivity.
One disadvantage of sapphire is that, due to its hexagonal crystalline structure, it
exhibits anisotropy in many of its properties, and is birefringent. In a birefringent or
double refracting material, light travelling parallel to the optical axis experiences no
double refraction and passes straight through the material. Light travelling perpendicular to the optical axis experiences one refractive index (ne) for light polarised
in the plane of the optical axis (the extra-ordinary or e-ray), while light polarised
perpendicular to the to the optical axis (the ordinary or o-ray) sees a dierent
refractive index (no). Optical databooks publish data sets for both polarisations
(Palik 1985), however for our purposes the dierence in optical properties remains
relatively small and birefringence causes only a refractive index change of 0.0085
for > 400nm values (Oriel Corporation 1990). For ns
1:77, this eect causes
less than 0.5% variation in ns.
As the SOS samples were manufactured for the electronics industry, the rear (nondeposited) surface of the substrate was roughened to act as a getter (Green 1995).
Thus, the substrate had to be polished in order to specularly transmit light. This
was performed for the author by the polishing unit in the School of Applied Geology.
Figure 3.5 shows the refractive index found from reection and transmission data
using unpolarised light, and widely accepted published data (Palik 1985, Malitson
1962). The refractive index can be described by the following Sellmeier dispersion
relation (Malitson 1962):
2
2
2
1
:
023798

1
:
058264

5
:
280792

nAl2 O3 ; 1 = 2 ; 0:061448212 + 2 ; 0:11069972 + 2 ; 17:926562 .
2
(3.1)
There is relatively little published data on the absorbing properties of sapphire in

the visible and NIR spectrum (Palik 1991). There were only two works found which
3.1 Substrates
33
1.80
Refractive index ns
1.78
1.76
1.74
1.72
Palik
Malitson
Reflection and transmission data
1.70
1.68
1.66
500
1000
1500
Wavelength (nm)
2000
2500
-1
Absorption coefficient s (cm )
Figure 3.5: Refractive index data of sapphire: The solid line is the Sellmeier relation (Eqn. 3.1) derived by Malitson (1962).
10
Reflection and transmission data

Mitchell
-4
sapphire () = 10 ^ [ -6.87209 + 0.05325 - 1.73977*10
10
-7
-17
-31
-10
2
-13
+ 2.90085*10 - 2.77298*10 + 1.57483*10
-21
-25
- 5.22965*10 + 9.3343*10 - 6.86665*10
- 3.25339*10 ]
10
-1
400
800
1200
1600
Wavelength (nm)
2000
2400
Figure 3.6: Absorption coecient data for sapphire: The solid line is a
polynomial t to reection and transmission data while published UV and
visible data from Mitchell et al. (1960) is shown for comparison.
contained absorption coecient values for the visible spectrum (Levy 1961, Mitchell
et al. 1960). The data from Mitchell et al. (1960) extended the furthest into the
visible and this is plotted in Figure 3.6 along with data obtained from reection
and transmission experiments, and Optikan analysis. As the data from Mitchell
et al. (1960) did not span over the desired range, the Optikan data set was chosen
to represent the sapphire absorption and was tted with a ninth-order polynomial,
as seen in Figure 3.6. This equation, along with Eqn. 3.1 are used to model the
optical properties of the sapphire substrate.
3.2 DC Magnetron Sputtering
34
7DUJHW
*DV,Q
9DFXXP
&KDPEHU
3ODVPD5HJLRQ
6XEVWUDWHV
6XEVWUDWH
+ROGHU
'&%LDV
6XSSO\
,QVXODWRU
$QRGH
*DV2XW
Figure 3.7: Schematic of typical DC sputtering system (from Materials

Research Corporation 1975).

3.2.1 System Description
Sputtering is a process which involves the transfer of almost any material from a
target to almost any substrate. The deposition of material is achieved by bombarding the target surface with gas ions accelerated by a high voltage. The transfer
of momentum from the gas ions to the target results in atoms being ejected from
the target. These travel through the vacuum chamber and are deposited onto the
substrate as a thin lm.
When the sputtering target is negatively charged, electrons are ejected into the gas,
argon in this case, near the target. The applied voltage accelerates the electron
towards the positively charged anode, gaining energy from the electric eld. If the
electron collides with a gas molecule it will transfer part of its energy and leave
behind an ion and another free electron. This cumulative eect is called a selfsustaining glow discharge or plasma, as the area where ionisation occurs glows. The
diagram in Figure 3.7 shows the layout of a simple direct current (DC) sputtering
system.
A DC or radio frequency (RF) power supply can be used depending on the type
of material to be deposited. The sputtering system at UNSW was always used
with a DC power supply, which is suitable for depositing conducting materials,
including doped silicon. Due to the often high gas pressures used, DC biasing is
designed to negatively bias the substrate to help eliminate the substantial amounts

Target Dopant Resistivity
No.
Type
().cm)
1
n: P 0:002 ; 0:08
2
p: B 0:005 ; 0:02
3
p: P
2:5 ; 7:5
4
n: P 0:08 ; 0:12
5
n: P
3:6 ; 5:0
76
p: B
0:2 ; 0:5
102
n: P
150
35
Doping Level
Growth Thickness
;
3
(cm )
(mm)
17
19
1:1 10 ; 3:6 10
CZ
1
2:5 1018 ; 1:9 1019
CZ
3
15
15
1:8 10 ; 5:7 10
CZ
3
16
17
6:2 10 ; 1:1 10
CZ
0.4
14
15
9:1 10 ; 1:2 10 Unknown
0.6
3:2 1016 ; 9:6 1016
CZ
0.33
3:0 1013
FZ
0.3
Table 3.1: Range of doping levels and types of sputtering targets available.
of gas that can be incorporated into the lm. As the lm is deposited, it is lightly
cleaned by ions which remove any weakly trapped gas atoms resulting in a lm
with better adherence and greater density (Materials Research Corporation 1975).
Additionally, the substrate may be heated up to around 600C, so poly-Si lms may
be deposited or in situ annealing performed, if desired.
The sputtering system uses a rotary pump to start evacuating the chamber and a
turbomolecular pump to achieve a relatively high vacuum, down to 1 10;6Torr,
in the chamber. Inside the chamber, a shutter is used so that the rst 30 seconds
of sputtered material from the target strike the shutter and not the substrate. This
"pre-sputtering" removes any impurities that were present on the target surface
from being incorporated into the lm. Silicon can typically be sputtered at deposition rates of around 200*
A s;1 using a DC power of 100W and an argon pressure
between 0.5Pa and 5Pa.
3.2.2 Targets and Sputtered Films

Special sputtering targets and 85mm diameter wafers with a wide range of doping
levels were available for use as targets, as given in Table 3.1. The two most commonly used dopants are available, boron (B) and phosphorus (P), and the majority
of the targets are produced by the Czochralski (CZ) process. It should be noted
that, rstly, the same doping level of the sputtered lm as the target will not necessarily be achieved as not all the dopants may be activated in the lm. Secondly, it
is only possible to deposit one lm at a time before the chamber has to opened. It is
suspected that the oxidation that occurs before the lm can be placed in a furnace
may inhibit the crystallisation process, however this has not been demonstrated
yet. Due to the low conductivity it was dicult to sputter highly resistive lms
such as target 102, a oat-zone (FZ) wafer. Ideally, RF sputtering would be used
to deposit such lms.
3.3 Crystallisation
36
3.3 Crystallisation
After depositing a lm, its transmission was usually measured immediately with the
spectrophotometer. Following this, lms were placed into a nitrogen purged furnace
at atmospheric pressure and annealed for a period of 60-80 hours at around 610C.
As mentioned previously, in situ annealing in the sputtering chamber is possible,
however this was not performed due to the high demand for the sputtering system.
The a-Si to poly-Si transition can be observed as the lm colour changes from
reddish-brown to yellow.
3.4 Spectrophotometry
The main focus of this work is the determination of the optical constants of the
Si lms. The machine used for all measurements was a Varian Cary 5G UV-VisNIR double-beam spectrophotometer, illustrated in Figure 3.8. Unfortunately, this
spectrophotometer is not very stable or reliable and it was constantly being repaired
throughout the year, and was out of operation for a total of ve months during 1997.
This meant that a lot of the initially planned work had to be discarded due to a lack
of time, and the majority of the author's time was spent simply trying to maintain
the system.
This section will include a brief description of how the spectrophotometer functions in transmission mode as well as highlighting several potential measurement
problems. Transmission mode was preferred over the use of an integrating sphere
for collecting reection data due to the larger errors and noise associated with the
latter.
Figure 3.8: The unreliable Varian Cary 5G UV-Vis-NIR double-beam

spectrophotometer.
37
3.4.1 System Description

The Cary 5 optics are based around a double monochromator with the optical arrangement shown in Figure 3.9. Double-monochromators have better resolution
and stray light rejection than single single-monochromators. The Cary uses a tungsten halogen lamp as the visible and NIR source, and a deuterium lamp as the UV
source. An automated carousel swaps the lamp being used at a specied wavelength
l , typically 300nm. Light from the lamp passes into the rst monochromator via
mirrors N1, N2, N3 and N4, then through the lter mechanism, designed to keep
stray light from entering the second monochromator.
The collimating mirror N5a directs the beam onto the diraction grating where it
is dispersed into its constituent wavelengths. The gratings are double sided and
ruled at 1200 lines mm;1 for the UV-Vis spectrum and 300 lines mm;1 for the NIR,
relying on a motor driven chain to ip between them at the detector change-over
wavelength dc. The light enters the second monochromator, and is reected o the
second collimating mirror N5b which directs the light through the exit slit.
A chopper, spinning at 30 revolutions per second splits the light into sample and
reference beams. The chopper produces three states during each revolution, namely
sample, reference, and dark. The rst state uses the mirror section of the chopper
to reect light into the detector compartment via mirrors N9S and N10S. In the
reference state, light passes straight through the chopper and o mirrors N8 and
N9R to the detector compartment. The dark state is where a black metal plate
blocks the beam, and during this period the monochromator changes wavelengths.
Light passing through the sample or along the reference beam path is detector
by a photomulitiplier tube (PMT) in the UV-Vis region and a lead sulphide (PbS)
detector in the NIR. The detectors are changed in unison with the gratings, typically
at dc values of 800 ; 850nm.
The principle advantage of a double-beam spectrophotometer is that uctuations
in lamp intensity do not aect the transmission measurements. This is because a
reference is constantly being taken throughout the scan, and the nal transmission
value does not rely only on a previously measured reference scan as a single-beam
machine does.
Before a transmission measurement can be performed, it is necessary to assign a
value to certain parameters, which include:
i. scan range, e.g. 300 ; 2600nm
ii. interval, usually set to 1nm steps for an accurate transmission spectra
iii. averaging time - the time that the monochromator remains at each . Typically set to 0.33s for a noise-free spectrum, this results in the average of ten
readings being recorded at each
iv. SBW - this parameter and its various options will be discussed at length in
the following section
v. slit height - options include full or reduced, producing a 13.4mm or 9.1mm
high beam image in the focal plane, respectively and,
Figure 3.9: Varian Cary 5G spectrophotometer optical layout.
38
39
vi. dc and l - typically 850nm and 299nm (to avoid unnecessary UV lamp
usage), respectively.
The Cary must be left on for at least two hours to warm-up, as the PbS detector is
sensitive to temperature variations and is constantly receiving blackbody radiation
emitted from the black plate in the chopper. Before transmission measurements
can begin, a `zeroline' is performed with a black metal plate blocking the sample
beam, followed by a baseline where no sample is present. These two scans must
always be performed as they dene the 0% and 100% transmission levels.
3.4.2 SBW and Energy Level

The SBW is determined by the physical slit width and the dispersion angle of the
grating, and setting the SBW can be performed in several ways. To resolve sharp
absorption peaks, the SBW should ideally be as small as practically possible, around
1nm. However, a low SBW reduces the beam size and the intensity of the beam.
This signal reduction poses no problem to the PMT due to its high internal gain,
but the PbS detector has a poor sensitivity just above the detector change-over
wavelength dc and at > 3m and the experimental data becomes extremely
noisy at low SBWs.
The method implemented by Varian to improve the signal-to-noise (S/N) ratio was
to introduce another parameter confusingly termed the ènergy level', EL, which
aects the amplication of the signal caused by the reference beam striking the
detector (Varian Australia OS/2 software version). In the NIR, the EL is set to be
a constant value of usually 3.0 to minimise non-linearity errors, as this EL value
used for calibration purposes. This results in the SBW being constantly varied at
each , presumedly, in order to maintain a high enough light intensity reaching the
PbS detector. A plot of how the SBW varies with at various ELs is plotted in
Figure 3.10. In the normal mode of operation, called àuto', the SBW will be large
and possibly at its maximum value of 20nm at the limits of the PbS detector, and
then suddenly jump to a low constant value throughout the UV-Vis spectrum.
Often it is desirable to have a constant SBW, and that the illuminated area on the
sample remains constant at all wavelengths. This is important for interference fringe
measurements as the thickness variation in samples will generally be greater over a
larger area, and if the SBW is of the same order of magnitude as the period of the
interference fringes then compression of the fringes will result. The requirements
of the envelope method are that the same area on the sample is illuminated at all
wavelengths, the thickness variation can be approximated as being linear, and the
SBW is kept to a small constant value (Swanepoel 1984).
This an is extremely dicult criteria to fulll for a UV-Vis-NIR spectrophotometer
covering such a large range and including a grating change-over. After exhaustive
experimentation, the solution in this case has been to use the settings SBW=2nm
in the visible and EL=3.0 in the NIR. This minimises any step that may appear in
the transmission spectrum due to non-linearity errors in detector calibration and
produces 'noise-free' (more than adequate S/N ratio) data. There have not been
any problems observed with the magnitude of the SBW compressing the interference
40
20
EL = 1
EL = 3
EL = 10
SBW (nm)
16
12
8
4
0
500
1000
1500
2000
Wavelength (nm)
2500
3000
Figure 3.10: Variation of SBW with for a range of energy levels in

'auto' mode, where the SBW is xed in the UV-Vis region. A signicant
step at the detector change-over wavelength dc = 850nm can be seen.
fringes, and the period of the fringes at 850nm is typically of the order of 100nm.
In the worst case, this may result in an interference fringe in the 850-900nm range
being slightly compressed, but since the spectra extend both well above and below
this region the error induced would be minimal.
3.4.3 The Step!

All UV-Vis-NIR spectrophotometers that use two detectors, so their hapless users
are faced with a multitude of problems when trying to avoid the appearance of a
'step' in transmission or reection data at the detector/grating change-over. This
investigation was complicated by the fact that the detector and grating change-over
wavelengths could not be de-coupled. The possibility of a step was already mentioned in the previous section, where a sudden change to a larger SBW illuminates
a greater area of the sample which may be of a dierent average thickness, thereby
changing the value of the transmission. Other possibilities, all investigated by the
author, include:
i. dierent optical paths for visible and NIR light
ii. misaligned detectors
iii. polarisation eects
iv. blackbody radiation and,
v. birefringent samples.
It is believed that the Cary is slightly optically misaligned, and that the sample
beam has a slight horizontal oset when changing between the gratings. This was
determined by measuring a non-uniformly thick sample in several positions, and
41
Figure 3.11: Measurement positions of a sputtered silicon on glass sample

with darker rings representing greater thickness and the white region the
illuminated area.
Transmission (%)
100
Measured at (a)
Measured at (b)
80
60
40
20
0
500
600
700
800
Wavelength (nm)
900
Figure 3.12: Evidence of a step due to horizontal beam oset at the

detector change-over, dc = 800nm.
nding that when the beam was aligned perpendicularly to the visible interference
fringes from in the lm no step resulted, while a beam aligned within a single fringe
produced a 5% step, Figures 3.11 and 3.12. A change in SBW at dc can be ruled
out as the cause of the step as it is the average optical thickness nf d", and thus
the period of the fringes, which has changed. This can be explained by observing
the curve in Figure 3.12, just above 800nm where it has reached a local maximum,
and then noticing that just below 800nm it reaches another maximum. This occurs
when d" has changed, therefore beam is no longer centred on the same location.
Misalignment of detectors, a problem also experienced with the Cary in 1997, will
produce a step at dc if the dierence between the visible and NIR signal levels is
too great for the Cary to correct for. Various electrically erasable programmable
read-only memory (EEPROM) chips which store tabulated values required by the
software to correct for the step were updated, although no improvement was noticed.
Extensive alignment of both detectors was performed by Varian Australia and the
problem has since disappeared.
42
Polarisation can often cause a step since the PMT is more sensitive to linearly
polarised light than unpolarised light. The baseline takes into account any polarisation of the light from the lamps, however if the sample introduces any polarisation
change an increase in transmission in the visible region is possible. Although this
is not usually a problem for normally incident light, it is a real concern for light
incident at angles greater than 30, and in this situation a depolariser should be
placed between the sample and the detector. An Oriel broadband (250 ; 2500nm)
depolariser (Oriel Corporation 1990) was purchased and tested, but no reduction
in the step was observed.
Blackbody radiation emitted from the chopper is problematic when small (less than
1nm) SBWs are used, as this radiation comprises a signicant fraction of the total
light striking the detectors. This was not an issue in the transmission measurements
performed though, as a SBW2 was always employed.
To date, there has not been a step which can be attributed to being caused by
the use of a highly birefringent sample, for example sapphire. Such a sample could
produce a step, either due to the emerging beams striking an increased area on the
detectors, or polarisation eects. The sapphire samples measured in this work were
less than 0.4mm thick, so any shift in the path taken by a beam would be small
and thus the beam is essentially striking the same area of the detector. This may
not be the case for samples of the order of a few millimeters thick.
3.4.4 Scattering Samples and Aperturing

Light striking a slightly rough interface will be partly specularly transmitted and
reected, and partly diusely transmitted and reected. The fraction of scattered
light and its angular distribution depend not only the refractive index, but also
the degree of surface roughness and angle of incidence (Tao 1994). In transmission
mode, light that is not specularly transmitted will not be collected and is therefore
lost. Accurate envelope method analysis cannot be performed on samples which are
scattering. A helium-neon (He-Ne) laser, incident at 20 on the lm, was used to
check any degree of scattering in the sputtered samples. The use of the integration
sphere to collect nearly all the diusely transmitted light may be useful for scattering
samples, however this has not been performed and one would need to consider the
eect that scattering has on the interference fringes. It would also be necessary to
determine what fraction of the scattered light passed out the front of the sample,
not being collected.
Aperturing of the sample in the focal plane using a sheet of black card was performed when it was absolutely necessary to ensure that the same area of the sample
was illuminated at all . This also introduces the question of scattering from the
edges of the aperture, however samples measured in this manner have been successfully analysed. The method for checking the overall accuracy of the results will be
described later in this chapter.
3.5 Other Characterisation Techniques Used
43
3.4.5 Rotating Sample Holder

A new sample holder, shown in Figure 3.13, was designed and constructed in order to
measure the transmission at various angles of incidence. An manual x-y translation
stage with 13mm of travel was employed to be able to position the front surface of
a sample (up to 5mm thick) about the axis of rotation. The rotation stage could
be read to an accuracy of greater than 0.1. The motivation for this was to use
the angular rotation method developed by Swanepoel (1985), briey described in
Section 2.2.1. Due to the extended length of time that the Cary was out of action,
this method has been developed but not tested.
Figure 3.13: Rotating sample holder designed to t inside the Cary sample compartment.

Various other characterisation techniques were used to analyse the samples. These
include FTIR and Raman spectroscopy, sheet resistance meter, and a thickness
proler.
FTIR Spectroscopy
As mentioned previously, FTIR spectroscopy was used to observe the absorption
peaks in the 1737 glass in the IR region of the electromagnetic spectrum. A Nicolet
Model 520 machine was used to perform this experiment on two clean glass plates.
Thickness Proling
A Dektak IIA thickness proler was used to determine the thickness of the sputtered
silicon samples. To perform a measurement it is necessary to etch a hole through
44
the silicon lm to the substrate. This can be achieved with either a drop of boiling
potassium hydroxide being placed on the lm, or by using the oxygen plasma etching
machine with a hole drilled in a mask placed over the front surface. The thickness
was not measured for all samples due to the destructive nature of the method, as
samples could not then undergo further optical characterisation.
Sheet Resistance Meter

To measure the sheet resistivity s ()=2) of the sputtered lms, a four-point-probe
(FPP) was used, where a known current is passed through two outer probes and
the voltage drop measured across two inner probes. From s , the resistivity of the
lm is f = d s ().cm), where d is the lm thickness.
Raman Spectroscopy
The Raman spectra of the samples were measured with a Renishaw Model 2000
machine located in the School of Materials Science at UNSW. Raman spectra are
useful for analysing the degree of crystallinity of the poly-Si and any stress or strain
that may be present in the lm. An IR laser, = 780nm, was used as the source
so that the beam was approximately uniformly absorbed throughout the whole
thickness of the lm. Typical Raman spectra for a-Si, poly-Si, and c-Si are shown in
Figure 3.14. Raman lines are usually expressed as a frequency shift in wavenumbers,
having the units of inverse centimeters, where 1cm;1 = 10000/ (m), relative to
the laser line at 0cm;1. The Raman peaks arise from the interaction of a photon
with an optical phonon(s), resulting in a phonon(s) either being absorbed or emitted
in the process. The Raman spectrum of a-Si is closely related to the phonon density
of states (DOS). The three broad peaks of a-Si at 150cm;1y, 300cm;1, and 480cm;1
correspond to interactions of a photon with a transverse acoustic (TA), longitudinal
acoustic (LA), and transverse optical (TO) phonons, respectively. An estimate of
the degree of disorder in the material can be obtained from the ratio of TO to TA
peak heights (Baba et al. 1994), and another measure is the width of the TA peak
at half-maximum (Beeman et al. 1985).
In crystalline material, energy and momentum must be conserved, and since a
photon has close to zero momentum the phonon must also have this same value. A
single optical phonon near the zone centre satises this criterion, and this gives rise
to a high intensity peak at 520cm;1, along with other smaller peaks at 300cm;1
and 960cm;1, corresponding to multiple phonon processes (Green 1995).
The broadening of the 520cm;1 peak on the low frequency side is attributed a relaxation of the zero phonon momentum rule, due to the presence of grain boundaries
in the material. This means that phonons with momentum greater than zero can
participate in a Raman scattering event. Thus, phonons of energy less than 64meV
(520cm;1) are involved, leading to a broadening of the peak on the low wavenumber side (Benrakkad et al. 1994). For very small grain sizes a shift in the peak to
y The TA peak at 150cm;1 appears to be closer to 180cm;1 in Figure 3.14, due to the cut-in
of the laser-line absorption lter
Norm. Raman Intensity (a.u.)
45
1.0
TO
LA
0.8
0.6
TA
a-Si
poly-Si
c-Si
0.4
0.2
0.0
200
300
400
500
-1
Frequency Shift (cm )
600
Figure 3.14: Typical Raman spectra for a-Si, poly-Si, and c-Si.
lower wavenumbers is also observed (Fauchet and Campbell 1990), however stress
or strain in lms is another mechanism which has the same eect.
Chapter 4
Optical Characterisation using the
Modied Envelope Method
Since the optical characterisation methods described in Chapter 2 were limited in
scope, it was necessary to develop a method that was capable of characterising a-Si
and poly-Si lms, which are absorbing over the whole wavelength range. In this
chapter, the development, details, and tests of the method will be described. In the
next chapter, the method is applied to the experimental samples of a-Si and poly-Si
on glass.
The modied envelope method developed by the author, is an extension to
the envelope method presented by (Swanepoel 1984), and is implemented as a
Mathematica (version 2.2.3) program. Written by the author, the complete program
listing is included in Appendix B. The program has been dubbed 'NAKED' as it
nds the lm's refractive index nf , absorption coecient f , extinction coecient
kf , the optical bandgap Eg , and thickness d { essentially revealing a lm's bare
optical essentials. Although this is actually the method used to obtain results, it
is, in itself, the major result of the present author's work and is therefore presented
its own chapter.
4.1 Overview of Procedure

Figure 4.1 is a ow diagram showing the necessary steps for nding the optical
constants and thickness of a thin lm. Parallelograms and diamonds in the diagram
are used to indicate that an input or a decision, respectively, from the user is
required, while T is an abbreviation for transmission. An improved version of
the original ENVELOPE (McClain et al. 1991) algorithm is used to accurately t
envelope curves to the transmission spectra (McClain 1997). Several executions of
the ENVELOPE program are necessary before the tightest tting tolerances can
be found, but this procedure does not take more than ve minutes. The output le
from ENVELOPE is then used as the primary input to NAKED, along with ns and
s data for the substrate. If the correct #d has been supplied then the transmission
extrema calculated from the determined optical constants and thickness should lie
exactly on the original transmission spectrum. If this is not the case, the program
46
4.2 ENVELOPE Fitting
47
will have to be re-executed and a lower value for #d used. This is explained fully
in Section 4.3.2.

The ENVELOPE algorithm is normally run in a DOS window operating with Windows 95. Modications to the program were performed by the author in conjunction
with McClain (1997), and several important improvements were made:
i. to obtain accurate results the maximum number of data points was increased
from 1200 to 3000, permitting analysis of spectra with a 1nm wavelength
interval
ii. in the original version, each data point was replaced by the average of itself and
its two neighbouring data points (McClain 1997). This was designed to handle
noisy data sets, however it often resulted in the extrema being intersected in
two places by the 'tangential' envelope curve. The section of code performing
this operation was commented out and the program re-compiled.
iii. the y-axis (transmission) on graphical output was altered so that the scale
would always be between 0% and 100% and,
iv. the size of the array which performs the nal smoothing of the envelope curves
was increased so that smoother ts of the envelopes to the transmission spectra
could be obtained. Previously, a problem was encountered with the accuracy
of the generated envelope curves, and tting errors of up to 0.3% (absolute
transmission) were observed. Increasing the array size so that lower nal
smoothing tolerances could be used greatly improved the situation. A comparison of two sets of envelope curves tted with the old and new versions is
given in Figure 4.2.
The rst step taken in tting the envelope curves involves the experimental data
from the Cary being sorted by ascending wavelength and manually deleting the data
for transmission values less than 0.05%. The latter is required since the uctuations
in the signal at this level due to noise are treated by the ENVELOPE algorithm as
being extrema. Both the initial and nal tolerances should be decreased to values
as low as possible to obtain the most accurate envelope curves possible. When
accurate envelope curves are achieved, the output le (*.tan extension) containing
the tangential points is saved. This format has three columns of data, , Tmax,
and Tmin , and is used as the input to NAKED. It is necessary to manually delete
the data associated with the rst and last extrema as the transmission values are
inaccurate due to the lack of two neighbouring extrema to provide an accurate t
(McClain et al. 1991). A PostScriptTM graphic of the transmission spectra and
envelope curves can also be generated by ENVELOPE.
48
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constants and thickness of a sample with the modied envelope method,
implemented with ENVELOPE and NAKED computer programs.
4.3 NAKED - The Modied Envelope Method
49
92
Transmission (%)
91
90
39
Transmission data
New version
Old version
38
37
1000
1200
1400
1600
1800
Wavelength (nm)
2000
2200
Figure 4.2: ENVELOPE version 2.01b ts the envelope curves much
more accurately than the original version.

4.3.1 Envelope Method Extensions
The modied envelope method, developed by the author, is an extension to the
envelope method Swanepoel (1984). Swanepoel developed the envelope method to
analyse inhomogeneous (in d or nf ) a-Si:H thin lms. These lms are essentially
transparent at wavelengths greater than 800nm (1.5eV), and this transparent region
is required by Swanepoel's (1984) method. For the present application, the lms are
a-Si and poly-Si which can absorb light over the whole range of the spectrophotometer, due to signicant defect levels in the material. Although the author's
extension which overcomes this requirement, and several other modications, will
be discussed later in the section, briey these are:
i. generating transmission data points, by feeding the optical constants (nf , f )
and thickness (d", #d) values back into the equation describing the transmission, and checking whether the points are in good agreement with the
original transmission spectrum. Due to the dierent eect of #d and f at
certain wavelengths, lms that are absorbing over the whole spectrum can be
characterised
ii. the inclusion of substrate absorption, which can be important at certain wavelengths. This was not included in Swanepoel's (1984) method, but even for
some types of glass, and especially sapphire, the absorption can be signicant
and,
iii. the use of the new version of the ENVELOPE algorithm (McClain 1997) which
50
has a much greater accuracy than the earlier version (McClain et al. 1991)
(see Section 4.2).
4.3.2 NAKED Operation

The ow diagram of Figure 4.3 shows the steps taken in NAKED to determine the
optical constants and thickness of a thin lm on a thick substrate. The program
takes the tangent data le (tabulated columns of , Tmax , and Tmin ) as its primary
input.
In order to obtain the most accurate answers from the program the user must supply
both the ns and s data for all wavelengths. Although Swanepoel (1984) used a
constant ns for the analysis, any signicant variation away from this ns value, or
substrate absorption, results in substrate properties being falsely attributed to the
lm. The ns and s values should be determined by reection and transmission
measurements if no data from the manufacturers or spectroscopic ellipsometry is
available. The data is implemented in the program by using interpolated values,
or by tting an Cauchy or other polynomial equation to the data, thus obtaining
expressions for ns and s as a function of (in nm).
To a rst approximation, absorption of the light passing through the glass can be
taken into account with the term exp;sds , where ds is the substrate thickness in
centimeters. When the whole transmission expression is divided by this term only
the rst pass through the substrate is being treated, however subsequent reections
within the substrate are of such a small magnitude that these can be neglected.
Considering the fraction of the primary beam that is internally reected within the
glass and nally passing out the rear of the sample to be collected, the contribution
that this secondary beam makes to the absorption is less than 0.7% in comparison to
the primary beam (calculated using nc;Si = 3:5, nglass = 1:5). As an example, in the
most absorbing substrate used in this work, sapphire (ds = 0:04mm,
0:1cm;1),
0.4% of the primary beam is absorbed in the sapphire, so the amount of absorption
in subsequent passes is well below the accuracy threshold of the spectrophotometer
and can be neglected. It is estimated that the Cary can measure transmission to
within 0:1% over the whole range, although the machine must only be accurate
to within 2% in the visible to pass its own validation and accuracy tests (Varian
Australia OS/2 software version). Thus, the transmission extrema are corrected for
primary beam absorption in the substrate by dividing the extrema by exp;s ds , and
a table is printed by the program showing the new extrema values.
The transcendental expressions for the maxima and minima, Eqns. 2.35 and 2.36,
are then solved simultaneously for #d and nf using the new extrema values and
the coecients given in Eqn. 2.37. As absorption is ignored in this instance, the
aim is solely to determine a value for #d and the values determined for nf are
ignored. Establishing the #d can be achieved by plotting #d vs. . If the lm
has a transparent region in the NIR, which is the case for a-Si:H and c-Si but
not a-Si or poly-Si, #d is the asymptotic value at these wavelengths. For a lm
which is absorbing over the whole measured spectrum, the asymptotic value at long
wavelengths should be used as an initial guess. It is likely that this value is too high,
as what is actually absorption in the lm is being falsely attributed to the thickness
51
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Figure 4.3: Flow diagram showing the steps taken by NAKED in determining the optical constants and thickness of a sample.
52
Transmission (%)
90
80
70
60
50
40
30
800
900
1000
Wavelength (nm)
1100
1200
Figure 4.4: Comparison of modelled transmission spectra for a 2000nm

thick lm with the following properties: Uniform lm (solid curve), #d
lm (short dashed curve), increased f lm (dotted curve), and the bare
substrate transmission (dashed curve).
variation. Fortunately, #d and f have dissimilar eects on the spectrum, which

is shown in Figure 4.4, where the transmission spectra of 2000nm thick lms with
the following properties are plotted:
i. #d = 0nm, f = c-Si, nf = c-Si
ii. #d = 20nm, f = c-Si, nf = c-Si and,
iii. #d = 0nm, f = 2c-Si, nf = c-Si.
The eect of #d on the extrema is to compress the maxima and minima at all wavelengths, while increased absorption reduces the geometric mean of the transmission
spectrum. The incorrect attribution of absorption to a #d eect will be seen at
the end of the analysis when the optical constants and thickness values are used to
regenerate the extrema. If these points do not lie on the original transmission spectrum then it is most likely that #d has a lower value than initially thought. This
method of checking the solution to the transmission equation can be relied upon
due to existence of a single solution (Minkov 1992b, Swanepoel 1984). An example
is given in Figure 4.5, where the generated transmission points for #d = 0nm and
#d = 12nm from the analysis of an experimental lm are compared to the original
transmission spectrum. The NIR data for #d = 0nm has up to a 4% (absolute)
error. The points generated using #d = 0nm do not have lower minima than for
#d = 12nm due to variation in the other parameters (nf , f ). For the example
shown in Figure 4.5, the f increased signicantly, while nf decreased by a lesser
amount.
Having found a value for #d, Eqns. 2.35 and 2.36 are again solved simultaneously,
this time for nf and f using the absorbing coecients ax and bx given in Eqn.
53
Transmission (%)
100
80
60
40
d = 0nm
d = 12nm
20
Original transmission spectrum

0
600
800
1000
1200
1400
1600
Wavelength (nm)
1800
2000
Figure 4.5: Plot showing error that results when #d is not taken into
account. This plot is used to determine whether #d has been determined
correctly or not.
2.34 in place of a and b. In the region of strong absorption the interference fringes
become small and experimental errors in the magnitude of the last few extrema can
cause large errors in f (Swanepoel 1983). The number of points, counted from
the NIR, which do not produce noisy f data is set by the variable strabs, taking
the default value of the number of extrema, leng. However, if, for example, the last
three extrema resolved in the strong absorption region produced wildly varying f
values, strabs could be set to leng-3 and the f at these wavelengths calculated
later. A Cauchy equation is tted to the non-noisy nf data points in the remainder
of the spectrum, and values for the noisy nf data replaced with extrapolated values.
Plotting Eqn. 2.30, shown in Figure 4.6, yields a straight line of slope 2d". The
y-intercept is the negative of the order number m1 of the rst extrema visible in
the NIR, labelled rstm in the program. The value for rstm has to be supplied by
the user, but this is simply a matter of determining the y-intercept to the nearest
half-integer or integer value, if the rst extrema visible in the NIR is a minima or
maxima, respectively. One should remember that the rst two NIR extrema are not
normally used as only one envelope curve is present, while the last extrema resolved
in the region of medium to strong absorption is often erroneous. The straight line
will be a poor t to the points if the wrong rstm value is given, and one (1) should
be added to or subtracted from rstm and the step repeated. After this stage d"
and #d have been determined.
The order number m of each extrema (7.5, 8, 8.5, etc. in the case of Figure 4.6) and
d" can now be fed back into Eqn. 2.17, yielding more accurate nf values. Equation
2.17 is not strictly valid in the absorbing region, however the use of the points where
the envelope curve is tangential to the transmission spectrum instead of the value
at the minima or maxima corrects for the absorption (Swanepoel 1984). Once these
54
15
10
5
0
-5
0
0.001
0.002
0.003
0.004
0.005
Figure 4.6: Graph of l=2 (vertical axis) vs. nf = (horizontal axis). The
straight line has a slope of 2d" and intercepts the y-axis at exactly m1 =
;7:5, as the rst observable NIR extrema in this case was a minima
(Swanepoel 1983).
nal values are determined, another Cauchy equation is used to extrapolate nf

values into the interference-free region. This is necessary as there is no means of
extracting nf values from the interference-free transmission curve alone. The nf
values are required to estimate the amount of light reected from the lm, and
thereby obtain f results. The error introduced by using an extrapolated nf is
small, due to the dominance of f terms at these wavelengths, but naturally this
will depend on how appropriately the Cauchy equation can describe nf ().
The value of x is then determined for the number of points given by strabs, using
the geometric mean T (Eqns. 2.28 and 2.29) rather than the maxima and Eqn.
2.26 as recommended by Swanepoel (1983). The geometric mean was found to
produce more satisfactory results for all the lms measured experimentally by the
present author. For wavelengths shorter than where the last extrema is resolved,
the same equation for calculating x can be used, simply taking the transmission
value directly from the original transmission spectrum and using the extrapolated
nf values. This completes the determination of the optical constants, and a table
displaying all results ( (nm), ns, nf , kf , E (eV), and f ) is displayed and saved in
the *.nak output le.
All the optical constants are then plotted, starting with nf , and comparisons made
with c-Si values (shown in red in NAKED). Log plots of poly-Si f data have proven
extremely useful, as information about absorption due to grain boundaries, defects
in
material, and free-carrier absorption (FCA) can be gained. Additionally,
pthe
and 2 vs. E graphs are displayed, as a straight line dependence will indicate
indirect and direct electron transitions, respectively, occurring at various photon
energies (B(oer 1990). In the a-Si lm analysed
in the program listing in Appendix
p
B, two straight sections of the curve in plot can be seen. The steeper slope is
an indirect electron transition at 1:41 0:01eV, while the shallower slope is another
absorption process in a-Si, known as band-tailing (Urbach tail). In a-Si the disorder
in the lm causes a broadening of the absorption tail, due to sub-bandgap defects
4.4 Modied Envelope Method Verication
55
(Kanicki 1992). The absorption in this region (f < 103cm;1) has an exponential
dependence on energy (Kanicki 1992),
f
expE=E0 ,
(4.1)
where E is the photon energy and E0 the Urbach parameter.

The optical bandgap Eg may be dened using the concept of indirect optical transitions, and accounting for the loss of the k-selection rule in disordered materials
(Kanicki 1992), where k is the wavenumber related to the momentum. The assumptions are (Kanicki 1992), rstly, that optical transitions occur between the
extended states of the valence and conduction bands where the density of states
have a square root dependence on energy. Secondly, the momentum matrix element remains constant. There is no particular structure at energy Eg , but the
optical bandgap has some physical signicance and is commonly used in optical
characterisation (Kanicki 1992).
p
From Tauc plots of h vs. E , one can determine Eg of the material by drawing a
line through a straight section of the curve and reading o the x-intercept value (see
for example Mott and Davis 1971, Dyer et al. 1993, Swanepoel et al. 1985, Bustarret
and Hachicha 1990, Saitoh et al. 1991). The Tauc plot can be applied to c-Si
below the direct bandgap and information about the indirect transitions
p obtained
(Bustarret and Hachicha 1990). Other researchers have found that 3 nf h vs.
E gives a better t to a-Si experimental data, and values for the Eg determined
in this manner have been found to be 10% lower than the Tauc determined value
(Swanepoel et al. 1985, Klazes et al. 1982).

Before analysing a-Si and poly-Si lms, it was necessary to establish the accuracy
and limits of the modied envelope method, and to determine whether NAKED
functioned correctly. Firstly, transmission data was generated for a theoretical
a-Si:H lm on glass, as used by other researchers, to check agreement of results.
Secondly, a theoretical c-Si lm, with optical constant data being taken from the
literature, was implemented to determine the accuracy limits of the method. Finally,
an epitaxial silicon-on-sapphire (SOS) lm was used as the 'test' sample, since the
properties of such lms are well documented and the optical constants have similar
values to bulk c-Si.
4.4.1 Theoretical a-Si:H Film on Glass

For the initial test of NAKED, the a-Si:H model lm used by Swanepoel (1983)
was employed (see Section 2.2.1). The refractive index of the glass (non-absorbing)
was set to a xed value of ns = 1:5, while the lm thickness was chosen to be
d = 100030nm. Figure 4.7 shows the transmission spectrum of the lm, calculated
by feeding all the parameters (ns, nf , f , d", and #d) into Eqn. 2.33, which describes
the transmission of light through a non-uniformly thick, thin lm and numerically
56
integrating using Mathematica. Transmission data was generated at 1nm intervals

over a similar range which could be measured with the spectrophotometer. The
envelope curves were tted using ENVELOPE with initial and nal tolerances of
0.005 and 0.0001, respectively.
Transmission (%)
100
80
60
40
simulated a-Si:H film, d = 100030nm

Envelope curves
Ts for ns = 1.51
20
0
600
800
1000
1200 1400 1600

Wavelength (nm)
1800
2000
2200
Figure 4.7: Plot showing the transmission spectrum and envelope curves
for an modelled a-Si:H lm on glass
As the transmission data was generated from a theoretical model, the aim of the
exercise was purely to see how close an agreement there would be between the
extracted optical constants and thickness, and the values used as inputs to the
equation. Additionally, any limits on the accuracy of nf in strongly absorbing
regions,where no interference fringes can be resolved, and the accuracy of f in
very weakly absorbing regions of the spectrum could be determined.
NAKED determined the thickness of the modelled a-Si:H sample to be d = 1000
30:0nm, which is accurate to within 0.1%. Plots comparing the calculated optical
constants, nf and f against the functions used for the input values are shown
in Figures 4.8 and 4.9. As can be seen, the agreement between the two sets of
data is excellent. The maximum deviation of calculated nf values, occurring in the
region of strong absorption, from that of Eqn. 2.5 is 0:012 (absolute), or 0.3%.
Absorption coecient data is accurate to within 10% down to f & 5cm;1, and
below this level the error in the results approaches 100%.
The results are poorer than expected around the
103cm;1 level, with errors in
f (when compared to theoretical values) at the extrema at 614nm and 597nm near
10%. As can be seen in Figure 4.10, this is due to a slight error in ENVELOPE locating the maxima and minima at 614nm and 597nm, instead of 616nm and 598nm,
respectively. The errors at f < 5cm;1 arise because the method is not designed to
detect very weak absorption, and any slight change in the intensity of the interference fringes at a certain can be interpreted as absorption. Swanepoel (1983) found
the f results obtained with the original envelope method were accurate only down
to a level of 100cm;1. As the only improvement to Swanepoel's (1984) basic method
3.6
3.2
2.8
600
1000 1400 1800

Wavelength (nm)
Figure 4.8: Theoretical and calculated nf data for a-Si:H
-1
NAKED
Theory
10
10
10
10
10
10
10
-1
Abs. Coeff. f (cm )
Refractive Index nf
4.0
57
NAKED
Theory
0.8
1.2 1.6 2.0

Energy (eV)
2.4
Figure 4.9: Theoretical and calculated f data for a-Si:H
Transmission (%)
64
a-Si:H film
Envelope
60
56
52
48
44
592
596
600
604
608
Wavelength (nm)
612
616
620
Figure 4.10: Slight error in ENVELOPE locating the maxima at 614nm

and the minima at 597nm.
that was used in determining the optical constants of a-Si:H was the ENVELOPE
program, it can be concluded that, despite the error at 614nm, a greater accuracy
in envelope curve tting can be obtained using ENVELOPE than can be achieved
by hand-drawn envelopes.
4.4.2 Theoretical c-Si Film on Corning 1737 Glass

Bulk intrinsic (undoped) c-Si values for nf and f (kf ), plotted in in Figure 4.11,
were taken from the literature (Green 1995, Palik 1985) and a transmission spectrum
generated using Eqn. 2.31. Intermediary values were obtained by interpolating
between neighbouring data points, as accurate functions describing c-Si nf and af
58
Refractive Index nf
6
nf
f
5
4
3
2
500
1000
1500
2000
Wavelength (nm)
2500
10
10
10
10
-2
10
-4
10
-6
10
-8
-1
10
Absorption Coefficient f (cm )
values exist only for wavelengths longer than 500nm (Green 1995, Palik 1985). The
thickness of the c-Si lm was 1000 30nm. The ns data for the 1737 glass was
generated using the polynomial expression displayed in Figure 3.1. Absorption in
the glass is not modelled in this example.
Figure 4.11: Intrinsic c-Si nf and f data (Green 1995, Palik 1985)
The main interest in testing NAKED with a second theoretical model, was that the
optical properties of c-Si dier greatly from that of a-Si:H, and the optical properties
of c-Si are similar to the poly-Si lms that were investigated experimentally upon.
Secondly, it was expected that the use of interpolated data for the optical constants
would be tougher to model, especially in the region of strong absorption where nf
values are extrapolated.
The thickness of the lm was determined by NAKED to be 999:8 30nm, an error
of less than 0.1%. Plots comparing the optical constants determined by NAKED
and published data are shown in Figures 4.12 and 4.13. For wavelengths where
the extrema are resolved by ENVELOPE ( > 533nm), the nf data is accurate to
within 0:02 (absolute), or 0.3%. For shorter wavelengths, where the nf is extrapolated, the error nf approaches 0.45 (absolute), which at the shortest (410nm)
corresponds to an error approaching 10%. Thus, as expected, the extrapolated data
cannot be accurately modelled using a Cauchy expression due to the strong dispersion in the strong absorption region. Even though the nf results are less accurate
for wavelengths less than 533nm, the f results obtained in this region are accurate
to within 2%. Absorption coecient values outside the region of strong absorption
were found to be accurate to within 10%, down to f
30cm;1. The f results
obtained using the modied envelope method are once again more accurate down to
lower absorption levels than reported by Swanepoel (1984), and this is attributed
by the present author to the use of the ENVELOPE algorithm. A poor t to
the envelope curves around f
103cm;1 was once again evident and the author
suspects a slight bug exists in the ENVELOPE algorithm. It was not possible to
determine whether the bug could be xed or not due to time constraints.
NAKED
Theory
4.4
4.0
3.6
400
800 1200 1600

Wavelength (nm)
Figure 4.12: Theoretical and

calculated nf data for c-Si on
Corning 1737 glass
-1
Refractive Index nf
4.8
59
Abs. Coeff. f (cm )
10
10
10
10
10
10
NAKED
Theory
1.0
1.5 2.0 2.5

Energy (eV)
3.0
Figure 4.13: Theoretical and

calculated f data for c-Si on
Corning 1737 glass
Therefore, from the above theoretical comparisons, it can be expected that for
actual deposited lms, the accuracy of the results will be limited to within:
i. thickness d" #d: 0.1%
ii. refractive index nf : 0.3% in the region resolved by ENVELOPE, and 10% in
the region of strong absorption and,
iii. absorption coecient f : 2% in the region of strong absorption, and 10% in
the region resolved by ENVELOPE (down to f
30cm;1).
4.4.3 Silicon-on-Sapphire
To test the method fully it was desirable to have a lm with well-known optical
properties on a transparent substrate that could be measured experimentally. As
it is impossible to grow c-Si on a foreign substrate, the author initially attempted
to glue a 50m thick c-Si wafer to a plate of 1737 glass. This was performed using
a slow drying glue (Araldite) and pressing the air bubbles trapped between the
c-Si and glass out. Araldite is reported to have a similar refractive index to glass
(Zheng 1997). The c-Si was then mechanically polished down to a thickness of a
few microns. Unfortunately, the thickness was very non-uniform, with some areas
of the lm being polished through to the glass, while other regions were still around
5m thick. The thickness was checked using the interference fringes obtained by
measuring the transmission at various locations on the sample.
An alternate idea was to utilise a commercially grown, epitaxial Si (epi-Si) lm on
a sapphire substrate, as epitaxially grown SOS lms have similar optical properties
to bulk c-Si (K(uhl et al. 1974). As mentioned in Section 3.1.2, the non-deposited
side of the substrate had to be polished before use, resulting in a substrate thickness
60
of 0.35mm, while the crystal orientation of the sapphire substrate is unknown. The
manufacturers specied that the thickness of the epi-Si lm should be 0.55m, with
no tolerance given. The transmission of the SOS sample was measured with the
Cary using the following settings: SBW=2nm, EL=3.0, reduced slit height, 0.33s
averaging time, and dc = 850nm. The equations given in Section 3.1.2 were used
to model the optical properties ns, s of the substrate.
The thickness was determined by NAKED to be 520:8 5:5nm. Figure 4.14
compares the nf values determined by NAKED, with published c-Si (Green
1995, Palik 1985) and epi-Si values from three research groups (Lubberts and
Burkey 1984, Hulth&en 1975, K(uhl et al. 1974). While the agreement between all
ve data sets is excellent at longer wavelengths, there is some disparity at shorter
wavelengths. The nf data from NAKED agrees well (within 1%) with the values of
Hulth&en and Green, although the other published works did not comment on why
epi-Si results would be expected to dier from c-Si values.
Refractive Index nf
5.5
NAKED
Lubberts
Khl
Hulthen
c-Si (Green)
5.0
4.5
4.0
3.5
400
600
800
1000
Wavelength (nm)
1200
1400
Figure 4.14: Comparison of nf values determined using NAKED and

published results of other researchers. All symbols represent epi-Si nf
values, while the solid line is the nf of c-Si
Figure 4.15 shows the f data determined using NAKED, and previously published
epi-Si f data (Lubberts and Burkey 1984, Hulth&en 1975, K(uhl et al. 1974), as
well as c-Si f data (Green 1995). The agreement between the values determined
by NAKED and that of Lubberts and Burkey (1984) is very good, to within 5%
over the full range of energies. Additionally, the NAKED f appear not to be
inuenced by noise, even at the lowest energies where the absorption is weakest.
Lubberts and Burkey reported that there is a greater disparity of published f
values between various researchers than the nf . Although sample conditions and
variations cannot be ruled out, it is thought that the method of measurement and
analysis technique chosen are likely to be responsible for the discrepancies (Lubberts
and Burkey 1984). The f values determined by Hulth&en are noticeably higher for
photon energies less than 2eV, and this has been attributed to the aforementioned
sources of error (Lubberts and Burkey 1984).
-1

10
10
10
10
61
NAKED
Lubberts
Khl
Hulthen
c-Si (Green)
1.2
1.4
1.6
1.8
2.0 2.2 2.4

Energy (eV)
2.6
2.8
3.0
3.2
Figure 4.15: Comparison of f values determined using NAKED and

published results of other researchers. All symbols represent epi-Si f
values, while the solid line is the f of c-Si
Hulth&en (1975) measured transmission and photoconductivity to obtain f results,

and mentioned that explanations for the increased f would be published in the
future. The present author has not been able to locate any publications by Hulth&en
which treat this anomaly. (Hulth&en 1975) estimated the errors in the f data to
be less than 5%, 2.5%, and 1%, at the energies 1.24, 2.07, and 0.48eV, respectively. K(uhl et al. (1974) tted envelope curves to reection spectra, and in the
visible-NIR region obtained the optical constants using the quotient method. In
the region where no interference fringes were observed, nf and f were determined
using Kramers-Kronig analysis. Although none of these methods can accurately
measure a non-uniformly thick sample, K(uhl et al. did perform a correction to
account for scattering of light from the sample surfaces. Agreement of f values
to within 4% was obtained when comparing results achieved using the roughness
correction and polished samples. Lubberts and Burkey (1984) used a numerical t
of the measured transmittance and the matrix method to obtain f values, and
noted that errors in f are primarily due to errors in transmission measurements,
and observed errors of 7% at E = 1:65eV, decreasing to 2% at E = 2:07eV.
Interestingly there has been quite a lot of research performed by one research group
(Siemens AG: see Schl(otterer 1976, K(uhl, Schl(otterer and Schwidefsky 1976, K(uhl,
Druminski and Wittmaack 1976) on the optical and electrical properties of an interface layer that forms between the sapphire substrate and the Si lm. Epitaxially
grown Si lms were gradually thinned from around 1.5m down to 0.2m, and the
optical properties measured at each step. The thickness of the interface layer was
found to be between 20 and 40nm, and secondary ion mass spectroscopy (SIMS)
measurements determined that the layer contained large amounts of aluminium silicates (AlSiO+) (K(uhl, Druminski and Wittmaack 1976, Schl(otterer 1976). The
interface layer was found to have a refractive index very similar to sapphire. A
distinct increase in the f of the epi-Si lms was noticed as thickness decreased
using Kramers-Kronig analysis which probes a very thin region near the lm sur-
62
face (K(uhl, Schl(otterer and Schwidefsky 1976). Measuring at E = 2:5eV, the f

rose from 2 104cm;1 at 1m thick, to around 2:7 104cm;1 at 0.5m, and approached 6 104 cm;1 when the lm was thinned down to 0.2m (K(uhl, Schl(otterer
and Schwidefsky 1976). Therefore, the poor crystal quality near the substrate-lm
interface causes the increased epi-Si f observed in Figure 4.15. Verication for the
increased f of the SOS sample was also obtained by Raman spectroscopy measurements. Figure 4.16 shows the increased Raman intensity away from the c-Si
peak at 520cm;1. The increased background intensity in the epi-Si spectrum and
broadening of the 520cm;1 peak is due to a larger number of defects in the epi-Si
lm (Benrakkad et al. 1994). The feature at 300cm;1 is a two phonon peak, while
the peaks at 380cm;1 and 420cm;1 in the epi-Si lm are possibly due to impurities
in the interface layer.
1.0
SOS sample
c-Si wafer
0.8
0.6
0.4
0.2
0.0
300
350
400
450
-1
500
550
Figure 4.16: The poorer crystal quality of epi-Si produces a higher Raman
intensity away from the 520cm;1 peak.
The optical bandgap of epi-Si was determined from Figure 4.17 below. Although
defect states below the bandgap make it slightly dicult, extrapolating the straight
section of the curve to intersect the x-axis, one obtains a value of Eg = 1:120:01eV.
This in good agreement with the values of 1.12eV published by Jackson
et al. (1983),
p
and correspondence with this result is also obtained from a plot of f vs. energy,
Figure 4.18, which indicates a indirect transition occurring slightly above 1.1eV.
To demonstrate the accuracy of the results, Figure 4.19 shows the comparison of
transmission points generated using the determined optical constants (nf , f ) and
thickness (d" #d) and the original transmission spectrum. The generated transmission points are seen to be in excellent agreement with the measured transmission
spectrum.
Thus, the modied envelope method developed by the author has proven to be a
useful and accurate tool for determining the optical constants and thickness of silicon lms on transparent substrates. Analysis on the SOS sample indicate that the
ENVELOPE and NAKED algorithms used produce results which are in excellent
agreement with published data, obtained by a variety of methods.
63
1/2
(f . E)
1/2
(cm
-1/2
1/2
(arbitrary units)
.eV )
1.0
1.5
2.0
Energy, E (eV)
2.5
Figure 4.17: Extrapolation of the

straight section of the curve in
a Tauc plot of epi-Si, indicating
Eg = 1:12 0:01eV.
1.0
1.5
2.0 2.5
Energy (eV)
3.0
Figure 4.18: Plot indicating an

indirect electron transition occurring just above 1.1eV.
Transmission (%)
100
80
60
40
NAKED transmission points
Original spectrum
20
0
400
600
800
1000
Wavelength (nm)
1200
1400
Figure 4.19: Excellent agreement between transmission points generated

by NAKED using nf , f , d" #d, and the original transmission spectrum.
Chapter 5
Optical Characterisation of
Sputtered Silicon Thin Films
5.1 Overview
Having demonstrated the accuracy of the modied envelope method on theoretical
data and SOS samples, the nal goal of the thesis had been reached, whereby
sputtered a-Si and poly-Si lms on glass could be optically characterised. The
sections within this chapter are organised by the type of lm characterised, namely
a-Si and poly-Si. Trends in the optical constants will be observed, however the
explanations will be brief as the scope of this work has to be limited.
Table 5.1 is a list of lms sputtered onto Corning 1737 glass. Blank entries in the
table indicate that the parameter is unknown or was not measured. The estimated
temperature was determined by AL from heating the substrate inside the chamber,
and is accurate at higher temperatures. At low heater settings the temperature
values are inaccurate due to the heating of the substrate caused by the bombardment
of atoms while sputtering. As an example, sputtering at 0% heater setting one could
expect a substrate temperature of about 140C (Lambertz 1997). For this reason,
heater settings (HS) will be quoted instead of deposition temperatures, as these
settings are reproducible. Thickness measurements were determined with Dektak
IIA surface proler.
5.2 Sputtered a-Si Films

Raman spectroscopy was used to determine whether lms exhibited amorphous or
crystalline properties. Figure 5.1 shows the Raman spectra of lms deposited with
the following HS: 0% (06-06), 10% (07-04), 12% (02-01), 20% (02-02). and 25%
(05-02). The solid line, a c-Si spectrum with a large peak at 520cm;1, is shown for
comparison. It can be seen that sample 02-02 has the beginnings of a peak near
520cm;1, indicating the presence of a small crystalline fraction in the lm.
64
65
Film Operator Target Base Dep DC Heat Est Heat Sput In Situ Thick Dep.
No.
No.
Pres Pres Power Set Temp Time Time Cool (nm)
Rate
(nm/min)
(Torr) (Pa) (W) (%) (C) (h:m) (h:m) (h:m)
11-01
11-02
02-01
02-02
02-03
04-01
04-02
04-03
04-04
05-01
05-02
05-03
05-04
05-05
05-07
05-08
05-09
05-11
06-01
06-02
06-04
06-03
06-05
06-06
06-07
06-08
06-09
07-01
07-02
07-03
07-04
07-06
07-07
07-08
08-01
AL
AL
AL
AL
AL
BSR&AL
BSR&AL
BSR&AL
BSR&AL
BSR&AL
BSR&AL
BSR&AL
BSR&AL
AL
AL
AL
AL
BSR&AL
AL
AL
AL
AL
AL
AL
AC&AL
AL
AL
AL
AL
AL
AL
AL
AL
MK&AL
MK&AL
102
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
1
1
1
1
2
2
260
350
310
280
70
82
280
280
250
78
330
3
65
290
75
370
330
260
280
140
350
110
110
67
480
140
110
73
120
600
300
220
100
99
200
0.55
0.55
0.56
0.55
0.55
5.00
5.05
4.96
5.00
0.56
0.52
0.50
0.51
0.55
0.50
3.00
1.51
0.50
0.70
3.25
0.52
0.51
0.54
0.52
0.63
0.51
0.52
0.56
0.56
0.55
0.55
0.57
0.55
1.00
1.51
100
100
100
100
100
100
100
200
100
100
100
100
100
50
180
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
50
12
12
12
20
0
40
55
55
45
30
25
0
0
0
0
0
0
25
55
55
25
25
0
0
55
25
20
0
0
0
10
10
10
10
10
260 3:30 0:17 0:05

260 2:11 0:17 0:05
260 2:30 2:30
375 2:00 2:30
21 17:00 2:30
500 1:30 0:40 0:15
600 2:30 0:57 0:20
600 2:09 0:25 0:30
550 3:45 1:00 0:20
450 0:15 0:45 0:10
400 2:30 0:45 0:10
21 2:45 0:40 0:40
21 13:00 0:30 0:00
21 2:30 0:50 0:00
21 2:30 0:20 0:03
21 2:15 0:20 0:05
21 2:00 0:35 0:05
400 0:20 0:20 0:20
600 0:41 0:20 0:30
600 1:00 0:35 0:40
400 2:04 0:20 0:20
400 0:30 1:47
21 2:29 0:20 0:20
21 16:00 1:40
600 2:45 0:45
400 0:20 0:15 0:30
375 0:20 0:15 0:20
21
0:15 0:05
21
1:50 0:03
21
1:10
200 2:00 1:10
200 4:00 0:10 0:19
200 0:20 1:15 0:10
200 0:20 0:10 0:10
200 3:30 3:17 12:00
3240
362
3153
3409
3498
304
599
595
499
958
828
833
610
451
788
300
488
379
470
485
417
2356
434
2184
191
216
233
227
210
76
105
238
83
213
184
208
203
90
394
150
139
189
235
139
217
220
217
218
Table 5.1: Conditions and parameters used to sputter a-Si and poly-Si
lms by Andreas Lambertz (AL) and various colleagues at the PVSRC
(BSR: the present author AC: Anatoli Chtanov MK: Mark Keevers).
Determine Eect of #nf

Initially, the transmission of sample 05-03 was measured at ve dierent locations
on the lm: A (centre), B (bottom-right), C (bottom-left), D (top-right), and E
(top-left). The purpose of this exercise was to determine whether variations in
the optical constants, and especially the refractive index, could be expected over

1.0
66
02-01
05-02
07-04
0.8
02-02
06-06
c-Si
0.6
0.4
0.2
0.0
200
300
400
-1
500
Figure 5.1: Raman spectra of a-Si lms deposited at a variety of temperatures.
05-03
#d
d"
Position (nm) (nm)
A
833
5
B
779 15
C
806 14
D
807 13
E
791 11
nf
(=750
nm)
4.29
4.27
4.27
4.30
4.27
nf
(=1500
EO3 EO4 EO5
nm) (eV) (eV) (eV)
3.79
3.76
3.77
3.79
3.78
1.02
0.99
0.99
1.02
1.01
1.52 ;
1.51 2.06
1.52 ;
1.53 2.06
1.52 2.06
Table 5.2: Comparison of optical properties and thicknesses at various

locations on sample 05-03.
a 5050mm sample. It is necessary to perform this test as variations in #nf

and #d have exactly the same compressive eect on the interference fringes in the
transmission spectra (Swanepoel 1984, Myburg and Swanepoel 1987). Therefore,
the shrinking of the interference cannot be solely attributed to thickness variations
before variations in nf have been assessed.
The results of the NAKED analysis of sample 05-03 are presented in Table 5.2,
and Figures 5.2 and 5.3. The values of the refractive index are compared at 750nm
and 1500nm, while EO3 , EO4, and EO5 are the energies where f equals 103cm;1,
104cm;1 and 105cm;1, respectively.
From Figure 5.2, there is less than a 1% variation in nf values over the ve locations. Although this is outside the 0.1% accuracy of the method (Swanepoel 1984),
the present author is of the opinion that a 1% variation is still within the error
limits and that the nf is independent of position. This is also conrmed by the d"
results, which correspond well to the convex shape of the deposited lm. Myburg
and Swanepoel (1988) observed similar results for a-Si:H lms measured at several
locations, although in this publication the error limits for nf of Swanepoel's (1984)
67
Refractive Index nf
4.2
A
B
C
D
E
4.1
4.0
3.9
3.8
3.7
800
1000
1200
1400
Wavelength (nm)
1600
1800
-1
Figure 5.2: Less than 0.5% variation in the refractive index of sample
05-03 is observed when measured at ve dierent locations.
10
10
10
A
B
C
D
E
10
0.6
0.8
1.0
1.2
1.4
Energy (eV)
1.6
1.8
2.0
Figure 5.3: Less than 2% variation in the absorption coecient of sample

05-03 is observed when measured at ve dierent locations.
envelope method were quoted as being 2%. Myburg and Swanepoel (1988) also
noted that the uncertainty in d", nf , and f increases as #d increases. As plotted
in Figure 5.3, there is a variation in f values of 1% and 2% at 1.52eV and 1.0eV,
respectively.
Variation of a-Si Optical Constants with Deposition Temperature

Having determined that compression of the interference fringes arises because of
thickness non-uniformity, the next experiment was to evaluate a-Si lms that were
deposited with various heater settings.

Sample
No.
05-03
06-06
07-04
02-01
02-02
05-02
HS
(%)
0%
0%
10%
12%
20%
25%
#d
d"
(nm) (nm)
833
5
2157 15
1278 27
3318 15
3304 15
857
2
68
nf
(=750
nm)
4.29
4.37
4.39
4.30
4.26
4.20
nf
(=1500
EO2 EO3 EO4
Eg
nm) (eV) (eV) (eV) (eV)
3.79
3.86
3.78
3.81
3.79
3.74
0.72
0.82
0.82
0.84
0.76
1.02
1.01
1.17
1.15
1.25
1.33
1.52
1.52
1.57
1.59
1.63
1.67
1.41
1.41
1.42
;
;
1.54
Table 5.3: Comparison of optical properties and thicknesses of various

sputtered a-Si lms.
Sample 06-06, the full analysis of which is included in the NAKED program listing in
Appendix B, is also included as a 0% HS sample as it was relatively thick. Therefore
the sample exhibits a greater number of interference fringes, and will produce more
nf and f data points in the NIR region, although the data will not extend as
far into the visible region due to increased absorption. Samples 07-04 (10% HS),
02-01 (12% HS), 02-02 (20% HS), and 05-02 (25% HS) were chosen to represent
a-Si material deposited at higher temperatures. All of the lms were sputtered
using target number 4 (n-type, 0.08{0.12 ):cm) except sample 07-04 which was
deposited using a lower resistivity target (no. 1, n-type, 0.002{0.08 ):cm). Table 5.3
summarises the results as before, including the optical bandgap Eg of the material
as determined from Tauc plots, and the energy EO2 where f = 100cm;1. All Eg
values presented in this chapter have an error of 0:01eV.
A general trend towards lower values for nf can be seen in Figure 5.4 as the substrate
temperature increases, although samples 05-03 and 07-04 do not follow this pattern.
Sample 07-04 has the highest nf , but due to the large #d Eqn. 2.33 is very close
to its upper validity limit, given by 0 < #d < =4nf . As mentioned previously,
Myburg and Swanepoel (1988) observed that the uncertainty in nf and f increased
as #d increased. Therefore, results from 07-04 should be regarded as having a large
error. It is not clear to the author why sample 05-03 has a signicantly lower nf
than sample 06-06, as there was no scattering observed. Good agreement is reach
between the author's data and that of K(uhl et al. (1974), although the material is
evaporated and not sputtered. Published nf data for DC magnetron sputtered a-Si
using argon gas from McKenzie et al. (1983) is plotted for comparison in Figure
5.4.
The trend observed for the f data, plotted in Figure 5.5, is less ambiguous. Films
deposited without substrate heating (05-03 and 06-06) have the highest f , and f is
observed to decrease as the substrate temperature was increased. Many unanswered
questions still remain, as to the structures observed at low energies (E < 0:75eV).
The degree to which the lm is amorphous and impurities (dopants, argon, or
oxygen) could all play a role here.
The optical bandgap was observed to increase as the substrate temperature increased. Figure 5.6 shows that samples 06-06 and 05-03 have an Eg of 1.41eV,
while 05-02, deposited with a 25% HS, has an Eg of 1.54eV. The Eg for the thicker
69
Refractive Index nf
4.8
05-03 (0% HS)

07-04 (10% HS)
02-02 (20% HS)
Khl
4.6
4.4
06-06 (0% HS)

02-01 (12% HS)
05-02 (25% HS)
McKenzie
4.2
4.0
3.8
3.6
600
800
1000
1200 1400 1600

Wavelength (nm)
1800
2000
2200
-1
Figure 5.4: Variation of nf of a-Si samples as the substrate temperature

increases.
10
10
10
10
10
10
05-03 (0% HS)

07-04 (10% HS)
02-02 (20% HS)
0.75
1.00
1.25
1.50
Energy (eV)
06-06 (0% HS)

02-01 (12% HS)
05-02 (25% HS)
1.75
2.00
Figure 5.5: The f of a-Si samples decreases as the substrate temperature

increases.
samples 02-01 and 02-02 could not be reliably determined due to the lack of data
at higher energies. McKenzie et al. (1983) determined the Eg of a-Si sputtered lm
onto a substrate heated to 50C (10):cm boron doped target, argon pressure of
1Pa) to be 1:7 0:1eV, signicantly higher than the 1.4eV observed by the present
author for similar substrate temperatures. Note that the nf values from McKenzie
et al. are also signicantly dierent. Klazes et al. (1982) found the optical bandgap
of a-Si sputtered in pure argon on a substrate heated to 200C to be 1.08eV using
(hnf )1=3 vs. E plots. The present author estimates that this would correspond
to an Eg of roughly 1.28eV if determined from a Tauc plot, which is close to the
result of Eg = 1:4eV determined in this work. Kanicki (1992) reported Eg values of
1.2-1.5eV range for sputtered material, while Schoenfeld et al. (1994) determined
5.3 As-Deposited poly-Si Films
70
the Eg of DC magnetron sputtered a-Si lms (50C substrate heating) to be 1.42eV.

Finally, Rizk et al. (1996) determined the bandgap of sputtered a-Si to be 1:25eV.
All of these results are in good agreement with the optical bandgaps of the sputtered
a-Si lms characterised in this work.
(f . E)
1/2
(cm
-1/2
1/2
.eV )
05-03 (0% HS)

06-06 (0% HS)
07-04 (10% HS)
02-01 (12% HS)
02-02 (20% HS)
05-02 (25% HS)
1.1
1.2
1.3
1.4
1.5
1.6
1.7
Energy, E (eV)
1.8
1.9
2.0
2.1
Figure 5.6: The Eg of a-Si samples is observed to increase as the substrate

temperature increases.

Raman spectra again proved useful for qualitatively determining the degree of crystallinity in the as-deposited poly-Si lms. Figure 5.7 shows the spectra of samples
05-01 (30% HS), 04-04 (45% HS), 04-02 (55% HS), and a c-Si reference wafer. The
resolution of the Renishaw machine is limited to over 1cm;1, and due to the design cannot be improved. Information about strain and stress can be obtained
from frequency shifts in the 520cm;1 peak, and poly-Si is often observed to have a
peak shifted towards lower wavenumbers (see for example Baba et al. 1994, Beeman
et al. 1985, Fauchet and Campbell 1990). Unfortunately, the environment where the
Renishaw machine is located is less than ideal, since extreme temperature changes
are witnessed. The author has observed changes in temperature shifting the c-Si
peak by up to ve wavenumbers over a two hour period. Therefore, results taken at
dierent times cannot be reliably compared to one another, and information about
strain and stress from the spectra must be disregarded.
The lms were expected to be microcrystalline silicon (c-Si), rather than poly-Si
due to small crystallites, typically up to 100nm in size, forming as the silicon atoms
strike the heated substrate. However, most lms remain a mixture of amorphous
and microcrystalline material and are termed diphasic (Luft and Tsuo 1993). This
mixed phase makes the material dicult to model, and it is generally thought that
the optical properties of c-Si lms are largely determined by the amorphous phase,
while the electrical properties are determined mostly by the crystalline phase (Luft
71
1.0
0.8
0.6
04-02
05-01
0.4
04-04
c-Si
0.2
0.0
460
480
500
520
-1
540
Figure 5.7: Raman spectra of as-deposited poly-Si lms, sputtered at a

variety of temperatures.
and Tsuo 1993). Luft and Tsuo also noted that the optical bandgap determined by
Tauc plots is largely meaningless because of the two phases.
Variation of poly-Si/c-Si Optical Constants with Deposition Temperature

Apart from determining any change in optical properties that could be expected
from an increased deposition temperature, sample 04-02 presents a challenge to the
modied envelope method due to its thinness and near c-Si nf . The incident light
" f , and only ten extrema
therefore sees a lm with a much thinner optical thickness dn
could be resolved by ENVELOPE. The last two extrema in the NIR are always
discarded due to the errors created in f values, and the rst extrema found is often
erroneous and must also be deleted from the tangent le. This leaves seven extrema
over the range 675{1293nm from which to determine the optical constants and
thickness. Tabulated results of the analysis on the three samples are given in Table
5.4, along with c-Si values for reference (Green 1995). Absorption coecient values
are also compared to a nanocrystalline silicon (nc-Si) lm, deposited by low pressure
chemical vapour deposition (LPCVD) at 350C (Bustarret and Hachicha 1990). No
nf data was available for the nc-Si lm.
A wide range of results were obtained, with nf varying from signicantly less than
to greater than bulk c-Si values. The reason for the nf of samples 04-04 and 04-02
dropping below that of c-Si could have been caused by any one of several reasons.
Firstly, several researchers have reported refractive indices of heavily doped (N
1020cm;3) poly-Si lms approaching nf = 3:0 at = 2m (Lubberts et al. 1981,

Peter et al. 1994), and Kamins (1988) attributes this decrease to the interaction of
light with the free carriers. However, sample 04-04 was sputtered using a lightly
doped (N = 6:21016 ;1:11017 cm;3) n-type (phosphorus) doped target - certainly
not heavily doped enough to cause this eect in the current situation. The second

Sample
No.
05-01
04-04
04-02
nc-Si
c-Si
HS
#d
d"
(%) (nm) (nm)
30% 993
8
45% 530
8
55% 603 40
;
;
;
;
;
;
72
nf
(=750
nm)
nf
(=1500
3.99
3.55
2.97
3.63
3.29
2.64
4.48
3.72
EO2 EO3 EO4
Eg
0:91 1.34
; 1.48
; 1.06
0.70 1.32
1.27 1.59
1.73 1.55
2.04 ;
1.60 ;
1.85 1.55
2.47 1.12

as-deposited c-Si sputtered lms.
4.8
Refractive Index nf
05-01 (30% HS)

04-02 (55% HS)
4.4
04-04 (45% HS)

c-Si
4.0
3.6
3.2
2.8
400
600
800
1000
1200
Wavelength (nm)
1400
1600
1800
Figure 5.8: The signicant surface roughness of samples 04-02 and 04-04
scattered the transmitted light, producing erroneous results, especially in
nf .
possibility was that a large void fraction in the lm existed, but this is unlikely
with lms deposited at high temperatures where the atoms have substantial energy
to position themselves upon striking the substrate. Finally, it was determined that
the lms were scattering a proportion of the transmitted light. This was visible as
a whitish colour on the lm surface, and thus the analysis of lms 04-02 and 04-04
cannot be regarded as accurate.
Figure 5.8 shows the nf of sample 05-01 being, as expected, closer to c-Si values
than the previous amorphous samples. The f of 05-01 lies between that of a-Si
and c-Si, as can be seen in Figure 5.9 and from the EO2 , EO3 , and EO4 values in
Tables 5.3 and 5.4. Plotted for comparison is the f of the nc-Si lm (Bustarret
and Hachicha 1990), and from Figure 5.10, the Eg of the lm was determined to be
1.55eV, although the data does not extend quite far enough into the high energy
region. Schoenfeld et al. (1994) measured the optical bandgap for c-Si at various
stages of crystallisation, nding Eg = 1:65eV after 2 hours at 993K, and 1.88eV
after 4 hours at the same temperature. Schoenfeld et al. attributed the shift of
Eg towards higher energies due to a decrease in the grain boundary fraction. Rizk
-1
5.4 Annealed a-Si Films

10
10
10
10
10
73
05-01 (30% HS)

04-04 (45% HS)
04-02 (55% HS)
nc-Si
c-Si
0.75
1.00
1.25
1.50
1.75 2.00
Energy (eV)
2.25
2.50
2.75
3.00
Figure 5.9: The f of c-Si is dominated by the amorphous phase component (Luft and Tsuo 1993).
(f . E)
1/2
(cm
-1/2
1/2
.eV )
05-01 (30% HS)

04-04 (45% HS)
04-02 (55% HS
1.0
1.2
1.4
1.6
1.8
2.0
2.2
Energy E (eV)
2.4
2.6
2.8
3.0
Figure 5.10: Tauc plots of the as-deposited c-Si samples. The diphasic
nature of the material makes Eg dicult to determine.
et al. (1996) found the bandgap of c-Si to be in the order of 1.4eV.

A variety of samples, mainly those deposited as a-Si, were divided into four pieces,
and two of these pieces were annealed. All samples were annealed at 600{620C
for a period of 60{80 hours in a nitrogen purged furnace at atmospheric pressure.
A variety of lms were selected for characterisation, including two lms (06-06-4
and 07-04-3) which were analysed before annealing (see Section 5.2). Sample 05-

Sample
No.
05-01-3
05-11-3
06-06-4
07-04-3
nc-Si
c-Si
74
HS
#d
d"
(%) (nm) (nm)
30% 950 14
25% 452
1
0% 2131 27
10% 1387 12
;
;
;
;
;
;
nf
(=750
nm)
nf
(=1500
3.79
3.77
3.77
3.74
3.53
3.51
3.50
3.48
4.48
3.72
EO2 EO3 EO4
Eg
0:95 1.41
; 1.29
0:90 1.42
; 1.39
0.70 1.32
1.27 1.59
1:09
0:93
1:13
2.05
2.00
2.00
1.98
1.85
2.47
1:55
1.12

annealed samples.
11-3 was taken directly from the sputtering machine to the furnace to minimise the
lm's exposure to air. Sample 05-01-3 was deposited with a mixed amorphous and
crystalline phase (see Section 5.3). Table 5.5 summarises the results obtained with
NAKED for the four samples, along with c-Si (Green 1995) and nc-Si (Bustarret
and Hachicha 1990) optical properties.
The refractive index values determined for all annealed samples, plotted in Figure
5.11 are within 0.1 (absolute) higher than c-Si over the range where extrema
can be resolved. In the region of strong absorption, the nf of sample 05-11-3 dips
below that of c-Si, however this is due to the Cauchy extrapolation and should be
disregarded.
5.0
Refractive Index nf
06-06-4
07-04-3
05-11-3
05-01-3
c-Si (Green)
4.6
4.2
3.8
3.4
400
600
800
1000
1200
Wavelength (nm)
1400
1600
1800
Figure 5.11: Close agreement between the refractive indices of all annealed samples.
Figure 5.12 shows the calculated f values for the annealed lms, as well as nc-Si
(Bustarret and Hachicha 1990) and c-Si (Green 1995) data. Above 1.75eV, the f
of all the lms is similar, sitting at a level 2.5 times greater than c-Si. At lower
energies, the f of samples 07-04-3 and 05-11-3 becomes larger than that of the
nc-Si.
-1

10
10
10
10
10
75
07-04-3
05-11-3
nc-Si (Bustarret)
c-Si (Green)
0.6
1.0
1.4
06-06-4
05-01-3
1.8
Energy (eV)
2.2
2.6
3.0
Figure 5.12: Comparison of the absorption coecients of annealed lms.
Jackson et al. (1983) determined that the increased sub-bandgap absorption (<
1:1eV) of poly-Si is due to dangling bond defects in the material, and the f was
found to decrease by a factor of two upon hydrogenation. From this it can be
determined that samples 06-06-4 and 05-01-3 have the lowest number of dangling
bond densities, while lms 05-11-3 and 07-04-3 have the highest number of these
defects.
The increased absorption above about 1.25eV is dominated by the grain boundary region, as the absorption for the disordered grain boundary is greater than
the indirect edge absorption of the crystalline material within the grains (Jackson
et al. 1983). Jackson et al. found that the increased absorption could be explained by considering the polycrystalline material as 30-50nm diameter columnar
grains surrounded by 1nm grain boundaries. This means that the grain boundaries comprise up to 10% of the total area, which corresponds well with the 10%
increase (above c-Si absorption levels) in the f of poly-Si observed experimentally
for E > 1:2eV (Jackson et al. 1983). Jackson et al. concluded that the reduction in
f of a-Si to that of poly-Si is primarily due to a reduction in area of the disordered
material.
Kamins (1988) reported that the f for annealed a-Si lms is signicantly lower
than for lms which are deposited as polycrystalline material. The f of the asdeposited poly-Si lm 05-01 is greater than the absorption coecients of all the
annealed lms at energies greater than 1.4eV. From the Raman spectra for 0501 in Figure 5.7, it can be seen that a signicant proportion of the material is
still amorphous, and agreement with the observation of Kamins (1988) cannot be
conrmed. Raman spectroscopy performed on the annealed poly-Si lms yielded
the spectra shown in Figure 5.13. Samples 06-06-4 and 05-01-3 have the narrowest
520cm;1 peak widths (measured at half maximum), while the broadening of the
peak on the low wavenumber side of the other samples is attributed to material with
a higher defect density (Benrakkad et al. 1994). Additionally, the spectra from lms
06-06-4 and 05-01-3 exhibit the lowest amount of a-Si features (broad peaks in the
76
150 to 480cm;1 range). Therefore, the Raman results support the outcome of the
absorption coecient analysis, and the trend of increased absorption and Raman
(520cm;1) peak widths with increased defect density in the lm is conrmed.
1.0
05-11-3
06-06-4
07-04-3
05-01-3
c-Si wafer
0.8
0.6
0.4
0.2
0.0
300
350
400
450
-1
500
550
Figure 5.13: Raman spectra of annealed samples, showing increased

520cm;1 peak width with increased defect density in the poly-Si material.
The optical bandgap for the samples was determined from Figure 5.14. Sample
06-06-4 had the highest bandgap, Eg = 1:13eV, while sample 05-01-3 and 05-11-3
had bandgaps of 1.09eV and 0.93eV, respectively. The bandgap of sample 07-04-3
could not be determined due to the lack of a straight section in the Tauc curve.
This bending of the Tauc plot has been observed to occur during the transition
from amorphous to microcrystalline material (Schoenfeld et al. 1994). The optical
bandgap of 1.13 (lm 06-06-4) is almost exactly the same as the bandgap of cSi, however the slopes of the two lines are quite dierent. Jackson et al. (1983)
found that poly-Si (deposited using LPCVD at 625) had an optical bandgap of
0:97 0:03eV, and this increased slightly upon hydrogenation.
Several researchers have observed trends in the optical bandgap. Kanicki (1992) and
Tsai and Fritzsche (1979) both mention that the value of Eg is dependent upon:
i. doping with phosphorus or boron
ii. the defect density and,
iii. the total hydrogen content (relevant for a-Si:H and c-Si:H lms).
Kanicki (1992) concluded that the optical bandgap is predominantly determined by
the degree of disorder within the amorphous phase. All of the annealed samples
analysed in this work exhibited a reduction in the optical bandgap upon annealing.
In contrast, Schoenfeld et al. (1994) found that Eg increased from 1.42eV for a
sputtered a-Si lm to 1.92eV for the same lm annealed for a period of 36 hours
77
(f . E)
1/2
(cm
-1/2
1/2
.eV )
07-04-3
06-06-4
05-11-3
05-01-3
c-Si (Green)
0.9
1.0
1.1
1.2
1.3
1.4
Energy E (eV)
1.5
1.6
1.7
Figure 5.14: Tauc plots to determine the optical bandgap of various sputtered, furnace annealed lms.
at 993K. This increase is attributed to a reduction in the amorphous fraction (i. e.

grain boundaries) (Schoenfeld et al. 1994). Kanicki (1992) presents a fuller picture,
stating that the Eg is observed to increase upon annealing only when the lms are
of poor quality (low substrate heating). This still does not explain the dierence
between the results of Schoenfeld et al. (1994) and the result obtained with sample
06-06-4, as these two samples were deposited with less than 50C substrate heating applied. Dyer et al. (1993) too, could not explain the 1.8eV optical bandgap
measured for a furnace crystallised poly-Si sample.
Chapter 6
Conclusions
The modied envelope method developed by the author proved to be a very useful
and accurate tool for determining the optical constants and thickness of inhomogeneous Si thin lms from transmission spectra. Based on the envelope method
of Swanepoel (1984), the author performed several improvements to enable the
modied envelope method, implemented as the Mathematica program NAKED, to
accurately determine the optical constants and thickness of sputtered a-Si and polySi lms. Such lms could not be characterised by Swanepoel's (1984) method due
to the requirement that lms must exhibit a transparent region in the measurable
wavelength range (as observed in a-Si:H and c-Si), and neither a-Si nor poly-Si, as
defected materials, fulll this criterium.
Additional improvements of the modied envelope method include, rstly, that all
substrates were optically characterised using a combination of spectroscopic ellipsometry, reection and transmission measurements, and manufacturers' data. This
enabled determining the substrate refractive index ns and absorption coecient s
as functions of wavelength. Accurate s values, signicant for sapphire and some
types of glass, avoids the attribution of undetermined substrate properties to the
lm being characterised. Swanepoel (1984) assumed the substrate to be transparent, and used a constant refractive index. Secondly, a more accurate version of
an existing envelope curve tting algorithm, ENVELOPE (McClain 1997), was developed in conjunction with the original algorithm's author (McClain et al. 1991).
Errors of up to 0.3% (absolute) in determining the intensity of the interference
fringes were reduced to less than 0.05% (well below the 0.1% estimated accuracy of
the warmed-up spectrophotometer) when the new version of ENVELOPE (2.01b)
was employed.
Testing of the modied envelope method was performed initially with the same
expressions for a-Si:H nf and f as used by Swanepoel (1983), and a transmission spectrum was generated using an equation describing the transmission of light
through a non-uniformly thick, thin lm. The optical constants and thickness values extracted from the transmission spectrum using ENVELOPE and NAKED were
then compared to the original expressions describing nf , f , and the values chosen
for the thickness d = d" #d. Results showed good agreement to within 0.1%, 0.3%,
and 10% for d" #d, nf (all wavelengths), and f (down to the low value of 5cm;1).
A similar test was performed using the modelled transmission of a c-Si lm on a
78
79
Corning 1737 glass substrate. The thicknesses, d" and #d, were again accurate to
within 0.1%. Results for nf are within 0.3% in the range where interference fringes
can be resolved by ENVELOPE. For shorter wavelengths, the nf values must be
extrapolated, leading to a maximum error of 10% at 410nm. In this strongly absorbing region, f values are accurate to within 2%, while at longer wavelengths
the f is within 10% of the c-Si values ( 30cm;1). The results are reliable down to
absorption levels lower than predicted by Swanepoel (1984) and this is attributed
to the ENVELOPE algorithm's excellent curve tting ability.
The transmission of an epitaxial silicon-on-sapphire sample (0.5m epi-Si on
0.35mm of sapphire) was measured using the spectrophotometer. The thickness
of the epi-Si lm was determined to be 520:8 5:5nm, while the refractive index
was found to be within 1% of results reported by another researcher (Hulth&en 1975)
and bulk c-Si values (Green 1995). The f of the epi-Si agreed to within 5% of the
results of Lubberts and Burkey (1984), and the increased absorption (above c-Si
levels) is attributed to the poorer quality crystal at the lm-substrate interface. An
increased number of defect levels was also observed using Raman spectroscopy. The
optical bandgap was observed to be 1:12 0:02eV, in excellent with the published
result of 1.12eV (Jackson et al. 1983).
The eect of ignoring any thickness variation was also investigated, and it was found
that if #d is assumed to be zero, the f will increase, to account for any reduction
in the maxima intensity below the transmission of the bare substrate, and nf will
decrease, to accommodate the reduction in amplitude of the interference fringes.
However, the dierent eects that nf , f , and #d have on the spectrum means that
only one combination of these parameters can produce a good t when comparing
the transmission points (generated using d" #d, nf , and f as determined by
NAKED) to the measured transmission spectrum. In other words, there exists an
unique solution to the envelope method (Minkov 1992b, Swanepoel 1984).
The development, programming, and successful testing of the modied envelope
method has been the primary result of this work, and after completing the above
comprehensive tests the author was satised that the results were indeed reliable,
and that the goal of analysing a-Si and poly-Si sputtered lms on glass could be
reached.
Since variation in the lm's refractive index #nf and #d have the same shrinking
eect on the interference fringes (Swanepoel 1984), an a-Si sample, with dimensions
5050mm, was measured at ve dierent locations. It was found that the variation
in nf observed was less than 1% and the author concluded that the eect was still
within the error limitations of the method.
The variation of the optical constants of a-Si was observed as a function of substrate
temperature. A general trend of decreasing nf with increasing substrate temperature was observed, with values sitting above the c-Si curve by about 0.25 (absolute)
at = 2000nm and rising to 0.8 (absolute) above at 600nm. Absorption coecients
for E > 0:9eV of the a-Si lms also decrease as the temperature is raised, while
at lower energies many structures observed in the f curves remain unexplained.
The range of optical bandgaps, determined from Tauc plots, for the a-Si samples
was 1:41 ; 1:54eV and in good agreement with at least two other published works
80
(Kanicki 1992, Schoenfeld et al. 1994).
As-deposited sputtered poly-Si was also investigated, however no trends were observed here since two of the samples deposited at temperatures above 500C were
unable to be characterised due to a signicant fraction of the transmitted beam
being scattered.
Furnace annealing (about 600 for 60 ; 80 hours) of several a-Si samples was performed in an environment of nitrogen at atmospheric pressure. The nf for all
annealed samples were determine to lie within 0.1 (absolute) higher than c-Si over
the range where extrema can be resolved. Above 1.4eV, the f of the annealed
samples is between two to three times greater than c-Si, while dangling bond densities were lowest in samples 06-06-4 and 05-01-3 in the sub-bandgap region (Jackson
et al. 1983). Jackson et al. (1983) explained that the reduction in f , relative to
a-Si, is primarily due to a decrease of amorphous material in the lm. Using Raman
spectroscopy, samples 06-06-4 and 05-01-3 were found to exhibit the lowest amount
of a-Si features and also had the narrowest 520cm;1 peak widths. Thus, the lms
that exhibited the most crystalline properties were those deposited as a-Si without
substrate heating. The optical bandgaps of the poly-Si samples were found to be
in the range 0:93 ; 1:13eV. These values are in good agreement with, rstly, the
value of 0:97 0:03 for poly-Si presented by (Jackson et al. 1983), and secondly the
1.12eV value for c-Si.
Thus, the modied envelope method, realised through the computer programs
ENVELOPE and NAKED, has successfully provided extensive optical information
over a wide wavelength range for the non-uniformly thick, defected a-Si and poly-Si
sputtered lms.
Appendix A
Thin Film Optical Theory
A.1 Introduction
This appendix will discuss thin lm optical theory and its application to semiconducting lms on foreign substrates. As the eld of thin lm optics is very wide, the
following models of increasing complexity will be presented, with the goal being to
eventually be able model a thin absorbing lm on a nitely thick, foreign substrate:

a single interface
a single layer or lm
a single lm on a foreign substrate of semi-innite thickness
a single lm on a thick foreign substrate.
These cases will be discussed for transparent and absorbing lms, obliquely and
normally incident light, and all interfaces are assumed to be optically at and
parallel. Finally, equations will be derived that accurately describe the thin lm
interference fringes that are experimentally observed in reection and transmission
spectra (Stenzel 1996).
A.2 Reectance and Transmittance at a Single

Interface
An optical medium can be described by its complex refractive index n~ = n ; ik,
where the real component n is called the refractive index. The imaginary component
k is called the extinction coecient, and is related to the absorption coecient
by
,
(A.1)
k =
4
where is the wavelength of the light in a vacuum.
81
A.3 Single Transparent Layer

82

__
7__
3
3
9__
Figure A.1: Fresnel coecients illustrated by incoming waves with Eelds normal to and parallel the plane of incidence.
When light is incident on an interface, the reectance and transmittance can be

described using the Fresnel coecients. The Fresnel coecients for a single interface
between two non-absorbing media, shown in Figure A.1, are
i ; ni cos t ,
rk = nnt cos
(A.2)
t cos i + ni cos t
cos i
tk = n cos2n i +
,
(A.3)
t
i ni cos t
i ; nt cos t ,
(A.4)
r? = nni cos
i cos i + nt cos t
cos i
t? = n cos2n i +
,
(A.5)
i
i nt cos t
where r and t are the electric eld coecients for reection and transmission, respectively. The transmittance of an interface is
T =1;R ,
(A.6)
where the reectance at the interface is given by R = r2. For normally incident
light, i = t = 0, of any polarisation
2

n
i ; nt
(A.7)
R = n +n .
t
i
For absorbing media, n~ instead of n in the Fresnel coecients, and then the reectance is given by R = r r.

A single lm of transparent (non-absorbing) material with two at interfaces is
shown in Figure A.2, where T12 and R12 are the transmission and reection coefcients for the interface between medium 1 and 2, respectively. The reectance is
83
dened as follows, noting that it is a geometrical series,
R = R12 + T12 R21 T21 + T12 R213 T21 +

= R12 + T12 R21 T21
= R12 + T112;R21RT2 21
21
2
R
12
:
=
1 + R12
And similarly for transmittance,
1
X
j =1
2 j ;1
(R21
)
(A.8)
T = T12 T21 + T12 R212 T21 +

= T12 T21
1
X
j =1
2 j ;1
(R21
)
= 1T;12 TR212
21
1
;
R
12
.
=
1 + R12
(A.9)
It should be noted that Eqns. A.8 and A.9 are independent of thickness, and do
not include interference eects due to phase dierences between the reected and
transmitted rays. For transparent media T + R = 1, and for the special case of
normally incident light
R12
T12
n1
= R21 = nn2 ;
2 + n1
2
(A.10)
n1
= 1 ; R12 = 1 ; nn2 ;
2 + n1
#
#
2
%
%
= 4n1 n2 2 .
(n2 + n1)
(A.11)
0HGLXP33
0HGLXP33
0HGLXP33
Figure A.2: Reectance and transmittance of a single layer.
It should be emphasised that T12 is not the same as jt12 j2, as jt12 j2 = 4n21 = (n1 + n2 )2,
whereas the transmittance T is dened as being the ratio of the transmitted power
A.4 Single Absorbing Film
84

~
E
H~ = n = (cE 2), then, as
to the incident power. Dening intensity as I =

shown in Eqn. A.11,
2
n2 jt j2 = 4n1 n2 .
I
n
2 cos t
2 jE2 j
T12 I cos =
2 =
n1 jE1 j n1 12
(n2 + n1 )2
1
i
(A.12)
For a transparent layer (n2 = n) in air (n1 = 1), the reectance and transmittance
for the situation depicted in Figure A.2, substituting Eqns. A.10 and A.11 into
Eqns. A.8 and A.9, are
;
2
2
2 nn;+11
2
R
(
n
;
1)
12
R = 1 + R = ; n;1 2 = n2 + 1 ,
12
1 + n+1
1 ; nn;+11 2
1
;
R
12
T = 1 + R = ; n;1 2 = n22+n 1 .
12
1 + n+1
(A.13)
(A.14)

To improve the model developed so far, to be able to deal with absorbing lms,
such as semiconductors, the earlier values of transmittance and reectance between
medium 2 and 1 become, for a lm of thickness d
T21 ! T21 exp;d
and R21 ! R21 exp;d :
Using the relation T12 = 1 ; R12 , which is still valid, the equivalent equations to
Eqns. A.8 and A.9 are, in the absorbing case (not including interference eects)
;d
;d
R = R12 + T12 R21 exp T;21de 2
1 ; (R21 exp )

R12 1 ; exp;2d (2R12 ; 1)
,
(A.15)
=
2 exp;2d
1 ; R12
;d
T = T12 T21 exp;2d 2
1 ; (R21 exp )
R12 )2 exp;d .
(A.16)
= (11 ;
; R122 exp;2d
Layers and Thin Films

Figure A.3 shows the transmission of a 1.1mm thick plate of Corning 1737 aluminosilicate glass that was measured by the author with various spectral bandwidths
(SBW) (see Section 3.4.2) using a spectrophotometer. With a large SBW of 5nm
(# = 2:5nm), we observe that the transmission is constant at T = 91.8%, and
rearranging Eqn. A.14 for n
r
1
n = T + T12 ; 1 ,
(A.17)
85
Transmission (%)
92.4
92.0
91.6
91.2
2000
2001
2002
2003
Wavelength (nm)
2004
2005
Figure A.3: Comparison between the experimentally measured transmission spectra for various spectral bandwidths: SBW = 5nm (solid), SBW
= 2nm (dashed), SBW = 0.5nm (dotted).
gives a value of n = 1:52 which is a reasonable value for the glass in the infrared
(IR) region. However, the theory developed up until now cannot correctly predict
the spectra for the lower SBWs. Previously, the model was only capable of nding
the intensity of reected and transmitted beams, and the phase shift of the light
was ignored. The constructive or destructive interference, observed only when the
SBW is small enough to resolve the fringes, occurs when the lm or layer is optically
coherent.
A lm is considered to be coherent if its optical thickness is much smaller than
the coherence length of the light. The coherence length is determined by the light
source and the SBW, and, for example, for a tungsten lament lamp it is of the
order of a mm (Tao 1994). The coherence length of the light of the monochromator
is given by (Tao 1994)
2
(A.18)
lc = # 21 .
When the distance between the front and rear surfaces is large, many interference
fringes can occur over the given range. However, when the pathlength dierence
is greater than lc, the phases of the waves are randomised and cannot interfere with
each other. In this situation, waves behave as incoherent sources, and the intensities, rather than the amplitudes, of the waves should be added (Rancourt 1996).
Therefore, if the optical path length nd through the lm is much less than lc then
the lm is coherent, creating the following condition for observing the maximum
thin lm interference
2 .
# 2nd
(A.19)
In the previous example, where # = 0.5nm, n = 1.52, d = 1.1mm, and =
2000nm, this condition is not met, as 0.5nm is 6 0.38nm. Practically however,
86
all lms that have the same order of thickness as the wavelength will exhibit some
interference (Stenzel 1996).
Before implementing this in the 1737 glass transmission case, the eect of thin
lm interference in a simple non-absorbing lm, as shown in Figure A.4, will be
determined. Multiple reections are neglected for the moment, and light is normally
incident, however it is drawn obliquely to clarify the diagram.
979H[SL3/.
7
3
3

3
Figure A.4: Thin lm interference in a non-absorbing lm.

As we would like to check whether the period observed in Figure A.3 is correct, the
two main reected beams of A.4 are added together, obtaining
i2!nd=c
E = r12E0 ;+ t12 r21 t21 E0 exp

r12E0 1 + a exp;i2 ,
(A.20)
where is the phase change in radians after one pass across a lm of thickness d.
From the diagram in Figure A.5, the phase change can be found geometrically.
The path dierence of the two beams multiplied by 2= (for n1 = 1) gives
D

D

Figure A.5: Geometric derivation of an expression for the phase change

.
2 = 2 (n2 a ; x) = 2v (n2 a ; x) ,

where a = cos2d , x = L sin i, and L = 2d tan r giving,
r
A.5 Single Film on a Semi-Innitely Thick Substrate
87
where
2n2d ; 2d sin sin

= v cos
r
i

r cos r
p
= 2vd 1 ; sin2 r ,
p
sin r = sinn i , and n2 cos r = n2 1 ; sin2 r .
(A.21)
It should be noted that possible absorption is taken into account here when the
complex refractive index is used, and that for case of normally incident light and
negligible absorption Eqn. A.21 reduces to = 2nd=.
The reected intensity is then given by
;
I / jE j2 1 + a2 + 2a cos 2 ,
(A.22)
which is a periodically changing function. Since neighbouring maxima and minima

must be separated by radians,
=)

4 1

; 1 nd =
min
max
jmin ; max j = 4nd .
(A.23)
For the observed minima min = 2003.0nm and maxima max = 2002.4nm, n =
1.52, and rearranging Eqn. A.23 for d, we get a value of 1.096mm, which lies well
within Corning's thickness tolerances, 1.10.1mm. Alternatively, for a known d,
this method can be used to get an estimate of n in regions of minimal dispersion
(small variation of n with ).
A.5 Single Film on a Semi-Innitely Thick

Substrate
This case is depicted in Figure A.6, where incoming light is incident on medium 2,
a thin lm, and some of the light is transmitted through to medium 3, a substrate
of semi-innite thickness d.
The reectance and transmittance for this case can be written as
r123 = r12 + t12 expi r23 expi t21 +

t12 expi r23 expi r21;expi r23 expi t21 +
= r12 + t12 r23 t21 expi 1 + r21 r23 exp2i +
2i
(A.24)
= r12 + 1t12;rr23 t21r exp
i ,
21 23 exp
t123 = t12 expi t23 h+ t12 expi r23 expi r21 expi t23 +
i
;
2
;
i
i
i
i
i
= t12 exp t23 1 + r21 exp r23 exp + r21 exp r23 exp +
i t23
= 1 ;t12r exp
,
(A.25)
2i
21 r23 exp
88
7

L
0HGLXP33
9
7
9
7
7
9
0HGLXP33
ILOP
0HGLXP33
VXEVWUDWH
9
Figure A.6: Thin lm on a semi-innitely thick substrate.
where the phase dierence in absorbing media will be complex. The reected and
transmitted intensities from the electric eld strength are found using the following
identity from the Fresnel formulae
t12 t21 = 1 ; r212 ,
(A.26)
simplifying Eqn. A.24 to
r23 exp2i .
r123 = 1r12; +
(A.27)
r21r23 exp2i
Using Eqn. A.21, we can write the transmittance, reectance, and absorptance as
s jt j2 ,
T = nn3 cos
(A.28)
123
1 cos i
R = jr123 j2 ,
(A.29)
A = 1;T ;R .
(A.30)
Practically, the incident medium is very often air (n1 = 1) and the substrate is
essentially non-absorbing (n3 is real). For this system with a non-absorbing lm,
Eqns. A.28 and A.29 simplify to
n3 cos s t2 t2
(A.31)
T = 1 + r2 nr12cos+ i2r12 23r cos ,
12 23
12 23
2
r232 + 2r12r23 cos 2 .
R = 1r12+ +
(A.32)
r122 r232 + 2r12 r23 cos 2
Examining the period of oscillation again, the model presented in Eqn. A.23 can
now be improved to include absorption and phase dierence. For neighbouring
extrema

1

1

(A.33)
; = p 2 1 2

min
max
4d n2 ; sin i
89
and for any two extrema

1

1
#m

p
,
(A.34)
; =
a
b
4d n22 ; sin2 i
where
#m ; 1 = no. of extrema observed between extrema a and b
=)
#m = 1 for neighbouring extrema:
For a material with minimal dispersion and normally incident light, the of the
mth extrema is at
(A.35)
m = 4nm2d for m = 1, 2, 3, : : : .
However, under strong absorption Eqns. A.33 and A.34 are not valid, as a constant
n is assumed, and in this case
s

1
n22

a a
; sin2 i ; 1 n ;
b
b
2
2

2
sin i

= #4m
d .
(A.36)
Thus, for a spectrum with normal dispersion, the interference fringes will appear
increasingly closer together as j increases, and as the lm becomes more absorbing.
Half and Quarter Waveplates

In thin lm optics, two very important cases exist for half-wavelength /2 and
quarter-wavelength /4 lms. A /2 lm can be realised with even m-values in
Eqn. A.34, as then optical thickness nd of the lm is half that of the incident
wavelength. The oscillating term is a maximum, cos 2 = 1, and from Eqn. A.31
2 2
n
t
3
12 t23
T=n
(A.37)
2 ,
1 (1 + r12 r23 )
which for normally incident light becomes
(A.38)
T = 4n1n3 2 .
(n1 + n3 )
This is the same result as would be obtained using Eqn. A.11 for the interface
n1 : n3 , so a /2 lm is optically totally inactive. To determine whether this
corresponds to a maxima or a minima in a spectrum, the denominator in Eqn.A.31
should be examined. When this, or the r12 r23 product, is small there will be a
transmittance maximum. This is true for n1 < n2 > n3, which is the case for a
silicon lm on glass in air. However, when n1 < n2 < n3 , for example an antireection (AR) coating (e.g. for TiO2 n
2.4) on silicon in air, the r12r23 product
is smaller, and a minima will be observed at the same in the transmittance
spectrum.
A /4 lm will occur when m has odd values, the term cos 2 = -1, and for normally
incident light, from Eqn. A.31
2 2
T = nn3 t12 t23 2
1 (1 ; r12 r23 )
90
4n1n22 n3 .
(n1n3 + n22 )2
(A.39)
This result is especially interesting for lms where n2 = pn1 n3 , as the transmittance
is unity, and the reectance must be zero. This is the principle of an AR coating.
Single Absorbing Film in Air

Before developing the model to predict the transmittance and reectance of a lm
on a thick substrate, a single absorbing lm is treated, including the eects of thin
lm interference in the analysis. For normally incident light in this two-media case,
the reectance and transmittance simplify to
i
,
(A.40)
t = 1 ;t12r t21r exp
2i
12 21 exp
r21 exp2i .
r = 1r12; +
(A.41)
r12 r21 exp2i
For an absorbing material, is complex and has the form = 0 + 00. The
transmitted intensity is then
jt12 j2 jt21 j2 exp;2
T=
,
(A.42)
1 + jr12 j2 jr21 j2 exp;4 $< (r12 r21 cos 20) ; = (r12r21 sin 20)]
where < and = denote the real and imaginary components, respectively.
It is quite complex to expand the applicability of Eqns. A.15 and A.16 to be valid
in the case of obliquely incident light, because the angle of refraction r and the
refractive index n~ 2 become complex quantities. This will not be performed here,
although from Eqn. A.41 the expression for a incoherent thick lm can be derived
by assuming the phase of the incident light as being randomly distributed
0
00
Z1
jt12 j2 jt21 j2 exp;2

1 + jr12j2 jr21j2 exp;4 $< (r12 r21 cos 20) ; = (r12 r21 sin 20)]
0
p~ ;sin i
2
2
;
4vd = n
j
t
j
j
t
j
exp
12
21
p
,
(A.43)
=
2
1 ; jr12j jr21 j2 exp;8vd = n~ ;sin i
T = 1
d0
00
2
2
2
2
using the identity

Z

ap; b tan x2 + c
dx
2

p
=
arctan
.
a + b cos x + c sin x a2 >b2 +c2
a2 ; b2 ; c2
a2 ; b2 ; c2
A similar expression for the reected intensity is
p
p
.
;8vd = n~ ;sin i
(A.44)
(A.45)
R = jr12 j2 + jt12 j jr212j jt21 j2
2
2
2
1 ; jr12 j jr21 j exp
For normally incident light, Eqns. A.43 and A.45 simplify to Eqns. A.16 and A.15,
respectively, if the phase terms are neglected, which is valid for an incoherent lm.
2
exp;8vd = n~22;sin2 i
A.6 Thin Film on a Thick Substrate
91

The nal goal is now to derive equations that can describe the reectance and transmittance of an absorbing thin lm on a transparent thick substrate in air, shown
in Figure A.7. The complex refractive index of the substrate and lm are indicated with n~ s and n~f , respectively, and ds is the substrate thickness. Substituting
Eqns. A.24 and A.25 into Eqns. A.45 and A.43, respectively, the transmittance
and reectance of this system is
jt123 j2 jt31 j2 exp;2=(s) ,

1 ; jr321 j2 jr31j2 exp;4=(s)
2
2
2
;4=(s )
R = jr123 j2 + jt123 j jr31 j2 jt3212j exp;4=(s) .
1 ; jr321 j jr31 j exp
T =
(A.46)
(A.47)
$LU3
)LOP 3 = 3
6XEVWUDWH 3 = 3 8
$LU3

Figure A.7: Diagram of a thin lm upon a thick substrate, d ds.
These equations are valid for absorbing lms and substrates, as well as obliquely
incident light, while polarisation must be taken into account with the correct choice
of Fresnel coecients. The most popular form of this equation, for an absorbing
lm (nf , kf ) on a transparent substrate (ns) was presented by Swanepoel (1983)
0
T = B 0 ; CA0xx+ D0x2 ,
(A.48)
where
A0 = 16ns n2f + kf2 ,

;

B 0 = (nf + 1)2 + kf2 (nf + 1) nf + n2s + kf2 ,
;
;

;

C 0 = n2f ; 1 + kf2 n2f ; n2s + kf2 ; 2kf2 n2s + 1 2 cos ,
;
;
;

;kf 2 n2f ; n2s + kf2 + n2s + 1 n2f ; 1 + kf2 2 sin ,

;

D0 = (nf ; 1)2 + kf2 (nf ; 1) nf ; n2s + kf2 ,
= 4n f d ,
x = exp;f d .
92
Eqn. A.48 can be simplied by neglecting terms containing kf , since kf nf ns

over the whole spectrum (Swanepoel 1983), and the resulting expression is extensively used throughout the remainder of this work:
Ax
(A.49)
T = B ; Cx
+ Dx2 ,
where
A
B
C
D

x
=
=
=
=
=
=
16nsn2f ,
;

2
(nf + 1);2 (nf + 1); nf + n
s ,
2 cos n2f ; 1 n2f ; n2s ,
;

(nf ; 1)2 (nf ; 1) nf ; n2s ,
4nf d ,

exp;f d .
Appendix B
NAKED: Program Listingy
NAKED - A Modified Envelope Method to Determine
n, a, k, Eg, d delta d of Inhomogeneous, Absorbing Films

%U\FH5LFKDUGV
3KRWRYROWDLFV6SHFLDO5HVHDUFK&HQWUH
7KH8QLYHUVLW\RI1HZ6RXWK:DOHV
__o
WHO
.HQVLQJWRQ
_-\<,_
ID[
1HZ6RXWK:DOHV
(_) (_)
HPDLOEULFKDUGV#XQVZHGXDX
$8675$/,$

/\
Global Options
(* loads necessary packages and sets plot options *)
SetOptions[ListPlot,PlotStyle->PointSize[0.01], Frame->True, GridLines->
Automatic,PlotRange->All];
SetOptions[Plot,PlotRange->All,Frame->True,GridLines->Automatic];
<<Statistics`NonlinearFit`
<<Statistics`LinearRegression`
<<Graphics`Graphics`
Off[LinearSolve::luc, NonlinearFit::lmpnocon, General::spell1,
General::spell, FindRoot::frnum, FindRoot::fjnum, Infinity::indet,
Power::infy, FindRoot::cvnwt,General::stop, General::ovfl];
Read in Extrema Data from ENVELOPE

(*Directory for input and output *)
SetDirectory[d:\\bryce\\charact\\films_06\\];
tanfile = "06-06aa.tan";
(* tangential points output file (.tan) from ENVELOPE *)
tanlist = ReadList[tanfile,{Number,Number,Number}];
tanpt = N[Reverse[Table[{tanlist[[i,1]],tanlist[[i,2]]/100,
tanlist[[i,3]]/100},{i,1,Length[tanlist]}]]];
(* Order from high to low wavelength lambda and convert T data from % to
decimal between 0 and 1. Wavelength, T(max), T(min) *)
leng = Length[tanpt];
outputfile = StringJoin[StringDrop[tanfile,-3],"nak"];
(* NAKED output file has *.nak extension *)
nakfile = OpenWrite[outputfile];
(* open nakfile for text output *)
y The Mathematica (version 2.2.3) le NAKED.ma is included on a disk in the inside rearcover.
93
94
Substrate n & k information
s := 1.65599 - 6.62248*10^-4*lambda + 1.36881*10^-6*lambda^2 - 1.59892*10^-9
*lambda^3 + 1.0667*10^-12 *lambda^4 - 3.97249*10^-16*lambda^5 +
7.56102*10^-20 *lambda^6 - 5.62614*10^-24 *lambda^7;
(* substrate refractive index (1737 glass) 's' expression *)
absfile = "c:\\bryce\charact\substrate\\corn-abs.txt";
(* Absorption coefficient data for 1737 glass *)
abslist = ReadList[absfile,{Number,Number}];
abs1737 = Interpolation[abslist];
(* Interpolate between data points (100nm interval, inverse mm) *)
dgls = 1.1;
(* glass thickness in mm *)
corr := N[Exp[-abs1737[lambda]*dgls]];
(* Correct for glass absorption by dividing measured maxima (TM) and
minima (Tm) by Exp[alpha.d] term at each extrema*)
(* Plot absorption corrected T spectrum for reference *)
rawspect = ReadList["06-06a.dat",{Number,Number}];
spectrum = Table[{rawspect[[i,1]], rawspect[[i,2]]/corr /. lambda->
rawspect[[i,1]]}, {i,1,Length[rawspect]}];
ListPlot[spectrum, FrameLabel->{FontForm["l",{"Symbol",10}],"Transmission
(%)"}, PlotRange->{Automatic,{0,100}}];
tanpts = Table[{tanpt[[i,1]], tanpt[[i,2]], tanpt[[i,3]],
tanpt[[i,2]]/corr /. lambda->tanpt[[i,1]], tanpt[[i,3]]/corr /.
lambda->tanpt[[i,1]], s /. lambda->tanpt[[i,1]]}, {i,1,leng}];
tanptsoutput = TableForm[tanpts,TableSpacing->{0}, TableHeadings->{{},
{"\n nm", "
Uncorrected: \n
TM", "\n
tm","
Corrected: \n
TM","\n
tm","\n
s"}}]
(* display table of corrected vs measured T values *)
nm
2182.
2050.
1933.
1830.
1738.
1655.
1580.
1513.
1451.
1395.
1343.
1296.
1252.
1211.
1173.
1138.
1106.
1075.
1047.
1020.
Uncorrected:
TM
tm
0.893468 0.332229
0.893124 0.333607
0.88873 0.333708
0.881635 0.332401
0.87092 0.330484
0.85633 0.327948
0.837099 0.324639
0.813773 0.320186
0.784841 0.314844
0.752976 0.309265
0.719539 0.303024
0.685353 0.296032
0.649361 0.288412
0.613136 0.280465
0.578214 0.272335
0.54476 0.264308
0.513496 0.256301
0.481974 0.24783
0.45222 0.239301
0.421606 0.230036
Corrected:
TM
tm
0.898755 0.334195
0.893943 0.333913
0.88945
0.333978
0.882078 0.332568
0.871435 0.330679
0.85696
0.328189
0.837682 0.324865
0.814303 0.320395
0.785968 0.315296
0.754533 0.309904
0.72067
0.3035
0.686099 0.296354
0.650141 0.288758
0.614008 0.280864
0.579128 0.272765
0.545672 0.264751
0.514381 0.256743
0.482796 0.248253
0.452966 0.239696
0.422268 0.230397
s
1.4841
1.48827
1.49088
1.49239
1.49326
1.49382
1.49426
1.49467
1.49514
1.49566
1.49625
1.49688
1.49756
1.49828
1.49901
1.49973
1.50044
1.50117
1.50185
1.50254
95
995.
972.
950.
930.
910.
892.
875.
859.
843.
828.
0.391011
0.35976
0.325178
0.29006
0.25102
0.213352
0.175637
0.140493
0.108245
0.079792
0.220146
0.209482
0.197316
0.18371
0.167414
0.149846
0.130754
0.109672
0.088428
0.070876
0.39159
0.360262
0.325601
0.290409
0.251294
0.213559
0.175782
0.140589
0.108305
0.0798271
0.220472
0.209774
0.197572
0.183931
0.167597
0.149991
0.130862
0.109747
0.0884771
0.0709072
1.5032
1.50382
1.50443
1.505
1.50558
1.50611
1.50662
1.50711
1.5076
1.50807
Divide transmission spectrum up into different regions of absorption:

i)
Transparent region (where maxima should be limited only by

transmission of substrate for a uniformly thick film)
(* Calculation to find thickness variation delta d *)

a := 16*n^2*s;
b := (n+1)^3*(n+s^2);
c := 2*(n^2-1)*(n^2-s^2);
d := (n-1)^3*(n-s^2);
(* coefficients for transmission expression *)
at := a/(b+d) /. {n->n2, s->tanpts[[i,6]]};
bt := c/(b+d) /. {n->n2, s->tanpts[[i,6]]};
(* want to solve minima and maxima for variables n2 (initial guess at nf) and
delta d (wavelength independent) *)
For[i=1; n2d={}, i<=(leng), i++,
n2deltad = FindRoot[{ tanpts[[i,4]] == tanpts[[i,1]]/ 2*Pi*n2*deltad)*
(at)/((1-(bt)^2)^0.5)*ArcTan[(1+(bt))/(1-bt)^2)^0.5*Tan[2*Pi*n2*
deltad/tanpts[[i,1]]]], tanpts[[i,5]] == tanpts[[i,1]]/(2*Pi*n2*
deltad)*(at)/((1-(bt)^2)^0.5)*ArcTan[(1-(bt))/(1-(bt)^2)^0.5*
Tan[2*Pi*n2*deltad/tanpts[[i,1]]]]}, {n2,3.5},{deltad,20}];
n2d = AppendTo[n2d,{tanpts[[i,1]],n2deltad[[1,2]], n2deltad[[2,2]]}];]
(* determine delta d from long wavelength (IR) asymptote of plot. N.B. If
film is not transparent in IR (e.g. free-carrier absorption, or defected
material) then estimate of delta d here will be too high. Continue analysis
to see whether calculated T points lie on the original T curve, and if not,
then repeat analysis with a lower delta d value *)
deltaddata = Table[{n2d[[i,1]],n2d[[i,3]]}, {i,1,leng}];
lam = FontForm["l",{"Symbol",10}];
ListPlot[deltaddata, PlotRange->{0,36},FrameLabel->{lam, "Thickness Variation
(nm)"}];
ii)
Weak and Medium Absorption Region
(* Using delta d calculate initial guesses for nf and x in abs. region *)

deltad = 15.3;
ax := a*x/(b+d*x^2) /. {n->n3, s->tanpts[[i,6]]};
bx := c*x/(b+d*x^2) /. {n->n3, s->tanpts[[i,6]]};
(* coefficents including absorption term x=Exp[-alpha.d] *)
96
n3xfind = Table[FindRoot[{
tanpts[[i,4]] == tanpts[[i,1]]/(2*Pi*n3*deltad) * ax/((1-bx^2)^0.5)*
ArcTan[(1+bx)/(1-bx^2)^0.5 * Tan[2*Pi*n3*deltad/tanpts[[i,1]]]],
tanpts[[i,5]] == tanpts[[i,1]]/(2*Pi*n3*deltad) * ax/((1-bx^2)^0.5)*
ArcTan[(1-bx)/(1-bx^2)^0.5 *Tan[2*Pi*n3*deltad/tanpts[[i,1]]]]},
{n3,3.5},{x,1}],{i,1,leng}];
n3x = Table[{tanpts[[i,1]], n3xfind[[i,1,2]], n3xfind[[i,2,2]]},{i,1,leng}];
(* n3x are nf and x values from solving the two eqns. for max. and min. *)
iii) Strong Absorption Region

Clear[a,b,c,d,e,f,g,h,w,x,lambda];
(* clears values of variables used - useful if have to recalculated firstm *)
strext = {}; lmint = {}; lmfit = {}; lmdata = {}; strabs = leng-4;
(* strabs = number of points up until the strong absorption region
which are not influenced by errors in T. Points at wavelengths shorter
than this can be considered to be interference free and calculated using
the mean of the extrema. *)
ndata = Table[{n3x[[i,1]],n3x[[i,2]]}, {i,1,strabs}];
nform = NonlinearFit[ndata, f/x^4 + g/x^2 + h, x, {{f,1000},{g,3},{h,2}}];
nfit = nform[[1,2]]/lambda^4 + nform[[2,2]]/lambda^2 + nform[[3,2]];
(* Since no nf data is available in the region of strong absorption there is
no means of finding nf here. Therefore, nf must be extrapolated into this
region using a Cauchy fit (= nfit) to data at longer wavelengths *)
n4 = Table[ReplacePart[n3x[[i]],nfit /. lambda->n3x[[i,1]],2],
{i,strabs,leng}];
n5 = Table[n3x[[i]],{i,1,strabs-1}];
n5 = FlattenAt[AppendTo[n5, Table[n4[[i]],{i,1,Length[n4]}]], strabs];
(* replaces nf values found previously in strong absorption region with
extrapolated values from nfit. n5 contains the new values of {Wavelngth (nm),
nf, x} *)
Determining the order number and average thickness

(* Plotting the equation l/2=2*d*(n/lambda)-m1 , where l = 0,1,2,3... , yields
a straight line of slope 2*d (yielding the thickness) and y-intercept m1 (the
first observable extrema in IR). m1
has an integer value for a maxima, and
half-integer value for a minima *)
lmdata = Table[{n5[[i+1,2]]/n5[[i+1,1]], N[i/2]},{i,0,leng-1}];
lmint = Fit[lmdata, {1,w},w];
firstm = -7.5;
(* firstm = m1 (the order number of the first observable extrema in IR *)
straight = 20;
lmnonlin = NonlinearFit[Table[lmdata[[i]],{i,1,straight}],f*w + firstm,
w, {f,1000}];
lmfit = firstm + lmnonlin[[1,2]]*x;
(* fits line w. slope 2d and y-int. firstm to the first 'straight' points*)
DisplayTogether[ListPlot[lmdata], Plot[lmfit,{x,0,0.006}, PlotStyle->
RGBColor[1,0,0]], AxesOrigin->{0,0}, FrameLabel->{FontForm["N/l",
{"Symbol",10}],"l/2"}];
d2 = N[lmfit[[2,1]]/2];
(* determine thickness d2 from slope *)
Print["Film thickness: ",NumberForm[d2,4,NumberPoint->"."]," ",nm];
Film thickness:
2157. nm
97
Improve nf values using the order values m and thickness d
(* nf values can be improved using the equation 2*nf*d = m*lambda *)
n6 = Table[{n5[[m,1]], N[(n5[[m,1]]*((m-(2*firstm+1))/2)/(2*d2))],
n5[[m,3]]}, {m,1,leng}];
ntest = Table[{n6[[i,1]],n6[[i,2]]},{i,1,leng}];
Clear[f,g,h];
range = {Ceiling[tanpts[[1,1]]/100]*100,Floor[spectrum[[1,1]]/100]*100};
(* sets standard x-range to plot *)
nform = NonlinearFit[ntest, f/x^4 + g/x^2 + h, x, {{f,1000},{g,3},{h,2}}];
nfit = nform[[1,2]]/lambda^4 + nform[[2,2]]/lambda^2 + nform[[3,2]];
DisplayTogether[ListPlot[ntest], Plot[nfit, {lambda,range[[1]],range[[2]]},
PlotStyle->RGBColor[1,0,0]], FrameLabel->{lam, "Ref. Index nf",
"Extrapolation of n"," "}, PlotRange->{range,Automatic}];
Determining x in the strong absorption region

i)
In the region where extrema exist
a := 16*n^2*s;
b := (n+1)^3*(n+s^2);
c := 2*(n^2-1)*(n^2-s^2);
d := (n-1)^3*(n-s^2);
(* Either Eqns. 12 and 13, or 18 and 19 from Swanepoel (1983) are used to
calculate the absorption in the interference free region *)
(* em := 8*n^2*s/tanpts[[i,4]]+(n^2-1)*(n^2-s^2); *)
(* xstrabs = Table[(em-(em^2-(n^2-1)^3*(n^2-s^4))^0.5)/((n-1)^3*(n-s^2))
/. {n->n6[[i,2]], lambda->n6[[i,1]]}, {i,strabs,leng}]; *)
ta := (tanpts[[i,5]]*tanpts[[i,4]])^0.5;
(* ta is the geometric mean of the maxima and minima *)
g := 128*n^4*s^2/ta^2+n^2*(n^2-1)^2*(s^2-1)^2+(n^2-1)^2*(n^2-s^2)^2;
xstrabs = Table[(g-(g^2-(n^2-1)^6*(n^2-s^4)^2)^0.5)^0.5/((n-1)^3*(n-s^2))
/. {n->n6[[i,2]], lambda->n6[[i,1]]}, {i,strabs,leng}];
n6x = Table[ReplacePart[n6[[i]],xstrabs[[i+1-strabs]],3],{i,strabs,leng}];
nx = Table[{n6[[i,1]],n6[[i,2]],n3x[[i,3]]},{i,1,strabs-1}];
nx = FlattenAt[AppendTo[nx, Table[{n6x[[i,1]], n6x[[i,2]], n6x[[i,3]]},
{i,1,Length[n6x]}]],strabs];
ii)
In the interference free region
(* Using nfit, extrapolate n into strong absorption region and

calculate
x from interference-free T data *)
strongpts = Table[{spectrum[[i,1]], spectrum[[i,2]]/100}, {i,(Last[n6][[1]] spectrum[[1,1]]),1,-1}];
(* find x in the region below where the first extrema is resolved (with
ENVELOPE)*)
(* em := 8*n^2*s/strongpts[[i,2]]+(n^2-1)*(n^2-s^2); *)
(* xstrong = Table[{strongpts[[i,1]], nfit /. lambda->strongpts[[i,1]],
(em-(em^2-(n^2-1)^3*(n^2-s^4))^0.5)/((n-1)^3*(n-s^2)) /. n->nfit
/. lambda->strongpts[[i,1]]}, {i,1,Length[strongpts]}]; *)
ta := strongpts[[i,2]];
g := 128*n^4*s^2/ta^2+n^2*(n^2-1)^2*(s^2-1)^2+(n^2-1)^2*(n^2-s^2)^2;
xstrong = Table[{strongpts[[i,1]], nfit /. lambda->strongpts[[i,1]],
(g-(g^2-(n^2-1)^6*(n^2-s^4)^2)^0.5)^0.5/((n-1)^3*(n-s^2)) /. n->nfit
/. lambda->strongpts[[i,1]]}, {i,1,Length[strongpts]}];
98
(* simply use the same expression as used above with the transmission curve as
the input, ignoring any interference *)
nx = FlattenAt[AppendTo[nx, xstrong], Length[nx]];
Display s, n, alpha, and k values at all wavelengths

nak = Table[{nx[[i,1]], s /. lambda->nx[[i,1]], nx[[i,2]],
N[-Log[nx[[i,3]]]/(d2*1 10^-7)*nx[[i,1]]*1 10^-7/(4*Pi)],
1239.75/nx[[i,1]], -Log[nx[[i,3]]]/(d2*1 10^-7)},{i,1,Length[nx]}];
nakoutput = TableForm[nak,TableSpacing->{0},TableHeadings->{{},
{"nm","s","n","k","eV","a (1/cm)"}}]
For[imcount=leng, Equal[Abs[Im[nak[[imcount,6]]]],0] &&
imcount<nakleng, imcount++,];
(* detect if there are any imaginary solutions given *)
For[infcount=leng, Less[nak[[infcount,6]],Infinity] &&
infcount<(imcount-1), infcount++, ];
infcount=infcount-1;
(* detect if there are any Infinite values for absorption coefficient *)
nakleng = Length[nak];
WriteString[nakfile,"Thickness: ",NumberForm[d2,4]," +- ",deltad," nm\n\n"];
Write[nakfile, Format[nakoutput,OutputForm]];
WriteString[nakfile,"\n\n"];
(* write this table to output data file too *)
nm
2182.
2050.
1933.
1830.
1738.
1655.
1580.
1513.
1451.
1395.
1343.
1296.
1252.
1211.
1173.
1138.
1106.
1075.
1047.
1020.
995.
972.
950.
930.
910.
892.
875.
859.
843.
828.
827
826
825
824
823
822
821
820
819
818
817
816
815
814
813
812
811
810
s
1.4841
1.48827
1.49088
1.49239
1.49326
1.49382
1.49426
1.49467
1.49514
1.49566
1.49625
1.49688
1.49756
1.49828
1.49901
1.49973
1.50044
1.50117
1.50185
1.50254
1.5032
1.50382
1.50443
1.505
1.50558
1.50611
1.50662
1.50711
1.5076
1.50807
1.5081
1.50814
1.50817
1.5082
1.50823
1.50826
1.50829
1.50833
1.50836
1.50839
1.50842
1.50846
1.50849
1.50852
1.50855
1.50858
1.50862
1.50865
n
3.79284
3.80095
3.80802
3.81718
3.82668
3.83572
3.84499
3.85727
3.86735
3.87975
3.89076
3.90478
3.9173
3.92935
3.94198
3.95624
3.97316
3.98637
4.00386
4.01881
4.03562
4.05497
4.07328
4.0953
4.11268
4.1347
4.15729
4.18082
4.20063
4.22184
4.22255
4.22411
4.22568
4.22725
4.22883
4.23042
4.23202
4.23363
4.23524
4.23687
4.2385
4.24014
4.24178
4.24344
4.2451
4.24677
4.24845
4.25014
k
0.00071121
0.000768972
0.000821009
0.00100164
0.00131513
0.00177002
0.00239786
0.00316238
0.00410659
0.00517282
0.00632517
0.00751007
0.00877303
0.0100757
0.0113567
0.0126267
0.0138421
0.0151207
0.0163823
0.0177669
0.0192568
0.0209419
0.0231122
0.0256114
0.0289132
0.0326987
0.0375115
0.0426509
0.0485834
0.0556992
0.0546408
0.0554718
0.0563973
0.0573744
0.0583941
0.0594206
0.0604489
0.0614354
0.0623796
0.0632596
0.0640708
0.0648292
0.0654781
0.0660463
0.0665427
0.0669867
0.0673369
0.0677111
eV
0.568171
0.604756
0.641361
0.677459
0.71332
0.749094
0.784652
0.819399
0.854411
0.88871
0.92312
0.956597
0.990216
1.02374
1.05691
1.08941
1.12093
1.15326
1.1841
1.21544
1.24598
1.27546
1.305
1.33306
1.36236
1.38985
1.41686
1.44325
1.47064
1.49728
1.49909
1.50091
1.50273
1.50455
1.50638
1.50821
1.51005
1.51189
1.51374
1.51559
1.51744
1.5193
1.52117
1.52303
1.52491
1.52679
1.52867
1.53056
a (1/cm)
40.9594
47.1375
53.3735
68.7811
95.089
134.397
190.711
262.654
355.651
465.976
591.843
728.197
880.552
1045.54
1216.65
1394.3
1572.74
1767.55
1966.25
2188.88
2432.04
2707.44
3057.23
3460.67
3992.68
4606.54
5387.24
6239.43
7242.19
8453.34
8302.74
8439.21
8590.42
8749.86
8916.18
9083.96
9252.41
9414.88
9571.25
9718.14
9854.8
9983.67
10096.
10196.1
10285.4
10366.8
10433.8
10504.7
99
809
808
807
806
805
804
803
802
801
800
799
798
797
796
795
794
793
792
791
790
789
788
787
786
785
784
783
782
781
780
779
778
777
776
775
774
773
772
771
770
769
768
767
766
765
764
763
762
761
760
759
758
757
756
755
754
753
752
751
750
749
748
747
746
745
744
743
742
741
740
739
738
1.50868
1.50871
1.50875
1.50878
1.50881
1.50884
1.50888
1.50891
1.50894
1.50897
1.50901
1.50904
1.50907
1.5091
1.50914
1.50917
1.5092
1.50924
1.50927
1.5093
1.50934
1.50937
1.5094
1.50944
1.50947
1.5095
1.50954
1.50957
1.5096
1.50964
1.50967
1.5097
1.50974
1.50977
1.5098
1.50984
1.50987
1.50991
1.50994
1.50997
1.51001
1.51004
1.51008
1.51011
1.51014
1.51018
1.51021
1.51025
1.51028
1.51032
1.51035
1.51038
1.51042
1.51045
1.51049
1.51052
1.51056
1.51059
1.51063
1.51066
1.5107
1.51073
1.51077
1.5108
1.51084
1.51087
1.51091
1.51094
1.51098
1.51102
1.51105
1.51109
4.25184
4.25355
4.25526
4.25698
4.25872
4.26046
4.26221
4.26397
4.26573
4.26751
4.2693
4.27109
4.2729
4.27471
4.27653
4.27836
4.28021
4.28206
4.28392
4.28579
4.28767
4.28956
4.29146
4.29337
4.29529
4.29722
4.29916
4.30111
4.30307
4.30504
4.30702
4.30901
4.31102
4.31303
4.31505
4.31709
4.31913
4.32119
4.32326
4.32533
4.32742
4.32952
4.33164
4.33376
4.3359
4.33804
4.3402
4.34237
4.34455
4.34675
4.34895
4.35117
4.3534
4.35564
4.3579
4.36016
4.36244
4.36473
4.36704
4.36936
4.37169
4.37403
4.37639
4.37876
4.38114
4.38354
4.38594
4.38837
4.3908
4.39325
4.39572
4.3982
0.0680278
0.0683553
0.0687148
0.0691119
0.0695597
0.0700892
0.0706641
0.07134
0.0721129
0.0729271
0.0738192
0.0747409
0.075787
0.0767883
0.0778002
0.0788286
0.0798247
0.0808233
0.0817543
0.0826657
0.0835151
0.0843215
0.0850923
0.085801
0.0865293
0.0872376
0.0879653
0.0886705
0.089429
0.0902103
0.0910694
0.0918991
0.0928259
0.0938086
0.0948194
0.0958617
0.0969631
0.0980091
0.0991302
0.10024
0.10134
0.102442
0.103492
0.104634
0.105694
0.106721
0.107772
0.108801
0.109839
0.110848
0.111917
0.112989
0.114055
0.115167
0.116267
0.117448
0.118622
0.119833
0.121087
0.122298
0.123513
0.124885
0.126138
0.127427
0.128681
0.129949
0.13131
0.13255
0.133821
0.135185
0.136508
0.137834
1.53245
1.53434
1.53625
1.53815
1.54006
1.54198
1.5439
1.54582
1.54775
1.54969
1.55163
1.55357
1.55552
1.55747
1.55943
1.5614
1.56337
1.56534
1.56732
1.5693
1.57129
1.57329
1.57529
1.57729
1.5793
1.58131
1.58333
1.58536
1.58739
1.58942
1.59146
1.59351
1.59556
1.59762
1.59968
1.60174
1.60382
1.60589
1.60798
1.61006
1.61216
1.61426
1.61636
1.61847
1.62059
1.62271
1.62484
1.62697
1.62911
1.63125
1.6334
1.63555
1.63771
1.63988
1.64205
1.64423
1.64641
1.6486
1.6508
1.653
1.65521
1.65742
1.65964
1.66186
1.66409
1.66633
1.66857
1.67082
1.67308
1.67534
1.6776
1.67988
10566.9
10630.9
10700.1
10775.3
10858.5
10954.8
11058.4
11178.1
11313.3
11455.4
11610.
11769.7
11949.4
12122.5
12297.7
12475.9
12649.5
12823.9
12988.1
13149.5
13301.4
13446.9
13587.1
13717.7
13851.7
13982.9
14117.6
14248.9
14389.2
14533.5
14690.8
14843.7
15012.7
15191.2
15374.7
15563.7
15762.9
15953.6
16157.
16359.1
16560.2
16762.1
16955.9
17165.3
17362.
17553.6
17749.7
17942.7
18137.8
18328.3
18529.5
18731.7
18933.3
19143.3
19351.7
19574.3
19796.2
20024.7
20261.3
20491.3
20722.4
20980.6
21219.5
21465.
21705.5
21948.7
22208.5
22448.4
22694.3
22956.5
23212.6
23469.8
100
737
736
735
734
733
732
731
730
729
728
727
726
725
724
723
722
721
720
719
718
717
716
715
714
713
712
711
710
709
708
707
706
705
704
703
702
701
700
699
698
697
696
695
694
693
692
1.51112
1.51116
1.51119
1.51123
1.51127
1.5113
1.51134
1.51137
1.51141
1.51145
1.51148
1.51152
1.51155
1.51159
1.51163
1.51166
1.5117
1.51174
1.51177
1.51181
1.51185
1.51188
1.51192
1.51196
1.512
1.51203
1.51207
1.51211
1.51214
1.51218
1.51222
1.51226
1.5123
1.51233
1.51237
1.51241
1.51245
1.51248
1.51252
1.51256
1.5126
1.51264
1.51268
1.51271
1.51275
1.51279
4.40069
4.4032
4.40572
4.40825
4.4108
4.41336
4.41594
4.41854
4.42115
4.42377
4.42641
4.42906
4.43173
4.43441
4.43711
4.43983
4.44256
4.44531
4.44807
4.45085
4.45365
4.45646
4.45929
4.46213
4.465
4.46788
4.47077
4.47369
4.47662
4.47956
4.48253
4.48551
4.48852
4.49153
4.49457
4.49763
4.5007
4.50379
4.50691
4.51004
4.51319
4.51635
4.51954
4.52275
4.52598
4.52922
0.139268
0.140434
0.142021
0.143109
0.144689
0.146111
0.147513
0.148932
0.15047
0.152082
0.153521
0.15489
0.156429
0.158301
0.159309
0.161008
0.162531
0.164204
0.165619
0.16661
0.168913
0.170485
0.172143
0.173785
0.175457
0.177851
0.179098
0.181868
0.182998
0.182841
0.185705
0.186728
0.188569
0.190771
0.191496
0.192286
0.195507
0.195331
0.201741
0.206776
Infinity
0.206392
0.206201
0.206009
Infinity
Infinity
1.68216
1.68444
1.68673
1.68903
1.69134
1.69365
1.69596
1.69829
1.70062
1.70295
1.7053
1.70764
1.71
1.71236
1.71473
1.71711
1.71949
1.72188
1.72427
1.72667
1.72908
1.73149
1.73392
1.73634
1.73878
1.74122
1.74367
1.74613
1.74859
1.75106
1.75354
1.75602
1.75851
1.76101
1.76351
1.76603
1.76854
1.77107
1.77361
1.77615
1.77869
1.78125
1.78381
1.78638
1.78896
1.79155
23746.1
23977.6
24281.5
24500.9
24805.
25083.1
25358.4
25637.4
25937.7
26251.6
26536.5
26810.
27113.8
27476.1
27689.2
28023.3
28327.6
28659.
28946.2
29160.
29604.3
29921.5
30254.7
30586.1
30923.7
31389.6
31654.2
32188.9
32434.8
32452.6
33007.7
33236.5
33611.8
34052.5
34230.6
34420.7
35047.2
35065.7
36268.3
37226.7
Infinity
37264.4
37283.3
37302.4
Infinity
Infinity
Load c-Si (Green 1995, Palik 1985) values for comparison

csidata = ReadList["d:\\bryce\\math\\si_nak2.dat",
{Number,Number,Number,Number}];
(* c-Si data file *)
csileng = Length[csidata];
ncsi = Table[{csidata[[i,1]],csidata[[i,2]]},{i,1,csileng}];
acsi = Table[{1239.75/csidata[[i,1]],csidata[[i,3]]},{i,1,csileng-1}];
(* alpha data in eV and inverse cm *)
kcsi = Table[{csidata[[i,1]],csidata[[i,4]]},{i,1,csileng}];
tauccsi = Table[{1239.75/csidata[[i,1]],
Sqrt[1239.75/csidata[[i,1]]*csidata[[i,3]]]}, {i,1,csileng}];
(* data for Tauc plot: (alpha.E)^0.5 vs E *)
Egcsi = Table[{1239.75/csidata[[i,1]], Power[1239.75/csidata[[i,1]]*
csidata[[i,2]]*csidata[[i,3]],1/3]}, {i,1,csileng}];
(* data for Eg plot: (alpha.E.n)^(1/3) vs E *)
Plot refractive index, absorption coefficent, and optical bandgap graphs

Clear[h,j,k];
nplot = Table[{nak[[i,1]],nak[[i,3]]},{i,1,nakleng}];
Print["n(lambda) = ", nfit];
WriteString[nakfile,"Cauchy: n(lambda) = ", Format[nfit,InputForm],"\n\n"];
DisplayTogether[ListPlot[ncsi, PlotJoined->True, PlotStyle->RGBColor[1,0,0]],
ListPlot[nplot], FrameLabel->{lam, "Refractive Index, n"},PlotRange->
{range,{3.4,Ceiling[nak[[nakleng,3]]*10]/10}}];
101
10
7.94496 10
207709.
n(lambda) = 3.749 + ------------ + ------4
2
lambda
lambda
Clear[h,j,k];
(* Stop plotting nak data set before points reach infinity!*)
alphaev = Table[{nak[[i,5]], nak[[i,6]]},{i,1,infcount}];
(* alpha data in cm-1 *)
evrange=N[{Floor[nak[[1,5]]*100]/100, Ceiling[nak[[nakleng,5]]*100]/100}];
alpharange = {1, N[Ceiling[Log[10,nak[[infcount,6]]]*10]/10]};
DisplayTogether[LogListPlot[acsi, PlotJoined->True, PlotStyle->
RGBColor[1,0,0]], LogListPlot[alphaev], FrameLabel->{"Energy,
eV",FontForm["a",{"Symbol",10}]}, PlotRange->{evrange,alpharange},
AxesOrigin->{1,1}];
(* alpha data displayed as a log alpha vs. eV plot is more useful *)
(* From alpha the type of transition can be determined:

- direct transitions have a alpha^2 dependence, while
- indirect transitions have an alpha^0.5 dependence. *)
alphahalf = Table[{nak[[i,5]], Sqrt[nak[[i,6]]]},{i,1,infcount}];
csihalf = Table[{acsi[[i,1]], Sqrt[acsi[[i,2]]]},{i,1,csileng-1}];
alpha2 = Table[{nak[[i,5]], nak[[i,6]]^2},{i,1,infcount}];
csi2 = Table[{acsi[[i,1]], acsi[[i,2]]^2},{i,1,csileng-1}];
DisplayTogether[ListPlot[csihalf, PlotJoined->True, PlotStyle->
RGBColor[1,0,0]], ListPlot[alphahalf], PlotRange->{evrange,{0,
Ceiling[alphahalf[[Length[alphahalf],2]]/10]*10}},
FrameLabel->{"Energy, eV","alpha^0.5"}];
102
DisplayTogether[ListPlot[csi2, PlotJoined->True, PlotStyle->
RGBColor[1,0,0]], ListPlot[alpha2], PlotRange->{{1,evrange[[2]]},
{0,Ceiling[alpha2[[Length[alpha2],2]]]}}, FrameLabel->{"Energy, eV",
"alpha^2"}];
kdata = Table[{nak[[i,1]], nak[[i,4]]},{i,1,infcount}];

DisplayTogether[ListPlot[kcsi, PlotJoined->True, PlotStyle->RGBColor[1,0,0]],
ListPlot[kdata], FrameLabel->{lam,"Ext.Coeff., k"}, PlotRange->
{range,{0,0.25}}];
(* The optical bandgap Eg can be determined from the x-intercept of a

stright line fit to the high energy region *)
103
tauc = Table[{alphaev[[i,1]],Sqrt[alphaev[[i,2]]*alphaev[[i,1]]]},
{i,1,infcount}];
egplot = Table[{alphaev[[i,1]],(nak[[i,3]]*alphaev[[i,2]]*
alphaev[[i,1]])^(1/3)},
{i,1,infcount}];
DisplayTogether[ListPlot[tauccsi, PlotJoined->True, PlotStyle->
RGBColor[1,0,0]], ListPlot[tauc], FrameLabel->{"Energy (eV)",
"(aE)^0.5","Tauc Plot",""}, PlotRange->{evrange,{0,
tauc[[infcount,2]]+25}}];
DisplayTogether[ ListPlot[egplot], ListPlot[Egcsi, PlotJoined->True,
PlotStyle->RGBColor[1,0,0]], FrameLabel->{"Energy (eV)",
"(naE)^(1/3)","Eg Plot",""}, PlotRange->{evrange,{0,
egplot[[(infcount),2]]+5}}];
Check the solution found

(* use determined parameters (d, delta d, n, alpha) as inputs to see if
the transmission expression generates points which lie on the original T
spectrum *)
thickmin = d2 - deltad;
thickmax = d2 + deltad;
(* max and min thicknesses for integration *)
a := 16*n^2*s;
b := (n+1)^3*(n+s^2);
c := 2*(n^2-1)*(n^2-s^2);
d := (n-1)^3*(n-s^2);
For[i=1; trans={}, i<=infcount, i++,
transpts = {nak[[i,1]],100/(thickmax-thickmin) *
NIntegrate[a*Exp[-alpha*thick] / (b-c*Exp[-alpha*thick]*
Cos[4*Pi*n*thick/lambda] + d*Exp[-2*alpha*thick]) /. {lambda->
nak[[i,1]], s->nak[[i,2]], n->nak[[i,3]],
alpha->nak[[i,6]]*10^-7}, {thick,thickmin,thickmax}]} ;
(* generates T points by numerical integration *)
trans = AppendTo[trans, transpts];
];
104
transfit = Table[{trans[[i,1]], 200*s/(s^2+1) /. lambda->trans[[i,1]],
100*tanpts[[i,4]], 100*tanpts[[i,5]], trans[[i,2]]},{i,1,leng}];
transfit = FlattenAt[AppendTo[transfit, Table[{strongpts[[i,1]],
200*s/(s^2+1) /. lambda->strongpts[[i,1]], " ", 100*strongpts[[i,2]],
trans[[leng+i,2]]},{i,1,Length[strongpts]-nakleng+infcount}]],leng+1];
(* Print table showing: i) substrate limited T; ii) maxima TM
found by ENVELOPE; iii) minima found by ENVELOPE; iv) the
extrema generated from the optical constants and thickness *)
transout = TableForm[transfit,TableSpacing->{0},TableHeadings->{{},
{" nm","
Ts","
TM","
tm"," T pt"}}]
Write[nakfile, Format[transout,OutputForm]];
nm
2182.
2050.
1933.
1830.
1738.
1655.
1580.
1513.
1451.
1395.
1343.
1296.
1252.
1211.
1173.
1138.
1106.
1075.
1047.
1020.
995.
972.
950.
930.
910.
892.
875.
859.
843.
828.
827
826
825
824
823
822
821
820
819
818
817
816
815
814
813
812
811
810
809
808
807
806
805
804
803
802
801
Ts
92.6824
92.5844
92.523
92.4875
92.4668
92.4537
92.4434
92.4336
92.4226
92.4102
92.3963
92.3814
92.3653
92.3484
92.3312
92.314
92.2972
92.28
92.2638
92.2475
92.2319
92.2171
92.2026
92.1892
92.1755
92.1629
92.1508
92.1392
92.1274
92.1162
92.1155
92.1147
92.1139
92.1132
92.1124
92.1117
92.1109
92.1102
92.1094
92.1086
92.1079
92.1071
92.1063
92.1056
92.1048
92.1041
92.1033
92.1025
92.1017
92.101
92.1002
92.0994
92.0987
92.0979
92.0971
92.0963
92.0956
TM
89.8755
89.3943
88.945
88.2078
87.1435
85.696
83.7682
81.4303
78.5968
75.4533
72.067
68.6099
65.0141
61.4008
57.9128
54.5672
51.4381
48.2796
45.2966
42.2268
39.159
36.0262
32.5601
29.0409
25.1294
21.3559
17.5782
14.0589
10.8305
7.98271
tm
33.4195
33.3913
33.3978
33.2568
33.0679
32.8189
32.4865
32.0395
31.5296
30.9904
30.35
29.6354
28.8758
28.0864
27.2765
26.4751
25.6743
24.8253
23.9696
23.0397
22.0472
20.9774
19.7572
18.3931
16.7597
14.9991
13.0862
10.9747
8.84771
7.09072
7.77183
7.54234
7.29633
7.04583
6.79384
6.54884
6.31181
6.09128
5.88625
5.69982
5.53154
5.3773
5.24612
5.13164
5.03147
4.94165
4.8685
4.79241
4.72642
4.65949
4.5884
4.5125
4.43009
4.337
4.23913
4.12909
4.00846
T pt
33.4763
89.4004
33.3748
88.2032
33.0318
85.6851
32.4456
81.4204
31.519
75.4274
30.3038
68.5943
28.8717
61.4112
27.3165
54.5868
25.6766
48.2918
23.9714
42.2421
22.0806
36.0499
19.7262
28.9676
16.6301
21.1857
12.7789
13.9084
8.87974
8.12169
8.39933
8.09299
7.74793
7.38671
7.02099
6.66684
6.33046
6.0239
5.74794
5.50623
5.29816
5.11936
4.97701
4.8642
4.77751
4.71203
4.67204
4.63778
4.61917
4.60339
4.58435
4.55824
4.52025
4.4632
4.39114
4.29494
4.17602
105
800
799
798
797
796
795
794
793
792
791
790
789
788
787
786
785
784
783
782
781
780
779
778
777
776
775
774
773
772
771
770
769
768
767
766
765
764
763
762
761
760
759
758
757
756
755
754
753
752
751
750
749
748
747
746
745
744
743
742
741
740
739
738
737
736
735
734
733
732
731
730
729
92.0948
92.094
92.0932
92.0924
92.0917
92.0909
92.0901
92.0893
92.0885
92.0877
92.087
92.0862
92.0854
92.0846
92.0838
92.083
92.0822
92.0814
92.0806
92.0798
92.079
92.0782
92.0774
92.0766
92.0758
92.075
92.0742
92.0734
92.0726
92.0718
92.071
92.0702
92.0694
92.0686
92.0678
92.0669
92.0661
92.0653
92.0645
92.0637
92.0629
92.062
92.0612
92.0604
92.0596
92.0587
92.0579
92.0571
92.0563
92.0554
92.0546
92.0538
92.0529
92.0521
92.0513
92.0504
92.0496
92.0487
92.0479
92.047
92.0462
92.0454
92.0445
92.0437
92.0428
92.042
92.0411
92.0403
92.0394
92.0385
92.0377
92.0368
3.88561
3.75627
3.6273
3.48765
3.35817
3.23202
3.10856
2.99284
2.88091
2.77933
2.6829
2.59511
2.51369
2.43763
2.36874
2.30008
2.23479
2.16973
2.10805
2.04418
1.98052
1.9135
1.85047
1.78331
1.71507
1.64765
1.58098
1.51369
1.45193
1.38886
1.32894
1.27183
1.21698
1.16653
1.11439
1.06754
1.02375
0.980809
0.940306
0.901067
0.864301
0.82713
0.791382
0.757283
0.723333
0.691153
0.658377
0.627243
0.596724
0.56671
0.538966
0.512451
0.484412
0.459802
0.435826
0.413552
0.392177
0.370583
0.351674
0.333306
0.314781
0.297683
0.281442
0.264991
0.251928
0.23579
0.22475
0.210344
0.19797
0.186435
0.175436
0.164331
4.0443
3.89687
3.74335
3.57459
3.41513
3.25978
3.10966
2.97108
2.8409
2.72591
2.62106
2.52948
2.44859
2.37688
2.31543
2.25686
2.20332
2.15088
2.10175
2.04958
1.99597
1.93673
1.87901
1.81436
1.746
1.67624
1.60547
1.53287
1.4653
1.39631
1.33087
1.269
1.21038
1.15722
1.10357
1.05622
1.01285
0.971117
0.932383
0.895276
0.860773
0.825824
0.792065
0.759597
0.726833
0.695367
0.662822
0.631514
0.600485
0.569727
0.541128
0.513728
0.484856
0.459542
0.435024
0.412387
0.390831
0.369227
0.350432
0.332279
0.314036
0.29724
0.281288
0.265089
0.252226
0.236217
0.225256
0.210851
0.198437
0.186828
0.175732
0.164518
106
728
727
726
725
724
723
722
721
720
719
718
717
716
715
714
713
712
711
710
709
708
707
706
705
704
703
702
701
700
699
92.036
92.0351
92.0342
92.0334
92.0325
92.0316
92.0308
92.0299
92.029
92.0281
92.0273
92.0264
92.0255
92.0246
92.0237
92.0229
92.022
92.0211
92.0202
92.0193
92.0184
92.0175
92.0166
92.0157
92.0148
92.0139
92.013
92.0121
92.0112
92.0103
0.153455
0.14423
0.135871
0.127172
0.117534
0.112169
0.104299
0.0975719
0.0908326
0.0852437
0.0814315
0.0739168
0.0689101
0.0642004
0.0597158
0.0553093
0.0501304
0.0472533
0.0425856
0.0395955
0.0396866
0.0350849
0.0325719
0.0303991
0.0275961
0.0263936
0.0245279
0.0224181
0.0194409
0.0176281
0.153562
0.14424
0.135825
0.127083
0.117429
0.11207
0.104217
0.0975471
0.0907794
0.0852941
0.0814184
0.0739473
0.0690235
0.0641994
0.0597314
0.0554963
0.0501494
0.0473273
0.0421335
0.0399223
0.0397346
0.0352209
0.0334976
0.0308689
0.0280494
0.0269731
0.025872
0.0225868
0.0224817
0.017333
If[Mod[firstm,1]== 0.5,
transerror = Sum[(transfit[[i,4]] - transfit[[i,5]])^2+
(transfit[[i+1,3]] - transfit[[i+1,5]])^2,{i,1,leng,2}] +
Sum[(transfit[[i,4]] - transfit[[i,5]])^2, {i,leng+1,
Length[transfit]}],
transerror = Sum[(transfit[[i,3]] - transfit[[i,5]])^2+
(transfit[[i+1,4]] - transfit[[i+1,5]])^2,{i,1,leng,2}] +
Sum[(transfit[[i,4]] - transfit[[i,5]])^2, {i,leng+1,
Length[transfit]}]];
Print["Sum-of-squares error: ", transerror];
WriteString[nakfile,"Sum-of-squares error", transerror];
Close[nakfile];
Sum-of-squares error: 2.01567
(* If the generated points are a good fit to the original T spectrum then the
analysis is complete. If not, it is likely that the films is absorbing over
the whole wavelength range and the estimate for delta-d is too large. Reduce
delta-d and repeat the analysis. *)
DisplayTogether[ListPlot[spectrum, PlotJoined->True, PlotStyle->
RGBColor[1,0,0], PlotStyle->Thickness[0.005]], ListPlot[trans],
Plot[200*s/(s^2+1),{lambda,range[[1]],range[[2]]},PlotStyle->
RGBColor[0,1,0]], PlotRange->{range,{0,100}}, FrameLabel->{lam,
"Transmission (%)"}];
107
DisplayTogether[ListPlot[spectrum, PlotJoined->True, PlotStyle->

Thickness[0.001]], ListPlot[trans], PlotRange->{{range[[2]]+100,
range[[2]]+250},{0,10}}, FrameLabel->{lam, "Transmission (%)"}];
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Optical Characterisation of

Sputtered Silicon Thin Films

Master of Engineering Science

Bryce Sydney Richards

Photovoltaic Special Research Centre

Publications from this Work (to date)

2.1 Use of Determining Optical Constants . . . . . . . . .

3 Materials and Methods

4 Optical Characterisation using the Modied Envelope Method

4.2 ENVELOPE Fitting . . . . . . . . . . . . . . . . .

5 Optical Characterisation of Sputtered Silicon Thin Films

A Thin Film Optical Theory

B NAKED: Program Listing2

the inclusion of substrate absorption, which is signicant at certain wave-

A commercially grown silicon-on-sapphire lm was used as a reference to establish

where R is reectance, A absorbance, and T transmittance. The denitions of these

2.2 Review of Methods for Determining Optical Constants

the charge on an electron 1.60210;19 J. eV. A photon absorbed in Si can generate

2.2 Review of Methods for Determining Optical

reection and transmission at a single location

{ angular rotation method

2.2 Review of Methods for Determining Optical Constants

Transmission and Re ection at a Single Location

Iterative Fitting Methods

2.2 Review of Methods for Determining Optical Constants

2.2 Review of Methods for Determining Optical Constants

2.2 Review of Methods for Determining Optical Constants

i. uniformly thick lms

Angular Rotation Method

could analyse inhomogeneous thin lms

The method was successfully applied by another group of researchers (Corrales

Direct Curve Fitting

2.2 Review of Methods for Determining Optical Constants

related to the iterative tting methods. As presented in Appendix A, the equation

2.2 Review of Methods for Determining Optical Constants

2.2 Review of Methods for Determining Optical Constants

*ODVV Q Q8 8 

2.2.2 The Envelope Method

Manifacier et al. (1976)

where C1 = (nf + n0 )(ns + nf ), C2 = (nf ; n0 )(ns ; nf ), x = exp;f d and =

2.2 Review of Methods for Determining Optical Constants

nf = N + (N 2 ; n20 n2s )1=2

2.2 Review of Methods for Determining Optical Constants

*ODVV Q Q8 8 

Figure 2.3: The thin-lm on nitely thick substrate model used by

The expression describing the transmission for such a sample, where nf  kf , as

2.2 Review of Methods for Determining Optical Constants

D = (nf ; 1)2 (nf ; 1) nf ; n2s ,

2.2 Review of Methods for Determining Optical Constants

G ; G2 ; (n2f ; 1)6 (n2f ; n4s )2 1=2

2.2 Review of Methods for Determining Optical Constants

l=2 = 2 d (nf =) ; m1 ,

where l = 0 1 2 3 : : :. If l=2 is plotted against nf = and a straight line tted to the

2.2 Review of Methods for Determining Optical Constants

Figure 2.5: A non-uniformly thick, absorbing thin-lm on a transparent

Envelope curves for d=40nm

2.2 Review of Methods for Determining Optical Constants

has a higher absorption coecient.

Td = 4n #d p ax 2 arctan

1 + bx tan 4nf dmax

and the envelope expressions are then (M&arquez et al. 1995)

p a arctan p1 + b tan 2nf #d , (2.35)

4 Optical Characterisation using the Modied Envelope Method

where R is reectance, A absorbance, and T transmittance. The denitions of these

reection and transmission at a single location

{ angular rotation method

i. uniformly thick lms

could analyse inhomogeneous thin lms

*ODVV Q Q8 8

*ODVV Q Q8 8

The expression describing the transmission for such a sample, where nf kf , as

has a higher absorption coecient.

Td = 4n #d p ax 2 arctan

1 + bx tan 4nf dmax

p a arctan p1 + b tan 2nf #d , (2.35)

In the transparent region of the transmission spectra the coecients become

n1737 = 1.65599 - 6.6224810 + 1.3688110

Figure 3.2: Absorption coecient s : The solid line is an interpolated

+ 2.9008510 - 2.7729810 + 1.57483*10

- 5.2296510 + 9.334310 - 6.86665*10

Figure 3.12: Evidence of a step due to horizontal beam oset at the

of the laser-line absorption lter

variation. Fortunately, #d and f have dissimilar eects on the spectrum, which