ELSEVIE R

Current Opinion in Colloid & Interface Science 4 (1999) 197-204 www.elsevier.nl/locate/cocis

Analysis methods in neutron and X-ray reflectometry

M.R. Lovell, R.M. Richardson*

School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, UK

Abstract

Reflectivity analysis has focused on two key areas; overcoming the phase problem and achieving reliable scattering length
density profiles using modelling methods. Significant recent advances are the application of Bayes’ theorem, the use of a
genetic algorithm and the exploitation of magnetic reference layers and anomalous reflection. 0 1999 Elsevier Science Ltd.
All rights reserved.

Keywords: Neutron reflection; X-ray reflection; Bayes’ theorem; Anomalous reflection; Genetic algorithm; Magnetic reference layer

1. Introduction the thickness and density of any layers at the inter-

Neutron and X-ray reflectometries are now two
well-established techniques for investigating surfaces
and interfaces. Part of their attraction is the opportu-
nity to study ‘buried’ interfaces both non-invasively
and with high spatial resolution (subnanometre length
scales). We begin this review of analysis methods by
outlining the experimental technique and introducing
some major aspects of data analysis. We then sum-
marise the common modelling methods for reflectivity
data and survey developments of recent years. In the
second part we examine briefly some practical ap-
proaches to confronting fundamental analysis prob-
lems.
2. The reflectometry technique
In the investigation of interfaces the experimental-
ist is often interested in obtaining information such as
+ +
*Corresponding author. Tel.: 44-117-928-7666; fax: 44-117-
925-0612.
E-mail addresses: mike.lovell@ bris.ac.uk (M.R. Lovell),
robert.richardson@bris.ac.uk(R.M. Richardson)
face and the roughness of the interface. A typical
experimental design is shown schematically in Fig. 1.
The specular reflectivity of an interface is determined
by changes in the scattering length density, p, in a
direction normal to the surface. p is determined by
the number density, n, and scattering length, b, of
each type of atom
p= &bi
i
where, for neutrons, bi is a, nuclear property and for
X-rays it is 2.85 X 10-5ZiA where Zi is the atomic
number. The reflectivity profile, R(Q), contains infor-
mation on the scattering length density gradient within
the interface. The density gradient in turn contains
information on the thickness, density and roughness
of the interfaces. We define the interface to lie in the
x-y plane and the z-direction is normal to this plane.
Thus reflectometry can be considered a depth profil-
ing technique sensitive to the scattering length density
gradient dp(z)/dz. The relationship between R(Q)
and dp(z)/dz is not straightforward, however, and
this fact has proven to be the ‘Achilles heel’ of
reflectometry. A single reflectivity measurement can-
not be directly inverted to produce a single, unique

1359-0294/99/$ - see front matter 0 1999 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 0 2 9 4 ( 9 9)O 0 0 3 9 - 4
198 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204

scattering length density profile p(z) (or, alternatively,
dp(z)/dz) [1,21. Therefore the experimentalist cannot
determine a unique set of structural parameters re-
garding the interface from a single reflectivity mea-
surement. This is the familiar ‘phase problem’ en-
countered in crystallography. In essence the phase
problem means that the inversion of R(Q>data leads
to many possible p(z>. There are other practical as-
pects that exacerbate the general problem of gaining
a unique p(z> from R(Q) and these arise from the
resolution in Q, the natural statistical noise in the
R(Q>data and restricted Q range over which R(Q>
may be measured. Since direct inversion is not practi-
cable, there are only two other approaches that are
being pursued at present. In the first, a model of the
scattering length density profile, p(z), is constructed
and refined to give good agreement with measured
reflectivity data. Progress in modelling and fitting
procedures is discussed in the next sections. A later
section discusses recent progress in data inversion
methods applied to multiple measurements.
3. Modelling methods
The most common numerical methods of data anal-
ysis involve at some stage iterative procedures that
refine an initial model p(z> until the calculated re-
flectivity matches as closely as possible the experi-
mental R(Q). A general fitting procedure is outlined
in Fig. 2. Text inside a box describes a general step
that must be taken and these are joined in flow-chart
type fashion. Comments appearing between steps
summarise the decisions that need to be made along
the way. It is the details of these decisions that form
the basis of this review.
In this section we use the terms ‘exact’ and ‘ap-
proximate’ to indicate the nature of the equations
used to transform p(z> to R(Q). Both the ‘exact’ and
‘approximate’ formalisms have been established for
some time. The exact method models the surface as a
series of strata and use formulae adapted from optics
to calculate the reflectivity. The approximate methods
use the weak scattering approximation (WSA) or Born
approximation so the reflectivity is calculated as a
modulus squared of a Fourier transform of the scat-
tering length density profile [31.
Recent progress in modelling methods may be di-
vided into two categories that we describe as ‘objec-
tive’ and ‘subjective’. In the former the final p(z> is
not strongly dependent on the initial choice of model
used to fit the data. The latter assume a form for the
model and so the final profile may be influenced by
this choice. These two approaches are discussed in
the following sections.

Fiaure 1

Q = kR-kl

collimating
tor

sample
/
incident ‘ribbon’ beam reflecied beam

Current Opinion in Colloid & InterfaceSciena

9 reflectivity experiment. Collimation produces a ribbon-shap5d beam that impinges on the sample surface at some known angle 0
typically < 2”)with an incident intensity I, and a wavelength A (A). The specular beam is reflected with some intensity I, as measured at the
letector (the difference between incident and reflected intensity is transmitted and/or adsorbed into the sample, or reflected non-specularly).
The wavevectors k , and k , define the incident and reflected beams, respectively. F e momentum transfer vector Q is defined as the
lifference in the wavevectors as given in the figure, thus allowing the magnitude I Q I (A-’) to be calculated (I Q I is denoted Q in the main
ext), and its direction is normal to the surface. Q is varied either by changing A or 8. The reflectivity R (the reflected intensity normalised by
he incident intensity) is then measured as Q is changed yielding the reflectivity profile R(Q).
 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204 199

Figure 2

Corrections.
design.

4 Compare R(QY with R(Q) I

I ‘Fitness’ Darameter.
Error weighting. Uniqueness.
Feasibility.

Analytical or
stochastic.
Refine model parameters

Current ODinion in Colloid & Interface Sciencc

A typical analysis procedure. An outline of a general numerical fitting procedure involves the various steps enclosed in the boxes. The text
between these steps indicate some of the decisions that need to be taken between steps.

A third area where progress is being made is the
actual route by which the initial p(z) is refined. Again
there are two approaches to this model optimisation
that we have termed ‘analytical’ and ‘stochastic’ and
these are discussed in Section 6 on optimisation
methods.
4. Subjective methods
The first step in the fitting procedure of Fig. 2 is to
define the initial p(z). The experimentalist chooses
the form of p(z) so the profile resulting from the
fitting process is inherently biased. This ‘subjective’
approach is valid when one is aware of some struc-
tural features of the sample, For example, a thin film
at a surface may have a known density but its thick-
ness needs to be monitored as it grows during some
deposition process. The application of reflectivity
equations to fit the data is then a relatively trivial
affair to monitor the thickness. The subjective ap-
proach is also suitable when one is aware of the
theoretical shape of p(z). In this case p(z) can be
explicitly defined by some ‘functional form’ that may
be transformed into reflectivity by an ‘exact’ or ‘ap-
proximate’ method. This has the obvious advantage of
greatly reducing the number of variable parameters
required to define a general profile and the resulting
solution will always be unique. This approach has
been used by Lee et al. [4] to fit directly reflectivity
data from amphiphilic layers adsorbed at the air-
water interface. Gaussian distributions described the
surfactant dispersal at the interface and the water
surface was modelled by a tanh function. The method
has its roots in the partial structure factor (PSF)
method (e.g. Lu et al. and Li et al. [5,61) but is more
versatile. Thus direct fitting allows neutron and X-ray
data to be fitted simultaneously, background subtrac-
tion effects are no longer an issue, and the reflectivity
data need not be truncated to restrictive Q ranges.
Regan et al. [7] have used theoretical models of
atomic layering to analyse synchrotron X-ray reflec-
tivity data from liquid gallium and mercury. Success-
ful application of this method confirmed theoretical
predictions for liquid metals. This example shows that
subjectivity is not only valid, but crucially important,
when an experimentalist is attempting to prove (or
otherwise) an hypothesis. Sferrazza et al. [SI have
obtained significant evidence for their hypothesis that
the extra broadening observed in immiscible
poly(styrene)-poly(methy1 methacrylate), PS-PMMA,
interfaces (beyond that predicted by self-consistent
field theory) is due to capillary waves. By prior mea-
surement of the densities and thicknesses of the lay-
ers by spectroscopic ellipsometry, some of the
parameters which define p(z) were fixed and so the
interfacial widths could be determined more accu-
rately from the neutron reflection results.
5. Objective methods
When no prior knowledge of the thin film is avail-
able then an impartial, or ‘objective’, approach is
200 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204

desirable. Such approaches are often termed ‘free-
form’ or ‘model-independent’. It should be noted that
solutions obtained from such methods suffer from the
inherent non-uniqueness due to the phase problem
and so there is always a necessary degree of subjectiv-
ity when the experimentalist decides which solutions
are physically reasonable.
A new Fourier analysis method by Voorma et al.
[9’] has been developed to gain p(z) information
directly from X-ray reflectivity data from multilayer
mirrors of Mo/Si and Co/C. This so-called Bragg
Maximum Reverse Fourier Transforms (BMFT)
method utilises approximate kinematical theory to
yield the average electron density profile within the
multilayer. Its objectivity lies in the fact that the
parameters are determined directly through the use
of analytical equations and so no model fitting is
required. Often no clear ‘Bragg’ maxima are present
in reflectivity data and in these cases direct Fourier
analysis is rendered unworkable. Indirect model-inde-
pendent methods should then be used and these have
been developed and employed with some success.
Zhou and Chen have developed a Groove Tracking
Method (GTM) based on Parratt’s exact formula. In
their original GTM [2,3] the surface is divided into an
initially small number of equally thick layers in a
manner similar to Fig. 3. As optimisation proceeds
each layer is subdivided into smaller-thickness layers
and this process continues until a satisfactory fit is
found. This method may yield a physically unrealistic
p(z) with too many subdivisions and sharp steps in
scattering length density between these sublayers. Re-
cent improvements have overcome the excessive sub-
division problem [lo]. The jagged nature of the pro-
files is common to all procedures of this type that
neglect interface roughness. This aspect has also been
improved by adding smoothing operations [ll], the
important advantage of which is the indirect develop-
ment of interfacial roughness/diffuseness between
layers. Such smoothing procedures are not con-
strained to use a particular functional form (e.g. an
error function) to describe the interfacial roughness
in cases where it is not appropriate.
The GTM method can require a significant amount
of iteration, and hence computing time, so an im-
proved smoothing procedure has recently been devel-
oped based on cubic spline interpolation [12]. The
main GTM layers are divided into sub-layers and
these are connected using cubic splines. The authors
tested the improved smoothed groove tracking method
(SGTM) successfully with the experimental data of
Regan et al. [7] by reproducing objectively the func-
tional-form p(z) used in the original reference.
The use of cubic splines to produce a model-inde-
pendent, smooth p(z) is not new in the analysis of
reflectivity data. Pedersen developed a model-inde-

Fiaure 3

SAMPLE MODEL p(z)

layer
0

IT..
1”

1 PI 8,

2 2
3
P2
P3
8,
63
01

02 .?I
In
5
i’

J-I PJ-1 8j.z I

-
- OJ-2
J

Current Opinion in Colloid & Interface Science

The modelling process. The initial model p ( z >of Fig. 2 is typically described by a series of J layers. Each layer j can then be defined by a
hickness a,, a density p, and by interfacial roughness terms q - and q.The ‘layer’ j = 0 corresponds to the bulk medium through which the
+
.adiation travels before striking the sample (the fronting medium - air in this example) and j 1 to the bulk medium on the opposite side of
he interface (the backing medium-usually a bulk substrate). The corresponding model p ( z ) can then be displayed as the profile inset. The
lashed lines represent the profile from the J layers in the absence of any roughness between the layer interfaces. Usually interfacial roughness
s described by assuming the interface has a Gaussian distribution about the mean position with a width u.This changes the profile from
laving ideal, sharp steps between layers to a smooth density transition (solid line) and so is physically more reasonable for most systems.
 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204
pendent technique [131 that utilised cubic b-splines to
describe the model p(z). An alternative parameterisa-
tion of p(z) in terms of a Fourier series of sine and
cosine terms [14-161 was also developed. The objec-
tivity of this splines method has recently highlighted
the structural organisation of copolymer micelles at a
quartz surface [171 and at the air-solution interface
[18]. The former work used spline fitting in conjunc-
tion with Monte Carlo simulations and, in the latter
study, the initial spline fitting provided invaluable
insights into the distributions of the copolymer at the
water surface, which formed the framework for the
subsequent PSF analysis. Pedersen demonstrated that
the spline method is ideally suited to cases where p(z)
is aperiodic whereas the Fourier sine/cosine series
description of p(z) is better for periodic structures
[14,15]. Asmussen and Riegler [19], in the investiga-
tion of the structure of Langmuir-Blodgett (LB) films
of behenic acid on SiO, substrates, parameterise the
internal LB film structure is as a Fourier cosine
series. This parameterisation has the advantage that
each Bragg maximum in R(Q) can be identified with
a corresponding Fourier component thus minimising
the number of fit parameters.
Model-independent methods often result in p(z)
profiles that display short-range oscillations, usually
due to the finite Q range of experimental reflectivity
data. Smoothing procedures can be applied to p(z) to
dampen such ‘fine-detail’ so that only the ‘gross’ fea-
tures are retained. The question then arises as to
whether the fine-detail was a real aspect of the sam-
ple. Sanyal et al. [20] have developed a free-form
approach that can be used to determine fine-detail
when all deviations in p(z) are small (i.e. no ‘gross’
features). Their method utilises the distorted-wave
Born approximation (DWBA) [3] for which it is as-
sumed that the surface possesses a nearly constant
scattering length density, po[2l0]. A small but real
deviation in scattering length density, Ap(z), thus
forms a small perturbation on p, that allows the total
density to be treated as p, + Ap(z). The authors were
interested in small electron density variations within a
thin, spin-coated polystyrene (PS) film on silicon and
employed X-ray reflection. Their fitting method
proceeded with the film modelled initially as a num-
ber of thin slices of equal thickness 6 and electron
density p, + Apj; the Apj being the only variable
parameters. Through simulations the authors demon-
strated that this approach could reproduce electron
density profiles accurately, even when the variation in
p, was of the order of 4%, and successfully applied
the method to experimental data from the thin PS
film. A small variation in p(z) of 5-7% was found at
roughly regular intervals of 194 A separations. This
was rationalised as coiled polymer balls forming lay-
ers at the sharp silicon interface.
20 1
The interfacial roughness that is observed in objec-
tively determined p(z) should not be necessarily con-
sidered model-independent since it develops from the
smoothing criteria or basis functions employed. One
method of extracting interfacial width information
objectively from R(Q) is through moments analysis as
discussed by Rieutord et al. [22”1. The authors de-
monstrate that, although in principle R(Q) contains
information about all moments, in practice only the
three lowest moments; M,, MI and M, can usually be
extracted. The effects of higher moments tend to be
observed only at large Q values that are outside the
maximum experimentally achievable range. M,, MI
and M, are related to the normalisation of p(z) [the
bulk scattering length density p(a)], the distance of
the interface from the origin and the interfacial width,
respectively. The third and fourth moments (M3 and
M,) are related to the asymmetry and the kurtosis
(extendedness, or long-tailedness) of the interface.
This work was discussed using simulated data but
Karim et al. [23] have analysed experimental data to
determine changes in M, and M, in studies of inter-
diffusion across polymer interfaces. In this work the
change in M, was determinable as its effect could be
seen in R(Q) at moderate Q values.
Moments analysis appears workable for only simple
interfaces and so other methods must be used when
investigating interfaces in more complicated systems.
We merely note here that non-specular reflection can
also be employed as it contains information on lateral
interface structure (e.g. [24-281). Tang et al. [28], e.g.
have shown that the interfacial roughness in a Co/Cu
multilayer is mainly uncorrelated roughness.
6. Optimisation methods
The comparison between a model and measured
reflectivity is usually made by calculating x2 (the sum
of squares of the weighted deviations). This is
minimised to achieve a good fit by adjusting the
model parameters. A major drawback of the usual
analytic methods (Levenberg-Marquardt or Simplex)
for reflectivity analysis is the possibility of finding a
local minimum rather than the overall global mini-
mum. Recent developments have focused on methods
of overcoming this problem. For example, Samoilenko
et al. [29] have applied the method of successive
descent from local minima with partial success. Other
analytical approaches have also been employed, again
with varying degrees of success. Maximum entropy
(MaxEnt) is one such method that is well established.
It carries some immunity against a large number of
solutions and, in its simplest form, reveals the most
likely profile by maximising an entropic term. MaxEnt
has been used successfully for the analysis of experi-
202 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204
mental reflectivity data [30,311 although the method
can be computationally intensive. The probability as-
pects of MaxEnt can be advanced by the use of
Bayesian probability theory [30,32,33", 341 to give a
powerful analysis tool. Sivia and Webster [33"] have
recently discussed the use of Bayes' theorem in the
analysis of reflectivity data. They discuss parameter
estimation and develop this to address problems of
model selection, free-form solutions employing Max-
Ent, and even experimental design. Although going
some way to finding the global minimum the MaxEnt
and Bayesian approaches cannot determine with ab-
solute certainty whether a solution actually is at a
global minimum. Indeed, such a definitive statement
from reflectivity data alone is an impossibility in the
absence of external information regarding the sample,
no matter by what route the minimisation has oc-
curred. Stochastic methods offer another way of deal-
ing with the local minimum problem that arises from
their inherently random nature. Zhou and Chen's
GTM method utilises a stochastic approach [2,3]: the
density of a layer in the model p(z) moves randomly
within a force field according to Newtonian mechan-
ics, the randomisation occurring through Monte Carlo
methods. Another is the established but little-used
simulated annealing method [35] wherein a layer of
the model p(z) is randomly selected and its density
and/or width is changed by a random amount. This
change is always accepted if it leads to a reduction in
x2. If x 2 is increased, however, there is a reduced
probability of accepting the change. The probability
of acceptance is governed by a quantity that is analo-
gous to temperature. The 'temperature' is decreased
as the number of fitting attempts increases thus simu-
lating an annealing process. It is the ability of the
method to accept immediately detrimental changes
that can enable escape from local minima.
These methods make only small changes in the
overall p(z) at each fitting step as only one layer is
randomly varied. For this reason they are still prone
to premature convergence in a deep local minimum.
A stochastic global minimisation technique has been
developed and recently used by de Haan and
Drijkoningen [36] and Dane et al. [37"] to analyse
reflectivity data. This method is based on genetic
algorithms in which each unknown parameter is con-
strained to lie between a maximum and minimum
value. The genetic algorithm explores a population of
trial solutions so it is possible, in principle, to offer
multiple solutions from a single reflectivity profile.
Hence, a genetic algorithm is less sensitive to local
minima and is capable of finding the vicinity of the
global minimum. Once in the region of the global
solution a standard analytical optimisation procedure
is often employed.
7. Practical solutions to the phase problem
Several practical methods have been developed to
determine p(z) profiles uniquely. These involve the
measurement of multiple reflectivity profiles from
samples where the scattering length density of one
component is varied. The effective neutron scattering
length of an element may be adjusted by changing its
isotopic composition or by varying the magnetisation
direction with respect to the neutron's polarisation. A
similar strategy can also be employed in X-ray reflec-
tometry by exploiting the change in scattering length
that occurs near an absorption edge of an element
(anomalous or resonant X-ray reflection). The neu-
tron contrast variation method is well known in the
form of partial structure factor analysis and numerous
experimental applications are documented (e.g. [38]),
but the method can be used more directly to enable
modelling of multiple data sets (e.g. [39]). We there-
fore do not review this particular method but concen-
trate on those that aim to directly invert reflectivity
data. Sanyal et al. [401 used their free-form DWBA
method to reconstruct electron density profiles of
Langmuir-Blodgett films on Ge from anomalous X-
ray reflectivity measurements. Recently Lee et al.
[41°] used resonant X-ray reflectivity to obtain ele-
ment-specific density profiles for a (Gd/Fe),, multi-
layer.
A versatile method for neutrons is to use a magne-
tised substrate, on which an unknown layer is present.
Two reflectivity profiles are then measured with the
neutron spins parallel and antiparallel to the mag-
netic field. Thus the substrate scattering length den-
sity is related to the neutron, b, and magnetic, p ,
scattering lengths through p = n(b k p ) . Penfold et al.
[42] used this strategy within the DWBA to determine
the thickness of a PS film on a nickel substrate and
compared the value favourably with that obtained
through conventional modelling. The technique, as
noted by the authors, is viable when sharp interfaces
are prepared and sufficient Q range is accessible. The
DWBA requires that reflectivity data should be ig-
nored near the critical edge. This limitation can be
overcome so that all R(Q) above the critical edge is
valid by the use of a known magnetic reference layer
having three possible scattering length densities
[43-461. Direct inversion of R(Q) to p(z) is then
possible through the Gel'fand-Levitan-Marchenko
(GLM) formalism [43,46] or by a layer stripping
method [44,45]. Majktrak et al. [47,48'] report recent
implementation of the GLM reference layer method
in the experimental investigation of PS films. Results
were encouraging but did highlight practical consider-
ations regarding the initial choice of magnetic refer-
ence material. Meanwhile Lipperheide et al. [49] have
proposed an alternative method for determination of
 M.R Lovell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204
the reflected phase by measuring the polarisation of
the reflected neutrons, rather than the reflectivity.
8. Conclusions
Many of the methods used to analyse reflectivity
data have been reviewed. Since a single reflectivity
profile cannot be directly transformed to a scattering
length density profile modelling methods must be
employed. We have discussed these modelling meth-
ods in terms of their objectivity and optimisation
route. Of particular note is the powerful combination
of MaxEnt with Bayesian probability theory. It is
interesting to consider whether the genetic algorithm
approach could be similarly enhanced by Bayes’ theo-
rem. In essence a genetic algorithm supplies a series
of randomly controlled solutions from which a global
minimum can be determined. Bayes’ theorem could
be utilised to determine the most likely solution from
the many possibilities. An alternative approach would
be to generate a series of random model p(z) profiles
from which standard analytical optimisation proce-
dures could be employed in the hope of finding the
global minimum. The initial randomisation could be
achieved through Monte Carlo methods. We note
that the Reverse Monte Carlo method appears to be
an area that has been neglected thus far in reflectivity
analysis. We have also looked at some of the recent
practical advances in overcoming the phase problem
and these seem promising for films deposited on
magnetic substrates, although this particular tech-
nique is not universally applicable and may be limited
in practical use.
References and recommended reading
of sDecial interest
,of outstanding interest
Pershan PS. X-ray or neutron reflectivity: Limitations in the
determination of interfacial profiles. Phys Rev E 1994;SO:
2369-2372.
Zhou X-L, Chen S-H. Model-independent method for recon-
struction of scattering-density profiles using neutron or X-ray
reflectivity data. Phys Rev E 1993;47:3174-3190.
Zhou X-L, Chen S-H. Theoretical foundation of X-ray and
neutron reflectometry. Phys Rep 1995;257:223-348.
Lee EM, Milnes JE, Wong IC. The simultaneous analysis of
multi-contrast neutron and X-ray grazing incidence reflection
data from amphiphilic layers. Physica B 1996;221:159-167.
Lu JR, Li ZX, Smallwood J, Thomas RK. Detailed structure
of the hydrocarbon chain in a surfactant monolayer at the
air-water interface: neutron reflection from hexadecyl-
trimethylammonium bromide. J Phys Chem 1995;99:
8233-8243.
Li ZX, Lu JR, Styrkas DA, Thomas RK. The structure of the
surface of ethanol-water mixtures. Mol Phys 1993;80
925-939.
203
[7] Regan MJ, Magnussen OM, Kawamoto E H et al. X-ray
studies of atomic layering at liquid metal surfaces. J Non-Cryst
Solids 1996;205-207:762-766.
[8] Sferrazza M, Xiao C, Jones RAL, Bucknall DG, Webster J,
Penfold J. Evidence for capillary waves at immiscible po-
.
lymer/polymer interfaces. Phys Rev Lett 1997;78:3693-3696.
[9] Voorma HJ, Louis E, Koster NB, Bijkerk F, Spiller E. Char-
acterisation of multilayers by Fourier analysis of X-ray re-
flectivity. J Appl Phys 1997;81:6112-6119.
The BMFI analysis allows accurate determination of multilayer
parameters such as d-spacing, layer densities, interfacial roughness
and layer thickness errors. It does not require the additional soft
X-ray measurements otherwise needed in the classical method and
yet yields nearly identical results. It is an extremely useful method
has a good accuracy and is fast.
Chou C-H. A necessary modification for groove tracking
method. Physica B 1997;233:130-133.
Chou C-H, Regan MJ, Pershan PS, Zhou X-L. Model-inde-
pendent reconstruction of smooth electron density profiles
from reflectivity data of liquid surfaces. Phys Rev E
1997;55:7212-7216.
Chou C-H. Improved smoothing procedures for a smoothed
groove tracking method. Physica B 1998;253:320-324.
Pedersen JS. Model-independent determination of the sur-
face scattering-length density profile from specular reflectiv-
ity data. J Appl Cryst 1992;25:129-145.
Pedersen JS, Hamley IW. Analysis of neutron and X-ray
reflectivity data by constrained least-squares methods. Phys-
ica B 1994;198:16-23.
Pedersen JS, Hamley IW. Analysis of neutron and X-ray
reflectivity data. 11. Constrained least-squares methods. J
Appl Cryst 1994;27:36-49.
Singh N, Tirrell M, Bates FS. Applications of Fourier-synthe-
sis to the analysis of specular reflectivity. J Appl Cryst
1993;26:650-659.
Gerstenberg MC, Pedersen JS, Smith GS. Surface induced
ordering of micelles at the solid-liquid interface. Phys Rev E
1998;S8:8028-803 1.
Dewhurst PF, Lovell MR, Jones JL, Richards RW, Webster
JRP. Organisation of dispersions of a linear diblock copo-
lymer of polystyrene and polfiethylene oxide) at the air-water
interface. Macromolecules 1998;31:7851-7864.
Asmussen A, Riegler H. Numerical analysis of X-ray reflec-
tivity data from organic thin films at interfaces. J Chem Phys
1996;104:8159-8164.
Sanyal MK, Basu JK, Datta A, Banerjee S. Determination of
small fluctuations in electron density profiles of thin films:
layer formation in a polystyrene film. Europhys Lett 1996;
36:265270.
Mikulik P, Baumbach T. X-ray reflection by multilayer
surface gratings. Physica B 1998;248:381-386.
The DWBA was believed to be valid only for small fluctuations in
p o but recent results have indicated that it is actually the scattering
from the fluctuation that needs to be small with respect to the
scattering from the strongest scattering interface, which is usually
the air-film or film-substrate interface.
[22] Rieutord F, Braslau A, Simon R, Hauter HJ, Pasyuk V.
0. Moments analysis of X-ray reflection profiles. Physica B
1996;221:538-541.
The authors extended the moments analysis from a single interface
to a thin film on a substrate whereby they demonstrated that the
presence of two interfaces, of which one is well characterised, may
make it more favourable to obtain information about the asymme-
try of the unknown interface. This facet makes the method poten-
tially extremely powerful for any thin film study where interface
asymmetry is important, particularly in the case of synchrotron
X-ray data for which reflectivities of the order of are possible.
204 M.R Louell, R.M. Richardson /Current Opinion in Colloid & Interface Science 4 (1999) 197-204
[23] Karim A, Felcher GP, Russell TP. Interdiffusion of polymers
at short times. Macromolecules 1994;27:6973-6979.
[24] Lee DR, Park YJ, Kim D, Jeong YH, Lee K-B. Non-specular
X-ray reflectivity study of partially correlated interface rough-
ness of a Mo/Si multilayer. Phys Rev B 1998;57:8786-8789.
[25] Richardson RM, Webster JRP. Zarbakhsh study of off-
specular neutron reflectivity using a model system. J Appl
Cryst 1997;30:943-947.
[26] Holg V, Giannini C, Tapfer L, Marschner T, Stolz W. Diffuse
X-ray reflection from multilayers with stepped interfaces.
Phys Rev B 1997;55:9960-9968.
[27] Kepa H, Kleinwaks LJ, Berk NF, Majkrzak CF, Berzina TS,
Troitslq VI, Antolini R, Feigin LA. Neutron and X-ray
reflectometry studies of rough interfaces in a Langmuit-
Blodgett film. Physica B 1998;241:1048-1054.
[28] Tang CC, Telling ND, Langridge S. Synchrotron X-ray re-
flectivity study of Co/Cu multilayer structure. Physica B
1998;248:395-398.
[29] Samoilenko 11, Shchedrin BM, Feigin LA. Global minimisa-
tion in reconstruction of the scattering-length density profile
by X-ray reflectivity data. Physica B 1996;221:542-546.
[30] Geoghegan M, Jones RAL, Sivia DS, Penfold J, Clough AS.
Experimental study of surface aggregation and wetting in
films of a partially miscible polymer blend. Phys Rev E
1996;53:825-837.
[31] Bucknall DG, Butler SA, Hermes HE, Higgins JS. Neutron
reflectivity investigations of semi-crystalline polymer inter-
faces. Physica B 1998;241-243:1071-1073.
[32] Sivia DS, David WIF, Knight KS. An introduction to Bayesian
model selection. Physica D 1993;66:234-242.
[33] Sivia DS, Webster JRP. The Bayesian approach to reflec-
DO tivity data. Physica B 1998;248:327-337.
The use of Bayesian theory justifies many statistical fitting proce-
dures, e.g. ,y minimisation, and can improve matters significantly
when such procedures fail. Moreover it can help in designing the
optimum experiment to perform and this is demonstrated in terms
of PSF analysis. This is a powerful method that can be used to
address many aspects of reflectometry at both practical and theo-
retical levels.
[34] Sivia DS, Hamilton WA, Smith GS. Analysis of neutron
reflectivity data: maximum entropy, Bayesian spectral analysis
and speckle holography. Physica B 1991;173:121-138.
[35] Kunz K, Reiter J, Gotzelmann A, Stamm M. Model-free
analysis of neutron reflectivity data from polymer thin films
with the simulated annealing technique. Macromolecules
1993;26:4316-4323.
[36] de Hann V-0. Drijkoningen: genetic algorithms used in model
finding and fitting for neutron reflection experiments. Physica
B 1994;198:24-26.
[37] Dane AD, Veldhuis A, de Boer DKG, Leenaers AJG,
DO Buydens LMC. Application of genetic algorithms for charac-
terisation of thin layered materials by glancing incidence
X-ray reflectometry. Physica B 1998;253:254-268.
The genetic algorithm was used to obtain thicknesses and rough-
ness for several thin film materials and was able to find an exact
answer in 61% of simulated experiments in a single run. The
method is capable of reducing human effort and experience and
lessens the chance of missing feasible solutions. Results for experi-
mental data were encouraging but highlighted the need for external
knowledge about the system under study in order to reduce the
unknown parameter ranges and hence provide more accurate solu-
tions. This method provides a useful alternative to analytical free-
form methods.
[38] Li ZX, Thirtle PN, Weller A, Thomas RK, Penfold J,
Webster JRP, Rennie AR. Some improvements and exten-
sions of the application of specular neutron reflection to the
study of interfaces. Physica B 1998;248:171-183.
[39] Penfold J, Staples EJ, Tucker I, Thompson LJ, Thomas RK.
The structure and composition of mixed cationic and non-
ionic surfactant layers adsorbed at the hydrophilic silicon
surface. Physica B 1998;248:223-228.
[40] Sanyal MK, Sinha SK, Gibaud A et al. Fourier reconstruction
of density profiles of thin films using anomalous X-ray reflec-
tivity. Europhys Lett 1993;21:691-696.
[41] Lee DR, Park YJ, Parh SH, et al. Resonant X-ray reflectiv-
ity measurements of a magnetic multilayer [Gd/Fel,,. Phys-
ica B 1998;248:146-151.
The authors fit simultaneously and model-independently the R(Q)
measured at three different X-ray energies, corresponding to Gd
L,, Fe K and 6.95 keV, the latter being far away from Gd and Fe
edges. This strategy enabled element-specific atomic density pro-
files of Gd and Fe to be obtained unambiguously. Furthermore,
X-ray resonant magnetic scattering measurements showed that Gd
was magnetised at room temperature. This work is an elegant
demonstration of the anomalous scattering technique and shows
the breadth of information that can be gained from x-ray reflectiv-
ity experiments.
[42] Penfold J, Webster JRP, Bucknall DG, Siva DS. Unique
density profile determination in thin films. Colloids Surfaces
A Physicochem Eng Aspects 1994;86:165-170.
[43] Majkrzak CF, Berk NF. Exact determination of the phase in
neutron reflectometry. Phys Rev B 1995;5210827-10830.
[44] de Haan V-0, van Well AA, Adenwalla S, Felcher GP.
Retrieval of phase information in neutron reflectometry. Phys
Rev B 1995;5210831-10833.
[45] de Haan V-0, van Well AA, Sacks PE, Adenwalla S, Felcher
GP. Toward the solution of the inverse problem in neutron
reflectometry. Physica B 1996221524-532.
[46] Majkrzak CF, Berk NF. Exact determination of the neutron
reflection amplitude or phase. Physica B 1996;221:520-523.
[47] Majkrzak CF, Berk NF, Dura J et al. Direct inversion of
specular reflectometry. Physica B 1998;241-243:llOl-1103.
[48] Majkrzak CF, Berk NF, Dura JA, et al. Phase determination
and inversion in specular neutron reflectometry. Physica B
1998;248:338-342.
The experimental feasibility of the direct inversion method is tested
with two examples, a deuterated polystyrene (dPS) film using Cu, Ni
and Mo magnetic reference layers and a symmetric film consisting
of a dPS film between non-magnetic media of equal scattering
length density. The paper demonstrates the direct inversion method
to be practical with existing instrumentation for types of systems
not far removed from those currently studied.
[49] Lipperheide R, Kasper J, Leeb H, Reiss G. The phase prob-
lem in neutron reflection. Physica B 1997;234-236:1117-1119.