Mechanical and Functional properties of Materials 6MSM40

Workgroup 1

Problem 1. Fourier transformation (from exam March 2009).

Below you see four different functions A-D. All four functions exist in the time domain
and are all real.
1 1 1 1
Amplitude

Amplitude

Amplitude
Amplitude
0 0 0 0

A B C D
-1 -1 -1 -1
-200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200
time time time time

We now consider the Fourier transform of these four functions. This gives functions in
the frequency domain. Below here you see four complex functions (1. -4.) in the
frequency domain. The real and imaginary part of each function are plotted above each
other.
50 50 50 50
40 40 40 40
30 30 30 30
20 1. 20 2. 20 3. 20 4.
Amplitude

Amplitude

Amplitude

10 10 10 Amplitude 10
0 0 0 0
Real

-10 -10 -10 -10

-20 -20 -20 -20
-30 -30 -30 -30
-40 -40 -40 -40
-50 -50 -50 -50
-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100
ω ω ω ω
50 50 50 50
40 40 40 40
30 30 30 30
Imaginary

20 20 20 20
Amplitude
Amplitude
Amplitude

Amplitude

10 10 10 10
0 0 0 0
-10 -10 -10 -10
-20 -20 -20 -20
-30 -30 -30 -30
-40 -40 -40 -40
-50 -50 -50 -50
-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100
ω ω ω ω
frequency frequency frequency frequency

For each time domain function A. –D. write down which of the four frequency domain
functions 1.-4. represents its Fourier transform.

A. ↔ … (choose 1.,2., 3., or 4.)

B. ↔ … (choose 1.,2., 3., or 4.)
C. ↔ … (choose 1.,2., 3., or 4.)
D. ↔ … (choose 1.,2., 3., or 4.)
Problem 2. Fourier Transform.

Let g(ω) be the Fourier transform of the time domain function f(t).

a. Prove that the Fourier transform of the function f(t+t0) is equal to exp(-iωt0) g(ω)

b. Prove that the Fourier transform of the function exp(iω0t)f(t) is equal to g(ω+ω0)

c. Assume that g(ω) is a Lorentzian function . Sketch graphs by hand for each of the
Fourier pairs of functions: f(t) & g(ω), f(t+t0) & exp(iωt0) g(ω) and, finally ,
exp(iω0t)f(t) & g(ω+ω0).

Problem 3. Fourier Transform.

Below you see four different functions A-D. All four functions exist in the time domain
and are all real.
1 1 1 1
Amplitude

Amplitude

Amplitude

Amplitude
0 0 0 0

A B C D
-1 -1 -1 -1
-200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200
time time time time

We now consider the Fourier transform of these four functions. This gives functions in
the frequency domain. Below here you see four real functions (1. -4.) in the frequency
domain.
20 20 20 20

10 10 10 10
Amplitude

Amplitude

Amplitude

Amplitude

0 0 0 0

-10 -10 -10 -10

1. 2. 3. 4.
-20 -20 -20 -20
-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100
ω ω ω ω

a. For each time domain function A. –D. write down which of the four frequency domain
functions 1.-4. represents the real part of the Fourier transform.

A. ↔ … (choose 1.,2., 3., or 4.)

B. ↔ … (choose 1.,2., 3., or 4.)
C. ↔ … (choose 1.,2., 3., or 4.)
D. ↔ … (choose 1.,2., 3., or 4.)

b. What can you say about the imaginary parts of the Fourier transforms of the time
domain functions A-D ?
Problem 4. Complex numbers.

a. Consider the complex numbers c1= 2 + i 2 and c2= 1 + i 1 where i is the

imaginary number. Calculate c1·c2 and c1/c2 and express your answer in the form
a+ i b.
b. c2* is the complex conjugate of c2 . Calculate c2·c2* and c2/c2* and express your
answer in the form a+ i b.

A complex number c can also be represented as c = exp(iφ).

c. Rewrite the complex number c with φ = π into the form c = a+ i b.

d. Rewrite the complex number c with φ = π - i ln10 into the form c = a+ i b.

Consider the complex number c3 = 1/√2 + i 1/√2

e. Rewrite the complex number c3 into the form c3= r exp ( i φ) with r and φ real
numbers.
f. Calculate c3·c3 and c3·c3*

Problem 5. Numerical simulation Dirac delta Function δ

The so-called representation of the Dirac delta function δ can be expressed symbolically
by
∞

∫ dω exp(− iω (t − t ))
1
δ (t − t0 ) =
2π
0
−∞

and may be approximated numerically by calculating

∑ exp(− iω (t − t ))
1
f (t − t0 ) =
2π
0
ω=− N

We use the MATLAB program “DiracDeltaFu.m” to plot the function f simulating δ

a. How does the width of the central peak of the function f vary if you increase the
number of waves contributing to f by varying N (first line of the code). Does f
resemble the δ function ?

b. How does the imaginary part of the function f look like for large N ?

c. Check the integral over f by monitoring the value of the variable “Int” . Is the
+∞
condition satisfied ?
∫ dt δ (t − t0 ) = 1
−∞
Problem 6. Fourier transform of a Gaussian function.

Use the MATLAB program “FourierGAUSS.m” to explore the Fourier transformation

g(ω) of the Gaussian function f(t)

(t ) exp  −(t / w) 2 
f=

The running the program gives two figures ( in separate windows): one of f(t) and one of
g(ω). Let us denote the width of the central peak of the function f by ∆f. Convince
yourself that g(ω) also has a central peak. Let ∆g be the width at half height of g(ω).

a. How do the widths ∆f and ∆g change when you vary the value of the parameter w
of f(w) in the first line of the code “FourierGAUSS.m” in the range [4…4000] ?

b. What happens to the product of the widths ∆f ∆g ? Estimate the width from e.g.
the plot on the screen

c. What is your best guess for functional form of g(ω) ?

Problem 7. Fourier transform of 1/√t

Use the MATLAB program “FourierSQRT.m” to explore the Fourier transformation of

the preprogrammed function f

0 for t ≤ 0
f (t ) =
1 / t for t > 0

Plot the Fourier transform of the preprogrammed function f by just running the program.

a. What is your best guess for the functional form of the Fourier transform g(ω) of
f(t) ?
 Mechanical and Functional properties of Materials 6MSM40
Workgroup 2

Problem 8. Kramers-Kronig transformation and the dielectric response (from

exam March 2009).

Below you see graph of the real part ε1 of the relative dielectric constant for three
different materials A, B and C
1.2
2.0
A. 80
1.0
60

ε1
1.5 0.8
ε1

ε1
40
1.0 0.6

20
0.5 C. 1 10 1E2 1E3

0
1E-3 1E-2 1E-1 1 10 1E2 1E3
1E-3 0.01 0.1 1 10 100 1000
photon energy (eV)
photon energy (eV)
0
B.
-5000

-10000
ε1

-15000

-20000

1E-3 0.01 0.1 1 10 100 1000

photon energy (eV)

a) For each of the three materials choose the correct corresponding imaginary part ε2 of
the complex dielectric constant from the graph below:

100000
0.20

0.15 1. 80000 2.
60000
ε2
ε2

0.10
40000

0.05 20000

0.00 0
1E-3 1E-2 1E-1 1 10 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
photon energy (eV) photon energy (eV)
1.5
40
3. 4.
30
ε2
ε2

20
1.0
10

0
1E-3 1E-2 1E-1 1 10 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
photon energy (eV) Photon energy (eV)
b) For each of the three materials A, B and C you are also looking for the corresponding
graph of the real part n of the complex refractive index ñ. Choose for each material A,B
and C the correct corresponding refractive index trace from the spectra 5,6,7,8 below.
0 300 1.0
-50 250
-100
200 0.5

n
-150
5. 6.

n
n

150
-200
100
-250 0.0
50 1E-1 1 10 1E2 1E3
-300
0
1E-3 1E-2 1E-1 1 10 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
photon energy (eV) photon energy (eV)
10
10

1.5

5 7. 8.
n
n

1.0

0 0.5
1E-3 1E-2 1E-1 1 10 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
photon energy (eV) photon energy (eV)
6

c) To make the dataset complete, for each material choose the correct imaginary part κ of
the complex refractive index ñ
300
20000
250

200
9.
15000 10.
150
κ

10000
κ

100
5000
50

0 0
1E-3 1E-2 1E-1
p 1gy10( ) 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
p gy ( )
photon energy (eV) photon energy (eV)
6
0.15
5

4
0.10
11. 3 12.
κ

0.05 2

0.00 0
1E-3 1E-2 1E-1 1 10 1E2 1E3 1E-3 1E-2 1E-1 1 10 1E2 1E3
photon energy (eV) photon energy (eV)

d) Among the three materials there is one insulator, one polar liquid and one metal. List
for A, B and C whether it is the metal, the liquid or the insulator.

Summarize your answers by making a small matrix:

 ε2 n κ Type of material
A
B
C

Problem 9. Dielectric relaxation of water

Water shows a peak in the imaginary part of the dielectric constant at ν = 10 GHz (20
o
C)

a) What type of motion is responsible for this resonance at 10 GHz ?

b) The motion mentioned under a) can be characterized by its characteristic frequency
ν=10 GHz but also by a characteristic time constant. Calculate this time constant and give
an interpretation of its meaning.

The dependence of the characteristic frequency on various parameters has been

investigated. Below we list a few results. For each observation give a possible
explanation.

c) Upon lowering the temperature, the characteristic frequency shifts to lower values.
Give a possible explanation.

Suppose that the change in ε2 upon lowering the temperature from 40 oC to 0.2 oC is
given in the graph below
 εε1 2 0.2 oC 40 oC

d) Which of the four graphs A,B,C or D below illustrates the correct behavior of ε1 vs
frequency corresponding to ε2 given above ?

ε1 ε1

A ν B ν

ε1 ε1

C ν D ν

e) Upon going to lower density of water (to values < 1 gr /cm3) the frequency goes up.
Give a possible explanation.

f) For heavy water (D2O), the maximum in ε2 occurs at a lower frequency in comparison
with normal water (H2O). The difference is quite large (20%). Give a possible
explanation.

g) Upon addition of salt (e.g. NaCl) the characteristic frequency also gets lower. Give a
possible explanation.
Upon addition of salt (NaCl) to water, the salt splits into free ions that move at relatively
slow speed. The motion of the charged ions raises the conductivity σ of the solution at
frequencies ν <108 Hz.

h) Does the dielectric response ε of the solution for frequencies ν <108 Hz also change
upon the addition of salt ? Explain whether you expect ε1 to go up or down ? Explain
whether you expect ε2 to go up or down.

Polyelectrolytes are polymers containing charged groups that dissolve in water. An

example is sodium polystyrene sulphonate. Here there are negatively charged groups (-
SO3-) on the main chain of the polymer. The positively charged sodium ions (Na+)
compensate the negative charge. The polymer chains can be very heavy (Mw 106 kg/mol
) but the sodium ions are very light.

i) Based on this difference in mass, do you expect the negatively charged polymer or the
positively charged sodium ions to contribute the most to the dielectric response and
conductivity at intermediate frequencies (103-109 Hz) ? Explain your answer.

Problem 10. Fourier transform and convolution

Use the matlab program FourierSIN.m and FourierCOS.m to calculate the Fourier
transform of the functions :

  x 2    x 2 
f ( x) = exp −    cos(ωt ) f ( x) = exp −    sin(ωt )
  w    w 
   

a. Draw a schematic sketch of the real and imaginary components of the Fourier
transform.
b. Determine the symmetry properties (even / uneven) of the real and imaginary
component of the Fourier transforms.
c. What happens to the Fourier transform when you change the value of w ?
d. What happens when you vary the value of ω (omega) ? (qualitative answer suffices)
e. According to mathematics, the Fourier transform of a product of two functions is a
convolution of the two Fourier transforms of the two separate functions .
Use your knowledge and intuition on the Fourier transforms of Gaussian curves and
monochromatic waves and discuss qualitatively whether the convolution of predicted by
mathematics can account for your observations under c.
 Problem 11. Fourier transformation.

Below you see four functions labelled 1,2,3,4. All four functions exist in the time domain
and are all real.

1 1 1 1
Amplitude

Amplitude

Amplitude

Amplitude
0 0 0 0

1 2 3 4
-1 -1 -1 -1
-200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200 -200 -100 0 100 200
time time time time

We now consider the Fourier transform of these four functions. This gives functions in
the frequency domain. Below here you see 8 functions (a-h) For each time domain
function 1-4 choose a function from the set a-h representing the real part of its Fourier
transform and a second function representing the imaginary part of the Fourier transform.
The inserts display the behavior of the function for small absolute values of ω
2 2

Amplitude
Amplitude
1 1
0 0
2 -1 -1
20
15
a 20
15
c e -2
-4 -2 0 2 4
2
g -2
-4 -2 0 2 4
1 ω ω
10 10 1
Amplitude
Amplitude

Amplitude
5
Amplitude

0 0 0 0
-5 -5
-10 -10 -1 -1
-15 -15
-20 -20 -2 -2
-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100
ω ω ω ω

20 20 20
b 50
40 d f h
10 30 10 10
20
Amplitude

Amplitude
Amplitude

Amplitude

10
0 0 0 0
-10
-20
-10 -30 -10 -10
-40
-50 -20 -20
-20
-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100
ω ω ω ω

In brief this problem can be solved by completing the table below:

Time domain Fourier transform.

Function
Real part Imaginary part
1. ↔ (choose a-h) (choose a-h)
2. ↔ … …
3. ↔ … …
4. ↔ … …
Problem 12. Kramers Kronig or Hilbert Transform

For the Lorentz oscillator we derived starting from Newtons law (F=m a):

χ 1 (ω ) ∝
(ω 0
2
−ω 2 ) χ 2 (ω ) ∝
− iωτ
(ω 0
2
−ω 2
)
2
+ (ω / τ )
2
(ω 0
2
− ω2 )
2
+ (ω / τ )
2

According to lecture 2 the real and imaginary part of a proper response function ought to
be related via the Kramers-Kronig relations or , equivalently via Hilbert transformation.
We have not yet checked whether this indeed holds for this for the Lorentz response ! Let
us do so. Run the MATLAB program InverseHilbert_Lorentz_Chi1_toChi2.m. In Figure
1 the program plots the function χ1(ω). In Figure 2 the program plots the Hilbert
transform of χ1(ω) (blue) together with χ2(ω) listed above (green)

1. Do the Hilbert transform and χ2(ω) resemble each other ? (Note that your computer
program makes small numerical errors that can account for some differences) . What do
you conclude from this ? What does your result imply for Newtons law (F=m*a) ?

2. Describe qualitatively what happens to χ2(ω) when you vary the values of parameters
(see First to lines of m-code)
omega ( w0 ) in the rage 200 - 400
tau (t) in the range 100 -1
 Mechanical and Functional properties of Materials 6MSM40
Workgroup 3

Problem 13.

The reflectivity R at normal incidence is given by :

(1 − n~ ) 2 (1 − n) 2 + κ 2
R= =
(1 + n~ ) 2 (1 + n) 2 + κ 2
Explain why gold has a yellow color in reflected light while aluminum seems color less.

Problem 14.

Copper and other metals have been deposited on solid substrate in the form of small
metallic nanoparticles by Van Duyne and coworkers. The metallic particles deposited
have a fixed size and shape for all metals used . Metal particles are 40 nm high,
approximately 150 nm wide and are arranged in an hexagonal pattern. The microscope
image below gives an impression.

Van Duyne and coworkers (J. Phys. Chem. C, 2008, 112, 13958-13963) measured the
transmission of light through a layer of these particles The find regions in the visible part
of the spectrum where there is a low transmission of light corresponding with a broad
extinction band. They find that wavelength of the maximum of the extinction band
depends on the metal that is used. For Al the maximum occurs at the shortest wavelength.
For Au the maximum occurs at the longest wavelength. For Ag and Cu the wavelengths
of the maxima are close together and in between Au and Al .

a) Give a qualitative explanation for this based on the dielectric properties of the pure
metals (see next page)
 0
Copper
−ε1 ε1 1E5
Copper
1E4 -1
1E4 1/ω3
1E3 -2 ε2
1E3
1/ω2
1E2
3 4 1E2
10
10
ε1
1 1

1E-1 1E-1
1E-2 1E-1 1 10 1E2 1E-2 1E-1 1 10 1E2
Photon Energy (eV) Photon Energy (eV)

1E5
−ε1
0
ε1 1E5
1/ω Gold

1E4 -1
1E4
1E3 -2
1E3
ε2
1/ω2 1/ω3
-3
1E2 2 3 4 1E2
Gold
10 10
ω 1≈/ 1τ / τ 1/τ
1 1
ε1
1E-1 1E-1
1E-2 1E-1 1 10 1E2 1E-2 1E-1 1 10 1E2
Photon Energy (eV) Photon Energy (eV)

0 1/ω
ε1 1E5
Aluminum
1E4
−ε1 -1
1E4 1/ω3
1E3 -2 ε2
1E3
1E2 1/ω2
8 9 10 1E2
Aluminum
10 10
1/τ
1/τ
1 1
ε1
1E-1 1E-1
1E-2 1E-1 1 10 1E2 1E-2 1E-1 1 10 1E2
Photon Energy (eV) Photon Energy (eV)

1E3 Silver
−ε1(ω) 2
1 ε1(ω) ε2(ω)
1E3
0 1E2
-1
1E2
-2
10
1/ω3
10 3 4 5
ε1(ω)
Silver 1
1

1E-1 1E-1
1E-1 1 10 1E2 1E-1 1 10 1E2
Photon Energy (eV) Photon Energy (eV)
Van Duyne et al also find that for a particular metal (here Al) the wavelength
corresponding to the maximum of the extinction band also shifts with the liquid
surrounding the metal particle. For example when the particle on a glass support are
immersed in benzene the maximum of the Al nanoparticles extinction band shifts to
lower photon energies in comparison with the metal particles in nitrogen atmosphere
(N2).

b) Can you give a qualitative explanation for this observation ?

Problem 15. A case study: Immersion lithography

In the chip industry, lithography is used to make a pattern in silicon wafer .

UV light is used to illuminate a polymer layer coated on top of the Si wafer. The
polymer, also called photoresist, becomes insoluble after illumination. The non-
illuminated parts of the polymer can be washed away by solvent and the underlying Si
can be modified by etching and other processes.
By putting a mask with the desired pattern in the light beam, the pattern can be
transferred on to the wafer. By putting in a lens, the patter on the mask can be shrunk in
size and nanometer sized features can be made in the photoresist. The minimum feature
size that can be realized depends on the wavelength of light λ used in the illumination.
The computer industry is interested in making the features as small as possible, so that
more integrated circuits can be made per unit surface area on the wafer.
 UV light Normal
Lithography

Mask Lens photoresist

on
Si wafer

UV light Immersion
Lithography

Immersion
liquid

- Twenty years ago, the computer industry started using deep UV laser to illuminate the
photoresist instead of Mercury lamps emitting in the visible. Explain why UV light was
chosen.

Recently immersion lithography was introduced. Here a liquid, also called the immersion
liquid, fills the empty space between the lens and the photoresist. The liquid has a
refractive index >1.
- Explain why the use of such a liquid allows one to make smaller patterns in the
photoresist

The use of immersion liquids started a world-wide quest for optimized liquids for this
kind of lithography

- Specify the criteria for such liquids with regards to their complex refractive index.

In the chemical industry people started investigating hydrocarbons as possible immersion

fluids. They find a linear correlation between refractive index and the density of the
hydrocarbon fluid.

- Give a qualitative explanation for this relation between n and density.

 Mechanical and Functional properties of Materials 6MSM40
Workgroup 4

Problem 16. The Boron-Nitrogen analogue of polyacetylene

Polyacetylene is a p-conjugated polymer whose structure is shown below. Of this

polymer also an isoelectronic boron nitrogen analogue exists.
H H H H H H
trans- polyacetylene

H H H H H

short bond (double) long bond (single)

Large βL Small βS

Boron-nitrogen analogue:

H H H H H H H H H H H H
N N N N N N N
_ N
_ N
_ N
_ N
_ N
_
B B B B B B B B B B
H H H H H H H H H H

iφ
a. Use the Bloch relations ai +2 = e ai and ai +1 = e ai to formulate the Schrödinger
ikL

equation in matrix form for the boron nitrogen analogue. Neglect the bondlength
alternatio

b. Consider the meaning of the parameters αN and αB . Can you relate the value αN to that
of αB and simplify the equation ?

c. Solve the Schrödinger equation for the BN polymer using the analogy with
polyacetylene. Would the BN polymer be a conductor in the absence of bondlength
alternation ?
Problem 17. π-conjugated polymers

Polyfluorene is a conjugated polymer having alternating single and double bonds. The
side groups R are often linear alkyl tails

[ ]n
R R

We investigate the frequency dependent dielectric properties of films of polyfluorene

a) The frequency dependent relative dielectric constant ε(ω) = ε1(ω) + iε2(ω) is a

function with a real (ε1(ω)) and an imaginary part ε2(ω). Is there any relation
between these real and imaginary parts ? Answer this question in word only.

Below you see graphs of the dielectric function of polyfluorene

4.5
(a)
4.0
ε1,||
in-plane
ε1

3.5

3.0
out-of-plane
2.5 ε1, |
2.0

1.5
ε2,||
in-plane
1.0 ε2, |
ε2

0.5
out-of-plane
0.0
4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6
Energy (eV)

Figure 6. Dielectric data for a film of polyfluorene

b) On the vertical axis displaying ε, no units are indicated. Could this be an error ? If
so, in what units should the magnitude of ε be expressed ?

The thin film of polyfluorene polymer shows anisotropy : the value for the dielectric
constant for electric fields in the plane of the thin film (ε1,|| (ω) and ε2,|| (ω) in plane) are
different from those for electric fields perpendicular to the plane of the thin film (ε1,⊥ (ω)
and ε2, ⊥ (ω) out of plane)

c) Can you give a possible explanation of this anisotropy ?

The dielectric constants for polyfluorene show a resonance at 3.2 eV

d) Considering the frequency of this resonance, does this resonance involve motion
of :

1. The mole molecule (rotation) ?

2. Vibrations of the atomic nuclei ?
3. Oscillatory motion of the σ-electrons ?
4. Oscillatory motion of the π-electons ?
5 Oscillatory motion of the 1s core electrons ?

Choose one of the five answers above and explain why you think this is the
correct answer.

e) What is the probability that a photon of 3.2 eV energy will be absorbed upon
travelling through a layer of polyfluorene of 100 nm thick. Assume that the
photon comes in at right angles to the plane of the thin film ( e.g. along the
surface normal) and neglect any possible reflection of light.

f) What is the probability that a photon of 2.6 eV energy will be reflected from the
surface of an infinitely thick film of polyfluorene when it approaches the film at
right angles ( e.g. along the surface normal) when traveling through vacuum.
 Mechanical and Functional properties of Materials 6MSM40
Workgroup 5

Problem 18. Graphite.

You are investigating the possibility to use graphite as a conductor in computers

operating at a cycle frequency ν of 2.4 GHz (=2.4 109 s-1). Here the conductivity of the
graphite at 2.4 GHz is important. You look up the relative dielectric constant of graphite
from your lecture notes:
1000
E // c axis
0 c-axis
-1000
ε1(ω) -1

-2000
-3000
-4000 E ⊥ c axis
-5000
-6000 T=20 K, 0.1 µm grain size
-7000

1E6 1/ω
1E4 1/ω3
E ⊥ c axis
1E2
ε2(ω)

1
1E-2
E // c axis
1E-4
1E-6
1E-8
1E-5 1E-4 1E-3 1E-2 1E-1 1 10 1E2 1E3 1E4
photon energy (eV)
Figure 3.1

a) Graphite is an anisotropic material. In which direction(s) does it show the largest

conductivity at a frequency of 2.4 GHz ? Explain your answer. Qualitative reasoning is
sufficient.

You want to calculate the conductivity at 2.4 GHz. You can use the Drude model in the
low frequency limit ω <<1/τ .

b) In order to calculate the conductivity σ0 you need to estimate a value for τ.

In the low frequency limit ω<<1/τ, an estimate for τ can be obtained from the ratio
ε1(ω)/ε2(ω). Explain how. Estimate a value for τ.

c) In the Drude model, the parameter τ characterizes the motion of the electron in the
conductor. Briefly explain the meaning of the parameter τ in words.
d) Compare the value for τ that you have obtained for graphite with the value for τ in
gold (25 fs = 25 × 10-15 s). Give a possible explanation for this difference between gold
and graphite in terms of the electronic band structure of graphene. (If you have no
estimate for τ from b) assume that it is longer than for gold.)

e) Using the estimate for τ from above you can now also calculate the plasma frequency
ωp for graphite using the values for ε1(ω) and ε2(ω) at 2.4 GHz and applying the low
frequency limit ω<<1/τ. What is your estimate for ωp ?

f) Using your estimates for the plasma frequency ωp and τ, calculate the conductivity σ0.
If you do not have an estimate for ωp and τ assume some values and calculate σ0 from
them).

From the dielectric data one can calculate the absorption coefficient α for graphite. This
is the result (note α is given in cm-1):
π electrons + π electrons σ elecs. 1s core
vibrations electrons
1E6
Absorption coefficient (cm-1)

1E5

E ⊥ c axis
1E4

1E3

E // c axis
1E2

10 T=20 K; 0.1 µm grainsize

1E-5 1E-4 1E-3 1E-2 1E-1 1 10 1E2 1E3 1E4

Photon energy (eV)

g) People claim that they can see a single layer of carbon atoms in graphite (=graphene)
with the naked eye. Calculate the percentage of light transmitted through a single layer
graphite for light with 620 nm wavelength. Assume that the electric field of the light is
parallel to the graphene sheet and thus perpendicular to the c-axis. Assume that the layer
is 0.5 10-9 m thick.

h) At low frequency the absorption coefficient α depends on the direction of the electric
field of the light. At high frequency (photon energy E > 200 eV) the magnitude of α is
practically independent of the direction of the light. Give an explanation for this
observation considering which electrons are oscillating at photon energy > 200 eV and
the amplitude of their motion at this frequency.
Problem 19. The Boron-Nitrogen analogue of grapheme.

Substituting carbon atoms with boron and nitrogen one arrives at the following
(hypothetical) grapheme like structure. It is isoelectronic with graphene:

B N
_ B N B _
N
_N N
B _ B _
N B
B _N B _N B _
N Lattice constant a:
2
2.456 Å
_N B _
N B _N B
B _N N
B _ B _
N
_N N
B _ B _N B 2.456 Å
1
B _
N B _
N B _N For simplicity we set
a=1
_N B _N B _N B
B _N B N
_ B N
_

ψ = ∑ ai , j piz, j + bi , j piz, j x
i, j

1. Starting with the matrix form of the Schrödinger equation for grapheme, which of
the parameters will have to be changed in order to describe the BN analogue ?
2. What is the meaning of the α’s in this case ? Can the values of α be related ?
3. In which respect do the solution of the Schrödinger equation for the BN sheet
differ from that of normal grapheme. ? Make a sketch of the band structure.
4. What can you say about the effective mass of the electrons in BN in comparison
with grapheme ?
Problem 20. Graphite and diamond.
π electrons + π electrons σ elecs. 1s core
vibrations electrons
1E6

Absorption coefficient (cm-1) 1E5

E ⊥ c axis
1E4

1E3

E // c axis
1E2

10 T=20 K; 0.1 µm grainsize

1E-5 1E-4 1E-3 1E-2 1E-1 1 10 1E2 1E3 1E4

Photon energy (eV)

Pure carbon occurs in different forms (called allotropes), for instance diamond and
graphite. Diamond is a largely transparent to visible light,while graphite carbon is black.
This means that carbon graphite absorbs all visible wavelengths very strongly. Explain
the differences in absorption of light by diamond and graphite based on their electronic
band structure.
Problem 21. InP: a semiconductor.

The refractive index for the semiconductor InP has been determined. See Figure 8 below.

Figure 8. Refractive index for InP. The dots and circles represent experimental data. The
solid line is a theoretical calculation.

a) From the data in Figure 8, calculate what the actual speed of light for propagation
inside the InP crystal for light that has a wavelength of 800 nm in vacuum.

b) Does the wavelength of the light change when it enters the crystal ? If yes, calculate
the wavelength inside the InP crystal for light which has 800 nm wavelength
outside the crystal in vacuum.
Below you see the band diagram calculated for InP. The Fermilevel is at E= 0 eV.

E (eV)

Figure 9. Band structure diagram calculated for InP.

c) Based on 9, is InP an indirect or direct bandgap semiconductor ? Estimate the

magnitude of the bandgap from the results of the theoretical calculations in Figure
9.

d) How can one experimentally distinguish a direct bandgap semiconductor from an

indirect bandgap semiconductor ?

e) Near E=0, two lines in the band diagram come together near the Γ point. What can
you say about the charge carrier that you will find at this point in the band diagram
?

InP can be doped with impurities that can donate an electron (n-type doping). At room
temperature these donors ionize, resulting in ‘free’ charge carriers.

e) What will happen to the bulk electrical resistivity of the InP upon doping with these
n-type impurities ?

Doping of InP with these n-type impurities also results in changes of the optical
properties. It has been observed that doping leads to a new absorption band in the infrared
part of the spectrum, that is not present for the undoped material. The intensity and shape
of the absorption band depend on the doping density (i.e. the number of dopants per cm-
3
); see Figure 10. Upon increasing the doping density, the absorption increases and
extends to higher photon energies.

Figure 10. Absorption coefficient for n-type doped InP in the infrared at different doping
densities: 1. 4·1016 cm-3 ; 2. 2·1017 cm-3; 3. 4·1017 cm-3

f) Give a possible explanation for the absorption in the infrared and name a classical
oscillator model that could describe the optical properties.

g) Suppose that you now wanted to determine the mobility of the charge carriers in the
n-type doped InP. What additional information apart from the absorption coefficient
and the doping level, do you need in order to be able to calculate this mobility ?
Explain in words how you would calculate this mobility if you were given the
information asked for above.