Answer ALL questions.

Each question carries marks distributed as shown [ ]

1. Processing materials for microelectronics applications [20 marks]

Answer all parts of the following:

a) Suggest a process that can be used to increase the thickness of a silicon wafer.
What are the main physical and/or chemical steps (or elementary processes) that
take place in this process?
[7]
b) Suggest a process that can be used to pattern an oxide layer on a silicon wafer.
What are the steps that this process entails?
Use schematics and brief explanations to illustrate each step.
[9]
c) Suggest a process that can be used to create connections (electrically conductive)
between different parts of an integrated circuit.
What are the main steps that take place in this process?
[4]

2. Behaviour of irradiated polymeric resist materials upon development [15 marks]

Experiments on two different positive resist materials generated the development plots shown
in Figure Q.2.
Each curve (labelled a, b, …, e) corresponds to a different dose, the latter taking the following
values in these experiments (in units of C cm-2): 0, 1.1, 2.2, 3.6, 5.1.

Figure Q.2 Development plots for two different resist materials.

a) For each of the two resists, match the dose value with the curve (i.e. for each of the
curves a, b, etc… say which dose they correspond to).
Justify your answer.
Would the matching change if these plots were for a negative resist?
Why (or why not)? [6]
TURN OVER
1
CENGM05P
 b) From the data of the above plots, draw the sensitivity curve for each resist.
Specifically, plot the thickness remaining, srem, as a function of the natural
logarithm of the dose (you will not be penalised for small errors, but try to read
the values from the diagrams to the best of your ability).
Calculate the contrast of each of the two resists. [6]

c) Making reference to the values for the contrast that you calculated in question
b), explain which of the two resists you would use in a microlithography
application and justify your answer. [3]

3. Low Pressure Chemical Vapour Deposition Reactor [15 marks]

A Low Pressure Chemical Vapour Deposition (LPCVD) reactor has the geometric
configuration illustrated in Figure Q.3.1.

Figure Q.3.1: Geometric configuration of a Low Pressure Chemical Vapour Deposition

(LPCVD) reactor.

The following reactions take place during the growth of a Si film on a wafer:
k1 

SiH 4  M   SiH   M 
k 4
2
 gas phase
 
SiH4 
k3
 SiH 2  H 2 
SiH 2 
ks
 Si  H 2 surface

where M denotes any inert species, and SiH4 denotes activated silane.
The decomposition of SiH4 has been observed to follow first order kinetics.

CONTINUED

2
CENGM05P
 a) Focusing on the gas phase reactions first, derive the effective first-order kinetic
constant, kg, for the decomposition of SiH4, assuming quasi-equilibrium for SiH4 .
Provide an expression of kg with respect to k1 , k 2 , k3 , and the concentration of M.
Calculate the value of kg for an inert concentration of [M] = 1.60 mol m-3,
k1 = 1.14 m3 mol-1 s-1, k 2 = 0.15 m3 mol-1 s-1, and k 3 = 0.23 s-1.
[5]

b) Based on the value of kg you calculated in a), now calculate the gas Thiele modulus
from the following equation:
k g  R 2w
 g2 
DSiH4
given the diffusion coefficient of SiH4, DSiH4 = 4.3 cm2 s-1, and the radius of the
wafer, Rw = 0.1 m. (Note: if you were unable to solve part a), use kg = 1 s-1 for this
question).
What does the value of this Thiele modulus quantify (i.e. what is its physical
meaning)?
[2]

c) The diagram in Figure Q.3.2 gives the steady state concentration profiles of the gas
SiH2 above the wafer as a function of the distance from the centre of the film.

Figure Q.3.2. Steady state concentration profiles of the gas SiH2 above the wafer.

TURN OVER

3
CENGM05P
 The diagram was calculated for the gas Thiele modulus for which we will operate the
reactor and for a range of the surface Thiele modulus,  s , defined as:
k s  R 2w
s2 
DSiH2 

where the diffusion coefficient of SiH2 is DSiH2  DSiH4, is the interwafer

separation, Rw is the radius of the wafer, and ks the surface reaction rate.
Explain the dependence of the concentration profiles on  s (i.e. why the profiles
look like this), and what the consequence of the shape of these profiles will be for
the uniformity of the film grown.
[3]

d) Based on the information found in part c), calculate the interwafer separation in
millimetres, so that we achieve as far as possible uniform films.
Calculate the rate of Si deposition (in mol cm-2 s-1) and the rate of film growth
(in nm s-1).
The surface reaction rate constant is ks = 0.1 cm s-1, the atomic mass of Si is
28 amu (atomic mass units), and the density of Si is 2.3 g cm-3.
[5]

4. Micelles, vesicles and polymersomes in soft nanotechnology [10 marks]

a) What are the similarities and differences between a micelle and a vesicle? Explain the
building blocks, draw the structure of both configurations, relate to the length scale and
mention in which technological applications these configurations are found.
[4]

b) Why is the mean lifetime of a molecule in a micelle much shorter than that of a
molecule in a vesicle?
[2]

CONTINUED

4
CENGM05P
 c) You are asked to produce polymersomes (artificial polymeric vesicles) from poly(2-methyl-
2-oxazoline) (PMOxa) -block- poly(dimethyl siloxane) (PMOxa-b-PDMS).

What molecular weight of PMOxa would you chose to ensure that the block copolymers
assemble into vesicles and why?

Note: You perform the experiment at 25°C in water. Assume the length of a MOxa repeat
unit to be 0.5 nm and the molecular weight of a single repeat unit is 83 g/mol. The radius of
gyration, Rg of PDMS is 1 nm. Assume PDMS and PMOxa to behave like ideal chains.

[4]

Figure Q.4.1. Chemical structure of a PMOxa-b-PDMS block copolymer

5. Block copolymers – fundamentals and applications in lithography [25 marks]

Figure Q.5 shows the theoretical phase diagram of a block copolymer melt after Matsen and
Bates (1996).

Figure Q.5. Theoretical phase diagram of a block copolymer melt after

Matsen and Bates (1996).

a) The phase behaviour of block copolymer melts is typically dependent on the type of
building blocks, the chain length of each block as well as the temperature.
Associate suitable variables to the plot above and argue in support of this statement using an
appropriate definition of the interaction parameter χ.
[3]

TURN OVER
5
CENGM05P
 b) Now examine the situation at the spherical marker (•).
What are the characteristics at this point? What is this point typically referred to? What role
does the molecular weight play, i.e. how is a polymer phase diagram different to one of
smaller molecular weight surfactants?

[3]
c) Different phases of the block copolymer melt are indicated in Figure Q.5 in framed letters
A-J.

Name and briefly explain (or sketch) the phases observable in the indicated regions.
[5]

d) A diblock copolymer of polystyrene and poly(methyl methacrylate) (PS-b-PMMA) phase

separates into a lamellar array for:
Mn(PS) = 10,600 g mol-1 and Mn(PMMA) = 10,000 g mol-1.

Assuming equal mass densities and phase behaviour as illustrated above with χ N > 100,
how would one need to change the degree of polymerisation for PS in a new synthesis in
order to obtain a microphase-separated morphology of PS cylinders in a PMMA matrix?

Note: the molecular weight of styrene is 104 g/mol.

Explain the underlying thermodynamic rationale that makes the newly synthesised block
copolymer form hexagonally arranged cylinders rather than lamellae.

Is there an alternative route to a new synthesis using the diblock copolymer described
above? Explain your answer briefly.
[5]

e) Block copolymers can be used to create patterned magnetic recording media. Differentiate
between additive and subtractive approaches and briefly explain the complete lithographic
process for one of the two.
What are the advantages and challenges of using block copolymers compared to
conventional lithographic masks?
How could you improve and promote the ordering of the block copolymers?
[9]

CONTINUED

6
CENGM05P
6. Colloidal interaction and stability [15 marks]

a) Consider a colloidal suspension containing spherical particles that have smooth surfaces.
Based on the DLVO theory, identify the components that contribute to the total potential
energy, V, explain their nature.
Schematically sketch V as a function of the separation between two colloidal surfaces for
different scenarios that depend on the magnitude of the interaction.
What are the limitations of this model to predict colloidal stability? [6]

b) The characterisation of the zeta potential is a useful tool to determine the magnitude of the
electrostatic or charge repulsion/attraction between particles and one of the fundamental
parameters known to affect colloidal stability.

i) Explain in words and with the aid of a sketch the context of the Zeta potential
and provide arguments that support this statement.
[3]

ii) Describe an experiment to determine the zeta potential.

[3]

c) Identify three synthetic tools to increase colloidal stability.

[3]

END OF PAPER

7
CENGM05P