"MODELLING OF A COMMERICAL CVD REACTOR"

Thesis submitted in partial fulfillment

For the Award of

“MASTER OF TECHNOLOGY”

in

Chemical Engineering

By

SHIVAM BHATIA

DEPARTMENT OF CHEMICAL ENGINEERING AND TECHNOLOGY

INDIAN INSTITUTE OF TECHNOLOGY
(BANARAS HINDU UNIVERSITY)
VARANASI – 221005

ROLLNO.: 19042035 YEAR OF SUBMISSION: 2020-21

 CERTIFICATE

It is certified that the work contained in the thesis titled “MODELLING OF A

COMMERCIAL CVD REACTOR” by “SHIVAM BHATIA” has been carried out

under my/our supervision and that this work has not been submitted elsewhere for a

degree.

It is further certified that the student has fulfilled all the requirements of the

Comprehensive Examination, Candidacy and SOTA for the award of M. Tech

Degree.

Signature : Supervisor Co-Supervisor External Supervisor

(Affiliation) (Affiliation) (Affiliation)

ii
 DECLARATION BY THE CANDIDATE

I, SHIVAM BHATIA, certify that the work embodied in this thesis is my own bona fide

work and carried out by me under the supervision of Dr. Vijay Shinde from June 2020

– May 2021, at the DEPARTMENT OF CHEMICAL ENGINEERING AND

TECHNOLOGY, Indian Institute of Technology (BHU), Varanasi. The matter embodied

in this thesis has not been submitted for the award of any other degree/diploma. I declare

that I have faithfully acknowledged and given credits to the research workers wherever

their works have been cited in my work in this thesis. I further declare that I have not

wilfully copied any other’s work, paragraphs, text, data, results, etc. , reported in journals,

books, magazines, reports, dissertations, thesis, etc. , or available at websites and have

not included them in this thesis and have not cited as my own work.

Date:

Place: Shivam Bhatia

CERTIFICATE BY THE SUPERVISOR(S)

It is certified that the above statement made by the student is correct to the best of

my/our knowledge.

Supervisor Co-Supervisor External Supervisor

(Affiliation) (Affiliation) (Affiliation)

Signature of Head of Department

iii
 ACKNOWLEDGEMENT

The satisfaction of successful completion of this task cannot be completed without

acknowledging those without whom this project would not have been a reality.

First, I would like to extend my heartfelt gratitude to the institution - IIT BHU for

imparting first class education. I would like to express my sincere gratitude to my project

guide, Dr. Vijay Shinde, Assistant professor, Department of Chemical Engineering and

Technology, for his continuous support and guidance in research and study. His

mentorship, insight and encouragement will continue to inspire me both personally and

professionally.

I am grateful to the Head of the Department, Dr. Vijay Laxmi Yadav, for her sterling

direction which inspires the department to keep up its pace and move on with graces.

I would also like to thanks Dr. Pramod Kumar Jain, Director, IIT BHU, for providing

all the facilities in the college.

I am also grateful to all other teaching and non-teaching staff members of the Department

of Chemical Engineering and Technology for their kind co-operation during the project.

Shivam Bhatia (19042035)

Department of Chemical Engineering and Technology

IIT BHU, Varanasi

iv
 ABSTRACT

This thesis emphasises on computer simulation & optimization of a horizontal flow CVD

process in particular of silicon carbide. A 2-dimensional simulation for steady state

deposition of silicon carbide from gas mixtures containing MTS-H2-Ar was set up on

commercial CFD code ANSYS FLUENT 2020 R2. The geometry creation was done

using ANSYS SpaceClaim and meshing was done using ANSYS Meshing. A 2 step rate

mechanism that describes the deposition of silicon carbide was introduced. Analysis of

various operating parameters and its coupling effects on silicon carbide deposition rate

and uniformity of deposition was carried out using RSM. An accurate RSM model was

obtained based on the CFD model to predict deposition rate and uniformity of deposition

using numerous parameters such as pressure, temperature, mole ratio of H2-Ar &

flowrate.

Analysis of variance (ANOVA) was conducted on Design Expert 11 for determining the

statistical importance of each parameter in an empirical equation of deposition rate and

uniformity of deposition. ANOVA analysis was conducted to indicate the accuracy of

regression model. Optimum set of operating parameters for the reactor taken into account

were susceptor and wall temperature of 850°C, operating pressure of 150mbar, H2:Ar

mole ratio of 1.5 and gas flowrate as 200lph. The maximum deviation between predicted

value and computational value of uniformity index was found to be 1.24% and that of

deposition to be 6.92%, which indicates results were very close to the CFD model.

A 3-dimensional reactor scale CFD theoretical model running at optimum conditions

obtained from a 2-dimensional model was proposed to describe mass transfer, heat

transfer and gas flow in a kinetically controlled chemical vapour deposition reactor.

v
 TABLE OF CONTENT

PAGE NO.
CERTIFICATE ii
DECLARATION BY THE CANDIDATE iii
ACKNOWLEDGMENT iv
ABSTRACT v
TABLE OF CONTENTS vi
LIST OF FIGURES viii
LIST OF TABLES x
LIST OF SYMBOLS xi

CHAPTER 1 Chemical Vapour Deposition 1

1.1 Introduction 1
1.2 Types of CVD Reactions 2
1.3 Classification of CVD Reactors 3
1.4 Components of CVD Reactor 5
1.5 Layer Morphology 6
1.6 Applications of CVD 8
1.7 Objective of work 9
CHAPTER 2 Thermodynamics and Transport Phenomena 10
2.1 Effect of Operating Parameters 10
2.2 Governing Equations 13
2.3 Thermodynamics of CVD 16
2.4 Kinetics of CVD 17
CHAPTER 3 Modelling of 2-D CVD Reactor 20
3.1 Introduction 20
3.2 Problem Description 20
3.3 Geometry 22
3.4 Mesh 22
3.5 Setup 24
3.6 Solution 30
3.7 Results 33

vi
CHAPTER 4 Mathematical Modelling using Design Expert 47
4.1 Introduction 47
4.2 Analysis of Results 47
4.3 Uniformity of SiC film on substrate deposition 50
4.4 Deposition rate of SiC on substrate 54
4.5 Optimisation of Process Parameters 58
CONCLUSION 64
REFERENCES 65

vii
 LIST OF FIGURES
FIGURE TITLE PAGE
NO. NO.
2.1 Schematic representation of series of steps involved in CVD 10
2.2 Graph of deposition vs velocity and temperature 11
3.1 2-Dimensional geometry of CVD reactor 22
3.2 Meshed geometry of 2-D CVD reactor 23
3.3 Graph of uniformity index vs number of elements 24

3.4 Graph of deposition rate vs 1/T 34

3.5 Graph of substrate deposition vs temperature 35
Case comparison study for surface deposition rate at 850° and
3.6 1000°C 35
3.7 Graph of overall deposition vs temperature for different pressure 36
Graph of substrate deposition vs pressure in kinetic controlled
3.8 regime 37
Graph of substrate deposition vs pressure in transport controlled
3.9 regime 37
Graph of substrate deposition vs flowrate in kinetic controlled
3.10 regime 38
Graph of substrate deposition vs flowrate in transport controlled
3.11 regime 39
Graph of substrate deposition vs mole ratio in kinetic controlled
3.12 regime 40
Graph of overall deposition vs mole ratio in kinetic controlled
3.13 regime 40
3.14 Graph of surface deposition rate for different mole ratio 41
Graph of overall deposition vs mole ratio in transport controlled
3.15 regime 42
Graph of substrate deposition vs mole ratio in transport controlled
3.16 regime 42
Graph of uniformity index vs mole ratio for kinetic controlled
3.17 regime 43
Graph of uniformity index vs mole ratio for transport controlled
3.18 regime 43
3.19 Graph of uniformity index vs temperature 44
Graph of uniformity index vs pressure in kinetic controlled
3.20 regime 45
Graph of uniformity index vs pressure in transport controlled
3.21 regime 45
Graph of uniformity index of deposition vs flowrate for transport
3.22 controlled regime 46
Graph of uniformity index of deposition vs flowrate for kinetic
3.23 controlled regime 46
4.1 Box-Cox plot for power transform for response 1 53

viii
4.2 Predicted vs actual value for response 1 53
3D surface model graph of uniformity vs temperature and
4.3 pressure 54
4.4 3D surface model graph of uniformity vs flowrate and mole ratio 54
4.5 Box cox plot for log transform for response 2 57
4.6 Predicted vs actual value for response 2 57
4.7 3D surface model graph of deposition vs temperature and pressure 58
4.8 3D surface model graph of deposition vs flowrate and mole ratio 58
4.9 3D surface model graph of desirability 59
4.10 Contours for 2-D CVD reactor operating at optimum conditions 60
4.11 Contours for 3-D CVD reactor operating at optimum conditions 63

ix
 LIST OF TABLES

TABLE TITLE PAGE

NO. NO.
Equations of conservation of mass, energy, momentum and
2.1 species 13
3.1 Reactor operating parameters and their range 21

3.2 Grid independency test readings 23

3.3 Reaction parameters 26
3.4 Properties of species 27
3.5 Boundary Conditions 30
3.6 Variables depicting ∅ in scalar transport equation 31
3.7 Effect of temperature on overall deposition 33
Effect of temperature on rotor and substrate wall
3.8 deposition 36
4.1 Table of experimental trials 48
4.2 Fit summary table for response 1 51
4.3 Analysis of variance for 2FI model for response 1 51
4.4 Fit summary model for response 2 55
4.5 Analysis of variance for 2FI model for response 2 56
4.6 Parameter and optimum value 59

x
 LIST OF SYMBOLS

Di, adsorbate Diffusion coefficient for surface diffusion of adsorbed species

DaII Damköhler Number
rs Surface reaction rate
JD Diffusion flux
b Flux density
t time
𝐹⃗ Conserved quantity flux
BV Generation of conserved quantity per unit volume
𝜌 Density
𝑢
⃗⃗ Velocity
ω Mass fraction of species
Mi Molecular weight of species i
Ri Molar consumption and generation of chemical species i
𝑔𝑖
⃗⃗⃗⃗ Acceleration due to gravity
cP Specific heat capacity
T Temperature
S Energy source
π Molecular momentum flux tensor
jic Diffusion flux due to concentration gradient
jip Diffusion flux due to pressure gradient
jig Diffusion flux due to external force
jit Diffusion flux due to temperature gradient or Soret Diffusion
xi Mole fraction of species i
Dij Diffusion coefficient for binary mixture
R Universal Gas Constant
K Thermal conductivity
σ Collision diameter
ε Characteristic energy of molecule
KB Boltzman constant
𝛿̿ Kronecker delta function
p pressure
𝜏̿ Viscous momentum flux tensor
k Thermal conductivity

xi
μ Dynamic viscosity
υ Stoichiometric Coefficient
°
ΔG𝑟𝑥𝑛 Gibbs free energy of chemical reaction
° Gibbs free energy of reactants
ΔG𝑓,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
° Gibbs free energy for products
ΔG𝑓,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
K Equilibrium constant
A Pre exponential factor
β Temperature coefficient
θ Fraction of occupied sites
EA Activation Energy
yi Mass fraction of species i
Kn Knudsen number
𝜆 Molecular mean free path
DC Length scale of substrate
V Volume
A Area
Τ∅ Diffusion coefficient for ϕ
u Velocity in x-direction
v Velocity in y-direction
Q Flowrate
M Mole ratio

xii
 Chapter: 1

Chemical Vapour Deposition

1.1 Introduction:

Chemical Vapour Deposition is a process in which a substrate is exposed to volatile

precursors which react in vapour phase to form a product which deposits on the wafer.

The gas moves through the reactor and distributes uniformly across the surface of the

wafer which begins to absorb them on their surface. The difference between chemical

vapour deposition and physical vapour deposition lies in the fact that in CVD, the

chemical structure of the deposited substance is different from that present in the gas

phase whereas PVD is generally a condensation process and therefore, the chemical

structure of deposited and gas phase species is the same. The main advantages of PVD

over CVD technique are purity of coating and availability of a broad range of precursors

which is compensated by low deposition rate and line of sight effects. Typical CVD

process consists of the following steps- [1]

i. Convective transport of reactants and carrier gas into reactor

ii. Chemical reactions of precursors in bulk gas phase

iii. Diffusion of species from bulk to substrate across boundary layer

iv. Heterogeneous chemical reaction taking place at substrate

v. Sticking of film to surface of the substrate

vi. Desorption of volatile by-products

vii. Exhaust of species out of the reactor

1.2 Types of CVD Reactions:

Chemical reactions in bulk phase are generally of four types:

i. Pyrolysis

ii. Reduction

iii. Oxidation

iv. Nitration

Pyrolysis: In this bulk phase chemical reaction, a molecule is split into its element. Such

reactions are simple as they require only one precursor gas. Reactions could be halide

decomposition, hydrocarbon decomposition, carbonyl decomposition or hydride

decomposition. Typical examples are as follows:

WF6(g) → W(s) + 3F2(g)

CH4(g) → C(s) + 2H2(g)

Reduction: In such type of bulk phase chemical reaction, the oxidation state of an

element is decreased or an electron is gained by the element. Examples of such reactions

are as follows:

SiCl4(g) + 2H2(g) → Si(s) + 4HCl(g)

WF6(g) + 3H2(g) → W(s) + 6HF(g)

Oxidation: In this type, the oxidation state of an element is increased or in other words

an element loses an electron. Usual sources of oxygen are elemental oxygen, ozone and

carbon dioxide. Examples of oxidation are:

SiH4(g) + O2(g) → SiO2(s) + 2H2(g)

2
-Carbidization and Nitridation: Carbide deposition is usually done by reacting

hydrocarbon with a halide; and nitride is generally based on ammonia which is preferred

over nitrogen since ammonia has a positive free energy of formation. A very common

example of the nitridation process used in semiconductor industry is as follows: [2]

3SiCl4(g) + 4NH3(g) → Si3N4(s) + 12HCl(g)

1.3 Classification of CVD Reactors:

Classification on the basis of flow over substrate:

i. Horizontal flow CVD reactor (HFCVD)

ii. Vertical flow CVD reactor (VFCVD)

Classification on the basis of temperature of wall of reactor:

i. Hot wall CVD reactor (HWCVD)

ii. Cold wall CVD reactor (CWCVD)

Classification on the basis of operating pressure of reactor:

i. Atmospheric Pressure CVD reactor (APCVD)

ii. Low Pressure CVD reactor (LPCVD)

iii. Plasma Enhanced CVD reactor (PECVD)

Horizontal flow CVD reactor: In this type of reactor, flow direction of precursors and

carrier gas is parallel to the substrate resulting in the boundary layer formation which

leads to more deposition in the leading edge hence adversely affecting uniformity of the

film formed. Film deposition can be made uniform by inclining the substrate, diluting the

precursor by introducing carrier gas at inlet or rotating the substrate.

3
Vertical flow CVD reactor: In this type of reactor, precursors and carrier gas are

introduced perpendicularly to the substrate which results in infinite residence time of

vapour in the vicinity of substrate; hence forming thicker film compared to horizontal

flow CVD reactor.

Cold Wall CVD reactor: In this type of reactor, the substrate is kept at the higher

temperature compared to the walls of the reactor (TS >> Tw). The advantage of using this

technique is that only heterogeneous nucleation occurs. Due to temperature gradient

within the reactor, vapours start moving away from the substrate resulting in less

deposition. This movement of vapours due to thermal gradient is termed as Soret

Diffusion. Also, CWCVD reactor offers less flexibility on substrate orientation.

Hot Wall CVD reactor: In this type of reactor, the temperature of walls of the reactor

are kept at the same temperature as that of the substrate (TS ≈ Tw). The advantage of this

technique is that Soret Diffusion is not observed. The disadvantage of HWCVD reactor

is that it may result in homogeneous nucleation which would result in formation of flaky

film. In this process, deposition occurs not only on substrate but also on reactor walls

leading to large consumption of precursors.

Atmospheric Pressure CVD reactor: Operating pressure of such reactors is kept close

to atmospheric pressure (1 atm). Advantage of such reactors is that they can be operated

in continuous as well as batch mode. Since no vacuum is needed, therefore the cost of

operation is low. The disadvantage of such reactors is that gas flow dynamics is difficult

to control. APCVD is generally operated as a cold wall reactor and is exposed to impurity.

Such reactors are used for films which do not have high sale value or rate of deposition

has to be very high (1000A/min)

4
Low Pressure CVD reactor: LPCVD reactor is operated at a pressure lower than

atmospheric pressure (about 1/10th of atmospheric pressure). The low pressure CVD

reactors can be operated as both cold wall and hot wall reactors but the latter is preferred.

The disadvantage of low pressure hot walled CVD reactors is that nucleation can happen

anywhere in the reactor but by driving to sufficient low pressure one can minimise

homogeneous nucleation in hot walled low pressure CVD reactor. The advantage of such

reactors is that there is no recirculation. Advantage of LPCVD reactor is that it offers

good step coverage and uniformity compared to APCVD. LPCVD reactors are more

expensive in comparison to APCVD reactors.

Plasma Enhanced CVD: PECVD reactors are generally operated at a pressure which is

about 1/100th of atmospheric pressure. In the PECVD reactor, most of the energy required

for the reaction is provided by a glow discharge plasma produced in precursors. The

colliding ions create a more active substrate surface which along with the produced

reactive species aids the deposition of the film on the substrate. The highly reactive

species enable deposition at a relatively low temperature of 450-650K. PECVD reactions

are less efficient.

1.4 Components of CVD Reactor:

A CVD reactor consists of the following components:

1. Reactor chamber

2. Gas delivering system

3. Vacuum system

4. Energy source

5. Substrate loading mechanism

5
6. Exhaust system

7. In-situ inspection system

8. Process control equipment

9. Exhaust treatment systems

The supply of precursors to the reactor chamber is achieved with the help of gas delivery

system. Reactor chamber is the space in which deposition occurs. The introduction and

removal of substrate is done using substrate loading mechanism. Energy required by the

precursors to react or decompose is provided by the energy source. Other gaseous species

excluding those needed for reaction or deposition are removed with the help of the

vacuum system. Withdrawal of volatile by-products from the reactor is achieved with the

help of exhaust system. Exhaust treatment system is used for treatment or conversion of

gases leaving the reactor to non-toxic compounds before releasing into the atmosphere.

Various process control equipment are needed to control process parameters such as

flowrate, temperature and pressure. In situ inspection system is used to check the quality

of film. Various physicochemical measurable properties are thickness, deposition rate,

uniformity, purity, hardness, density, step coverage, refractive index etc. [3]

1.5 Layer Morphology:

Layer Morphology helps in determination of the physicochemical properties and

practicality of the film. The two main processes that determine the layer morphology are

nucleation and surface diffusion which depend on parameters such as partial pressure of

gaseous species, substrate temperature and total pressure of the reactor. Various analytical

methods implemented to determine layer morphology are AFM, SEM, XRD, etc. Three

main types of morphology are:

6
 i. Epitaxial layers: In epitaxial layers or crystalline film a fine layer of crystals is

grown on a single crystalline substrate. To produce an epitaxial layer it is essential

to have a substrate free of contamination and defect. High temperature (> 700°C)

increases epitaxy as it increases desorption of impurities and surface mobility of

adsorbed precursor species. Equation 1.1 quantifies the diffusion coefficient for

surface diffusion of adsorbed species.

E  (1.1)
Di,adsorbate =Geometry factor  (lattice dimension)2  exp  D   (Attempted jump frequency)
 RT 

For crystalline film, growth rates should be low as surface diffusion has to be fast in

comparison to the new growth initiating species reaching the surface. This permits

adsorbed species to diffuse uniformly throughout the substrate resulting in the

formation of a layer identical to the underlying substrate.

ii. Amorphous layers: In Amorphous layers, precursors reach the surface faster than

the surface diffusion of adsorbed species. Low substrate temperature and high

growth rates favour formation of amorphous films. Etching rate of amorphous films

is higher compared to crystalline films. Amorphous films can be converted to

crystalline films by high temperature annealing of amorphous film.

iii.
Polycrystalline layers: Polycrystalline layers have growth rate between crystalline

and amorphous films and are formed at intermediate temperatures. Polycrystalline

growth is assisted by polycrystalline surfaces where nucleation takes place at various

sites, which leads to the formation of islands. These islands coalesce to form

polycrystalline film. [4]

7
1.6 Applications of CVD:

CVD is one of the most popular methods used for preparation of coatings and films. CVD

offers relatively high deposition rate, high purity along with wide range of precursors that

can be used for deposition. Some of the industrial applications of CVD are as follows:

1. Coatings: One of the early applications of CVD involves deposition of coatings for

erosion protection, wear resistance, temperature resistance and corrosion resistance,

and combination thereof. Certain nitrides and carbides provide wear resistance. CVD

coatings are also used to reduce friction. Most common application for CVD coating

is metal forming tools.

2. Semiconductors and optoelectronics: CVD processes are used for deposition of

films of the semiconductor material such as doped germanium, silicon, etc., insulating

dielectrics such as SiO2, conductive interconnects such as tungsten. Optoelectronic

components like solid state diode lasers are often grown by CVD. Ga-As &

amorphous polysilicon are used in some photovoltaic devices and integrated circuits.

3. Composites: CVD techniques are used to manufacture ceramic composites like

silicon carbide-silicon carbide, carbon silicon carbide and carbon-carbon composites.

This process is referred as CVI (Chemical Vapour Infiltration). Ceramic Matrix

Composites (CMC) are light weight, high temperature and corrosion resistant

materials that are substituting high nickel super alloys in certain applications like

industrial power turbines.

4. Catalyst: CVD is a feasible choice for surface modification of a variety of nano

structured catalysts and carbon nanotube synthesis. Chemical vapour deposition

shows great advantage over conventional wet methods for preparation of supported

catalyst.[5]

8
1.7 Objective of the work:

1. To set up a 2-dimensional simulation for steady state deposition of silicon carbide

from gas mixtures containing MTS-H2-Ar on ANSYS FLUENT.

2. To find optimum combination of operating parameters using Design expert.

3. Mathematical Modelling of uniformity of deposition and rate of deposition on

substrate.

4. To develop a 3-dimensional reactor scale CFD theoretical model running at

optimum conditions obtained from a 2-dimensional model which describes gas flow,

heat transfer and mass transfer.

9
 Chapter: 2

Thermodynamics and Transport Phenomena

2.1 Effect of Operating Parameters:

Many steps involved in the CVD process are transport related. Although, the effect of

transport phenomena is a function of the process parameters like substrate temperature,

flowrate, reactants partial pressure and the reaction chemistry involved. These parameters

determine whether the deposition process is kinetic controlled, diffusion controlled or

thermodynamic controlled. Figure 2.1 represents the series of steps involved in a CVD

process.

Figure 2.1: Schematic representation of series of steps involved in CVD

In a mass transport limited process, the diffusion or transport of reactant to the substrate

surface i.e. step 3 or step 8 are the slowest hence rate determining steps. In transport

limited process deposition characteristics are determined by diffusion of reactants, heat

10
transfer and fluid flow. In a kinetic limited step, surface processes are the slowest i.e.

steps 4-7 are not as fast as step 1 or 9 and 3 or 8. In this regime, fluid flow has a marginal

effect whereas substrate temperature has a significant effect. In a thermodynamic

controlled regime, mass transfer towards and away from the substrate is much slower than

any other step i.e. rate controlling steps are the step 1 and step 9.

Temperature is the key parameter in kinetically controlled regime and flowrate is the key

parameter in transport controlled regime. Generally at low temperatures, the process is

kinetically controlled and at high temperature it is transport controlled. To check if the

operating regime is transport controlled or kinetic controlled, deposition vs temperature

curve or deposition vs velocity curve is plotted as shown in figure 2.2. Region on the left

side of the red line in figure 2.2 represents transport limited and that on the right side

represents kinetically controlled.

Figure 2.2: Graph of deposition vs velocity and temperature

11
In mass transport limited process, the controlling factors are diffusion of reactants across

the boundary layer and volatile by-products out of this layer. It mostly happens at high

pressure and temperature as decomposition of reactants occurs more rapidly and also

molecules reaching the surface react immediately. Hence, velocity is low making the

boundary layer thicker making which results in less reactants reaching the deposited

surface.

When the process is surface reaction controlled, the rate of the reaction depends upon the

concentration of reactant gas. This usually happens at low temperature and pressure, as

reaction occurs slowly and due to thin boundary layer reactants diffuse to the surface with

ease.

Damköhler number is used to determine whether the process is kinetic controlled or

transport controlled. Damköhler number is the ratio of surface reaction rate to diffusion

flux and is given as,

rs
DaII = (2.1)
JD

For a typical CVD reactor Damköhler number varies from 10 -3 to 103. If DaII >>1, it

means the surface reaction is faster compared to diffusion and hence the process is

transport controlled and if DaII <<1, it means the process is kinetic controlled.

At a very low flowrate the reactants residence time is high enough to equilibrate with the

substrate. The deposition is thermodynamically limited and increases linearly with flow

rate. At increased flowrates diffusional transfer becomes the rate controlling. At

sufficiently high flowrates, the decomposition becomes kinetically controlled and is

independent of the total flowrate. Thus, in order to optimise the CVD reactor, a profound

knowledge of transport phenomena, gas and surface chemical reactions is needed. [6]
12
2.2 Governing Equations:

This part deals with the general conservation equations of energy, momentum, overall

mass and individual elements. Flow is assumed to be incompressible, continuum, laminar

and Eulerian control volume is used. The general form of these equations in differential

control volume is:

b
  F  BV (2.2)
t

⃗⃗ is
In the above equation b is field density (or conserved quantity per unit volume), 𝑭

conserved quantity flux (consist of both convective and diffusive terms) and BV is

generation of conserved quantity per unit volume.

Table 2.1: Equations of conservation of mass, energy, momentum and species

Equation Field density Conserved quantity flux Generation

𝑸𝒖𝒂𝒏𝒕𝒊𝒕𝒚 𝑸𝒖𝒂𝒏𝒕𝒊𝒕𝒚 𝑮𝒆𝒏𝒆𝒓𝒂𝒕𝒊𝒐𝒏

𝑽𝒐𝒍𝒖𝒎𝒆 (𝑨𝒓𝒆𝒂)(𝒕𝒊𝒎𝒆) 𝑽𝒐𝒍𝒖𝒎𝒆

Diffusive Flux Convective

Flux

Mass balance 𝜌 0 𝜌𝑢
⃗⃗ 0

Species 𝜌𝜔 𝑗𝑖 𝜌𝜔𝑢
⃗⃗ 𝑀𝑖 𝑅𝑖

balance

Momentum 𝜌𝑢
⃗⃗ 𝜋 𝜌𝑢
⃗⃗𝑢
⃗⃗ 𝜌𝑖 ⃗⃗⃗⃗
𝑔𝑖

13
 Energy 𝜌𝑐𝑝 𝑇 𝑘∇𝑇 𝑐𝑝 𝜌𝑢
⃗⃗𝑇 𝑆

Equations for a multicomponent mixture are given as follows:

Continuity:


  u  0 (2.3)
t

Chemical species:

i g

  i u   ji   M i Rig  0
n
(2.4)
t j 1 ij

ji  jic  jip  jig  jit (2.5)


i 1
i 1 (2.6)

𝒑
In equation 2.5, 𝒋𝒊 represents the diffusive flux of ith species due to pressure gradient.

𝒈
Generally this flux is negligible in CVD reactors. The forced diffusion term 𝒋𝒊 is also

zero if there is no external force other than gravity. According to Wilke, the diffusional

flux 𝒋𝒊 is given as:

ji    Di i  DT ,i  ln T (2.7)

The first term in the equation 2.7 represents diffusion due to concentration gradient and

the second term represents Soret diffusion or thermal diffusion.

14
 1  xi
Di  (2.8)
n  
x
  i
j 1  Di , j

 i j

The diffusion coefficient for a binary mixture 𝑫𝒊𝒋 is given by Chapman-Enskog formula.

In the equation 𝜺 𝒂𝒏𝒅 𝝈 are the characteristic energy and collision diameter of the

molecule respectively and is usually obtained from Lennard-Jones potential. [7]

3  1 1  2 R3T 3
Dij     (2.9)
16  M i M j  N  2  K BT 
 
  ij
A


The thermo-diffusion coefficient is given by

n
c2
DT ,i   M i M j Dij KijT (2.10)
j i 

Using diluted species in horizontal flow CVD (𝜔𝑖 → 0), makes the Wilke’s

approximation same as Stefan Maxwell equation which can be written as: [8]

N Xi X j T N X i X j  DT , j DT ,i 

j 1, j i Dij
(V j  Vi )  di 
T

j 1, j i

Dij   j

i 
 (2.11)

Momentum:

 u
 
n
   uu     i gi  0 (2.12)
t i 1

    p (2.13)

 
 2 
   u  u    k    ( u )
T
(2.14)
  3  

15
Energy:

  cPT  p
 
N N SP NRe act
Sp
DiT n
Hi
     c p  uT    K T    RT   ln i   ji    ij H i RJ    u  S
 t  t i 1 M i i 1 M i i 1 j 1

(2.15)

In case of CVD operations which deal with low Mach number (Ma < 0.3) and low viscous

flow, effect of change of pressure on temperature and viscous energy dissipation are

negligible. Dufour effect and inter diffusion results in little influence on energy flux at

normal conditions. Hence equation 2.15 can be rewritten as:

T N N Re act
cP  cP   uT    K T    ij H i R j  S (2.16)
t i 1 j 1

2.3 Thermodynamics of CVD:

Chemical thermodynamics deals with the inter conversion of one form of energy to

another as well as transport of energy between chemical systems. For Chemical Vapour

Deposition, the transport of energy takes place when the gaseous reactants enter the

reactor and heterogeneous reaction on substrate takes place.

2.3.1 Reaction Feasibility:

The first step in the CVD reactor taken into account is to determine the viability of the

chemical reaction. To determine the feasibility of reaction free energy is calculated. The

reaction of the CVD process is said to be thermodynamically favourable only when the

free energy is negative (ΔGrxn <0). Gibbs free energy is calculated by the formula:

Grxn   G f , products  G f ,reac tan ts (2.17)

Gibbs free energy of the species can be determined by the equation 2.18:

16
 T T
cP
G f (T )  H f (298)   c dT  TS (298)  
298
P
298
T
dT (2.18)

JANAF tables are used for determining the thermodynamic data such as Gibbs free

energy, enthalpy, entropy, and specific heat. Precise values of specific heat and entropy

can be calculated theoretically.

The Gibbs free energy of formation depends on various factors like temperature, pressure,

mole ratio and nature of precursors.

Grxn  Grxn  RT ln K (2.19)

Grxn  i G f ,i (2.20)

K   ai (2.21)

Out of all probable chemical reactions the one having highest negative free energy forms

the most stable products. Also free energy analysis helps in selecting the precursor for the

given CVD process. Along with this, precursors have to be stable enough to get

transferred at lower temperature. [9]

2.4 Kinetics of CVD Process:

In this, the rapidity with which reaction proceeds is studied. For a reaction,

𝒂𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫

The rate of reaction is given by equation 2.22,

1 d [ A] 1 d [ B] 1 d [C ] 1 d [ D]
    (2.22)
a dt b dt c dt d dt

17
For the reactions taking place at constant temperature and which are far away from

equilibrium the reaction rate is given by rate law expression,

1 d  A
  k  A  B 
P q
(2.23)
a dt

Where, p and q are order of reaction with respect to A and B respectively and p+q is the

overall order of reaction. k is called the reaction rate constant and it incorporates the

temperature effect of the reaction. Quantitative relationship between reaction rate

constant and temperature is given by Arrhenius equation,

 E 
k  A exp  A  (2.24)
 RT 

Sometimes, the temperature dependence deviates appreciably from Arrhenius equation

and in order to take this effect into account, modified Arrhenius equation has to be applied

for calculation of rate constant,

 E 
k  AT  exp  A  (2.25)
 RT 

2.4.1 Surface Chemistry:

The detailed surface chemistry model includes the adsorption of reactants and

intermediates, reaction of adsorbed species to form new species and desorption of

reaction by products. It is almost impossible to quantify a model that is effective for all

conditions as the process is very complex. Hence simplified semi-empirical models are

applied. Surface reaction can be generally written as,

18
 𝑵𝒈 𝑵𝑺 𝑵𝒃

∑ 𝒂′𝒊 𝑨′𝒊 (𝒈) + ∑ 𝒃′𝒊 𝑩′𝒊 (𝒔) + ∑ 𝒄′𝒊 𝑪′𝒊 (𝒃)

𝒊=𝟏 𝒊=𝟏 𝒊=𝟏

𝑵𝒈 𝑵𝑺 𝑵𝒃

↔ ∑ 𝒂′′ ′′ ′′ ′′ ′′ ′′
𝒊 𝑨𝒊 (𝒈) + ∑ 𝒃𝒊 𝑩𝒊 (𝒔) + ∑ 𝒄𝒊 𝑪𝒊 (𝒃)
𝒊=𝟏 𝒊=𝟏 𝒊=𝟏

The net surface reaction rate is expressed as,

NG NS NG NS
ai' bi' ai'' bi''
rf  k f   Ai'    Bi'   kr   Ai''    Bi''  (2.26)
i 1 i 1 i 1 i 1

Sometimes surface reaction rate also depends on the surface coverage and pressure of few

components. For such cases surface reaction rate are specified in terms of sticking

coefficient or by Langmuir isotherms. In the Langmuir model it is assumed that the

adsorption and desorption are not dependent on the fraction of occupied sites and number

of finite sites are constant. Therefore at equilibrium, [10]

 E    Edes 
pi bi (1   ) exp  ads   b2 exp   (2.27)
 RT   RT 

api
 (2.28)
1  bpi

19
 CHAPTER: 3

Modelling of 2-D CVD Reactor

3.1 Introduction:

Computer simulations which drastically reduce scale-up and experimental efforts are used

by engineers worldwide to evaluate numerous reactor designs and effects of operating

parameters on various film properties. In laminar flow chemical vapour deposition,

accurate modelling of time dependent hydrodynamics, mass transfer, chemical reactions-

both surface phase and gas phase and heat transfer is important. The model incorporates

complexities of industrial reactors and the effect of the temperature, pressure, mole ratio

and flowrate of gas.

3.2 Problem Description:

In the present study, a horizontal flow, low pressured, hot wall CVD reactor for growth

of silicon carbide was modelled. The process gases, methyl-trichloro-silane (MTS) and

hydrogen (H2) entered the reactor at 353K from two 9mm diameter inlet pipe at bottom.

These gases flown over hot cone shaped substrate depositing a thin layer of silicon carbide

on it in a uniform, repeatable manner. These gases flown in a laminar manner inside the

reactor and finally discharged out of the reactor through a long pipe of diameter 80mm.

The surface deposition on the heated surface was given by 2-step rate mechanism which

is as follows:

𝑪𝒍𝟑 𝑺𝒊𝑪𝑯𝟑 + 𝑯𝟐 → 𝑺𝒊𝑪𝒍𝟐 + 𝑪𝑯𝟒 + 𝑯𝑪𝒍

20
 𝑺𝒊𝑪𝒍𝟐 + 𝑪𝑯𝟒 → 𝑺𝒊𝑪 + 𝟐𝑯𝑪𝒍 + 𝑯𝟐

The inlet gas was a mixture of methyl-trichloro-silane, hydrogen and argon. Flowrate of

MTS in the inlet feed is 600mg/hr and rest is H2 and Ar. The mole ratio of H2:Ar was

varied from 0.2 to 1.5. Flowrate of gas was also varied from 100lph to 200lph. Operating

pressure of the reactor was varied from 100mbar to 300mbar. The wall of the reactor and

susceptor both were kept at the same temperature and was varied from 850°C to 1400°C.

The operating parameters and their range is summarised in the table below:

Table 3.1: Reactor operating parameters and their range

Parameters Range

Flowrate 100-200 lSTP/hr

Pressure 100-300 mbar

Temperature 850-1400 °C

Feed gas mixture 600mg/hr MTS

0.2-1.5 H2:Ar

Substrate dimensions Diameter of top face = 100mm

Height of cone = 400mm

Diameter of bottom face = 250mm

21
3.3 Geometry:

The 2-D reactor geometry used for running 32 simulations was created using ANSYS

SpaceClaim. The dimensions of the geometry are shown in the figure. The reactor has

an inlet nozzle of 9mm and two such nozzles were taken on the plane of the reactor. The

substrate is cone shaped with upper diameter as 100mm and bottom diameter as 250mm

and height of the cone is 400mm. The inner diameter of the outlet is taken as 80mm. The

inner diameter of the reactor is 540mm. Before exporting the model to ANSYS Meshing,

tools like fit curves, curve gaps, duplicate curves, and small curves were used to repair

the geometry. Metric type of units with millimetre as length was used for the geometry

creation.

Figure 3.1: 2-Dimensional geometry of CVD reactor

3.4 Mesh:

A quadrilateral dominant method with free face mesh type as quad/tri was used for

meshing. Since the flow was laminar therefore there was no need for inflations at

boundaries. The size of the element was taken to be 4.5mm and element order was kept

22
linear. The total number of elements were 33122. The maximum skewness of the mesh

was 0.6 which was far away from the upper limit of 0.98. Similarly, the aspect ratio value

was 2.4738 which was also far from the upper value of 11. Meshed 2-D geometry is

shown in figure. Grid independency test was also carried out and a graph of uniformity

and number of elements is plotted. It was observed that variation of uniformity index with

number of elements was less than 1%.

Figure 3.2: Meshed geometry of 2-D CVD reactor

Table 3.2: Grid independency test readings

Number of elements Uniformity Index

33900 0.8571

54309 0.8637

74166 0.8562

106533 0.8635

23
 1.0
0.9
0.8
Uniformity Index

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
40000 60000 80000 100000 120000
Number of elements

Figure 3.3: Graph of uniformity index vs number of elements

3.5 Setup:

3.5.1 Solver: A pressure based steady state solver was used along with planar spatial

definition in 2D space list. The direction of gravity was specified in y direction as -9.81

m/s2. None- explicit source chemistry solver was used for chemical reaction solver.

3.5.2 Model Specification: This problem solved energy, continuity, momentum, and

species conservation equations were solved. In species model-diffusion energy source,

full multicomponent diffusion and thermal diffusion were enabled along with heat of

surface reaction and mass deposition on surface. Diffusion energy enables the effect of

enthalpy transport caused by diffusion of species in the energy equation. Full

multicomponent diffusion incorporates Stefan-Maxwell equation and calculates the

24
diffusive fluxes for each constituent in the mixture with respect to the concentration

gradients. Thermal diffusion causes lighter components to diffuse more quickly towards

the heated surface compared to heavy molecules. The flow was modelled as laminar flow

since the Reynolds number is less than 2300.

3.5.3 Materials and Properties: Gas phase species methyl-trichloro-silane, hydrogen,

argon, methane, silicon dichloride and hydrogen chloride were selected from ANSYS

Fluent database. Properties of the species are listed in the table 3.4. Chemical kinetics

was modelled as 2-step mechanism given by following reaction using the reaction

parameters stated in table 3.3:

𝑪𝒍𝟑 𝑺𝒊𝑪𝑯𝟑 + 𝑯𝟐 → 𝑺𝒊𝑪𝒍𝟐 + 𝑪𝑯𝟒 + 𝑯𝑪𝒍

𝑺𝒊𝑪𝒍𝟐 + 𝑪𝑯𝟒 → 𝑺𝒊𝑪 + 𝟐𝑯𝑪𝒍 + 𝑯𝟐

Rate of reaction of the above reactions is given by,

r1  k1  MTS   H 2 
1 0.1
(3.1)

r2  k2  SiCl2  CH 4 

0.25 0.25
(3.2)

In the above equation k1 and k2 are given by modified Arrhenius theory and are calculated

by,

 E 
k  AT  exp  A  (3.3)
 RT 

Where, A is pre-exponential factor (PEF)

β is temperature exponent (TE)

25
EA is activation energy (AE)

Table 3.3: Reaction parameters

Parameters Volumetric Reaction Surface Reaction

Number of Reactants 2 2

Species cl3sich3, h2 sicl2, ch4

Stoichiometric cl3sich3 = 1, h2 = 1 sicl2 = 1, ch4 = 1

Coefficient

Rate Exponent cl3sich3 = 1, h2 = 0.1 sicl2 = 0.25, ch4 = 0.25

Arrhenius Rate PEF = 1e+15, AE = PEF = 2.815e-04, AE =

1.2e+08, TE = 0 5e+07, TE = 0

Number of Products 3 3

Species sicl2, ch4, hcl sic, hcl, h2

Stoichiometric sicl2 = 1, ch4 = 1, hcl = 1 sic = 1, hcl = 2, h2 =1

Coefficient

Rate Exponent sicl2 = 0, ch4= 0, hcl = 0 sic = 0, hcl = 0, h2 =0

26
 Table 3.4: Properties of species

Parameters Cl3SiCH3 H2 Ar HCl

Name Methyl- Hydrogen Argon Hydrogen

trichloro-silane Chloride

Specific Heat Piecewise- Piecewise- Piecewise- Piecewise-

polynomial Polynomial Polynomial Polynomial

Thermal Kinetic-Theory Kinetic-Theory Kinetic-Theory Kinetic-Theory

conductivity

Viscosity Kinetic-Theory Kinetic-Theory Kinetic-Theory Kinetic-Theory

Molecular 149.4801 2.01594 39.948 36.46097

Weight

Standard -5.76e+08 0 -3117.711 -9.232e+07

Enthalpy

Standard 356831.3 130579.1 154719.3 186797.8

Entropy

L-J Energy 100 38 100 100

Parameter

Characteristic
4 2.92 4 4
length

27
 Parameters CH4 SiCl2 SiC

Name Methane Silicon Dichloride Silicon Carbide

Specific Heat Piecewise- Piecewise- Constant

Polynomial Polynomial

Thermal Kinetic Theory Kinetic Theory Kinetic Theory

Conductivity

Viscosity Kinetic Theory Kinetic Theory Kinetic Theory

Molecular Weight 16.04303 98.992 40.09715

Standard -7.49e+07 -1.686e+08 7.1971e+08

Enthalpy

Standard Entropy 186040.1 281180.1 213110.8

L-J Energy 148.6 0 0

Parameter

Characteristic
3.758 4 0
Length

28
For a gas mixture, the incompressible ideal gas was adopted. The density variation of the

flow primarily happens due to temperature variation and is given by following expression:

P
 (3.4)
y
RT  i
M W ,i

Specific heat of the mixture was calculated by the mixing law which was mathematically

given by,

cP   yi c p ,i (3.5)

Thermal conductivity and viscosity of the mixture were calculated by following

expression,

k   yi ki (3.6)

   yi i (3.7)

Mass diffusivity and thermal diffusion coefficient were calculated by kinetic theory.

3.5.4 Boundary Conditions: Mass flow inlet boundary condition was specified for both

the inlets as flowrate was specified in standard temperature and pressure conditions

(STP). Pressure –outlet type of boundary condition was specified to outlet and prevent

reverse flow condition was given as long pipe was used for the same. Outer wall, substrate

and rotor all were kept at the same temperature and no slip boundary condition was given

as Knudsen Number was less than 0.01. Zero reaction rates for each of the chemical

species was used for reactor walls and inner heating walls. Boundary conditions for

various zones are summarised in table 3.5.

29
 
Kn  (3.8)
DC

K BT
 (3.9)
2 d 2 P

Table 3.5: Boundary conditions

Zone Boundary Condition

Inlet velocity Dirichlet condition, mass flow inlet

Inlet temperature Dirichlet condition, inlet temperature

Temperature at reactor wall Isothermal condition, wall temperature

Velocity at reactor wall No-slip condition, u=0

Temperature at substrate wall Isothermal condition, wall temperature

Velocity at substrate wall No slip condition, u=0

Surface Reaction at substrate Enabled, Mechanism-1

Temperature at rotor wall Isothermal condition, wall temperature

Surface reaction at rotor wall Enabled, Mechanism-1

Outlet Pressure outlet

3.6 Solution:

30
Coupled scheme was used for pressure velocity coupling. Momentum, energy and species

were solved using second order upwind technique and pressure was solved using second

order scheme. Least square gradient spatial discretization was used for evaluation of

gradients and derivatives.

The pressure based coupled algorithm solved a coupled system of equations consisting of

momentum equations and pressure based continuity equations. Rest of the equations were

solved in the decoupled manner as solved in the segregated model. ANSYS FLUENT

uses a control volume based technique to convert a general scalar transport equation to

an algebraic equation that can be solved numerically. General integrated and

differentiated form of scalar transport equation is given by, [11]


 t
dV    u  d A      d A   S dV (3.10)


    u       S (3.11)
t

Where,

Table 3.6: Variables depicting ∅ in scalar transport equation

Equation ∅

Continuity 1

x-momentum u

y-momentum v

Energy h

31
The equation was applied to each control volume or element in the computational domain.

Since the reactor was operated at steady state therefore first term could be neglected from

the equation and the equation in 2-D becomes:

 u  v        
         S (3.12)
x y x  x  y  y 

On integrating above equation for element,

 u  v        
n e n e n e n e n e

s w x dxdy  s w y dxdy  s w x   x dxdy  s w y   y dxdy  s w Sdxdy

(3.13)

𝚻
Taking 𝜌u as F and 𝛿𝑥∅ as De we get,

               
Fee y  Fwwy  Fnn x  Fss x   e     w    y    n     s    x  S xy
  y   y s 
  x e  x w   n

(3.14)

The calculation of Φe, Φw, Φn and Φs were done by second order upwind scheme and for

𝝏∅ 𝝏∅ 𝝏∅ 𝝏∅
all schemes (𝝏𝒙) , (𝝏𝒙) , (𝝏𝒚) , (𝝏𝒚) were calculated using centre difference scheme.
𝒆 𝒘 𝒏 𝒔

      
e    e  E P  (3.15)
 x e  x 

e
De  (3.16)
x

Similarly other gradients were also found and the equation reduces to

aPP   Nb  b (3.17)

NB

32
Where ∑Nb depicts sum of neighbouring cells. Under relaxation factors for momentum,

pressure, all species and energy were kept at default values.

3.7 Results:

3.7.1 Effect of temperature on overall deposition:

The net deposition on the substrate was the result of both surface reaction and mass

transfer process. Since both the steps were in series therefore slower of the two dominated

at particular temperature. Generally, at lower temperatures surface kinetics was the

limiting step and diffusion was rate limiting at higher temperature. Therefore, it was

possible to switch from a kinetically controlled regime to a transport controlled regime

just by changing the temperature. In practice the crossover temperature and the

temperature range for different regimes depend on various factors, such as precursors,

activation energy of reaction, pressure and flow condition in the reactor. It can be seen

from figure 3.4 that the deposition was controlled by surface reaction kinetics in

temperature range of 575°C -1000°C and was transport controlled beyond 1000°C.

Temperature and its effect on deposition rate (both rotor and cone wall deposition) at

200mbar pressure, 150lph flowrate and 0.85 H2:Ar is summarised in table 3.7.

Table 3.7: Effect of temperature on overall deposition

Temperature (°C) Overall Deposition Rate (mg/hr)

575 56.88

750 117

33
 850 144

1000 158.76

1125 161.64

1400 162.72

1675 163.26

2.2
log Deposition

2.0

1.8

1.6

0.2 0.4 0.6 0.8 1.0 1.2 1.4

1000/T (1/K)

Figure 3.4: Graph of deposition rate vs 1/T

3.7.2 Effect of temperature on substrate deposition alone:

It was observed that the deposition on a substrate surface first increased and then

decreased with increase in temperature as more deposition occurred on the rotor wall than

34
on the substrate wall at high temperature. Figure 3.5 shows the deposition of silicon

carbide on substrate as a function of temperature. Maximum deposition of silicon carbide

on substrate occurred at 850°C. A case comparison contour of deposition at 850°C and

1000°C is also shown. In fig. the top left photo represents surface deposition rate at 850°C

and top right represents surface deposition rate at 1000°C. The surface deposition rate

difference contour at bottom shows that deposition rate on rotor wall increases with

increase in temperature and that on substrate wall decreases. Table 3.8 summarises the

same.

80
Deposition on substrate (mg/hr)

70

60

50

40

30

20

10

0
0 500 1000 1500 2000
Temperature (K)

Figure 3.5: Graph of Substrate Deposition vs Temperature

35
Figure 3.6: Case Comparison Study for surface deposition rate at 850°C and

1000°C

Table 3.8: Effect of temperature on rotor and substrate wall deposition

Surface Deposition
Temperature
Deposition on rotor wall Deposition on substrate wall

850°C 67.68 73.62

1000°C 86.4 69.804

36
3.7.3 Effect of pressure on overall deposition:

In kinetically controlled regime as pressure increases overall deposition at substrate and

rotor together should increase as reaction rate increases whereas in transport controlled

regime lowering pressure increases deposition rate as diffusivity varies inversely with

deposition. Effect of pressure on overall deposition in both kinetic controlled regime and

transport controlled regime is shown in figure 3.7. Figure 3.7 was drawn for flow rate of

150 standard litre per hour and mole ratio of 0.85.

Overall Deposition (mg/hr)

150

100

100 mbar
50 200 mbar
300 mbar

500 1000 1500 2000

Temperature (C)

Figure 3.7: Graph of overall deposition vs temperature for different pressure

3.7.4 Effect of pressure on substrate deposition:

In a kinetically controlled regime as pressure increases deposition on substrate also

increases. The same is shown in figure 3.8, whereas in transport controlled regime as

37
pressure increases deposition on substrate decreases as shown in figure 3.9. Both graphs

were drawn for flowrate of 200 standard litre per hour and mole ratio of 1.5.

80
Deposition (mg/hr)

60

40

20

0
100 200 300
Pressure (mbar)

Figure 3.8: Graph of substrate deposition vs pressure in kinetic controlled regime

38
 75

60
Deposition (mg/hr)

45

30

15

0
100 200 300
Pressure (mbar)

Figure 3.9: Graph of substrate deposition vs pressure in transport controlled

regime

3.7.5 Effect of flowrate on substrate deposition:

As flowrate increases in kinetic controlled regime, residence time of precursors decreases

in the reactor and therefore less deposition of silicon carbide is observed. The same is

shown in figure 3.10, whereas as when flowrate increases in transport controlled regime

boundary layer thickness decreases hence substrate deposition increases as shown in

figure 3.11. Boundary layer thickness is inversely proportional to velocity of precursors

in the reactor. Therefore increasing flowrate in transport controlled regime favours the

deposition on substrate.

x
 (3.18)
Re x

39
  ux
Re x  (3.19)


90
Substrate Deposition (mg/hr)

75

60

45

30

15

0
100 150 200 250
Flowrate (lph)

Figure 3.10: Graph of substrate deposition vs flowrate in kinetic controlled regime

40
 Substrate Deposition (mg/hr) 61

60

59

58

100 150 200 250

Flowrate (lph)

Figure 3.11: Graph of substrate deposition vs flowrate in transport controlled

regime

3.7.6 Effect of mole ratio of H2:Ar:

As mole ratio or concentration of H2 in carrier gas had negligible effect in overall

deposition in kinetic controlled regime as MTS was the limiting reactant whereas

substrate deposition increased slightly with increase in mole ratio of H2:Ar. Increase in

concentration of hydrogen in carrier gas also led to increase in uniformity which is

discussed later. Figure 3.12 shows the increase in substrate deposition with increase in

H2:Ar ratio. This is because with increase in heavier gas concentration in carrier gas,

deposition rate increases along the axial distance up to a certain height and then starts

decreasing due to consumption of SiCl2 and CH4. The same is suggested by Teng Yin et

al. in their work [12]. Also surface deposition rate curves are shown for different mole ratio

in figure 3.14.
41
 70
Substrate Deposition (mg/hr)

68

66

64

62
0.0 0.5 1.0 1.5
Mole Ratio (H2:Ar)

Figure 3.12: Graph of substrate deposition vs mole ratio in kinetic controlled

regime

140
Overall Deposition (mg/hr)

120

100

80

60

40

20

0
0.0 0.5 1.0 1.5
Mole Ratio (H2:Ar)
-

Figure 3.13: Graph of overall deposition vs mole ratio in kinetic controlled regime

42
 Figure 3.14 (a): H2:Ar = 0.2

Figure 3.14 (b): H2:Ar = 0.85

Figure 3.14 (c): H2:Ar = 1.5

Figure 3.14: Graph of surface deposition rate for different mole ratio

43
 180

Overall Deposition (mg/hr) 160

140

120

100
0.0 0.5 1.0 1.5
Mole Ratio (H2:Ar)

Figure 3.15: Graph of overall deposition vs mole ratio in transport controlled

regime
Substrate Deposition (mg/hr)

60

58

56

54
0.0 0.5 1.0 1.5
Mole Ratio (H2:Ar)

Figure 3.16: Graph of substrate deposition vs mole ratio in transport controlled

regime

44
3.7.7 Effect of mole ratio on uniformity:

As mole ratio or concentration of H2 in carrier gas increased, uniformity of silicon carbide

film increased. Hydrogen improved the stability of the flow field and also the reactant

distribution was much more uniform in hydrogen as compared to argon. The same is

shown in the figures 3.17 and 3.18. The figures 3.17 and 3.18 were drawn for operating

pressure of 100mbar, substrate and wall temperature of 850°C and flowrate of 200lph.

98

96
Uniformity Index (%)

94

92

90 Substrate Deposition
Overall Deposition
88
0.0 0.5 1.0 1.5
Mole Ratio (H2:Ar)

Figure 3.17: Graph of uniformity index vs Mole ratio for kinetic controlled regime

45
 Uniformity Index (%) 72

70

68
Substrate Deposition
Overall Deposition

0.0 0.5 1.0 1.5

Mole Ratio (H2:Ar)

Figure 3.18: Graph of uniformity index vs mole ratio for transport controlled

regime

3.7.8 Effect of temperature on uniformity:

As temperature was increased, uniformity of deposition decreased irrespective of the

regime in which the reactor was operating. The same is shown in figure 3.19. This was

due to decrease in precursor concentration along axial direction resulted from deposition

substrate and rotor wall.

46
 100

90
Uniformity Index (%)

80

70

60 Substrate Uniformity
Overall Uniformity
50
500 1000 1500
Temperature (C)

Figure 3.19: Graph of uniformity index vs temperature

3.7.9 Effect of pressure on uniformity:

As pressure increased, uniformity of SiC film decreased in both kinetic as well as

transport controlled regime. At high pressure reaction rate increases and concentration of

precursor decreases along the length of the reactor. Also, increase of pressure results in

more recirculation within the reactor hence adversely affecting the uniformity. The same

is shown in figure 3.20 and 3.21.

47
 98

Uniformity Index (%) 96

94

92

90

88 Substrate Uniformity
Overall Uniformity
86
100 200 300
Pressure (mbar)

Figure 3.20: Graph of uniformity index vs pressure in kinetic controlled regime

75
Uniformity Index (%)

70

65

60
Substrate Deposition
Overall Deposition
55
100 200 300
Pressure (mbar)

Figure 3.21: Graph of uniformity index vs pressure in transport controlled

48
3.7.10 Effect of flowrate on uniformity:

As flowrate increased, overall as well as substrate uniformity increased for the transport

limited regime whereas for kinetic controlled regime flowrate had insignificant effect on

uniformity of film. It was observed that uniformity index was more sensitive to flow rate

in transport controlled regime in comparison to kinetic regime. The same could be seen

in figure 3.22 and 3.23.

73
Uniformity Index (%)

72

71

70
Substrate Uniformity
Overall Unifromity
69
100 150 200 250
Flowrate (lph)

Figure 3.22: Graph of uniformity index of deposition vs flowrate for transport

controlled regime

49
 Uniformity Index (%) 98

96

94

92
Substrate Uniformity
Overall Uniformity
90
100 150 200 250
Flowrate (lph)

Figure 3.23: Graph of uniformity index of deposition vs flowrate for kinetic

controlled regime

50
 CHAPTER: 4

Mathematical Modelling Using Design Expert

4.1 Introduction:

An effective method for describing the combined effect of various factors is Response

Surface Methodology (RSM) - a group of mathematical techniques and statistical data

used for process optimisation. Central Composite Design and Box-Behnken Design are

the two major factorial designs, used to assess response surface and for developing

models. The most important benefit of this technique is the reduction in the number of

experimental trials required to estimate the effect of various factors as well as the

corresponding interactions. It is extensively used in literature to optimize the CVD

processes. Ramadan Z. used the RSM technique in his research paper for optimization of
[13]
operating parameters in planetary CVD reactor. Alledin also used RSM to examine

and optimise the effects of operating parameters on the synthesis of Nano carbons in a

CVD reactor. [14]

In the present work, Response Surface Methodology was employed to examine the impact

of operating parameters i.e. inlet flowrate, mole ratio of H2:Ar, operating temperature and

reactor pressure on silicon carbide deposition and uniformity. 30 runs were performed to

create the design of experiments as shown in table 4.1. Anova was employed to evaluate

contribution of process parameters and their interactions. The optimised parameters were

eventually obtained for maximising the SiC deposition and uniformity.

4.2 Analysis of Results:

The statistical tests- F-value, P-value, R-squared value, predicted R-squared value and

adjusted R-squared value were used to indicate the goodness of fit of the model. The

51
model with P-value less than 0.05 was considered to be statistically significant. P-value

greater than 0.1 indicated model terms were not significant. The R-squared value ranges

from 0 to 1 and has better prediction when R-squared values are close or equal to 1. Also,

closeness of value of Adjusted R-squared and predicted R-squared is an indicator of

goodness of fit of the model. Plot of predicted response values and actual response values

were used to detect the values that were not easily predicted by the model.

Table 4.1: Table for experimental trials

Response Response
Factor 1 Factor 2 Factor 3 Factor 4
1 2

D:mole
Run A:Temperature B:Pressure C:Flowrate Uniformity Deposition
ratio

Celsius mbar slph mg/hr

1 1125 100 150 0.85 0.8384 71.712

2 1125 200 150 0.85 0.7406 58.608

3 1125 200 200 0.85 0.7532 59.976

4 1125 300 150 0.85 0.6757 49.428

5 1400 300 100 0.2 0.5505 30.438

6 1125 200 150 0.85 0.7406 58.608

7 850 100 200 0.2 0.9514 66.204

8 850 100 200 1.5 0.9639 67.356

52
9 850 300 200 1.5 0.9172 75.132

10 1125 200 150 0.85 0.7406 58.608

11 850 100 100 1.5 0.9634 76.88

12 1125 200 150 2.15 0.7785 64.478

13 1125 200 250 0.85 0.7653 61.452

14 1400 300 200 1.5 0.5985 41.288

15 850 100 100 0.2 0.9473 74.016

16 1675 200 150 0.85 0.5632 39.636

17 1125 200 150 0.85 0.7406 58.608

18 1125 400 150 0.85 0.6444 43.477

19 1400 300 200 0.2 0.5845 32.878

20 1400 100 100 1.5 0.6989 58.14

21 850 300 100 1.5 0.9092 77.904

22 1400 100 200 1.5 0.719 60.12

23 1400 100 200 0.2 0.6814 55.188

24 1400 100 100 0.2 0.6519 51.516

25 850 300 100 0.2 0.8698 71.388

53
 26 850 300 200 0.2 0.889 71.28

27 850 100 150 1.5 0.963 71.57

28 1125 200 100 0.85 0.7281 57.6

29 1125 200 150 0.2 0.7144 54.612

30 1400 300 100 1.5 0.5802 39.88

4.3 Uniformity of SiC film on substrate deposition:

Power transform with lambda value -1.92 was used to model the uniformity of SiC film.

Two factor interaction process order was suggested by the software. Sequential p-value

for the model was less than 0.0001 and predicted R2 of 0.9876 was in reasonable

agreement with adjusted R2 of 0.9928. High R-squared value of 0.9876 means only 1.24%

of the total variations were not explained by the model. The current lambda value lied

between low and high confidence interval (-2.41, -1.4). Fit Summary report is shown in

the table 4.2. Analysis of variance results of two factor interaction model for uniformity

are shown in table 4.3. Model F-value of 398.84 implied the model was statistically

significant. In this case A, B, C, D, AB, AC, AD were significant model terms. Adequate

precision ratio of 66.45 indicated an adequate signal and model could be used to navigate

in the space. The actual vs predicted value of uniformity is shown in figure 4.2. Variance

inflation factor for all factors is one indicating all factors were orthogonal to each other.

A response equation in terms of actual factors that can be used to predict uniformity of

SiC film is given by equation 4.1. 3D surface model graph of uniformity with various

operating parameters are shown in figure 4.3 and 4.4.

54
 𝑼𝒏𝒊𝒇𝒐𝒓𝒎𝒊𝒕𝒚−𝟏.𝟗𝟐 = −𝟎. 𝟓𝟏𝟎𝟖𝟗𝟐 + 𝟎. 𝟎𝟎𝟏𝟖𝟎𝟒 × 𝑻 − 𝟎. 𝟎𝟎𝟑𝟕𝟑𝟓𝟎 × 𝑷 +

𝟎. 𝟎𝟎𝟐𝟕𝟏𝟖 × 𝑸 + 𝟎. 𝟎𝟖𝟖𝟓𝟖𝟐 × 𝑴 + 𝟔. 𝟎𝟎𝟗𝟒𝟐 × 𝟏𝟎−𝟔 × 𝑻 × 𝑷 − 𝟑. 𝟐𝟒𝟐𝟏𝟖 ×

𝟏𝟎−𝟔 × 𝑻 × 𝑸 − 𝟎. 𝟎𝟎𝟎𝟐𝟒𝟓 × 𝑻 × 𝑴 − 𝟑. 𝟒𝟗𝟏𝟖𝟗 × 𝟏𝟎−𝟔 × 𝑷 × 𝑸 − 𝟎. 𝟎𝟎𝟎𝟎𝟖𝟎 ×

𝑷 × 𝑴 + 𝟎. 𝟎𝟎𝟎𝟓𝟕𝟓 × 𝑸 × 𝑴 (4.1)

Table 4.2: Fit summary table for response 1

Sequential p- Lack of Fit Adjusted Predicted

Source
value p-value R² R²

Linear < 0.0001 0.9347 0.9111

2FI < 0.0001 0.9928 0.9876 Suggested

Quadratic 0.6653 0.9921 0.9806

Cubic 0.0009 0.9998 Aliased

Table 4.3: Analysis of Variance for 2FI model for response 1

Sum of Mean
Source df F-value p-value
Squares Square

<
Model 10.87 10 1.09 398.84 significant
0.0001

A- <
8.50 1 8.50 3119.85
Temperature 0.0001

55
 <
B-Pressure 1.45 1 1.45 533.75
0.0001

<
C-Flowrate 0.0709 1 0.0709 26.04
0.0001

<
D-mole ratio 0.1259 1 0.1259 46.21
0.0001

<
AB 0.4708 1 0.4708 172.81
0.0001

AC 0.0318 1 0.0318 11.67 0.0029

AD 0.0323 1 0.0323 11.85 0.0027

BC 0.0049 1 0.0049 1.79 0.1967

BD 0.0004 1 0.0004 0.1649 0.6892

CD 0.0056 1 0.0056 2.05 0.1685

Residual 0.0518 19 0.0027

Lack of Fit 0.0518 16 0.0032

Pure Error 0.0000 3 0.0000

Cor Total 10.92 29

56
Figure 4.1: Box-Cox Plot for Power Transform for response 1

Figure 4.2: Predicted vs actual value for response 1

57
 Figure 4.3: 3D surface model graph of uniformity vs temperature and pressure

Figure 4.4: 3D surface model graph of uniformity vs flowrate and mole ratio

4.4 Deposition rate of SiC on substrate:

Log transform with lambda value 0 was used to model the deposition rate of silicon

carbide. Two factor interaction model process order was suggested by the software.

Sequential p-value for the model was less than 0.0001and predicted R 2 value of 0.9308

was in reasonable agreement with adjusted R2 value of 0.9659. High R-squared value of

0.9308 means only 6.92% of the total variations were not explained by the model. The

58
current lambda value lied between low and high confidence interval (-0.58, 0.7). Fit

summary report is shown in the table 4.4. Analysis of variance results of two factor

interaction model for deposition rate are shown in table 4.5. Model F-value of 83.19

implied model was statistically significant. In this case A, B, D, AB, AC, AD and BD

were significant model terms. Adequate precision ratio of 33.951 indicates an adequate

signal and model can be used to navigate in the space. The actual vs predicted value of

deposition rate is shown in figure 4.6. Variance inflation factor for all factors was one

indicating all factors were orthogonal to each other. A response equation in terms of actual

factors that could be used to predict deposition rate of SiC film is given by equation 4.2.

3D surface model graph of deposition rate with various operating parameters are shown

in figure 4.7 and 4.8.

𝐥𝐧(𝑫𝒆𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏) = 𝟒. 𝟖𝟎𝟎𝟏𝟖 − 𝟎. 𝟎𝟎𝟎𝟒𝟑𝟏 × 𝑻 + 𝟎. 𝟎𝟎𝟑𝟏𝟑𝟗 × 𝑷 − 𝟎. 𝟎𝟎𝟐𝟕𝟔𝟖 ×

𝑸 − 𝟎. 𝟏𝟓𝟑𝟓𝟏𝟔 × 𝑴 − 𝟒. 𝟒𝟔𝟔𝟒𝟖 × 𝟏𝟎−𝟔 × 𝑻 × 𝑷 + 𝟐. 𝟐𝟓𝟑𝟏𝟑 × 𝟏𝟎−𝟔 × 𝑻 × 𝑸 +

𝟎. 𝟎𝟎𝟎𝟏𝟖𝟏 × 𝑻 × 𝑴 + 𝟐. 𝟔𝟗𝟑𝟗𝟔 × 𝟏𝟎−𝟔 × 𝑷 × 𝑸 + 𝟎. 𝟎𝟎𝟎𝟑𝟕 × 𝑷 × 𝑴

(4.2)

Table 4.4: Fit summary table for response 2

Sequential p- Lack of Fit Adjusted Predicted

Source
value p-value R² R²

Linear < 0.0001 0.7701 0.6872

2FI < 0.0001 0.9659 0.9308 Suggested

Quadratic 0.1355 0.9722 0.9169

Cubic < 0.0001 1.0000 Aliased

59
 Table 4.5: Analysis of variance for 2FI model for response 2

Sum of Mean F-
Source df p-value
Squares Square value

Model 1.74 10 0.1744 83.19 < 0.0001 significant

A-
1.09 1 1.09 518.17 < 0.0001
Temperature

B-Pressure 0.3101 1 0.3101 147.94 < 0.0001

C-Flowrate 0.0004 1 0.0004 0.1989 0.6606

D-mole ratio 0.0669 1 0.0669 31.91 < 0.0001

AB 0.2529 1 0.2529 120.63 < 0.0001

AC 0.0154 1 0.0154 7.33 0.0140

AD 0.0175 1 0.0175 8.36 0.0093

BC 0.0029 1 0.0029 1.38 0.2538

BD 0.0097 1 0.0097 4.61 0.0448

CD 0.0011 1 0.0011 0.5291 0.4759

Residual 0.0398 19 0.0021

Lack of Fit 0.0398 16 0.0025

Pure Error 0.0000 3 0.0000

Cor Total 1.78 29

60
Figure 4.5: Box-Cox plot for log transform for response 2

Figure 4.6: Predicted vs actual value for response 2

61
 Figure 4.7: 3D surface model graph of deposition vs temperature and pressure

Figure 4.8: 3D surface model graph of deposition vs flowrate and mole ratio

4.5 Optimisation of Process Parameters:

Numerical Optimisation feature of design expert was used to optimise the process

parameters. The ultimate goal was to maximise the uniformity and deposition by keeping

process parameters in the specified range. The optimised operating conditions were

determined to be a wall and substrate temperature of 850°C, operating pressure of 100

mbar, flowrate of 100lph and mole ratio of 1.5.The optimum operating parameters

62
obtained are summarised in table 4.6. Under these operating conditions deposition

uniformity was 0.9648 and deposition rate was 76.48 mg/hr. The contours of the 2D

reactor for the optimum conditions are shown in figure 4.10. Also 3D contours of

commercial size CVD reactors are shown in figure 4.11.

Table 4.6: Parameters and optimum value

Parameters Optimum Value

Temperature 850°C

Pressure 150 mbar

Flowrate 100 slph

Mole Ratio 1.5

Figure 4.9: 3D surface model graph of desirability

63
Figure 4.10 (a): Contour of Figure 4.10 (b): Contour of mole
temperature for 2-D reactor fraction of hydrogen for 2-D reactor

Figure 4.10 (c): Contour of mole Figure 4.10 (d): Contour of mole
fraction of argon for 2-D reactor fraction of methane for 2-D reactor

64
Figure 4.10 (e): Contour of mole Figure 4.10 (f): Contour of
fraction of hydrogen chloride mole fraction of silicon
for 2-D reactor dichloride for 2-D reactor

Figure 4.10 (g): Contour of mole Figure 4.10 (h): Contour of surface
fraction of methyl trichloro deposition rate of silicon carbide for
silane for 2-D reactor 2-D reactor

65
Figure 4.10 (i): Contour of Figure 4.10 (j): Pathlines for 2-D
velocity for 2-D reactor reactor

Figure 4.10: Contours for 2-D CVD reactor operating at optimum condition

66
 Figure 4.11(a): 3D Geometry of Figure 4.11(b): Meshed section
CVD Reactor view of CVD Reactor

Figure 4.11(c): Contour of Figure 4.11(d): Contour of

surface deposition rate of SiC temperature for 3D CVD
for 3D CVD reactor reactor

Figure 4.11: Contours of 3D CVD reactor operating at optimum conditions

67
 CONCLUSION

It was observed that deposition rate first increases with increase in temperature, reaches

a maximum value and then starts decreasing with further increase of temperature.

Uniformity on the other hand showed linear decrease with increase of temperature.

Deposition rate on substrate increases with increase in pressure in kinetic controlled

regime but showed opposite behaviour in transport controlled regime whereas uniformity

of substrate deposition decreased with pressure irrespective of controlling regime. Both

deposition rate on substrate and uniformity of deposition increased with increase in mole

fraction of hydrogen in carrier gas irrespective of the operating regime. It was also

observed that with surface deposition rate increased with increase in mole fraction of

argon in carrier gas. As flowrate was increased in kinetic controlled regime deposition

rate decreased while increase of flowrate in transport controlled regime increased the

deposition rate. Uniformity of deposition in transport controlled regime was more

sensitive to flowrate in comparison to kinetic controlled regime. In both cases the increase

in flowrate increased the uniformity of deposition of film. Based on optimisation

performed using design expert optimised parameters obtained for CVD reactor were

operating pressure of 100mbar, substrate and wall temperature of 850°C, mole ratio of

H2:Ar =1.5 and flowrate of 100 lph.

68
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70