Chapter 2

Thermodynamics of Physical
and Chemical Vapour Deposition

The ultimate goal of this chapter is to formulate the driving force for deposition of
diamond in the chemical vapour deposition. Before reaching that goal, we will
study the basics of the related topics in several steps. First, we will study how to
formulate the thermodynamics of ideal gases. Then we will study how to formulate
the driving force for evaporation and condensation of water, which we experience
during our everyday lives, such as drying wet clothes and mist formation. Then, we
will study how we formulate the driving force for deposition in the physical vapour
deposition process. In the next step, we will study how to formulate the irre-
versibility when chemical reactions are involved. Finally, we will study how to
formulate the driving force for deposition in the CVD process. At the end of the
chapter, some kinetic concept will be briefly described. The motivation for for-
mulating the driving force for deposition was to compare the nucleation curves
between diamond and graphite. This allows us to compare not only the stability but
also the activation energy for nucleation between diamond and graphite.

2.1 Ideal Gases

For a closed system of fixed composition at constant temperature, dG becomes

(Gaskell 1995)

dG ¼ VdP ð2:1Þ

Since V = RT/P for one mole of ideal gas,

RT
dG ¼ dP ¼ RTd ln P ð2:2Þ
P

For an isothermal change of pressure from P1 to P2 at T,

© Springer Science+Business Media Dordrecht 2016 21

N.M. Hwang, Non-Classical Crystallization of Thin Films and Nanostructures
in CVD and PVD Processes, Springer Series in Surface Sciences 60,
DOI 10.1007/978-94-017-7616-5_2
22 2 Thermodynamics of Physical and Chemical Vapour Deposition

P2
GðP2 ; T Þ  GðP1 ; T Þ ¼ RT ln ð2:3Þ
P1
P
GðP; T Þ ¼ GðPo ; T Þ þ RT ln ð2:4Þ
Po

where G(Po,T) is a reference state. Since the choice of a reference state is arbitrary,
it would be good if we make a convenient choice. If the reference state is chosen as
Po = 1 atm at the given temperature, (2.4) is simplified to

G ¼ Go þ RT ln P ð2:5Þ

Due to the simplicity of (2.5), this special reference state is called the standard
state, which is defined by the state of 1 mol of pure gas at 1 atm pressure and the
temperature of interest.
The chemical potential of pure gas is equal to the molar free energy. Therefore,
(2.5) can also be written as

l ¼ lo þ RT ln P ð2:6Þ

However, the chemical potential of a component A in a mixture gas is equal to

the partial molar Gibbs free energy, which is written as

 A ¼ Go þ RT ln pA
G ð2:7Þ
A

where pA is the partial pressure of the component A in the mixture gas.

And the corresponding chemical potential is

lA ¼ loA þ RT ln pA ð2:8Þ

(Q) What would be the driving force for wet clothes to dry?

2.2 Driving Force for Evaporation

The evaporation process is the irreversible transfer of atoms or molecules from the
liquid to the gas phase. Water will evaporate when its chemical potential of the
liquid is higher than that of the gas phase. This can be expressed as
liquid!gas liquid
DlH 2O
¼ lgas
H2 O  lH2 O ð2:9Þ
2.2 Driving Force for Evaporation 23

If it is assumed that the water vapour follows the ideal gas behaviour, the
chemical potential of water in the gas phase is expressed as

lH2 O;gas ¼ loH2 O;gas þ RT ln pH2 O ð2:10Þ

where pH2 O is the vapour pressure of water in the gas phase. Then, what remains to
do is to determine the chemical potential of water.
As in (2.1), the molar free energy or the chemical potential of liquid water can be
expressed at the given temperature as

dl ¼ VdP ð2:11Þ

The molar volume of liquid is insensitive to the change of pressure, (2.11) can be
integrated with respect to P.

lðP; T Þ ¼ lðPo ; T Þ þ V ðP  Po Þ ð2:12Þ

If the reference state is defined as the pure water at 1 atm pressure and the tem-
perature of interest, which is identical to the standard state, (2.12) can be written as,

lH2 O;liquid ¼ loH2 O;liquid þ V ðP  1Þ ð2:13Þ

Since the molar volume of liquid is much smaller than that of gas, the term V
(P − 1) is negligibly small compared with the chemical potential of the standard
state. So (2.13) can be safely approximated as

lH2 O;liquid ¼ loH2 O;liquid ð2:14Þ

The approximation in (2.14) is valid for most condensed phases unless the
pressure is very high.
The chemical potential in (2.14) cannot be directly compared with that in the gas
phase in (2.10) because the reference state is different. For comparison, the same
reference state should be used. If the standard state for gas is used as a reference
state, (2.14) can be written as

lH2 O;liquid ¼ loH2 O;gas þ RT ln peq

H2 O ð2:15Þ

where Peq
H2 O is the equilibrium vapour pressure of water at the given temperature.
If (2.10) and (2.15) are substituted in (2.9),
!
liquid!gas pH O
DlH 2O
¼ loH2 O;gas þ RT ln pH2 O  loH2 O;gas  RT ln peq
H2 O ¼ RT ln eq2
pH2 O
ð2:16Þ
24 2 Thermodynamics of Physical and Chemical Vapour Deposition

which can also be written as

!
peq
liquid!gas
DlH 2O
¼ RT ln H2 O ð2:17Þ
pH 2 O

If the relative humidity is 50 %, the value in the parenthesis is 2 and the driving
force for evaporation would be
liquid!gas
DlH 2O
¼ RT ln 2 ð2:18Þ

The ratio in the parenthesis in (2.17) is defined as the supersaturation ratio for
evaporation.
(Q) What would be the driving force for precipitation of water when the water
vapour, which was saturated at 300 K, is suddenly supercooled to 290 K?

2.3 Driving Force for Condensation

In this process, the water molecule is transferred from the vapour to the liquid state.
Using the similar scheme above, the driving force can be written as

Dlgas;300K!liquid;290K
H2 O ¼ lliquid;290K
H2 O  lgas;300K
H2 O ð2:19Þ
 
¼ loH2 O;gas þ RT ln p290K
H2 O  lH2 O;gas þ RT ln pH2 O
o 300K
ð2:20Þ

where P290K 300K

H2 O and PH2 O represent the equilibrium vapour pressure of water respec-
tively at 290 and 300 K.
The driving force for condensation becomes
!
P300K
H2 O
Dl300K!290K ¼ RT ln ð2:21Þ
P290K
H2 O

The ratio of the parenthesis is called the supersaturation ratio for condensation.

2.4 Driving Force for Deposition in the Physical Vapour

Deposition Process

In the physical vapour deposition (PVD) process, the materials to be deposited are
evaporated thermally or by sputtering. The species in the vapour state are super-
saturated for condensation or precipitation. Therefore, the PVD process consists of
2.4 Driving Force for Deposition in the Physical … 25

evaporation and condensation. When the metal evaporates at equilibrium vapour

pressure of Peq at temperature T with the ambient hydrostatic pressure P of the
evaporant vapour, the evaporation flux is expressed by the Hertz-Knudsen
equation as

ae ðPeq  PÞ
J ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffi mols/s cm2 ð2:22Þ
2pmkT

where αe is the evaporation coefficient for vapour molecules onto the surface. The
evaporation coefficient is usually much less than unity because the evaporant
vapour molecules impinging upon the condensed phase surface are reflected back.
Since the mass of the evaporated flux is conserved, the number density of the
evaporated molecules decrease along with the distance from the evaporation
source. If the evaporation source is a point, the number density decreases with
distance, being inversely proportional to the square distance. If the evaporation
source is an infinite line, the number density decreases, being inversely proportional
to the distance. In the steady state, a certain pressure P will be maintained in the
vicinity of the growing surface. This pressure will be in equilibrium with the
adatoms on the growing surface or substrate. If this pressure is denoted as P* and
the equilibrium vapour pressure of the evaporant at the substrate temperature is
Peq
Tsub , the supersaturation ratio for deposition is given as

P
a¼ ð2:23Þ
Peq
Tsub

And the driving force for deposition is given as

Dl ¼ RT ln a ð2:24Þ

(Q) In the chemical vapour deposition, chemical reactions are involved. How can
you formulate the irreversibility of chemical reactions? What would be the driving
force for chemical reactions?

2.5 Irreversibility for Chemical Reactions

Consider the chemical reaction where gases A and B react with each other and
produce gas 2C (Gaskell 1995). Initially there are 1 mol of A and 1 mol of B with C
being absent. If 2x mole of C is formed by chemical reaction after time t, the number
of moles of both A and B would be 1 – x as shown by the following equation.
26 2 Thermodynamics of Physical and Chemical Vapour Deposition

AðgÞ þ BðgÞ , 2CðgÞ

at t = 0, 1 1 0 ð2:25Þ
at t = t, 1x 1  x 2x

The Gibbs free energy of the system becomes

G0 ¼ ð1  xÞlA þ ð1  xÞlB þ 2xlC ¼ lA þ lB þ xð2lC  lA  lB Þ ð2:26Þ

The derivative of G′ with respect to x can be positive, zero or negative. If the

derivative is positive, the reaction to produce C would increase the Gibbs free energy
of the system, which is not allowed. This means that the reaction would be back-
ward. C is unstable and decomposes into B and C. The sum of chemical potential on
the right hand side of the chemical reaction is larger than that on the left side.
 
@G0
¼ 2lC  lA  lB [ 0 ! lA þ lB \2lC ð2:27Þ
@x

If the derivative is zero, the chemical reaction is in equilibrium. The sum of

chemical potential on the right hand side is equal to that on the left side.
 
@G0
¼ 2lC  lA  lB ¼ 0 ! lA þ lB ¼ 2lC ð2:28Þ
@x

If the derivative is negative, the reaction to produce C would decrease the Gibbs
free energy, which is allowed. This means that the reaction would be forward. C is
stable and would be formed at the expense of B and C. The sum of chemical
potential on the right hand side of the chemical reaction is smaller than that on the
left side.
 
@G0
¼ 2lC  lA  lB \0 ! lA þ lB [ 2lC ð2:29Þ
@x

This conclusion is generally valid for any chemical reaction. If the sum of
chemical potentials on the left side is larger than that on the right side, the forward
reaction will be irreversible. If the sum of chemical potentials on the left side is
smaller than that on the right side, the backward reaction will be irreversible. If the
sum of chemical potentials on the left side is equal to that on the right side, the
chemical reaction is in equilibrium.
If the reactants are on the left side and the products are on the right side, the
driving force for the forward reaction can be written as
X p p X
Dl ¼ l i ni  lri nri ð2:30Þ
2.5 Irreversibility for Chemical Reactions 27

This driving force changes with time or the chemical reaction. Consider the
simple reaction of (2.25).

Dl ¼ 2lC  lA  lB ¼ 2loC þ 2RT ln pC  loA  RT ln pA  loB  RT ln pB

ð2:31Þ

p2C
Dl ¼ Dlo þ RT ln ð2:32Þ
p A pB

Since C is initially absent, PC is equal to zero. Then the driving force in (2.32)
becomes infinite. This infinite driving force comes from the entropy of mixing,
which goes to infinity when something new is formed infinitesimally. This means
that the driving force for existence from non-existence is infinite. In other words,
nature tries to experience all the possible things it can.
The driving force for the chemical reaction in (2.32) continues to decrease as the
reaction goes on until Δμ becomes zero, where the equilibrium state is reached. If
the chemical reaction proceeds further, it will increase Δμ, which is not allowed by
the second law of thermodynamics. Therefore, once the equilibrium is reached, the
irreversible chemical reaction stops. However, the reversible chemical reaction
continues, satisfying the constraint of the dynamic equilibrium that the rates of the
forward and backward reactions are the same.

2.6 Driving Force for Deposition in the Chemical Vapour

Deposition Process

Consider a chemical reaction similar to (2.25) but this time the component C is not
gas but solid.

AðgÞ þ BðgÞ , C ðsÞ ð2:33Þ

This reaction would be one example of chemical vapour deposition. The driving
force for the forward reaction of (2.33) is expressed as

1
Dl ¼ Dlo þ RT ln ð2:34Þ
p A pB

where Δμo, pA, and pB are respectively standard chemical potential change (or
standard molar Gibbs free energy change), partial pressure of A and partial pressure
of B. It should be noted that since the chemical potential of the condensed phase is
equal to that of its standard state, pC = 1. Equation (2.34) represents the driving
force for the forward chemical reaction, which should be distinguished from the
driving force for deposition of C (Hwang and Yoon 1994a).
28 2 Thermodynamics of Physical and Chemical Vapour Deposition

(Q) What would be the driving force for deposition of solid C as a result of the
chemical reaction of (2.33)?
This question may not be easy to answer. It would be better to answer an easier
question as follows. Consider the A–B binary alloy, where the α solid solution is
stable at high temperature and the β solid solution is stable at low temperature. If the
alloy of the composition XaBo is supercooled from the α one phase region into the
two phase region of α + β, the α phase will be decomposed as follows.

a ! a0 þ b ð2:35Þ

(Q) What would be the driving force for precipitation of β?

In Fig. 2.1, the molar Gibbs free energies of the α and β phases for the A–B alloy
are shown with respect to XB. The final equilibrium state of α′ + β is defined by the
common tangent QS. The molar Gibbs free energy at the composition XaBo in the
equilibrium state is denoted as R. And the driving force for the reaction of (2.35) is
OR in Fig. 2.1. However, this driving force should be distinguished from the
driving force for precipitation of β. The driving force OR is dissipated in the
decomposition of α into α′ and β. However, we do not use this value as a driving
force for nucleation of β. In other words, this driving force is not used to calculate
the critical nucleus or the nucleation barrier of β. The driving force for precipitation
bo
of β should be evaluated at the composition of β, which   is XB in Fig. 2.1. The
b b
molar Gibbs free energy of β at XBo , which is Gbm XBo , is designated as Q in
b
Fig. 2.1. At the composition of XBo , we need to determine the Gibbs free energy of
the state which is supersaturated with respect to precipitation of β. This supersat-
urated state should be in equilibrium with the initial state, which is the α phase at
the composition of XaBo . The tangent on the molar Gibbs free energy curve of the α
phase at XaBo represents the molar Gibbs free energy of varying composition in
equilibrium with the α phase at XaBo . For example, the intercept of the tangent at the
axis of XB = 1 represents laB ðXBao Þ, which is the chemical potential of B in equi-
librium with the α phase at XaBo . Likewise, the intercept of the tangent at the axis of

Fig. 2.1 Molar Gibbs free

energy of α and β phases in
the binary A–B alloy,
illustrating the driving force
b
for precipitation of β at XBo
ao
from the α matrix at XB
(Hillert and Aaronson 1975)
2.6 Driving Force for Deposition in the Chemical … 29

XB = 0 represents laA ðXBao Þ, which is the chemical potential of A in equilibrium with

b
the α phase at XaBo . Therefore, the molar Gibbs free energy at the composition of XBo
ao
in equilibrium with the α phase at XB is determined by the intercept of the tangent
b
with the axis of XB ¼ XBo . This value is designated as P in Fig. 2.1. Therefore, the
driving force for precipitation of β is PQ in Fig. 2.1. It should be noted that the
driving force for precipitation of β changes as the composition of the α matrix
changes with the precipitation process because the tangent should be made at the
new composition of the α matrix.
With this thermodynamic scheme in mind, consider the driving force for
deposition of the solid C in the chemical reaction of (2.33). It should be noted that
the driving force should be evaluated at the composition of the solid C. The driving
force should be the difference of the chemical potential of C between solid and gas.
If the standard state for gas is used as a reference state, the chemical potential of C
in solid, lC;solid , is expressed as

lC;solid ¼ loC;gas þ RT ln peq

C ð2:36Þ

where Peq
C is the equilibrium vapour pressure of C at the substrate temperature.
Since the driving force for deposition is the difference in the chemical potential
C between solid and gas in the vicinity of the growing film, the remaining problem
is to identify the chemical potential of C in gas, lC;gas , made by the chemical
reaction of (2.33). If the steady state partial pressure of C in the vicinity of the
growing film is denoted as PC;gas , the driving force is expressed as

DlCgas!solid ¼ lC;solid  lC;gas ¼ lo þ RT ln peq

C  l  RT ln pC;gas
o
ð2:37Þ

Arranging (2.37) gives (Hwang and Yoon 1994a)

pC;gas
DlCgas!solid ¼ RT ln ð2:38Þ
peq
C

And PC;gas PeqC is the supersaturation ratio α for deposition. To determine α or
driving force for deposition, we need to determine pC,gas. The steady state value of
pC,gas in the CVD process depends on the kinetics of chemical reactions under the
given processing conditions with temperature as a major factor. If plasma is used in
the CVD process, it drastically increases the kinetics of chemical reactions.
Think about the extreme case where the chemical reaction of (2.33) hardly
occurs in the CVD reactor. This would happen if the reactor temperature is too low
to decompose the reactant gases. Then, there will be no deposition because pC,gas
would be practically zero. pC,gas would increase with the extent of the chemical
reaction. Depending on the extent of chemical reaction, pC,gas can have the three
ranges of values as follows.
30 2 Thermodynamics of Physical and Chemical Vapour Deposition

0  pC;gas \peq
C ð2:39Þ

pC;gas ¼ peq
C ð2:40Þ

peq
C \pC;gas  pC;gas
max
ð2:41Þ

where pmax
C;gas represents the maximum value that pC;gas can have. In the range of
.
(2.39), the supersaturation ratio a ¼ pC;gas peq
C is less than 1 and the driving force
is for etching rather than for deposition. In (2.40), α is 1 and the driving force is
zero, indicating neither deposition nor etching occurs. Only in the range of (2.41), α
is larger than 1 and the driving force is for deposition.
(Q) How can pmax
C;gas be determined?

pmax
C;gas represents the partial pressure of C that is obtained by the maximum extent
of reaction or the maximum metastable state without precipitating the solid. It can
be determined by minimizing the Gibbs free energy excluding the condensed phase
of C. In other words, pmax
C;gas can be determined by minimizing the Gibbs free energy
of the gas phase only (Hwang and Yoon 1994a). Therefore, the maximum super-
saturation ratio and driving force can be expressed as
eq
a ¼ pmax
C;gas =pC ð2:42Þ
 
eq
Dl ¼ RT ln pmax
C;gas =p C ð2:43Þ

In the real practice of CVD, if PC;gas  Pmax

C;gas , most reactant gases flow out of
the CVD reactor without undergoing an appreciable extent of chemical reactions,
resulting in very low efficiency. Therefore, such a CVD condition would not be
adopted. In most processes, process parameters would be adjusted to maximize the
chemical reactions of reactants so that the condition of PC;gas  Pmax C;gas may be
achieved. In this sense, PC;gas  PC;gas may be a reasonable approximation. Since
max

Pmax
C;gas can be determined by minimization of the Gibbs free energy of the gas phase
.
eq
only, a ¼ pmax
C;gas pC can be calculated with respect to thermodynamic parameters
such as temperature, pressure and composition.
Equations (2.42) and (2.43) as a reasonable approximation can be used if the
nucleation occurs in the gas phase. In most CVD processes, however, nucleation
and growth are believed to occur on the substrate or surface. Besides, it is known
that most flux contributing to the film growth does not directly come from the gas
phase but come from the diffusion of adatoms on the surface. First, the gas atoms
are adsorbed on the terrace. And then the adatoms diffuse to the ledge of monoa-
tomic height. Since monoatomic ledges have abundant kinks, the adatoms will find
kink sites, where they become incorporated into the crystal. This means that we
2.6 Driving Force for Deposition in the Chemical … 31

need to evaluate the supersaturation ratio in terms of the adatoms on the surface.
The composition of the adsorbed species may be different from that of the gas phase
because the desorption energies are different for each species.
(Q) How can you formulate the supersaturation ratio and the driving force for
deposition on the surface?

2.7 Consideration of the Substrate or Surface

eq
Considering the surface, pmax
C;gas and pC in (2.42) should be replaced by the corre-
sponding adsorbed concentrations. If the equilibrium between the gas phase and the
surface is maintained, the ratio in (2.42) does not change and thus (2.43) does not
change because the chemical potentials of the species in the gas phase are the same
as those on the adsorbed species. If the process is in the steady state, it is safely
assumed that the equilibrium between the gas and the surface is maintained. If the
equilibrium between the gas phase and the surface is not maintained, the adsorbed
concentration may not be in the steady state but depend on time. Then, the
supersaturation ratio and the driving force are different from (2.42) and (2.43)
respectively. In such a non-steady state, it is difficult to determine the superstation
ratio and the driving force.
When the species to be deposited is a compound or a solid solution by the CVD
process, the partial pressure or the equilibrium vapour pressure is often difficult to
define. For example, compounds such as SiC, SiO2 and Si3N4, do not have vapour
species corresponding to the same stoichiometry of the solid phase.
(Q) How can you formulate the supersaturation ratio and the driving force for
deposition of compounds or solid solution?

2.8 Driving Force for Deposition of Compound or Solid

Solution

The compound AaBb does not have the vapour species of the same stoichiometry,
where A and B are the element. If (2.42) is applied, the supersaturation ratio for
deposition of AaBb is expressed as

pmax
Aa Bb ;gas
a¼ ð2:44Þ
peq
Aa Bb

eq
The problem is that pmax
Aa Bb ;gas and pAa Bb cannot be determined because the com-
eq
pound AaBb does not exist in the gas phase. However, the ratio of pmaxAa Bb ;gas to pAa Bb
can be determined by considering the gas species that are in equilibrium with the
32 2 Thermodynamics of Physical and Chemical Vapour Deposition

hypothetical gas compound AaBb. Consider the two hypothetical equilibria: one for
the metastable gas phase equilibrium and the other for the stable equilibrium.

aAgas;eq þ bBgas;eq ¼ Aa Bbgas;eq ð2:45Þ

aAeq þ bBeq ¼ Aa Beq

b ð2:46Þ

From these two equilibria of (2.45) and (2.46), the following relationship is
derived.
 a  b
pmax pmax
A;gas pmax
B;gas
A B ;gas
a ¼ aeqb ¼  eq a eq b ð2:47Þ
pAa Bb pA ð pB Þ
eq eq
A;gas ; pB;gas ; pA and pB can be determined by the metastable gas phase
And pmax max

equilibrium and the stable equilibrium of the chemical reaction. From (2.47), the
driving force for deposition can also be determined. (Hwang and Yoon 1994b)
This result can be extended to the solid solution by assuming that the stoi-
chiometry coefficients a and b can continuously change within the solid solution
range with the constraint of a + b = 1, which is needed when the driving force is
evaluated per mole of the solid solution.
Let’s take an example of SiC deposition using the reactant gases of SiH4 and
CH4. The overall chemical reaction would be as follows.

SiH 4 þ CH 4 ¼ SiC þ 4H 2 ð2:48Þ

If the thermodynamic scheme of (2.47) is applied to the reaction in (2.48), the

supersaturation ratio is expressed as
 4
pmax pmax max eq
SiH 4 ;gas CH 4 ;gas pH 2
p
SiC;gas
a¼ ¼  4 ð2:49Þ
peq
SiC peq eq max
SiH 4 pCH 4 pH ;gas
2

The supersaturation ratio can be expressed in a more simplified form by con-

sidering a following reaction satisfying the law of mass action.

Si þ C ¼ SiC ð2:50Þ

If the thermodynamic scheme in (2.47) is applied to (2.50), the supersaturation

ratio is expressed as

pmax
SiC;gas pmax max
Si;gas pC;gas
a¼ eq ¼ eq eq ð2:51Þ
pSiC pSi pC

which is much simpler than (2.49)

2.9 Calculation Examples Using Thermo-Calc 33

2.9 Calculation Examples Using Thermo-Calc

2.9.1 Si–Cl–H System

At the temperature of 1323 K and the pressure of 10,666 Pa with the gas mixture of
SiH4 : HCl : H2 = 0.14 : 0.92 : 99, the following conditions are set for calculation
by Thermo-Calc (Sundman et al. 1985).
Set-Conditions: T = 1323, P = 10,666, N(Si) = 1.4E–1, N(Cl) = 9.2E–1,
N(H) = 199.36
Here, N represents the number of moles. The Gibbs free energy minimization
under these conditions produces the following amount of solid silicon and gases.
Here, SI1, which has a mole fraction of 7.97411E–10, corresponds to the equi-
librium vapour pressure of silicon at the given temperature.

H2 9.91047E–01 CL2H2SI1 3.78938E–06 SI1 7.97511E–10

CL1H1 8.72066E–03 CL4SI1 7.88797E–07 CL2 5.88841E–13
CL2SI1 2.12707E–04 H4SI1 8.60203E–08 SI2 2.60034E–13
CL3SI1 5.55192E–06 CL1 3.56902E–08 SI3 3.14674E–14
H1 4.83980E–06 CL1SI1 9.72339E–09 H6SI2 6.50693E–15
CL3H1SI1 4.57379E–06 H1SI1 2.01285E–09

SI1_S#1 Status ENTERED Driving force 0.0000E+00

Number of moles 1.1722E–01 Mass 3.2921E+00 Mole fraction
SI 1.00000E+00 CL 0.00000E+00 H 0.00000E+00

The Gibbs free energy minimization by suspending condensed phases of silicon

in the calculations produces the following amount of gases. Here, SI1, which has a
mole fraction of 9.40131E−10, corresponds to the maximum partial pressure of
silicon in the supersaturated gas phase, where condensed phases of silicon did not
precipitate.

H2 9.92254E−01 H1 4.84275E−06 SI1 9.40131E−09

CL1H1 6.34253E−03 CL4SI1 2.59578E−06 SI3 5.15678E−11
CL2SI1 1.32491E−03 H4SI1 1.01663E−06 SI2 3.61445E−11
CL3SI1 2.51360E−05 CL1SI1 8.33246E−08 H6SI2 9.07768E−13
CL2H2SI1 2.36321E−05 CL1 2.59417E−08 CL2 3.11097E−13
CL3H1SI1 2.07202E−05 H1S1 2.37455E−08
34 2 Thermodynamics of Physical and Chemical Vapour Deposition

The supersaturation ratio for deposition of Si can be determined as

pmax 9:40131  109

a¼ eq ¼
Si
¼ 11:79
pSi 7.97411  1010

2.9.2 Si–C–H System

At the temperature of 1400 K and the pressure 1000 Pa with the gas mixture of
SiH4 : CH4 = 1 : 1, the following conditions are set for calculation by Thermo-Calc
(Sundman et al. 1985).
Set-Conditions: T = 1400, P = 1000, N(Si) = 1, N(C) = 1, N(H) = 8
The Gibbs free energy minimization under these conditions produces the
following.

H2 9.99951E−01 C2H4 3.00948E−13 C3H4_1 1.09232E−19

H 4.87045E−05 C1H2 6.00656E−15 C 1.05200E−19
C1H4 1.64031E−07 C2H3 1.17540E−15 C3H6_2 1.59231E−21
SI 9.98049E−08 C2SI1 1.02915E−15 C3H6_1 2.53376E−24
H1SI1 5.25792E−08 H6SI2 1.31302E−16 C2 1.05475E−24
H4SI1 1.16175E−08 C2H6 5.95508E−17 C3 2.51092E−25
C1H3 1.67072E−10 C2H1 1.49582E−17 C3H8 5.92461E−26
SI2 8.01027E−11 C1SI1 6.96977E−18 C4 1.00000E−30
C1SI2 6.87487E−11 C2H5 2.43303E−18 C4H12SI1 1.00000E−30
C2H2 3.82934E−11 C1H1 1.39138E−18 C5 1.00000E−30
SI3 1.48834E−11 C3H4_2 3.16405E−19

The Gibbs free energy minimization by suspending all condensed phases related
to silicon, carbon and silicon carbide in the calculations produces the following
amount of gases.

H2 8.30213E−01 C1H3 5.15943E−06 C1SI1 5.66556E−11

C1SI2 1.11284E−01 C3H4_1 5.12173E−06 C3 1.70796E−11
C1H2 5.29783E−02 SI2 3.17637E−06 H6SI2 2.97979E−12
C1H4 4.61561E−03 H4SI1 1.59469E−06 C3H8 1.91491E−12
C2H4 3.45682E−04 C2H3 1.48171E−06 C5 5.42009E−13
C2SI1 3.41494E−04 C3H6_2 6.19877E−08 C1H1 5.17529E−14
SI3 1.17524E−04 C2H6 5.67915E−08 C 4.29435E−15
H 4.43787E−05 C2H1 2.27117E−08 C4 2.46159E−15
SI 1.98744E−05 C2H5 2.54647E−09 C2 1.75758E−15
C3H4_2 1.48358E−05 C1H2 2.03572E−10 C4H12SI1 5.68974E−16
H1SI1 9.54028E−06 C3H6_1 9.86377E−11
2.9 Calculation Examples Using Thermo-Calc 35

If the supersaturation ratio for deposition of silicon carbide is calculated based

on (2.49)
 4
pmax
SiC;gas
pmax max
SiH4 ;gas CH4 ;gas pH2
p eq
a1 ¼ ¼  4
peq
SiC peq p
SiH4 CH4
eq
p max
H ;gas
2

6
1:59469  10  4:61561  103  ð0:999951Þ4
¼ ¼ 8;128;785
1:16175  108  1:64031  107  ð0:830213Þ4

If the supersaturation ratio for deposition of silicon carbide is calculated based

on (2.51),

pmax
SiC;gas pmax max
Si;gas pC;gas
a2 ¼ ¼
peq
SiC peq eq
Si pC
1:98744  105  4:29435  1015
¼ ¼ 8;128;752
9:98049  108  1:052  1019

Therefore, the supersaturation ratio (α1) calculated based on (2.49) is equal to

that (α2) calculated based on (2.51) within a round-off error.

2.10 Validity of the Thermodynamic Scheme

Figure 2.2 shows the CVD phase diagram of the Si–Cl–H system at 10,666 Pa and
composition of N(H) = 200 and N(Cl) = 1. The line of the phase diagram divides
into regions of gas and gas + solid. In the gas region, only the gas phase is stable
and the solid cannot precipitate. Therefore, the supersaturation ratio for deposition
should be less than unity (α < 1). Along the line, the supersaturation ratio should be
unity (α = 1). In the gas + solid region, both gas and solid are stable and the solid
can precipitate. Therefore, the supersaturation ratio should be larger than unity
(α > 1).
The supersaturation ratio, α = 1, based on (2.42) corresponds to the phase
boundary of gas/(gas + solid) in Fig. 2.2. And, the regions of α < 1 and α > 1
represent respectively the one-phase region of gas and the two-phase region of
gas + solid. This means that the thermodynamic scheme for the supersaturation
ratio for CVD given by (2.42) is valid, agreeing with the CVD phase diagram.
Equation (2.42) provides additional information in the CVD phase diagram as
shown in Fig. 2.3, where the lines of iso-supersaturation ratio, α = 0.01, α = 0.1,
α = 10, and α = 100 are drawn. Note that a melting point of the solid silicon is
1687 K above which the solid silicon is metastable with respect to its liquid.
36 2 Thermodynamics of Physical and Chemical Vapour Deposition

Fig. 2.2 The CVD phase

diagram of the Si–Cl–H
system at 10,666 Pa and
composition of N(H) = 200
and N(Cl) = 1

Fig. 2.3 The CVD phase

diagram of the Si–Cl–H
system at 10,666 Pa and
composition of N(H) = 200
and N(Cl) = 1. The dashed
lines of the
iso-supersaturation ratios,
0.01, 0.1, 10 and 100 are
evaluated from (2.42) (Hwang
and Yoon 1994b)

Figure 2.3 shows a relatively sensitive change of the iso-supersaturation ratio

with N(Si) at *1500 K, indicating the gradient of the undersaturation with N(Si) is
high. By this thermodynamic scheme, lines of iso-supersaturation or driving force
for etching or deposition can be evaluated with respect to any independent CVD
thermodynamic variables.
2.11 Maximum Film Growth Rate in the CVD Process 37

2.11 Maximum Film Growth Rate in the CVD Process

C;gas in (2.41) represents the maximum partial pressure of ‘C’ for the given
Since pmax
CVD process, the flux for the maximum deposition rate can be evaluated using the
Hertz-Knusen equation as

pmax
C;gas
JCmax ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffi mols/s cm2 ð2:52Þ
2pmkT

This equation is under the assumption that the metastable equilibrium among gas
species without condensed phases is maintained at the given temperature. In order
to consider the supercooling effect of the gas in the presence of the temperature
gradient, pmax
C;gas at the temperature, from which the gas is expected be supercooled,
should be used.
Using (2.52), not only the maximum film growth rate can be estimated, but also
the minimum partial pressure of the species to be deposited can be estimated if the
film growth rate is given. However, in estimating the maximum film growth rate
using (2.52), it is implicitly assumed that the gas phase nucleation does not occur
and the film grows by individual atoms or molecules. If the gas phase nucleation
occurs and thereby gas phase generated nanoparticles begin to contribute as a
building block to film growth, (2.52) is not valid.

2.12 Driving Force for Deposition in the Diamond

Chemical Vapour Deposition Process

One of typical processing conditions for diamond deposition by hot filament CVD
(HFCVD) is the gas mixture of 1 % CH4–99 % H2, the reactor pressure of 2700 Pa,
the substrate temperature of 1200 K and the hot filament temperature of 2300 K.
By the hot filament, the reactant gases will be decomposed into many species
including the solid carbon.

CH4 þ H2 ! Cgas þ CH þ CH2 þ    þ Csolid ð2:53Þ

where Cgas and Csolid represent respectively the gas and solid carbon, which can be
graphite or diamond depending on the kinetics.
The minimization of the Gibbs free energy of the mixture gas at 2700 Pa and
1200 K excluding all the condensed phases produces the metastable gas phase
equilibrium which specifies each mole fraction of species as follows.

) C + C2 H2 + C2 H + CH4 + CH3 + C2 H4 +    ð2:54Þ

38 2 Thermodynamics of Physical and Chemical Vapour Deposition

where * represents the metastable gas phase equilibrium. If pi is defined to rep-
resent the metastable partial pressure of the species i, pC represents the maximum
partial pressure of carbon that can be achieved metastably at the given thermody-
namic condition.
The minimization of the Gibbs free energy excluding the stable graphite would
produce the metastable equilibrium which specifies each mole fraction of species
including diamond as follows.

) Ceq;d + C2 Heq;d + C2 Heq;d + CHeq;d + CHeq;d + C2 H4eq;d +   

2 4 3
ð2:55Þ
þ diamond

where all the gas species are in metastable equilibrium with diamond. Likewise,
peq;d
C represents the equilibrium vapour pressure of diamond at 1200 K.
The minimization of the Gibbs free energy without excluding any condensed
phase would produces the stable equilibrium which specifies each mole fraction of
species including graphite as follows.

) Ceq + C2 Heq
2 + C2 H
eq
+ CHeq eq eq
4 + CH3 + C2 H4 þ    þ graphite ð2:56Þ

where all the gas species are in stable equilibrium with graphite. Likewise, peq
C
represents the equilibrium vapour pressure of graphite at 1200 K.
Then, the maximum supersaturation ratio and driving force for graphite depo-
sition are expressed respectively as

pC
a¼ ð2:57Þ
peq
C

and
 
pC
Dlgas!gra ¼ RT ln : ð2:58Þ
peq
C

The calculation under the condition of T = 1200 K and P = 2700 Pa by

Thermo-Calc (Sundman et al. 1985) based on the scientific group thermodata
Europe (SGTE) substance database shows that α = 23.3 and
Dlgas!gra = −31413 J/mole (Hwang et al. 1994).
Similarly, the maximum supersaturation ratio and the driving force for diamond
deposition are expressed as

pC
a¼ ð2:59Þ
pCeq;d
2.12 Driving Force for Deposition in the Diamond … 39

Fig. 2.4 Variation of the

partial pressure of carbon in
the gas phase with
temperature for four different
ratios of carbon to hydrogen
(total pressure, 2700 Pa); Δ,
C:H = 1:50; ■, C:H = 1:100;
▲, C:H = 1:200; ○,1:400; ★,
equilibrium vapour pressure
of graphite or diamond
(Hwang et al. 1994)

!
pC
Dl
gas!dia
¼ RT ln ð2:60Þ
peq;d
C

The calculation shows that α = 11.7, Dlgas!dia = −24540 J/mole and

Dldia!gra = −6873 J/mole. As seen from the supersaturation ratio, the equilibrium
vapour pressure of diamond is twice larger than that of graphite. Based on this
thermodynamic scheme, the metastable partial pressure of carbon can be deter-
mined with varying temperature and various mixtures of carbon and hydrogen,
which is shown in Fig. 2.4 at a reactor pressure 2700 Pa. In Fig. 2.4, the equilib-
rium vapour pressure of graphite or diamond is also shown for comparison. It
should be noted that since the vertical axis of pressure is a logarithmic scale, the
slight difference in equilibrium vapour pressure between graphite and diamond is
not distinguishable.
The gas mixtures of 0.5 % CH4–99.5 % H2, 1 % CH4–99 % H2, 2 % CH4–
98 % H2 and 3 % CH4–97 % H2, which cover the composition range mostly used
in the diamond HFCVD process, have the ratios of C to H of 1/402, 1/202, 1/102
and 1/69, respectively. For the ratio of C : H = 1 : 200, the maximum partial
pressure of carbon is higher than its equilibrium vapour pressure over the tem-
perature range between roughly 890 and 2290 K. This means that in the temper-
ature range of *890 K < T < *2290 K, the driving force is for deposition of
solid carbon and in the temperature range of T < *890 K, and T > *2290 K, the
driving force is for etching of solid carbon.
This deposition condition appears to agree with the actual deposition at least to
an extent. First, in the diamond HFCVD process, the deposition hardly occurs
below the substrate temperature of 900 K if the gas mixture of 1 % CH4–99 % H2
is used. The general tendency is that the quality of diamonds is degraded when the
40 2 Thermodynamics of Physical and Chemical Vapour Deposition

filament temperature decreases or the concentration of CH4 increases. It is exper-

imentally observed that under the condition where the solid carbon deposits on the
hot filament, poor quality diamonds are formed on the substrate (Sommer et al.
1989). In order for carbon to deposit on the hot filament, the driving force should be
for deposition at the hot filament temperature. Considering the above calculation,
this condition is achieved when the filament temperature is decreased or the con-
centration of CH4 is increased. These results indicate that in the steady state of the
diamond HFCVD process, most of the reactant gases decompose.
The experimental observation that under the condition where the solid carbon
deposits on the hot filament, poor quality diamonds are deposited is not a problem
of thermodynamics but related with the growth mechanism of diamond. The carbon
deposited filament surface can have quite a different property in its catalytic effect,
which is not clearly understood. It would be better to treat this problem after the
growth mechanism of diamonds is studied in Chap. 6.
From (2.60), the chemical potential of carbon in the gas can be written as
!
pC
l gas
¼l dia
þ RT ln ¼ ldia þ RT ln aC ð2:61Þ
peq;d
C

This means that if diamond is set as a reference state, the supersaturation ratio for
diamond deposition becomes an activity of the gas phase. Using (2.61), the carbon
activities of gas, diamond and graphite can be compared with temperature at a gas
mixture of 1 % CH4–99 % H2 at a reactor pressure of 2700 Pa, which is shown in
Fig. 2.5.

Fig. 2.5 Temperature

dependence of carbon
activities of gas, diamond and
graphite at a gas mixture of
1 % CH4–99 % H2 at
2700 Pa (Hwang et al. 1996)
2.12 Driving Force for Deposition in the Diamond … 41

Fig. 2.6 Temperature

dependence of carbon activity
of gas for four different gas
mixtures of 0.5 % CH4–
99.5 % H2, 1 % CH4–99 %
H2, 2 % CH4–98 % H2 and
3 % CH4–97 % H2 at
2700 Pa. The supersaturation
ratio is with respect to
graphite (Yoon and Hwang
1995)

The activity of graphite is about a half of that of diamond. The carbon activity of
the gas has maximum at *1350 K. At temperature higher than *1350 K, the
activity of the gas decreases with increasing temperature and at temperature lower
than *1350 K, it decreases with decreasing temperature. Figure 2.5 shows that the
activities of gas and diamond intersect at temperature at *2050 K, which means at
temperature lower than this intersection, the driving force is for deposition of
diamond and at temperature higher than this intersection, the driving force is for
etching of diamond. The temperature at which the activities of gas and graphite
intersect, is a little higher than 2200 K.
The carbon activity of the gas can be evaluated as a function of temperature for
different concentration of CH4 as shown in Fig. 2.6. As expected, the activity,
which is the same as the supersaturation ratio for graphite deposition, increases with
increasing concentration of CH4.
Based on the thermodynamic scheme of (2.59) and (2.60), the lines of
iso-supersaturation ratio or iso-activity of carbon in the gas can be calculated as a
function of the atomic fraction of carbon and temperature as shown in Fig. 2.7.
Since the supersaturation ratio is evaluated for diamond deposition, diamond can be
deposited only in the region of α > 1. Figure 2.7 can be divided into three regions.
The first region is outside the graphite line, where only gas is stable. In this region,
neither graphite nor diamond can be deposited. The second region is between the
graphite and diamond lines, where graphite and gas are stable. In this region,
graphite can be deposited but diamond cannot be deposited. The third region is
inside the diamond line. In this region, graphite and gas are stable but diamond is
metastable. In order that metastable diamond may be deposited, it is necessary that
the thermodynamic condition should be in the third region. In addition to the
diamond line of α = 1, Fig. 2.7 shows other lines of α = 0.1 and 10. Comparison of
42 2 Thermodynamics of Physical and Chemical Vapour Deposition

Fig. 2.7 Lines of

iso-supersaturation ratio for
diamond deposition as a
function of temperature and
atomic fraction of carbon in
the C–H system (Hwang
1994)

the three lines of α = 0.1, 1 and 10 gives the information as to how steeply the
supersaturation or the undersaturation varies with temperature and composition.
The vertical dashed line represents the composition of 1 % CH4–99 % H2. At this
composition, diamond deposition is possible below *2050 K in agreement with
Figs. 2.4 and 2.5.
The line of α = 1, which corresponds to the phase boundary of the CVD phase
diagram, represents a solubility limit of carbon in the gas phase. In the region of
α < 1, carbon is soluble in the gas phase in the form of all kinds of hydrocarbon
such as CH, CH2, and CH3. In the region of α > 1, carbon in the gas phase exceeds
the solubility limit of the gas phase and diamond can be precipitated. Figure 2.7
shows that the solubility limit is minimum at *1350 K and increases with
decreasing temperature. This increase of the solubility limit with decreasing tem-
perature is rather an unusual case and called a retrograde solubility; normally the
solubility limit decreases with decreasing temperature.
The list of commands to calculate the iso-activity lines with diamond as a
reference state shown in Fig. 2.7 by Thermo-Calc is as follows. A brief explanation
for each command is given.
$TC
go ges → Go to Gibbs Energy System Module
read chd → Read the data file saved with a file name of chd in the GES module
go poly-3 → Go to Poly-3 modules
“Set the thermodynamic condition so that the degree of freedom may be zero.”
set-condition t = 1200 p = 2700 x(c) = 0.0049261 n = 1
→ temperature in K, pressure in Pa, the atomic fraction of carbon, x
(c) = 0.0049261, corresponds to the composition of 1 % CH4−99 % H2, n = 1
means that the total number of mole is equal to 1.
2.12 Driving Force for Deposition in the Diamond … 43

set-automatic-starting value
Yes → accept an automatic starting value
compute-equilibrium → compute Gibbs free energy minimization for the given
condition
set-reference-state c diamond → set reference state carbon as diamond
change-status phase c_s = suspend → change status of the phase solid carbon to
be suspended
change-status phase graphite = suspend → change status of the phase graphite to
be suspended
change-status phase diamond = suspend → change status of the phase diamond
to be suspended
set-axis-value 2 t 1000 2800 → Designate y axis as temperature with its range
from 1000 to 2800 K.
list-equilibrium → list the values of equilibrium calculations
TERMlNAL → Show the result on the computer terminal
VWCs
compute-equilibrium → Compute Gibbs free energy minimization for the given
condition
add
set-condition X(c) = none, acr(c) = 1 → Set the constraint of the relative activity
with a defined reference state being equal to 1.
compute-equilibrium → Compute Gibbs free energy minimization satisfying the
constraint of the set-condition
add
The region where diamond and gas are stable in Fig. 2.7 is the two phase region,
where the lever rule can be applied to determine the equilibrium amount of diamond
precipitation. When the gas mixture of 1 % CH4–99 % H2 is used, the atomic
fraction of 1 % CH4–99 % H2 is 5 × 10−3 as shown by the vertical dashed line in
Fig. 2.7. If the minimum carbon solubility is 10−4 at *1350 K, the mole fraction of
diamond can be determined by the lever rule as

5  103  104
Mole fraction of diamond ¼ ¼ 0:0049 ð2:62Þ
1  104

Then, the mole fraction of gas is 1 − 0.0049 = 0.9951. Since the mole fraction
of diamond is evaluated at the minimum solubility of carbon at *1350 K, this mole
fraction is maximum and would decrease with decreasing temperature.
This decrease in the amount of precipitation with decreasing temperature is a
unique feature of the retrograde solubility. This fact has a very special meaning in
the deposition of diamond and silicon by HFCVD, where the temperature decreases
monotonously from the hot filament to the substrate. In such cases, if the gas phase
nucleation takes place, the equilibrium amount of gas phase nuclei would decrease
toward the substrate temperature, considering the temperature gradient. This means
44 2 Thermodynamics of Physical and Chemical Vapour Deposition

that in the presence of gas phase nuclei, the driving force is for etching at the
substrate temperature.
If any film grows on the substrate in this situation, it can be inferred that the film
grow by the gas phase nuclei because the driving force is for etching. In other
words, the gas phase nuclei deposit on the substrate as a film and simultaneously
the deposited film would undergo etching atomically. Simultaneous deposition and
etching are often macroscopically observed in the CVD process (Badzian et al.
1988; Salvadori et al. 1992; Kumomi and Yonehara 1990). This phenomenon
provides the indirect evidence that the film should grow 100 % by gas phase nuclei
because atomic contribution is negative by etching. This aspect will be explained in
more detail in Chaps. 6 and 7.
If the gas phase nucleation takes place, which turns out to be very general in the
thin film process by CVD or even by some PVD, the information about the equi-
librium amount of precipitation is important because this amount is related with the
deposition rate. Figure 2.8 shows the temperature dependence of the equilibrium
amounts of diamond and graphite that can be precipitated from the gas phase when
the gas mixture of 1 % CH4–99 % H2 is used at the reactor pressure of 2700 Pa
(Hwang and Yoon 1996). In the entire range of temperature, the equilibrium
fraction of graphite is larger than that of diamond in agreement with the fact that
graphite is more stable than diamond.
Figure 2.8 provides an important fact that the equilibrium amount of diamond to
be precipitated in the gas phase decreases with decreasing temperature, which can
explain the well-known but extremely puzzling experimental observation of
simultaneous diamond deposition and graphite etching in the diamond CVD
process.
The reactor pressure is an important process parameter. What would be the effect
of pressure on the C–H phase diagram? As mentioned earlier, the line of α = 1

Fig. 2.8 The temperature

dependence of the equilibrium
mole fraction of diamond and
graphite when the gas mixture
of 1 % CH4–99 % H2 is used
at 2700 Pa. The dashed and
solid lines are for graphite and
diamond, respectively
(Hwang and Yoon 1996)
2.12 Driving Force for Deposition in the Diamond … 45

Fig. 2.9 Metastable CVD

phase diagram of the C–H
system: in the left of the
curve, only a gas phase is
stable and in the right of the
curve, two phases of
gas + diamond are stable
(Gueroudji and Hwang 2000)

corresponds to the phase diagram, which represents the thermodynamic limit of

deposition. In the C–H system using a gas mixture of CH4 and H2, it is known that
there is a lower limit of the substrate temperature that diamond can be deposited and
this temperature increases with increasing reactor pressure. The effect of the pres-
sure on the line of α = 1 or the metastable diamond CVD phase diagram is shown
in Fig. 2.9, which divides the region into the gas phase and the gas + diamond
phase (Gueroudji and Hwang 2000). The curves drawn in Fig. 2.9 correspond to the
temperature dependence of the solubility limit of carbon separating a diamond
deposition domain from its etching or non-deposition domain at different values of
the total pressure in the system.
At 101,325 Pa for a gas mixture of 1 % CH4–99 % H2 indicated by the left
vertical dashed line in Fig. 2.9, the lower limit of temperature for diamond depo-
sition is *1400 K. It should be noted that the substrate temperature cannot be
increased too much because diamond starts to transform to graphite. This tem-
perature is *1500 K, which would be the practical upper limit of the deposition
temperature. With increasing the methane concentration to 5 % CH4–95 % H2
indicated by the right vertical dashed line in Fig. 2.9, the deposition domain can be
extended and the lower limit is *1200 K. In experimental reality, however,
increasing the methane concentration tends to degrade the quality of diamond or to
produce the non-diamond phase. Normally, the methane concentration in typical
conditions is less than 3 % in the C–H system. Figure 2.9 shows that the lower limit
of the substrate temperature for diamond deposition can go down to *900 K at
1013.25 Pa and *600 K at 10.1325 Pa for the gas mixture of 1 % CH4–99 % H2.
However, the reactor pressure cannot be reduced much in the HFCVD process
because the evaporation rate of tungsten hot filaments increases, which will degrade
the diamond film quality.
46 2 Thermodynamics of Physical and Chemical Vapour Deposition

Fig. 2.10 A simplified form of the Bachmann C–H–O diagram for diamond deposition. Below
the H–CO tie line, no growth was achieved. Above the H–CO tie line, non-diamond carbon is
generally deposited except in a narrow window close to the tie line, which produces polycrystalline
diamond (May 2000)

The gas mixture of CH4 and H2 is just one example to deposit diamond. It turned
out that various sources can be used to deposit diamond. For examples, not only
pure methanol and pure acetone, but various gas mixtures containing carbon,
hydrogen, and oxygen such as CH4–H2–O2, CH4–H2–H2O, CH4–CO–H2, CH4–
CO2–H2, CO–H2, C2H2–O2, C2H4–O2, C2H6–O2, C2H2–CO2, C2H2–O2–H2,
C2H2–O2–H2, CH3COCH3–H2, CH3COCH3–O2, CH4–CH3COCH3–O2, CO–CO2–
H2, and CO–H2–O2. Besides, in addition to HFCVD, various CVD processes such
as microwave plasma, DC plasma jet, and flame could be used. By examining vast
compiled reports on diamond CVD, Bachmann et al. (1991) found out that the
diamond deposition is highly correlated with some composition range in the C–H–
O system regardless of the sources of reactants nor the method of processes.
Diamond deposition was possible only in the narrow composition range centred at
the ratio of C/O = 1 with varying hydrogen in the C–H–O system. In the
carbon-rich side of the line of C/O = 1, non-diamond is generally deposited and in
the oxygen-rich side, there was no growth. This aspect is shown in Fig. 2.10.
There must be some reason behind this high correlation of the diamond depo-
sition behaviour with the specific composition range. Before going further, it is
worth thinking why this is so.
2.12 Driving Force for Deposition in the Diamond … 47

(Q) What do you think is the reason for this deposition behaviour?
Among the possibility we can think of, the thermodynamics should come first. In
other words, this deposition behaviour might be related with the thermodynamic
driving force for diamond deposition. If the thermodynamic scheme for the su-
persaturation ratio for diamond deposition given in (2.59) is applied, the lines of
iso-supersaturation ratio can be evaluated at 1200 K in the C–H–O system as
shown in Fig. 2.11.
The supersaturation ratio for diamond deposition is unity almost along the line of
C/O = 1. In the carbon-rich side of this line, the supersaturation ratio increases
steeply with increasing carbon. This tendency is strong especially when the
hydrogen content is small. In the oxygen-rich side, the supersaturation ratio is less
than unity and the driving force is for etching of diamond. If Fig. 2.11 is compared
with Fig. 2.10, the diamond deposition behaviour is related with the supersaturation
ratio. No growth in the oxygen-rich side of the line of C/O = 1 might be related
with the supersaturation ratio being less than unity. In other words, this region is
undersaturated and the driving force is for etching of diamond. And non-diamond
deposition is related with the high supersaturation ratio. It may be asked why
non-diamond deposits under the condition of the high supersaturation ratio. This
problem is related with the diamond deposition mechanism, which will be
explained in Chap. 6.
The thermodynamic analysis made so far shows that the diamond deposition is
thermodynamically sound in that diamond deposition occurs under the thermody-
namic condition where the driving force is for deposition of diamond. The depo-
sition of less stable diamond instead of stable graphite is not a problem of
thermodynamics but a problem of kinetics, which will be explained in Chap. 5.

Fig. 2.11 The ternary

composition diagram of the
C–H–O system at 1200 K
under 2700 Pa showing five
different lines of the
iso-supersaturation ratio for
diamond deposition (Hwang
1994)
48 2 Thermodynamics of Physical and Chemical Vapour Deposition

2.13 Kinetics

The important thermodynamic functions such as E (internal energy), H (enthalpy),

G (Gibbs free energy), and S (entropy) are state functions, which does not depend
on the path. The information about two out of the three state variables P, T and V is
enough to determine these state functions. For example, if P and T are known for
states A and B, the Gibbs free energy, G, for each state can be determined. Then,
we can determine the direction of irreversibility or whether A → B or B → A. If
GA > GB, the state A irreversibly changes to the state B and vice versa. This is
illustrated in Fig. 2.12.
Although thermodynamics can powerfully predict the direction of irreversibility
of A → B from the knowledge of GA > GB, it does not say anything about how
long it will take for state A to change to state B. Time is not a parameter in
thermodynamics. How long the process will take is not a problem of thermody-
namics but a problem of kinetics.
(Q) If thermodynamics allows the irreversibility of A → B as shown in Fig. 2.12a
and the process is thermally activated, what would be the factors that determine the
rate?
The important factor is the kinetic barrier for the process A → B. If the kinetic
barrier is ΔG*, the probability to overcome the kinetic barrier would be identical to
the Boltzman probability for the thermally-activated process. Therefore, the prob-
ability would be proportional to exp(−ΔG*/kT).
There is a case where there exist multiple kinetic paths. For example, consider
the situation where GA > GB > GC. In this case, nature has two choices, either
A → B or A → C.
(Q) In this case, which path will nature choose, A → B or A → C?
Since GA > GB > GC, the magnitude of ΔGA→C is larger than that of ΔGA→B.
Does this mean that nature chooses the path A → C instead of the path A → B?
Thermodynamics does not say anything about this possibility. Larger driving force
does not guarantee faster kinetics. The determining factor is the kinetic barrier. If
the kinetic barrier of the A → B path is smaller than that of the A → C path,
nature will choose the path of A → B. In this sense, it can be said that nature

Fig. 2.12 The direction of

irreversibility of a A → B or
b B → A is determined by
the relative magnitude of
Gibbs free energy at constant
temperature and pressure
2.13 Kinetics 49

proceeds in the most probable way. This kinetic law can be compared with the
second law of thermodynamics, which says that nature does not proceed in a less
probable way.
The kinetic statement that nature proceeds in the most probable way exactly
describes what nature does whereas the thermodynamic statement that nature does
not proceed in a less probable way rather vaguely describes what nature does. For
the nature’s way of doing, the kinetic statement provides a necessary and sufficient
condition but the thermodynamic statement provides a necessary condition.
Considering this, the kinetic statement sounds much more attractive and powerful
than the thermodynamic one.
(Q) Then, why do we bother to learn thermodynamics? What is the advantage of
thermodynamics over kinetics?
The advantage of thermodynamics lies in the fact that important thermodynamic
functions are a state function, which makes thermodynamics very simple, powerful
and generally formulated. This is why we bother to learn thermodynamics, which is
worth our laborious efforts. This is highly in contrast with kinetics which depends
on the path. This means that there is no general way to formulate the kinetics. This
is why the general formulation for kinetics is not available and each kinetics should
be approached case by case.

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