Activation Energy

Activation energy represents the energy barrier that should be overcome to start a
reaction. The activation energy can be regarded as constant if the temperature of the
reaction is in a certain range. In the iCVD reaction, the apparent activation energy is
influenced by two different temperatures: the filament temperature and the substrate
temperature. Only when one temperature is fixed, the activation energy based on the
other temperature can be calculated.
When the temperature of the substrate is fixed, the activation energy upon the filament
temperature can be expressed upon the Arrhenius equation and BET theory [12]:
DR ~ [reactant]m
In [reac] ~ -Ea/R *(1/Tw)
Where k is the reaction rate constant, Ea is the activation energy of the reaction, Tw is
the filament temperature, and A is the Arrhenius constant. DR is the deposition rate, m
is the reaction order, and [reactant] is the concentration of the reactant. So, we can
get:
In (DR) ~ mIn[rea]
Combine the two equations and plot the figure between the DR and 1/Tw, the Ea can
be calculated from the curve.
BET constant
Since the driving force of iCVD polymerization is physical adsorption, the BET theory
and BET constant are important for the basic understanding of iCVD adsorption.

Fig 2.12 [55]

The BET theory explains the equilibrium of multilayer adsorption on the substrate. In
this theory, each surface spot occupied by a single molecule is assumed to have the
same adsorption energy and the molecule will be adsorbed infinitely layer by layer.
Also, it is not necessary that the previous layer should be completed before the second
or third layer starts to form [56]. The dynamic equilibrium of this process will be
reached if the rate of adsorption is equal to that of desorption [55].
As for the iCVD reaction, the BET constant can be expressed as:

[12]
Here c is the BET constant, dHdes is the heat of desorption, dHvap is the heat of
vaporization. From the literature [12], the dHdes can be calculated as follows:
 (如果可，换成正比)

Here [M] is the monomer concentration, Ts is the substrate temperature, Ea is the

activation energy based on the substrate temperature.
The dHvap can be calculated by the boiling point of V3D3 and one known saturated
vapor pressure of V3D3 at a certain temperature of the substrate by the Clausius–
Clapeyron relation:

[52]
Here P1 and T1 are for the saturated situation, P2 and T2 are for the boiling point of
V3D3. Then the dHvap can be calculated.
Next, the BET constant can be calculated with the equation x.xx.

emperature. Only when one temperature is fixed, the activation energy based on the
other temperature can be calculated.
When the temperature of the substrate is fixed, the activation energy upon the filament
temperature can be expressed by the Arrhenius equation and the BET theory [12]:
m
DR [reactant ] 2.7

m Ea 1 2.8
¿ [reactant ] − ×
R Tw
Where Ea is the activation energy of the reaction. DR is the deposition rate, m is the
reaction order, and [reactant] is the concentration of the reactant. So, we can get:
InDR mIn[reactant ] 2.9
Combine the two equations and plot the figure between the DR and 1/T w, the Ea can be
calculated from the curve.
BET constant
Since the driving force of iCVD polymerization is physical adsorption, the BET theory
and BET constant are important for the basic understanding of iCVD adsorption.
 Figure 2.1 BET sketch [55]

The BET theory explains the equilibrium of multilayer adsorption on the substrate. In
this theory, each surface spot occupied by a single molecule is assumed to have the
same adsorption energy and the molecule will be adsorbed infinitely layer by layer.
Also, it is not necessary that the previous layer should be completed before the second
or third layer starts to form [56]. The dynamic equilibrium of this process will be
reached if the rate of adsorption is equal to that of desorption [55].
As for the iCVD reaction, the BET constant can be expressed as [12]:
∆ H des −∆ H vap
c ≈ exp ⁡[ ] 2.10
RT
Here c is the BET constant, ∆ H des is the heat of desorption, ∆ H vap is the heat of
vaporization. From the literature [12], the ∆ H des can be calculated as follows:
E a=−2 ∆ H des 2.11
Here Ea is the activation energy based on the substrate temperature. From the
literature [12] the deposition under different substrate temperatures is a secondary
reaction.
The∆ H vap can be calculated by the boiling point of V3D3 and one known saturated
vapor pressure of V3D3 at a certain temperature of the substrate by the Clausius–
Clapeyron relation [52]:

¿
( )
P1 −∆ H vap 1
P2
=
R
1
( − )
T2 T1
2.12

Here P1 and T1 are for the saturated situation, P2 and T2 are for the boiling point of
V3D3. Then the ∆ H vap can be calculated.
Next, the BET constant can be calculated with the equation 2.10.