26: Diffusion Numerical

MM 305: Kinetic of Materials Processes (S2)

Triratna Muneshwar
Autumn 2022
MEMS, IIT Bombay
 Q1) 1D slab with symmetric boundaries

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

2
 Transient Finite Planar Diffusion
Using separation of variables technique
• Symmetric boundary conditions
• D remains independent of concentration

2 1 𝑑𝑓 𝑡 1 𝑑2 𝑓 𝑥
𝑑𝑓 𝑡 𝑑 𝑓 𝑥 =
𝑓 𝑥 = 𝐷𝑖 ∙ 𝑓 𝑡 𝐷𝑖 ∙ 𝑓 𝑡 𝑑𝑡 𝑓 𝑥 𝑑𝑥 2
𝑑𝑡 𝑑𝑥 2
1 𝑑𝑓 𝑡
𝑑2 𝑓 𝑥 = −𝜆2 ∙ 𝐷𝑖
2
= −𝜆2 ∙ 𝑓 𝑥 𝑓 𝑡 𝑑𝑡
𝑑𝑥

𝑓 𝑥 = 𝐴′ 𝑠𝑖𝑛 𝜆𝑥 + 𝐵′ cos 𝜆𝑥 𝑓 𝑡 = 𝑓 𝑡0 exp −𝜆2 ∙ 𝐷𝑡

∞

𝑐 𝑥, 𝑡 = 𝐴𝑜 + ෍ 𝐴𝑛 𝑠𝑖𝑛 𝜆𝑛 𝑥 + 𝐵𝑛 cos 𝜆𝑛 𝑥 ∙ exp −𝜆2𝑛 ∙ 𝐷𝑡

𝑛=1

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

3
 Solution:
Boundary conditions

Solution:

If 𝒕 ≥ 𝑳𝟐 /𝝅𝟐 𝑫 , approximating ci(x,t) with first term only yields < 0.01% error

𝐿
Calculation: Find t* such that 𝑐𝑖 (𝑥 = , 𝑡 ∗ ) = 𝑐𝑖𝑜 /10
2

𝑡 ∗ ≈ 0.258 𝐿2 /𝐷

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

4
 Solution:
Boundary conditions

Solution:

If 𝒕 ≥ 𝑳𝟐 /𝝅𝟐 𝑫 , approximating ci(x,t) with first term only yields < 0.01% error

𝐿
Calculation: Find t* such that 𝑐𝑖 (𝑥 = , 𝑡 ∗ ) = 𝑐𝑖𝑜 /10
2

𝑡 ∗ ≈ 0.258 𝐿2 /𝐷

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

5
 Solution:
Boundary conditions

Solution:

If 𝒕 ≥ 𝑳𝟐 /𝝅𝟐 𝑫 , approximating ci(x,t) with first term only yields < 0.01% error

𝐿
Calculation: Find t* such that 𝑐𝑖 (𝑥 = , 𝑡 ∗ ) = 𝑐𝑖𝑜 /10
2

𝑡 ∗ ≈ 0.258 𝐿2 /𝐷

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

6
 Solution:
Boundary conditions

Solution:

If 𝒕 ≥ 𝑳𝟐 /𝝅𝟐 𝑫 , approximating ci(x,t) with first term only yields < 0.01% error

𝐿
Calculation: Find t* such that 𝑐𝑖 (𝑥 = , 𝑡 ∗ ) = 𝑐𝑖𝑜 /10
2

𝑡 ∗ ≈ 0.258 𝐿2 /𝐷

Chapter 4 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

7
 Q2) Dry etching: Ti (s) etch using HCl (g)

Dry etching of Ti metal in presence of HCl (g) vapors involves 3 sequential steps:
(1) Transport of HCl gas reactants to Ti (s) surface
(2) Surface reaction between HCl (g) and Ti (s) producing TiCl4 (g) and H2 (g)
(3) Transport of TiCl4 (g) and H2 (g) away from the surface

Surface reaction controlled

Kinetics of Ti etching or etch rate (𝑑𝑥/𝑑𝑡) could be either: OR
Diffusion controlled
OR
Mixed controlled

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

8
 Q2) Surface reaction-controlled etching:
𝑜
For surface reaction-controlled etching (CHCl same as 𝐶𝐻𝐶𝑙 )

Considering 1st order etching rate w.r.t HCl(g) for reaction

𝑑𝐽𝑇𝑖 𝑜
= −𝑘 ′ 𝐶𝐻𝐶𝑙 JTi is the number of Ti atoms etched per unit surface area per unit time
𝑑𝑡
Calculate etch-rate for surface
Expressing JTi as etch rate dx/dt reaction controlled process :
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
𝑜
𝑑𝑥 𝑀𝑇𝑖 ′ 𝑜 𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 • ρTi = 4.5 g/cm3
OR OR =− 𝑘 𝐶𝐻𝐶𝑙 = − • T = 1500 K
𝑑𝑡 𝜌𝑇𝑖 𝜌𝑇𝑖 𝑅𝑇

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

9
 Q2) Surface reaction-controlled etching:
𝑜
For surface reaction-controlled etching (CHCl same as 𝐶𝐻𝐶𝑙 )

Considering 1st order etching rate w.r.t HCl(g) for reaction

𝑑𝐽𝑇𝑖 𝑜
= −𝑘 ′ 𝐶𝐻𝐶𝑙 JTi is the number of Ti atoms etched per unit surface area per unit time
𝑑𝑡
Calculate etch-rate for surface
Expressing JTi as etch rate dx/dt reaction controlled process :
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
𝑜
𝑑𝑥 𝑀𝑇𝑖 ′ 𝑜 𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 • ρTi = 4.5 g/cm3
OR OR =− 𝑘 𝐶𝐻𝐶𝑙 = − • T = 1500 K
𝑑𝑡 𝜌𝑇𝑖 𝜌𝑇𝑖 𝑅𝑇

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

10
 Q2) Surface reaction-controlled etching:
𝑜
For surface reaction-controlled etching (CHCl same as 𝐶𝐻𝐶𝑙 )

Considering 1st order etching rate w.r.t HCl(g) for reaction

𝑑𝐽𝑇𝑖 𝑜
= −𝑘 ′ 𝐶𝐻𝐶𝑙 JTi is the number of Ti atoms etched per unit surface area per unit time
𝑑𝑡
Calculate etch-rate for surface
Expressing JTi as etch rate dx/dt reaction controlled process :
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
𝑜
𝑑𝑥 𝑀𝑇𝑖 ′ 𝑜 𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 • ρTi = 4.5 g/cm3
OR OR =− 𝑘 𝐶𝐻𝐶𝑙 = − • T = 1500 K
𝑑𝑡 𝜌𝑇𝑖 𝜌𝑇𝑖 𝑅𝑇

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

11
 Q2) Surface reaction-controlled etching:
𝑜
For surface reaction-controlled etching (CHCl same as 𝐶𝐻𝐶𝑙 )

Considering 1st order etching rate w.r.t HCl(g) for reaction

𝑑𝐽𝑇𝑖 𝑜
= −𝑘 ′ 𝐶𝐻𝐶𝑙 JTi is the number of Ti atoms etched per unit surface area per unit time
𝑑𝑡
Calculate etch-rate for surface
Expressing JTi as etch rate dx/dt reaction controlled process :
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
𝑜
𝑑𝑥 𝑀𝑇𝑖 ′ 𝑜 𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 • ρTi = 4.5 g/cm3
OR OR =− 𝑘 𝐶𝐻𝐶𝑙 = − • T = 1500 K
𝑑𝑡 𝜌𝑇𝑖 𝜌𝑇𝑖 𝑅𝑇

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

12
 Q2) Surface reaction-controlled etching:
𝑜
For surface reaction-controlled etching (CHCl same as 𝐶𝐻𝐶𝑙 )

Considering 1st order etching rate w.r.t HCl(g) for reaction

𝑑𝐽𝑇𝑖 𝑜
= −𝑘 ′ 𝐶𝐻𝐶𝑙 JTi is the number of Ti atoms etched per unit surface area per unit time
𝑑𝑡
Calculate etch-rate for surface
Expressing JTi as etch rate dx/dt reaction controlled process :
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
𝑜
𝑑𝑥 𝑀𝑇𝑖 ′ 𝑜 𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 • ρTi = 4.5 g/cm3
OR OR =− 𝑘 𝐶𝐻𝐶𝑙 = − • T = 1500 K
𝑑𝑡 𝜌𝑇𝑖 𝜌𝑇𝑖 𝑅𝑇

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

13
 Q2) Diffusion controlled etching
For diffusion-controlled etching (OR CHCl ~ 0)

Considering a diffusion zone of width δ, across which the

𝑜
HCl (g) concentration changes from 𝐶𝐻𝐶𝑙 to CHCl

Incident flux of HCl species on Ti surface (JHCl) is:

For reaction

Etched atomic flux of Ti would be: Calculate etch-rate for

diffusion controlled process:
Combine: • DHCl(g)@1500 K = 0.2 cm2/s,
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
• T = 1500 K
Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)
14
 Q2) Diffusion controlled etching
For diffusion-controlled etching (OR CHCl ~ 0)

Considering a diffusion zone of width δ, across which the

𝑜
HCl (g) concentration changes from 𝐶𝐻𝐶𝑙 to CHCl

Incident flux of HCl species on Ti surface (JHCl) is:

For reaction

Etched atomic flux of Ti would be: Calculate etch-rate for

diffusion controlled process:
Combine: • DHCl(g)@1500 K = 0.2 cm2/s,
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
• T = 1500 K
Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)
15
 Q2) Diffusion controlled etching
For diffusion-controlled etching (OR CHCl ~ 0)

Considering a diffusion zone of width δ, across which the

𝑜
HCl (g) concentration changes from 𝐶𝐻𝐶𝑙 to CHCl

Incident flux of HCl species on Ti surface (JHCl) is:

For reaction

Etched atomic flux of Ti would be: Calculate etch-rate for

diffusion controlled process:
Combine: • DHCl(g)@1500 K = 0.2 cm2/s,
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
• T = 1500 K
Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)
16
 Q2) Diffusion controlled etching
For diffusion-controlled etching (OR CHCl ~ 0)

Considering a diffusion zone of width δ, across which the

𝑜
HCl (g) concentration changes from 𝐶𝐻𝐶𝑙 to CHCl

Incident flux of HCl species on Ti surface (JHCl) is:

For reaction

Etched atomic flux of Ti would be: Calculate etch-rate for

diffusion controlled process:
Combine: • DHCl(g)@1500 K = 0.2 cm2/s,
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
• T = 1500 K
Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)
17
 Q2) Diffusion controlled etching
For diffusion-controlled etching (OR CHCl ~ 0)

Considering a diffusion zone of width δ, across which the

𝑜
HCl (g) concentration changes from 𝐶𝐻𝐶𝑙 to CHCl

Incident flux of HCl species on Ti surface (JHCl) is:

For reaction

Etched atomic flux of Ti would be: Calculate etch-rate for

diffusion controlled process:
Combine: • DHCl(g)@1500 K = 0.2 cm2/s,
• PHCl = 0.01 atm
• MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
• T = 1500 K
Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)
18
 Q2) Mixed control for etching
In case of a mixed-control etch, etch rate depends upon surface reaction and diffusion

Kinetic resistance (R = 1/rate) is analogous to electrical resistance

Calculate etch-rate for mixed

controlled process:
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• DHCl(g)@1500 K = 0.2 cm2/s,
𝑜 • PHCl = 0.01 atm
𝑑𝑥 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙 • MTi = 47.9 g/mol
=−
𝑑𝑡 4𝛿 1 • ρTi = 4.5 g/cm3
𝑡𝑜𝑡 𝑅𝑇𝜌𝑇𝑖 𝐷 + ′
𝐻𝐶𝑙 𝑘 • T = 1500 K

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

19
 Q2) Mixed control for etching
In case of a mixed-control etch, etch rate depends upon surface reaction and diffusion

Kinetic resistance (R = 1/rate) is analogous to electrical resistance

Calculate etch-rate for mixed

controlled process:
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• DHCl(g)@1500 K = 0.2 cm2/s,
𝑜 • PHCl = 0.01 atm
𝑑𝑥 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙 • MTi = 47.9 g/mol
=−
𝑑𝑡 4𝛿 1 • ρTi = 4.5 g/cm3
𝑡𝑜𝑡 𝑅𝑇𝜌𝑇𝑖 𝐷 + ′
𝐻𝐶𝑙 𝑘 • T = 1500 K

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

20
 Q2) Mixed control for etching
In case of a mixed-control etch, etch rate depends upon surface reaction and diffusion

Kinetic resistance (R = 1/rate) is analogous to electrical resistance

Calculate etch-rate for mixed

controlled process:
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• DHCl(g)@1500 K = 0.2 cm2/s,
𝑜 • PHCl = 0.01 atm
𝑑𝑥 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙 • MTi = 47.9 g/mol
=−
𝑑𝑡 4𝛿 1 • ρTi = 4.5 g/cm3
𝑡𝑜𝑡 𝑅𝑇𝜌𝑇𝑖 𝐷 + ′
𝐻𝐶𝑙 𝑘 • T = 1500 K

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

21
 Q2) Mixed control for etching
In case of a mixed-control etch, etch rate depends upon surface reaction and diffusion

Kinetic resistance (R = 1/rate) is analogous to electrical resistance

Calculate etch-rate for mixed

controlled process:
• ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
• DHCl(g)@1500 K = 0.2 cm2/s,
𝑜 • PHCl = 0.01 atm
𝑑𝑥 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙 • MTi = 47.9 g/mol
=−
𝑑𝑡 4𝛿 1 • ρTi = 4.5 g/cm3
𝑡𝑜𝑡 𝑅𝑇𝜌𝑇𝑖 𝐷 + ′
𝐻𝐶𝑙 𝑘 • T = 1500 K

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

22
 Q2) Dry etching: Summary

Crossover temperature

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

23
 Q2) Crossover temperature
At crossover temperature (T*), process switches from reaction-control to diffusion-control
For dry-etching example, at T = T*

𝑜 𝑜
𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙
= 𝐷
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 Calculate cross-over temperatue
for etching process:
Note: D (T1/2) is weakly dependent on T as compared to k’ • ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
∗
𝑜
𝑀𝑇𝑖 𝑘𝑜′ 𝑒 −∆𝐺𝑎𝑐𝑡/𝑅𝑇 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑜
𝑃𝐻𝐶𝑙 • DHCl(g)@1500 K = 0.2 cm2/s,
= 𝐷 • PHCl = 0.01 atm
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 • MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
∆𝐺𝑎𝑐𝑡 1 • T = 1500 K
𝑇∗ =
𝑅 𝑘𝑜′ 4𝛿
ln 𝐷
𝐻𝐶𝑙

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

24
 Q2) Crossover temperature
At crossover temperature (T*), process switches from reaction-control to diffusion-control
For dry-etching example, at T = T*

𝑜 𝑜
𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙
= 𝐷
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 Calculate cross-over temperatue
for etching process:
Note: D (T1/2) is weakly dependent on T as compared to k’ • ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
∗
𝑜
𝑀𝑇𝑖 𝑘𝑜′ 𝑒 −∆𝐺𝑎𝑐𝑡/𝑅𝑇 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑜
𝑃𝐻𝐶𝑙 • DHCl(g)@1500 K = 0.2 cm2/s,
= 𝐷 • PHCl = 0.01 atm
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 • MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
∆𝐺𝑎𝑐𝑡 1 • T = 1500 K
𝑇∗ =
𝑅 𝑘𝑜′ 4𝛿
ln 𝐷
𝐻𝐶𝑙

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

25
 Q2) Crossover temperature
At crossover temperature (T*), process switches from reaction-control to diffusion-control
For dry-etching example, at T = T*

𝑜 𝑜
𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙
= 𝐷
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 Calculate cross-over temperatue
for etching process:
Note: D (T1/2) is weakly dependent on T as compared to k’ • ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
∗
𝑜
𝑀𝑇𝑖 𝑘𝑜′ 𝑒 −∆𝐺𝑎𝑐𝑡/𝑅𝑇 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑜
𝑃𝐻𝐶𝑙 • DHCl(g)@1500 K = 0.2 cm2/s,
= 𝐷 • PHCl = 0.01 atm
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 • MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
∆𝐺𝑎𝑐𝑡 1 • T = 1500 K
𝑇∗ =
𝑅 𝑘𝑜′ 4𝛿
ln 𝐷
𝐻𝐶𝑙

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

26
 Q2) Crossover temperature
At crossover temperature (T*), process switches from reaction-control to diffusion-control
For dry-etching example, at T = T*

𝑜 𝑜
𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙
= 𝐷
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 Calculate cross-over temperatue
for etching process:
Note: D (T1/2) is weakly dependent on T as compared to k’ • ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
∗
𝑜
𝑀𝑇𝑖 𝑘𝑜′ 𝑒 −∆𝐺𝑎𝑐𝑡/𝑅𝑇 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑜
𝑃𝐻𝐶𝑙 • DHCl(g)@1500 K = 0.2 cm2/s,
= 𝐷 • PHCl = 0.01 atm
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 • MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
∆𝐺𝑎𝑐𝑡 1 • T = 1500 K
𝑇∗ =
𝑅 𝑘𝑜′ 4𝛿
ln 𝐷
𝐻𝐶𝑙

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

27
 Q2) Crossover temperature
At crossover temperature (T*), process switches from reaction-control to diffusion-control
For dry-etching example, at T = T*

𝑜 𝑜
𝑀𝑇𝑖 𝑘 ′ 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑃𝐻𝐶𝑙
= 𝐷
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 Calculate cross-over temperatue
for etching process:
Note: D (T1/2) is weakly dependent on T as compared to k’ • ko‘ = 30 cm/s,
• ΔGact = 50 kJ/mol
∗
𝑜
𝑀𝑇𝑖 𝑘𝑜′ 𝑒 −∆𝐺𝑎𝑐𝑡/𝑅𝑇 𝑃𝐻𝐶𝑙 𝑀𝑇𝑖 𝑜
𝑃𝐻𝐶𝑙 • DHCl(g)@1500 K = 0.2 cm2/s,
= 𝐷 • PHCl = 0.01 atm
𝜌𝑇𝑖 𝑅𝑇 ∗ 𝜌𝑇𝑖 𝐻𝐶𝑙 4𝑅𝑇 ∗ 𝛿 • MTi = 47.9 g/mol
• ρTi = 4.5 g/cm3
∆𝐺𝑎𝑐𝑡 1 • T = 1500 K
𝑇∗ =
𝑅 𝑘𝑜′ 4𝛿
ln 𝐷
𝐻𝐶𝑙

Chapter 5 – Ryan O’Hayre, “Materials Kinetics Fundamentals” (2015)

28