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Ideal Gas Law, Maxwell distribution

EE669: VLSI Technology
For sufficiently low densities, all gases follow:
Revision of some relevant PV = nRT

concepts R = 8.3 J. mol-1 K-1 = NA kB

Maxwell distribution of molecular speeds:
Anil Kottantharayil,
HAL R&D Chair Professor, #⁄$ &' !
𝑚 $ % $(" )
Department of EE, IIT Bombay 𝑓 𝑐 = 4𝜋𝑐 𝑒
2𝜋𝑘! 𝑇

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Ideal Gas Law, Maxwell distribution Chemical Reactions

General reaction example:
Exercise: Calculate and plot the PDF for H2, O2 and Ar at
aA+bBècC+dD
1273K and 300K
Specific example:
Notes:
2H2 + O2 è 2H2O
1. Plot all the data in one graph using any of the plotting 𝒎[𝑩]𝒏
Rate of reaction = 𝒌 𝑨
software you can work with
2. Take care to use appropriate units
3. Comment on the temperature dependence
4. Comment on the dependence on the molecular weight Rate constant

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Temperature dependence of reaction rate Arrhenius Plot

𝑘 = 𝐾𝑒 %&! /(" )
𝐸*
ln 𝑘 = ln 𝐾 − Intercept = ln(A)
𝑘+ 𝑇

Activation energy
Slope = -Ea/kB

𝑘 = 𝐾𝑒 %&! /(" )

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2H2 + O2 è 2H2O Rate determining process

Possible intermediate steps in a Pt catalyzed process:
H2 (a) è 2H (a) Serial rate limiting steps Parallel, competing reactions

O2 (g) è 2O (a)
H (a) + O (a) è OH (a)

ln(rate)

ln(rate)
H (a) + OH (a) è H2O (a)
2OH (a) è H2O (a) + O (a)
H2O (a) è H2O (g)
1/T 1/T
• Several sequential steps
• Multiple parallel reaction pathways 4th step and the faster of 5th and 5th step and 6th steps
• Reaction rate in a pathway to be decided by the 6th steps
slowest in the pathway
• Fastest pathway to dominate the overall reaction rate
W. R. Williams et al., J. Phys. Chem., vol. 96, pp. 5922-5931, 1992.
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Example from MOSFET reliability Fick’s laws of diffusion

Δx

n1 n2 n3

1 2 3 4
• Flux from left to right of boundary 2:
ν
F1,L −R = n1
2
ν
• Flux from the right to left of boundary 2: F n
1,R −L =
Arrhenius plot of the H diffusion coefficient (D) at a-SiO2. Each point is the 2 2
average of the D over the four silica samples. The dashed lines represent
the two linear fits, with their corresponding activation energies. • Net flux from left to right: €
"Reduced hydrogen diffusion in strained amorphous SiO2: understanding ageing in ν ν ν 2 ΔC ΔC
MOSFET devices”, S. A. Sheikholeslam et al., Journal of Materials Chemistry C, J.
F = − (n 2 − n1 ) = − Δx(C
€ 2 − C1 ) = − Δx = −D
Mater. Chem. C, 2016, https://doi.org/10.1039/C6TC02647H
2 2 2 Δx Δx
J. D. Plummer, M. D. Deal, P. G. Griffin, Silicon VLSI Technology, Pearson Education, 2001

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Fick’s laws of diffusion (2) Pressure and mean free path

∂C
• Fick’s first law of diffusion: F = −D
∂x • Mean free path is the average distance between collision events

kB T 0.7
λ= = cm
2σP P
FIN € FOUT • Where, kB is the Boltzman’s constant (1.38 x 10-23 JK-1), T is the
Δx temperature in Kelvin, P is pressure in Pascal, σ is the collision
cross section in cm2
ΔC FIN − FOUT • σ ~ 4 x 10-15 cm2 at 300K
= €
Δt Δx • Flux of atoms striking a surface (e.g. a wafer),
∂C ∂F ∂ % ∂C ( P
=− = 'D * Fick’s second law of diffusion
∂t ∂x ∂x & ∂x ) F = 2.63 × 1017 cm −2 s−1
mT
∂C ∂ 2C • Where, T is the temperature in Kelvin, P is pressure in Pascal, m is the
• If D is independent of position: =D 2 atomic mass in atomic mass units (AMU)
∂t ∂x
€ 𝐷 = 𝐷,𝑒 %&! /(" )
€
J. D. Plummer, M. D. Deal, P. G. Griffin, Silicon VLSI Technology, Pearson Education, 2001 Angus Rockett, “Material Science of Semiconductors”, Springer Verlag, 2008

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