A Parametric Study of Surface Diffusion and its

Application to Pattern-Constrained Epitaxy

ME 523 Course Project

Krishnan Swaminathan-Gopalan
Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign,

12th Dec 2017 ME 523 Fall 2017

 Outline

▪ Motivation
▪ Factors affecting Surface Diffusion
▪ Simulation Methodology
▪ Parametric Study
• Effect of Dimensionality
• Effect of Surface-Interaction barrier
• Effect of Surface Coverage
• Effect of Lateral Interactions
▪ Application to Pattern-Constrained Epitaxy

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 Motivation

Objective:
• To understand the
factors influencing
surface diffusion.
• Practical application to
pattern-constrained
Surface catalysis
epitaxy

Epitaxy on crystals3
Chemical vapor deposition1 Biological systems2
1 www.azonano.com
2wikipedia.com
3 Hiura, Hidefumi, Michael V. Lee, Anastasia V. Tyurnina, and Kazuhito Tsukagoshi. Carbon 50, no. 14 (2012): 5076-5084.
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 Factors Influencing Surface Diffusion

Gases Surface

Image courtesy: https://prateekvjoshi.com/

▪ Diffusion in gases determined by collisions.

▪ Diffusion on the surface is determined by surface bond strength,
surface coverage, and lateral interactions

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Factors Influencing Surface Diffusion: Surface bonding

Ebarrier

▪ Cross high energy region for motion

▪ Thermal fluctuations should provide
this energy.

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Factors Influencing Surface Diffusion: Surface Coverage

Ebarrier

▪ Presence of another adsorbate on neighbor site increases the energy

due to repulsion.
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Factors Influencing Surface Diffusion: Lateral Interactions

Ebarrier

Repulsion

Attraction

▪ Repulsive interactions increases energy – reduces barrier

▪ Attractive interactions decreases energy – increases barrier

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 Simulation methodology: kMC

▪ kinetic Monte Carlo (kMC).

▪ Motion of the atoms is not

explicitly solved.

▪ Surface hopping - rare event

similar to collisions in gases.

▪ Statistical modeling of motion

based on rates.

▪ Each process is assumed to

−𝐸𝑏 −𝑙𝑛 𝑅𝑛 follow a Poisson distribution.
𝑘 = 𝜈 ∗ 𝑒𝑥𝑝 Δ𝑡 =
𝑘𝑏 𝑇 𝑘

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 Simulation methodology: Formulation

▪ Square lattice

▪ Atoms can move only to first

nearest neighbor sites.

▪ Lateral interactions only up to

first nearest neighbor
considered.

▪ One type of surface site

2
▪ One type of adsorbate
1 𝑥 𝑡 − 𝑥0
Einstein’s relation 𝐷 =
2𝑁𝑑 𝑡

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 Parametric Study: Effect of Dimensionality

1 𝑥 𝑡 − 𝑥0 2
Einstein’s relation 𝐷 =
2𝑁𝑑 𝑡

▪ Increase in dimensions – More DOF of particles.

▪ Could have non-uniform directional diffusion.

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 Parametric Study: Effect of Surface Bonding

−𝐸𝑏
𝑘 = 𝜈 ∗ 𝑒𝑥𝑝
𝑘𝑏 𝑇

𝐸𝑏
𝐸𝑏∗ =
𝑘𝑏 𝑇

▪ Log (D) is linear with the value of the non-dimensional barrier.

▪ Consistent with the rate equation.

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Parametric Study: Effect of Surface Coverage

▪ Increase in surface coverage restricts the motion of the atoms.

▪ Diffusion decreases linearly with the coverage.
▪ Such general data can be directly used for modeling.

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Parametric Study: Effect of Lateral Interactions

▪ Attractive interactions decreases D, repulsive interactions increases D.

▪ D decreases with the coverage for attractive interactions.
▪ D can have complex dependence with coverage for repulsive interactions.
▪ Such general data can be directly used for modeling.
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 Pattern-Constrained Epitaxy

Pattern-constrained epitaxy4

▪ In order to form particular shapes on the surface with epitaxy, a pattern

is introduced to constrain the atoms from diffusing.
▪ Many ways to introduce patterns: nanogrooves, chemical, etc.
4 ECS J. Solid State Sci. Technol.2015 vol. 4 no. 12 M73-M76

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 Pattern-Constrained Epitaxy

▪ % of diffused particles decreases with increasing pattern barrier.

▪ % of diffused particles decreases with increasing flux.

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 Pattern-Constrained Epitaxy

▪ % of diffused particles decreases with increasing pattern barrier.

▪ % of diffused particles decreases with increasing flux.

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 Conclusions

▪ Parametric Study
• Effect of Dimensionality – Extra DOF with more dimensions, but D constant
• Effect of Surface-Interaction barrier – Logarithmic decrease
• Effect of Surface Coverage – Linear decrease
• Effect of Lateral Interactions – Attractive LI: D↓, Repulsive LI: D↑

▪ Application to Pattern-Constrained Epitaxy

• % of diffused particles decreases with increasing pattern barrier.
• % of diffused particles decreases with increasing flux.

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