Surface physics I and II

Lectures: Mon 12-14 ,Wed 12-14 D116 Excercises: TBA Lecturer: Antti Kuronen, antti.kuronen@helsinki.fi Exercise assistant: Ane Lasa, ane.lasa@helsinki.fi Course homepage: http://www.physics.helsinki.fi/courses/s/pintafysiikka/ Objectives

To study properties of surfaces of solid materials. The relationship between the composition and morphology of the surface and its mechanical, chemical and electronic properties will be dealt with. Technologically important field of surface and thin film growth will also be covered.
2012: 1. Introduction
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Surface physics I

Surface physics I and II

Course in two parts

Surface physics I (SPI) (530202)

Period III, 5 ECTS points Basics of surface physics

Surface physics II (SPII) (530169)

Period IV, 5 ECTS points 'Special' topics in surface science

Surface and thin film growth Nanosystems Computational methods in surface science

You can take only SPI or both SPI and SPII

Surface physics I

2012: 1. Introduction

How to pass

Both courses:

Final exam Exercises

50% 50%

Exercises

Return by email to ane.lasa@helsinki.fi or

on paper to course box on the 2nd floor of Physicum

Return by (TBA)

Surface physics I

2012: 1. Introduction

Table of contents

Surface physics I

Introduction: What is a surface? Why is it important? Basic concepts. Surface structure: Thermodynamics of surfaces. Atomic and electronic structure. Experimental methods for surface characterization: Composition, morphology, electronic properties.

Surface physics II

Theoretical and computational methods in surface science: Analytical models, Monte Carlo and molecular dynamics sumilations. Surface growth: Adsorption, desorption, surface diffusion. Thin film growth: Homoepitaxy, heteroepitaxy, nanostructures.

Surface physics I

2012: 1. Introduction

Course material

These lecture notes on course home page

http://www.physics.helsinki.fi/courses/s/pintafysiikka/

There are useful links under 'Links and literature' Lecture notes username: surfphys, password: pfyssa

Textbooks

M. Prutton: Introduction to Surface Physics, Oxford Science Publications A. Zangwill: Physics at surfaces, Cambridge University Press J. A. Venables: Introduction to Surface and Thin Film Processes, Cambridge University Press A. Pimpinelli, J. Villain: Physics of Crystal Growth, Cambridge University Press M. Manninen, R. Nieminen: Pintafysiikka (in Finnish), Suomen Fyysikkoseuran julkaisuja 1

Journals

Surface physics I

Surface Science: http://www.sciencedirect.com/science/journal/00396028 Surface Science Reports: http://www.sciencedirect.com/science/journal/01675729 Progress in Surface Science: http://www.sciencedirect.com/science//journal/00796816 Thin Solid Films: http://www.sciencedirect.com/science/journal/00406090 Physical Review B: http://prb.aps.org/
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What is a surface?

Atomic view: Top few atomic layers of a solid. Continuum view: Dividing surface
vacuum, vapor dividing surface

c1

c2

Surface physics I

2012: 1. Introduction

Why study surfaces?

Technologically important

Thin film growth: electronics, nanostructures Miniaturization surface-to-volume ratio grows Catalysis, corrosion Surface chemistry (2007 Nobel Prize in chemistry)

Surfaces and interfaces important

Development of experimental methods

Development of various microscopy and spectroscopy methods 7 Development of vacuum techniques (ultra high vacuum, UHV p 10 Pa ) Film growth methods (MBE, MOCVD, ALD): preparation of surfaces with controlled composition and morphology 'Real' surfaces vs. 'clean' surfaces

Development of theoretical and computational methods

Models for atomic level structure of surfaces Computational modeling of surface chemistry (ab initio methods) Modeling of crystal growth (Monte Carlo and molecular dynamics simulations)
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Surface physics I

What kind of surfaces?

In everyday life surfaces are not clean

Surfaces of many materials react with oxygen and other gases in environment Formation of so called native oxide layer

May be very thin: e.g. Si surface has a SiO2 layer of thickness ~1nm. In the case of Si high temperatures and pressures needed to grow the layer thicker. Similarly for many metals (Al, Cu, ...) Often this layer passivates the surface: no further reactions (prevents corrosion).

The green patina on copper objects

Copper oxides, chlorides and carbonates. Takes years to form.

http://en.wikipedia.org/wiki/File:Hancoin1large.jpg

Surface physics I

2012: 1. Introduction

What kind of surfaces?

Many covalent materials (e.g. semiconductors Si, Ge, etc. and diamond) may have so called dangling bonds on the surface: bonds not bound to any neighbors.

These are often saturated by e.g. hydrogen.

Clean crystalline surface can be produced by various crystal growth methods Particularly clean surfaces are needed in manufacturing electronic components

Many layers of thin films. Interface (surface) structure more and more important as length scale becomes smaller.

http://navier.engr.colostate.edu/whatische/ChEL04Body.html

Surface physics I

2012: 1. Introduction

Some basic concepts

Classification of crystal surfaces

Surfaces of crystalline material (grown or cleavage) consist of single crystal plane Crystal direction:

Crystal structure (lattice points) determined by vectors a, b, c.

Set up a vector of arbitrary length in the direction of interest. Decompose the vector into its components along the principal axes. Using an appropriate multiplier, convert the component values into the smallest possible whole-number set.

Crystal planes: example

Plane intercepts crystal axes a, b, c at 3a, 2b, 2c Take the reciprocals of the numbers: , , The smallest integers having the same ratio are 2, 3, 3 The Miller indices of the plane are (233) For cubic crystals, a plane and the direction normal to the plane have precisely the same indices (except for possible scaling)
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Surface physics I

2012: 1. Introduction

Some basic concepts

Classification of crystal surfaces

Miller indices of a lattice plane = coordinates of the shortest reciprocal lattice vector normal to that plane Reminder: reciprocal lattice A , B , C of lattice a , b , c is defined as
b c A=2 a b c a B=2 ac b c b C = 2 aa b c

Reciprocal lattice of a simple cubic crystal = simple cubic For diamond, fcc and bcc lattices we almost always use the cubic unit cell (and not the primitive cells) for these lattices Miller indices tell the normal of the lattice plane. For non-cubic lattices (e.g. hcp) one must remember that this is not the case.

Surface physics I

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Some basic concepts

Crystal structure (unit cell) determined by vectors a, b, c. And possibly the basis: locations of atoms in the unit cell. Crystal plane determined by its Miller indices Notation: crystal direction: [hkl] = ha+kb+lc family of directions: <hkl> (crystal symmetry) crystal plane: (hkl) family of planes: {hkl} (crystal symmetry) Example: face centered cubic (fcc) lattice

(001)

(110)

(111)

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Some basic concepts

Corresponding surfaces look like below (001) (110) (111)

We immediately(?) see that atoms on certain surfaces are more tightly bound than on others. This has effect on the surface energy of a particular crystal surface.

Surface physics I

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Some basic concepts

Surface energy

Creating surface from a bulk material costs energy (you must do work in order to create surface) You must break atomic bonds Energy needed = Area A

2A

E1

E2 E 1 2A

E2

Surface energy has the unit of J/m2 of eV/2 etc. Difficult to determine experimentally; theoretical calculations needed. We will delve into this subject in more detail in the following chapters.

Surface physics I

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Some basic concepts

The effect of surface energy is nicely manifested in the equilibrium shape of nanoclusters (sizes from few nanometers). For small clusters the surface energy is minimized by the expense of introducing defects inside the cluster. When cluster size increases defects cost more energy and a lower-energy shape has also non-optimal surface facets. This is confirmed by experiments for many metals.

(001) (111) (111)

Surface physics I 2012: 1. Introduction
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Some basic concepts

Surface energies of the three fcc surfaces (from semiempirical atomistic simulations): (001) (110) (111)

eV/2 J/m2

0.0802 1.29

0.124 1.99

0.0735 1.18

Literature values ab initio calculations: 2.17 (001), 2.24 (110), 1.95 (111) experimental: 1.79, 1.83 (111)

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Some basic concepts

Surfaces of other crystal structures

diamond (001) (reconstructed) bcc (001)

diamond (001)

bcc (110) diamond (111)

bcc (111)

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Some basic concepts

Surfaces of crystalline materials most often observed are the low-index ones.

They have the highest atomic densities and consequently the lowest surface energies. High-index surfaces may often viewed as containing facets and steps.
facet, terrace step

These surfaces slightly miscut from a low-index direction are also called vicinal. In growing smooth surfaces vicinal surfaces are often used: step flow growth.

The exact structure of a crystal surface is in most cases not bulk-terminated (or bulk-exposed).

There may be relaxation and reconstruction of the outermost atomic layers

bulk-terminated
Surface physics I 2012: 1. Introduction

relaxed

reconstructed
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Some basic concepts

Surface atoms of an ideal crystal surface form a 2D lattice.

The surface structure may differ from the structure of the substrate: different symmetry, adatoms etc. Let a and b be the lattice vectors of the substrate on the surface plane, and as and layer.

square

hexagonal

bs the corresponding vectors in the surface

c-rectangular

p-rectangular

In case of bulk-terminated surface

as = a

bs = b

oblique

In general case we can write (G is a 22 matrix)

[ ] []
as =G a b bs
Surface physics I 2012: 1. Introduction
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Some basic concepts

The deteminant of the matrix G describes the relationship between substrate and surface lattice vectors.
u.c. area G= a b =surface bulk u.c. area

as b s

If |G| is an integer there is a simple relationship. If |G| is diagonal

G=

[ ]
p 0 0 q

then the following notation is used R{hkl} pq or R(hkl) pq where R is the chemical symbol of the material and {hkl} the surface orientation.

Surface reconstructions reduce the symmetry of the surface. Unreconstructed surface can be denoted as 11

Surface physics I

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Some basic concepts

Sometimes the relationship is not so simple.

E.g. if we have an ad-atom layer of another material on a surface their structures may be incommensurate.

One example is Xe adatoms on graphite surface. There is an interplay between the two interaction: between ad-atoms and between ad-atoms and substrate.
FrenkelKontorova model

Cf. thin film heterostructures, critical layer thickness, misfit dislocations etc. (We will deal with these thing later in SPII).
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Surface physics I

Some basic concepts

A simple example: Si (001)

Si {001} 11

Si {001} 21

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Some basic concepts

A simple example: Si (001)

Dimer rows can be easily seen in STM figures

step edge

step edge

2323 nm2
T. Yokoyama, K. Takayanagi Phys. Rev. B 61 (2000) R5078

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Some basic concepts

A less simple example: Si (111) Si {111} 77

S.H.Ke et al, Phys. Rev. B 62 (2000) 15319.

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Some basic concepts

Basic concepts in crystal growth

Epitaxy: film has the same crystal structure as substrate. Processes on a growing surface deposition
desorption If we want smooth surfaces adatoms must diffuse fast enough to be able to diffusion reach step edges. advacancy High enough temperature T or small enough deposition rate D (atoms/s). In some cases growth can be characterized by the ratio D/T. Substrate T can not be increased without limit: defects Another possibility: low-energy ion beams for local heating.
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Surface physics I

Some basic concepts

Heteroepitaxy

Substrate and growing film have different lattice constants (but same structure) film will be stretched or compressed. Lattice misfit is defined as f = a f as / a s where a f, a s are lattice constants of the film and substrate, respectively. When the film is thick enough it is energetically favourable to create defects: misfit dislocations start growing islands instead of a smooth layer The relative strengths of film-substrate and film-film interactions determine the behavior. Traditionally the growth modes in heteroepitaxy are classified as below.

Frank-van der Merve (FM) Stranski-Krastranov Vollmer-Weber (VW) layer by layer islands with wetting layer island growth growing
Surface physics I 2012: 1. Introduction

f
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Some basic concepts

Example: growth of Ge on Si:

f = 5.66 5.43 / 5.43 =4.2 %

Only a few atomic layers of pure Ge can be grown in a pseudomorphic fashion. After this islands start to form:
A.J.Steinfort et al, Phys. Rev. Lett. 77 (1996) 2009.

6 ML Ge on Si(001) at 430 oC 22002200 2

Island growth is a complicated phenomenon where kinetic effects play a crucial role. By alloying Si and Ge thicker films can be grown.
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Surface physics I