Surface and Interface Science

Physics 627; Chemistry 542

Surface Properties

Structure
Chemical composition
Bonding properties
Kinetics (adsorption, diffusion, desorption, catalysis)
Dynamics of surface processes
Statistical mechanics of 2-D systems

Applications of Surfaces

Catalysis
Corrosion
Friction, lubrication
Semiconductor devices
Electrochemistry

Probing Surface Properties

E-field

atoms, molecules
heat
e- ions

atoms, molecules
ions

e-

hu
(IR X-rays)

hu

Usually, strongly interacting probes!!

The first half of this course will focus on:

Atomistic properties of surfaces

Electronic properties
Chemical composition
Adsorption properties

The second half of this course will deal with applications:

Biomedical applications
Surface magnetism
Calculation procedures
Devices

Examination:
Homework problem set (?)
3 labs
Term paper

Primary text: Zangwill Physics at Surfaces

Also: Woodruff and Delchar: Modern Techniques of Surface Science

Lectures 1 and 2
Surface crystallography

References:
1) Zangwill, Chapter 1
2) A.W. Andersen, Physical Chemistry of Surfaces, Fifth Edition (J. Wiley, New
York, 1990) Chapter VII
3) J.M. Blakely and M Eizenberg in Vol. 1, Clean Solid Surfaces, The Chemical
Physics of Solid Surfaces and Heterogeneous Catalysis, ed. By D.A. King
and D.P. Woodruff (Elsevier, Amsterdam, 1981) p. 1
4) G. A. Somorjai, Introduction to Surface Chemistry and Catalysis, Chapter 3.
5) A. Keijna and K.F. Wojcieckowski, Metal Surface Electron Physics, Chapter 3;
Chapter 8.

Surface structure starting with the bulk

Simple cubic (sc)

hcp

vs

fcc

Miller Indices
For simple cubic lattice,
consider plane that is shaded.
Vector from origin intercepts
that plane at x, y, z = 1, ,
The Miller indices of this plane are:

1 1 1
, , 1,0,0
1

In two dimensions (2D crystals)

intercept (, 1) (0, 1)
intercept (1, 1) (1, 1)

A. Bulk truncation structures

Miller Indices (more)

1 1 1

For plane with intersections bx, by, bz write: b , b , b

x y z

bz
by
bx

[100]

(100)
z

4
x

[ 420]

cd cd cd
In general: (i j k) = , ,
b b b
x y z
where cd = smallest common denominator

12 12 12
Here (i j k) = , , (364)
4 2 3
In fcc and bcc
x, y, z, -x, -y, -z all equivalent (100), (010), ( 1 00) , etc.
all equivalent.

[ 403]

If all quotients intergers or 0, this is a Miller Index.

e.g., 1, 1, 0.5 (112)
For cubic 1 (100)

y
NOTE: (i j k) identifies plane;
[i,jk] identifies vector ^ plane defines direction.7

A. Bulk truncation structures

Very different surfaces:

Close packed: fcc(111)
Very rough:
fcc(210)

bcc(110)
bcc(111)

bcc: 8 n.n.

fcc: 12 n.n.

Note: Cross product of two vectors in a plane defines direction perp. to plane:
[i j k] = [s t w] x [p q r] where latter vectors lie in (i j k).
Angle between two planes:
[i j k]

cos

ijk lmn
i 2 j 2 k 2 l 2 m2 n2

[l m n]
e.g., for [1 1 1] and [2 1 1] : cos

2 11
19.47
3 6

A. Bulk truncation structures

fcc(100)

bcc(100)

hcp(100)

fcc(110)

bcc(110)

hcp(110)

fcc(111)

bcc(111)

hcp(111)

10

A. Bulk truncation structures

For HCP surfaces:

cd cd cd

bx by bw bz

ijkl cd
But i + j = -k

So often use 3-digit notation

Basal plane (b): (0 0 0 1) = (0 0 1)

1 1 1 1
Side (c)
10 1 0
1

1 1 1 1
Side (d) 1 1 1 01 1 1

In hcp, (1 0 0) (0 0 1)
NOTE: fcc(111) and hcp (0001) have same top layer structure,
but stacking is different: hcp: ABAB; fcc: ABCABC

11

More than one kind of atoms

Wurtzite = hcp + basis

Example: GaN

Zinkblende = two
interpenetrating fcc
lattices
Example: GaAs, ~ Si (all
atoms the same)
12

Polar surfaces

Side view of 4-H silicon carbide. A,

B and C are three inequivalent
rows of atoms.
Stacking: a-b-c-b-a
A B C

Red = Si, Black = C

Note the two different

terminations

13

A. Bulk truncation structures

14

B. Relaxations and reconstructions

Crystal termination often not bulk-like
Shifts in atomic positions may be perpendicular and/or parallel to surface
Selvedge region extends several atomic layers deep
Rationale for metals: Smoluchowski smoothing of surface electronic charge
dipole formation
Relaxation: no lateral motion
Usually vertically inwards,
sometime outwards

For semiconductors: heal dangling bonds;

often lateral motion. Relax. Often oscillatory
d23

d45

dbulk
surface

d12

d34
bulk

d56

Surface d12(%)
Ag(110) -8
Al(110) -10
Au(100)
0
Cu(110) -10
Cu(310)
-5
Mo(100) -12.5

15

C. Classification of 2-D periodic structures

Periodic Lattice: repeat unit is unit cell

Unit cell is not unique.

Propagate lattice: n, m integers

T na1 ma2
Primitive cell: unit cell w/smallest
area, shortest lattice vectors,
smallest number of atoms
(if possible: |a1| = |a2|; g = 60, 90, 120;
1 atom)
Symmetry:
translational symmetry // surface;
rotational symmetry: 1, 2, 3, 4, 6
mirror planes; glide planes.
All 2-D structures w/1 atom/unit cell have
at least one two-fold axis.
16

C. Classification of 2-D periodic structures

For 1 atom/cell and 2-D periodic structure, only 5 symmetrically different lattices
Bravais Lattices
When more than 1 atom/cell, more
complicated
5 Bravais lattices
10 2-D point symmetry groups
17 types of surface structure

D. Substrate and Surface Structures

Suppose overlayer of substrate surface layer has lattice different from bulk:
Substrate:
Overlayer:

Ta na1 ma2

Tb nb1 mb2
17

D. Substrate and Surface Structures

Woods Notation: Simplest, most descriptive notation method
(NOTE: fails if a a or bi/ai irrational)
ai

aj

b1

a1

b2

bi

a2
bj
Determine relative magnitude of respective as and bs.
Identify angle of rotation ( = 0 here).
Notation: b1 b2
for above overlayer, (2 x 2) [often called p(2 x 2)]

Hexagonal

R
a1 a2

(2 x 2)

3 3 R30

18

D. Substrate and Surface Structures

Classification of Lattices

19

D. Substrate and Surface Structures

Examples of
coincidence lattice

Note that symmetry

does not identify
adsorption sites
all (2 X 2)
= 1/4

Domain structures:
(1 X 2) = (2 X 1)
20

D. Substrate and Surface Structures

Ambiguity: fcc(110) reconstruction models for (2 X 1) periodicity
Missing Row

Paired Row

Saw Tooth

Another complication:
indexing of stepped surfaces

21