Lecture 2.

Surface atomic structure

“Kinetics of heterogeneous catalytic surface reactions” (Boudart, 1984)

2. Surface atomic structure/reconstruction

2-1. Crystal structure (3D structure)

Crystal: 3D periodic array of atoms

Crystal structure = Lattice + Basis
Lattice: regular periodic arrangement of points in space
Basis: a group of atoms attached to every lattice point

. . . . . .

. . . . . .

. . . . + -> . . .

. . . . . .

. . . . . . .

Lattice Basis Crystal

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14 lattice types in 3D: Table 1 in Kittel, figure 2.17 in Masel

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 2-2. Surface structure (2D structure)

periodic surface non-periodic surface

repeats at regular interval amorphous structure
single-crystal surface most real surface

Surface reconstruction: the surface has a different arrangement than the bulk.

2-2-1. Surface symmetry: 2D Bravais lattice

Unit cell (net): basic repeat unit for the lattice

Primitive unit cell (net): unit cell with smallest area or volume
5 Bravais net + point groups
oblique
p-rectangular
c-rectangular
square
hexagonal

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Fig.2.1 ~ 2.3 & table 2.1 in Woodruff

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2-2-2. Crystallographic orientation of the surface

Single crystal surface is produced by cutting bulk crystal.

Miller indices
- Find intercepts at xyz axis of unit lattice with plane. Then, obtain the
reciprocals of intercepts and multiply by constants to make them
integers, which are Miller indice.
- If the intercept is  (infinity), then 1/ becomes zero.
(Figure 16 in Kittel, p15)

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2-2-3. Overlayer structure: Notations

A. Park and Madden: Matrix Notation

a, b : unit vector of primitive bulk (substrate) net

a*,b* : unit vector of the adsorbate or reconstructed surface
a* = C11 a + C12 b
b* = C21 a + C22 b

 a *  C11 C12   a  a

  =     = C  
22  
 b *  21
C C b b

B. Wood Notation

X(hkl)pq-R-A or X{hkl}(pq)R-A
X : substrate material
{hkl} : surface plane index
p, q : ratio of unit vector lengths

p= a* / a , q= b* / b
 : rotation angle
used only if the included angles of the surface and substrate unit meshes are
the same

Examples : clean unreconstructed Ni(100) = Ni{100}(11)

clean reconstructed Si(100) = Si{100}(21)
Si(100) passivated by H = Si{100}(11)

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2-2-4. Ideally terminated surface structure

A. FCC Lattice

B. BCC Lattice

(100) (111) (110)

C. HCP lattice

(0001) surface plane

e.g. Ru(0001)

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2-2-5. Relaxation and Surface reconstruction

* Rearrangements of Ideally terminated surface

reconstruction: - surface periodicity is different from that of bulk.

- driving force: reduce surface free energy and dangling
bonds.

relaxation: - top atomic layers move in or out with respect to the bulk.
- arrangement of atoms in each atomic layer is unchanged.

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* “Electron density change” Model:

Surface atoms have lower electron density due to less coordination number

Relaxation increases electron density of top layers

Displacement is largely damped by fifth layer

* “Embedded atom model” (EAM): example of studying surface atomic position

Ei = j Vcore(rij) + FEAM(ei)

Ei : Potential energy of atom i, Vcore : core-core repulsion, rij : atomic distance,

FEAM : Electrostatic attraction due to overlap of atom with electrons
ei : Electron density on i due to overlap with i’s neighbors

Energy minimization to calculate surface relaxation

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* Reconstruction of semiconductor surfaces

- Competition between pairing and strain controls final surface structure

- Depends on preparation method and temperature

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 Investigation of surface structure

Direct probing method: STM (scanning tunneling microscopy)

AFM (atomic force microscopy)
Indirect method: LEED (low energy electron diffraction)
RHEED (Reflection high energy electron diffraction)

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 2-2-6. Reconstruction of compound semiconductor

A. Ideally terminated structure of zincblende

(100) (100) (100)

(100)

(110) (111)
(010) (010)
(010)

(001)
(001) (001)

(100) (110) (111)

(111)Cd

(111)Te
Non-polar
(111)

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B. Non-polar surface (110)

- GaAs(110) is stable, while GaAs(100) and GaAs(111) surfaces

reconstruct or facet.
- GaAs(110) is relaxed but no change in periodicity
- Universal relaxation of compound semiconductor (110) face : GaAs,
CdTe, GaP, InP, ZnSe, and etc

C. Polar surfaces : (100), (111)

- (100) and (111) undergo complex reconstructions
- reconstruction depends on preparation method
- for example, GaAs(100) has seven metastable reconstructions
- Compound semiconductor consists of two different atoms, thus
depending on preparation method, it can be cation-rich or anion-
rich.

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2-2-7. Effects of adsorbates on surface structure
- The presence of a chemisorbed layer removes the relaxation and
often the reconstruction observed for clean surfaces
- New surface restructuring
- When adsorbates are removed, substrate surface returns to its
clean-state configuration

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