Vicinal Surfaces

Cyrille BARRETEAU 1 Marie Catherine Desjonqures Daniel Spanjaard 2 and Fayal Raouafi 1
1

SPCSI

Service de Physique et Chimie des Surfaces et Interfaces (SPSCI) Groupe Modlisation Surfaces Interfaces et Nanostructures (MSIN) DRECAM, CEA-Saclay, 91191 Gif sur Yvette
2

Laboratoire de Physique des Solides (LPS) Universit Paris Sud, 91405 Orsay

Overview
1) Introduction 2) Calculation Methods
Tight-Binding Empirical potential

Published in
3) Geometry and calculation details 4) Energetics of vicinal surfaces
Step and kink energy Effective Pair Potential Step-step interaction Island shapes

Surface Science
505 (2002) 183

5) Electronic Structure 6) Phonons 7) Stability of vicinal surfaces Surface Science

In press

Physical Review Letters

88 (2002) 56104

Phys. Rev B: submitted

Why study vicinal surfaces?

1) Any surface has steps

2) surface morphology
Crystal shape Step roughening transition Epitaxial growth
Equilibrium shape of adislands

from ( , )

T Fstep

3) Stability with respect to faceting

Vicinal surface Faceted surface

OR
Monoatomic steps Factory roof

Which model and what you get ? Phenomenological description Discrete Hamiltonian Continuous model f(p)
General behaviors

Empirical potentials EAM EMT Second Moment

Step energies, elastic step-step interaction, no QM Step energies, elastic step-step interaction, no QM

Electronic structure methods Ab-initio Tight-binding

Step energies, step-step interaction, electronic structure Step energies, step-step interaction, electronic structure

Tight-Binding Method Hamiltonian Basis

< i | H | j > i j

H = T + V (r R i)
| i > = s, p( x , y , z ), d ( xy, yz , zx, x 2 y ,3 z 2 r 2)
2

10 Hopping integrals
(2 center approximation)

ss , sp , sd , pp , pp , dd , dd , dd = SK

Rij // Oz

SK = SK ( R ) f c ( R )

< i | H | i >

3 on-site terms
orthogonal

a b +c = (R ) f (R )
i

2 /3 i

4/ 3 i

2 i

ij

ij

j i

Non-orthogonal

< i | j >= ij
Eigenvalue eq.

< i | j >= S ij
Generalized eigenvalue eq.

H X = X
tot

HX = SX
V
i

Total Energy Local charge neutrality

E =
nocc
0 i

+ V
=
i

tot

nocc

Empirical Potential Embedding potential

E=
i , ji j

V (R ) f
ij

c ( Rij ) +

F ( )
i i

i =

g (R ) f ( R )
ij c ij ji

Embedding function

density

i = Z 1 + Z i2 g 2 i (rigid lattice) g ( R1 ) = 1

Second Moment Second Moment (SMA) (SMA)

EAM/EMT EAM/EMT
F ( ) = .....

Modified SMA Modified SMA F ( ) =

F ( ) =

Vicinal Surface Geometry

p (hkl ) (h' k ' l ' )

energetics
( n) tan( ) = (n 0 ) + ( ) cos( ) h
Surface energy per unit projected area
Step energy per unit length

Calculation procedure Convenient formulation

E step ( p ) = E S ( p ) ( p 1 + f ) E S ( )
Step energy per step atom Surface energy per surface atom

Slab geometry
N layers

ES =

E slab NEbulk 2

Calculation details
Number of vicinal planes: Fermi broadening: Number of k points: Energy convergence: 11xp 0.2eV 64 1meV

E ( 0) E (Tel ) 1 Tel S (Tel ) 2

Step energies
E step = E step ( p )

Vicinal surface

Step energy (eV/atom)

p
Rh
p ( 111 ) ( 100 ) (A) p ( 111 ) ( 1 11 ) (B) p ( 100 ) ( 111 ) p ( 100 ) ( 010 ) p ( 110 ) ( 111 ) p ( 111 ) ( 100 ) (A)

TB
0.638 0.645 0.393 0.747 0.056 0.425 0.432 0.289 0.536 0.027 0.348 0.345 0.191 0.352 0.060
2V1 + 4V3 2V1 + 4V3 V1 + 2V 2 2V1 + 2V2 V2 + 2V3 2V1 + 4V3 2V1 + 4V3 V1 + 2V 2 2V1 + 2V2 V2 + 2V3 2V1 + 4V3 2V1 + 4V3 V1 + 2V 2 2V1 + 2V2 V2 + 2V3

Effective Pair Potential

0.657 0.657 0.407 0.738 0.035 0.429 0.429 0.295 0.533 0.006 0.347 0.347 0.192 0.359 0.020

TB

Pd

p ( 111 ) ( 1 11 ) (B) p ( 100 ) ( 111 ) p ( 100 ) ( 010 ) p ( 110 ) ( 111 ) p ( 111 ) ( 100 ) (A)

Cu

p ( 111 ) ( 1 11 ) (B) p ( 100 ) ( 111 ) p ( 100 ) ( 010 ) p ( 110 ) ( 111 )

0.583 0.583 0.288 0.550 0.043 0.460 0.460 0.106 0.265 0.045 0.380 0.380 0.200 0.363 0.046

Vitos

0.520 0.520 0.265 0.480 0.070 0.423 0.423 0.222 0.427 0.015

Methfessel

0.650 0.650 0.295 0.580 0.045

Eichler

0.670 0.670 0.285 0.596 0.011 0.500 0.500 0.298 0.548 0.024 0.426 0.426 0.241 0.456 0.011

Galanakis

Effective Pair Potential

Edefect =

i =1

nieff Vi

(Vitos et al.)

fcc (111) fcc (100) fcc (110)

V1 V2 V3

E defect

EPP works suprisingly well Large discrepancy between different calculations Good agreement for (111) surfaces Very small step energy for (110)

BUT
No distinction between A and B steps No step-step interaction

Pair interactions
Surface energies (ev/atom)

(111)

(100) 1.379 1.310 1.27 1.47 1.404 0.828 1.152 0.89 1.049 0.748 0.906 0.874

(110) 2.112 1.919 1.84 2.13 2.047 1.317 1.559 1.33 1.596 1.121 1.323 1.327

V1
0.332 0.262 0.215 0.285 0.311 0.238 0.159 0.205 0.250 0.166 0.163 0.215

V2
0.038 0.013 0.025 0.005 -0.013 0.029 -0.027 0.008 0.014 0.013 0.018 0.013

V3
-0.001 0.015 0.023 0.020 0.012 -0.011 0.036 0.003 0.000

Reference This work Vitos et al Methfessel et al Eichler et al Galanakis et al This work Vitos et al Methfessel et al Galanakis et al

V10
0.352 0.324 0.313 0.360 0.344 0.217 0.269 0.223 0.269 0.188 0.224 0.221

Rh

Pd

1.091 1.002 0.99 1.11 1.034 0.655 0.824 0.68 0.822 0.581 0.707 0.675

Cu

0.004 This work 0.014 Vitos et al -0.001 Galanakis et al

Island Shapes

-plot

rA A = rB B

Island shape

Fcc(111)

Fcc(100)
2 A / B < 1
square

A = B
Regular hexagon

LA 2 A / B = LB 2 A / B 1

L A > LB A < B

LA = LB

2 A / B 2 A / B 1

2 A / B > 1
broken corners square

Comparison with experiment Only available data for Copper Fcc(111) Experiment
E 111 = 0 .27 eV/step atom step
A Estep B Estep

Tight-binding
E 111 = 0. 346 eV/step atom step
A Estep B Estep

= 1.1% + 1

= 0.9% + 1

Fcc(100) Experiment
A E step = 0.22 eV/step atom B E step rB = = 1.24 A rA 2 E step

Tight-binding
A E step = 0.191 eV/step atom B E step rB = = 1.30 A rA 2 E step

Step-step interaction Different types of interactions entropic

Non-crossing of steps

1 / L2

elastic
Atomic relaxation

1 / L2

1 / L2

dipole-dipole

Electric dipole at step edges

cos(2k F L + ) Ln

electronic Friedel oscillation

kink energies
Supercell geometry

4 E kink = 2 Ekinked ( r , s, v ) [ E ( s, v ) + E ( s 1, v + 1)]

(terrace)x(ledge)

Rh
0.339 0.329 0.349 0.332

Pd
TB 0.249 0.242 0.247 0.238 0.143 0.148 0.146 0.166

Cu
Other Calc. 0.092 0.117 0.139 Experiments 0.1130.007 0.1210.007 0.123 ; 0.129

(111) (100)

(111) (111)
(100) (111)

V1

Electronic structure
Local density of states

surface sites

step sites

kink sites

Electronic structure No LCN

Rh(111) surface

LCN

Surface state

Ab-initio (Eichler)

Electronic structure
Rh p(111)x(100) surface

Surface state

Spectral density of states at

Phonons Generalized Second Moment Potential

E=A
i, ji j

(R

/ R ij) f c ( Rij )

exp( 2 q ( Rij / R0 )) f c ( R ij ) j i

2/ 3

Fit on

cohesive energy Ec bulk Modulus B C, C ' shear moduli

Rc = 4 (2nd neighbours )

Copper
A = 0 .206 eV = 1.102 eV p = 7. 206 q = 2 .220

Harmonic approximation
Energy minimization: conugate gradient algorithm

Dynamical Matrix
Dij

1 2E = M ri r j

Vibrational spectra

Bulk Cu

Cu(001)

Vibrational spectra

Cu (211)

Cu (511)

3(111) (100)

3(100) (111)

Stability of vicinal surfaces Faceting or not faceting?

(that is the question)

S < 0 S 0 + 1S1
Same average orientation

S > 0 S 0 + 1 S1
= tan( ) , f ( ) = ( ) cos( )
f(?) > 0
Position of f( ) wrt straight-line f ( ) (1 / 1 ) f (0) + / 1 f (1 )
= (n, n 0 ), 1 = ( n1 , n 0 )

f(? ) < 0

Stability of vicinal surfaces p(100)x(111) and p(111)x(100)

= tan( ) = 0

(2p-1,1,1)
p

(p+1,p-1,p-1)
Intermediate surface p=2

= tan( ) =
Vicinals of (100)

2 3

Vicinals of (111)

= tan( ) = 2

Stability of vicinal surfaces Rigid lattice Pair potential

f ( )

Rc < R5
f ( )

No step interaction

V3
(100)

(311)

V3 > 0 stable

(111)

(100)

V3 < 0 unstable

(311)

(111)

Embedding potential
d 2F >0 2 d
f ( )
(311)

Rc < R3
(111)

No step interaction

[ F (7 + g 2 ) F (9 + 3 g 2 )] [ F (8 + 5 g 2 ) F (10 + 5 g 2 )]

outer edge

(100)

inner edge

(100)

(111)

Always unstable

Stability of vicinal surfaces Embedding potential further neighbours Effect of atomic relaxation
Short range Interaction influence on the stability Repulsive elastic interaction positive curvature small influence on stablity

Stability of vicinal surfaces Tight-binding Great variety of scenarii Faceting between 2 vicinals

Faceting between (100) and (111)

Vicinal surface stable

Stability of vicinal surfaces What about Phonons?

From Frenken and Stoltze: stabilization but Einstein model, S only, and one term missing
+

Vibrational Free energy

Fvib = 3k B T ln[2 sh ( 2 k
0

h )]n( )d T B

Very small effect destabilization effect

Conclusions Vicinal surfaces have a rich and subtle behavior Empirical potentials lead to a too schematical behavior Only calculations based on the determination of the electronic states allow to account for the diversity of experimental possibilities.