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Adhesion of water
molecules to tube surface
is stronger than cohesion
between water molecules.
or
2) by altering the local
surface atomic geometry
reconstructing in a way
which reduces the surface
Reconstructed fcc(110)
free energy Relaxed Surface (d1-2 < dbulk )
or
3) by adsorption
form the gas
phase
fcc(100)+c(2x2)-Ad
For more complicated situations, eg. alloys,
the surface energy may be reduced :
1. by segregation
Increasing concentration
of red element
2. by adsorbate induced
segregation
Before adsorption After adsorption
4. by clustering
3. by forming a
superstructure
PtCo(100)
Pt bright
Co black (almost
invisible)
Bulk Thermodynamics: A Short Reminder
Any one-component system, in equilibrium, is described completely by the
internal energy U
U U(S,V, N)
where S is the entropy, V the volume, and N the number of moles.
The infinitesimal variation of U is thereby
U U U
dU dS dV dN
S V ,N V S,N N S,V
which becomes
dU TdS pdV dN
with T the absolute temperature, p the pressure, and the chemical potential.
The extensive property U is described as U(S, V, N) U(S,V, N)
Reminding that U TS pV N
And combining its differential with the above equations one arrives at the Gibbs-
Duhem equation among the intensive variables
SdT Vdp Nd 0
Bulk + Surface Thermodynamics
The question is now: How does all this stuff change when treating a system
with a free surface?
When a surface of area A is created, via a cleavage process, the total internal
energy of the system must increase by an amount proportional to A, since
otherwise this process would occur spontaneously.
with ij and ij the components of stress (N/m) and strain (pure number) tensors
which have 6 independent components
Definition of the interface region: At equilibrium, at any finite T and p, the semi-
infinite solid co-exists with its vapor and the system can be modeled as:
Once the surface volume Vs is chosen, the other surface variables, Ss and Ns, are
defined as excesses N A S
[ ( z ) ( z )]dz
interface
s 1, 2
Ss S1 S2
We then have the following relations: Vs V1 V2
Ns N1 N2
Adg S s dT Vs dp N s d A (g ij ij )d ij 0
i, j
The interesting thing is that one can now show that the quantity in brackets
is independent of the arbitrary boundary conditions which define Ns, Vs,
and Ss.
Gibbs assumed for the surface volume that the number of particles outside the surface
plane is equal to those missing in the inside. This is known as the equal area
convention. However, one can assume Vs 0 and N s 0
with no loss of generality.
Adg S s dT A (g ij ij )d i , j 0
i, j
and obtain:
The surface tension g can be measured by opposing the creep with known external
forces.
An estimate of surface tension can be obtained from
g Ecoh Zs Z Ns
where Ecoh is the bulk cohesive energy, (Zs/Z) the fractional number of
bonds broken (per surface atom), and Ns the surface areal density.
Using typical values:
Since this stress takes place over the surface thickness (1nm) the
corresponding pressure is 1 Gpa. This means that neglecting the external
pressure in surface thermodynamics is in general justified.
Anisotropy of g
The surface tension of a planar solid depends on the crystallographic
orientation of the sample.
[1n0]
q d)
Vicinal surfaces:
surfaces slightly misaligned with respect to a
specific direction
The anisotropy of the surface tension is represented
via the g-plot constructed by drawing a vector from the
origin in the direction n (defined by its polar and
azimuthal angles q and f) with a length equal to the
surface tension, g(n), of the surface plane perpendicular
to n.
The asphericity of the g-plot reflects the anisotropy of g which has minima in
the directions n0 corresponding to close-packed surfaces.
bq
g (n) g (n 0 )
d
where n0 defines a close-packed surface, q is the angle between n and n0, and d is
the interplanar distance along n0. |q|/d is the density of steps.
dg
dg/dq has discontinuities at q = 0, more precisely: 2b d
dq q 0
and the g-plot shows cusps in directions typical of the most close-packed surfaces.
For large q values, the density of steps increases and one has to include the
energy of interaction between steps.
dg 1
4
dq n
Finite Crystal limited by a surface S.
The equilibrium shape must minimize the excess surface free energy
while preserving the volume:
Fs g (n)dS
S
The variational geometric problem was solved by Wulff (1901).
Draw a radius vector intersecting the polar plot at one point and making a fixed angle
with the horizontal.
Construct the plane perpendicular to the vector at the intersection.
Repeat this procedure for all angles.
g p (q ) g0
cos(q ) d
is thereby the line tension for up and down steps (not identical for (111)
surfaces where A and B steps have different structures). The expression can be
considered as the first order of a series expansion
g p (q ) g 0 g 1 p g 2 p 2 ...
in which the higher order terms correspond to the step - step interactions
(proportional to 1/L for the 2p2 term).
Semi-infinite Crystal limited by a plane S with normal at q =0
Now let us study its stability relative to a small polar buckling preserving
the average orientation.
The free energy of the buckled S surface is
dA
FS g (q )dA' g (q )
S S
cos q
An expansion up to second order in q gives:
dg 1 d 2
g
Fs g (0) A q dA q
2
g (q ) dA
dq q 0 dq
2
S
2S q 0
The second term vanishes for symmetry reasons and the energy involved
in the deformation is thus the last term.
g (0) (d g dq )q 0 0
2 2
g (0) (d g dq )q 0 0
2 2
Imagine to have a planar surface with a large surface free energy in a highly
anisotropic crystal.
Some energy can be gained by replacing the smooth surface with a saw-tooth
profile while preserving the average orientation.
Construction
of the Wulff
equilibrium
shape
bcc crystallite
Tensile and compressive stress at bare
and adsorbate covered surfaces
>0 <0
The charge which is not shared by the missing atoms redistributes on the
surface plane causing an attractive force on the ion cores. A free standing 2D
layer of atoms would thus have a smaller lattice constant. Since teh atoms are
kept in register by the substrate lattice a tensile tension of approx 1N/m builds
up (corresponding to a bulk stress of 1 Gpa)
Consequencies for crystal growth
Warning growth occurs in conditions
far from equilibrium
For an anisotropic solid the condition of
equilibrium of i different phases is:
For a deposit, and assuming a rough surface in order to neglect the derivative of
otherwise
Roughening Transition
Warning: One must now include explicitly also entropy effects when
treating these T-dependent phenomena
As T increases
fluctuations appear
along with more and
more defects.
1) The cubes are arranged into columns of different heights, hi
2) These columns (one for each surface atom) can interact each other
3) J represents the finite energy cost if nearest neighbor columns differ in
height by one lattice constant
2
4) In general one takes H J hi hj
i, j
under the condition that the surface is perfectly flat at T = 0K
SOS Model:
The lowest energy excitations are monoatomic steps coalescing into plateaus
z=0
The number of possible loops of this length is equivalent to the number of self-
avoiding random walks returning to the origin in L/d steps.
The number of these loops is zL/d
L
The contribution to free energy is thereby F U TS ( J kT ln z )
d
Below the roughening transition temperature, kTR = J/ln z
the contribution to F is positive and L = 0 is favored.
Above TR, loops of arbitrarily large length occur and the surface
becomes rough.
Equilibrium shapes of Pb crystals at selected Ts
Morphology of Pb
crystals as a function
of the growth
temperature T
T393 K
323 K T 393 K
Facets
T323 K
The hierarchy of
equilibria
Noteworth exceptions are the reconstructed Au(111), Au(100), Ir(100) and Pt(100).
The borders are then stabilized when the reconstruction matches the terrace width
making the system effectively 2 dim.
The surface reconstruction of Au is lifted in contact with an
electrolyte. In such cases the shape of the islands behaves
differently than in ultra high vacuum
Surface tension and
thin film growth