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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
Relaxed Surface (d1-2 < dbulk ) Reconstructed fcc(110)
free energy
or
3) by adsorption
form the gas
phase
fcc(100)+c(2x2)-Ad
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 + µdN
with T the absolute temperature, p the pressure, and µ the chemical potential.
The extensive property of U is described as U( λS, λV, λN) = λU(S,V, N)
Reminding that U = TS − pV + µN
And combining its differential with the above equations one arrives at the Gibbs-
Duhem equation among the intensive variables
with σij and εij the components of stress and strain 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 ∫
[ ρ ( z ) − ρ ( z )]dz
interface
i 1, 2
Ad γ + S s dT − V s dp + N s d µ + A ∑ (γδ ij − σ ij ) d ε 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 V s = 0 and Ns = 0
with no loss of generality.
Ad γ + S s dT + A ∑ ( γδ ij − σ ij ) d ε i , j = 0
i, j
and obtain:
Warning: surface tension (γ) and surface stress (σ) are not identical in general
except for liquids and the surface stress must be relieved in other ways, e.g. by
creating dislocations and by elastic buckling
For Au(111) ∂γ ∂ε < 0
and Au foils contract (so called creep) when atom diffusion is activated (e.g. by
heating a gold foil near the melting point) because atomic diffusion occurs under
the influence of surface forces.
The surface tension γ can be measured by opposing the creep with known external
forces.
An estimate of surface tension can be obtained from
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 γ
The surface tension of a planar solid depends on the crystallographic
orientation of the sample.
[1n0]
θ d)
Vicinal surfaces:
surfaces slightly misaligned with respect to a
specific direction
The anisotropy of the surface tension is represented
via the γ-plot constructed by drawing a vector from the
origin in the direction n (defined by its polar and
azimuthal angles θ and φ) with a length equal to the
surface tension, γ(n), of the surface plane perpendicular
to n.
The asphericity of the γ-plot reflects the anisotropy of γ which has minima in
the directions n0 corresponding to close-packed surfaces.
βθ
γ (n ) = γ (n 0 ) +
d
where n0 defines a close-packed surface, θ is the angle between n and n0, and d is
the interplanar distance along n0. |θ |/d is the density of steps.
dγ
dγ/dθ has discontinuities at θ = 0, more precisely: ∆ = 2(β d )
dθ θ =0
and the γ-plot shows cusps in directions typical of the most close-packed surfaces
which persist unless the surface becomes rough.
For large θ values, the density of steps increases and one has to include the
energy of interaction between steps.
dγ 1
∆ ≈ 4
dθ n
Finite Crystal limited by a surface S.
The equilibrium shape must minimize the excess surface free energy
while preserving the volume:
Fs = ∫∫ γ (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.
γ (θ ) β ± tan θ
γ p (θ ) = = γ0 +
cos( θ ) d
β± 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
γ p (θ ) = γ 0 + γ 1 p + γ 2 p 2 + ...
in which the higher order terms correspond to the step - step interactions
(proportional to 1/L for the γ2p2 term).
Making reference to the figure and
defining the shape function around a
facet as z(x) with z the orientation
parallel to θ=0. We can write:
R R R
γ p (θ ) / γ 0 = cos( 90 ° − θ − α ) = sin( θ + α ) = (sin( α ) cos θ + cos( α ) sin θ )
z0 z0 z0
1
γ p (θ ) / γ 0 = ( z cos θ + x sin θ )
z0
) xγ 0 ) zγ 0
with the reduced coordinates x= z =
z0 z0
) )
γ p ( p) = z + xp
The parametrized form of the shape
function is thus:
)
x = γ 'p ( p ) = γ 1 + 2 γ 2 p + 3γ 3 p 2 ...
) )
z = γ p ( p ) − x p = γ p ( p ) − γ 'p ( p ) p
= γ 0 − γ 1 p 2 − 2 γ 2 p 3 − ...
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 ′ = ∫ γ (θ )dA' = ∫ γ (θ )
S′ S′
cos θ
An expansion up to second order in θ gives:
d γ 1 d 2
γ
Fs′ = γ ( 0 ) A + ∫ θ dA + ∫ θ
2
+ γ (θ ) dA
dθ θ =0 dθ
2
S
2 S θ =0
The second term vanishes for symmetry reasons and the energy involved
in the deformation is thus the last term.
γ (0) + (d γ dθ )θ =0 > 0
2 2
γ (0) + (d γ dθ )θ =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.
When ever the surface stiffness is negative the surface facets generating
more stable nanosized surface areas (as e.g. for surface reconstruction)
Crystal temperature dependence of γ
The Helmholz free energy decreases
with as U-TS and so does the surface
tension. The cusps become less and less
well defined. When γ becomes isotropic
the surface is said to be rough and the
crystal assumes a spherical shape
Strongly anisotropic case
Construction
of the Wulff
equilibrium
shape
bcc crystallite
Tensile and compressive stress at bare
and adsorbate covered surfaces
σ>0 σ<0
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 γ
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 correspond are monoatomic steps coalescing
into plateaus
323 K ≤T ≤393 K
Facets
T≤323 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