Surface states

Surface states are electronic states found at the surface of materials. They are formed due to the sharp transition from solid material
that ends with a surface and are found only at the atom layers closest to the surface. The termination of a material with a surface leads
to a change of the electronic band structure from the bulk material to the vacuum. In the weakened potential at the surface, new
[1]
electronic states can be formed, so called surface states.

Contents
1 Origin of surface states at condensed matter interfaces
1.1 Shockley states and Tamm states
1.2 Topological surface states
2 Shockley states
2.1 Surface states in metals
2.2 Surface states in semiconductors
2.3 Surface states of a three-dimensional crystal
2.4 True surface states and surface resonances
3 Tamm states
4 Extrinsic surface states
5 Angle resolved photoemission spectroscopy (ARPES)
6 References

Origin of surface states at condensed matter interfaces

As stated by Bloch's theorem, eigenstates of the single-
electron Schrdinger equation with a perfectly periodic
potential, a crystal, areBloch waves [2]

Here is a function with the same periodicity as the

crystal, n is the band index and k is the wave number. The
allowed wave numbers for a given potential are found by
applying the usual Bornvon Karman cyclic boundary
conditions .[2] The termination of a crystal, i.e. the
formation of a surface, obviously causes deviation from
perfect periodicity. Consequently, if the cyclic boundary
conditions are abandoned in the direction normal to the
surface the behavior of electrons will deviate from the Figure 1. Simplified one-dimensional model of a periodic
behavior in the bulk and some modifications of the crystal potential terminating at an ideal surface. At the
electronic structure has to be expected. surface, the model potential jumps abruptly to the vacuum
level (solid line). The dashed line represents a more
A simplified model of the crystal potential in one realistic picture, where the potential reaches the vacuum
dimension can be sketched as shown in figure 1 .[3] In the level over some distance.
crystal, the potential has the periodicity, a, of the lattice
while close to the surface it has to somehow attain the value
of the vacuum level. The step potential (solid line) shown
in figure 1 is an oversimplification which is mostly
convenient for simple model calculations. At a real surface
the potential is influenced by image charges and the
formation of surface dipoles and it rather looks as indicated
by the dashed line.
Figure 2. Real part of the type of solution to the one-
dimensional Schrdinger equation, which correspond to the
Given the potential in figure 1, it can be shown that the
bulk states. These states have Bloch character in the bulk,
one-dimensional single-electron Schrdinger equation gives
while decaying exponentially into the vacuum.
two qualitatively different types of solutions.[4]

The first type of states (see figure 2) extends into

the crystal and has Bloch character there. These
type of solutions correspond to bulk states which
terminate in an exponentially decaying tail
reaching into the vacuum.
The second type of states (see figure 3) decays
exponentially both into the vacuum and the bulk
crystal. These type of solutions correspond to
surface states, with wave functions localized
close to the crystal surface. Figure 3. Real part of the type of solution to the one-
dimensional Schrdinger equation, which correspond to
The first type of solution can be obtained for both metals surface states. These states decay into both the vacuum
and semiconductors. In semiconductors though, the and the bulk crystal and thus represent states localized at
associated eigenenergies have to belong to one of the the crystal surface.
allowed energy bands. The second type of solution exists in
forbidden energy gap of semiconductors as well as in local
gaps of the projected band structure of metals. It can be shown that the energies of these states all lie within the band gap. As a
consequence, in the crystal these states are characterized by an imaginarywavenumber leading to an exponential decay into the bulk.

Shockley states and Tamm states

In the discussion of surface states, one generally distinguishes between Shockley states[5] and Tamm states,[6] named after the
American physicist William Shockley and the Russian physicist Igor Tamm. However, there is no real physical distinction between
the two terms, only the mathematical approach in describing surface states is dif
ferent.

Historically, surface states that arise as solutions to the Schrdinger equation in the framework of thenearly free
electron approximationfor clean and ideal surfaces, are calledShockley states. Shockley states are thus states
that arise due to the change in the electron potential associated solely with the crystal termination. This approach is
suited to describe normal metals and somenarrow gap semiconductors. Figures 1 and 2 are examples of Shockley
states, derived using the nearly free electron approximation.
Surface states that are calculated in the framework of atight-binding model are often called Tamm states. In the
tight binding approach, the electronicwave functions are usually expressed aslinear combinations of atomic orbitals
(LCAO). In contrast to the nearly free electron model used to describe the Shockley states, theamm T states are
suitable to describe alsotransition metals and wide gap semiconductors.[3]

Topological surface states

All materials can be classified by a single number, a topological invariant; this is constructed out of the bulk electronic wave
functions, which are integrated in over the Brillouin zone, in a similar way that the genus is calculated in geometric topology. In
certain materials the topological invariant can be changed when certain bulk energy bands invert due to strong spin-orbital coupling.
At the interface between an insulator with non-trivial topology, a so-called topological insulator, and one with a trivial topology, the
interface must become metallic. More over, the surface state must have linear Dirac-like dispersion with a crossing point which is
protected by time reversal symmetry. Such a state is predicted to be robust under disorder
, and therefore cannot be easily localized.
SEE http://rmp.aps.org/abstract/RMP/v82/i4/p3045_1

Shockley states

Surface states in metals

A simple model for the derivation of the basic properties of states at a metal surface is a semi-infinite periodic chain of identical
atoms.[1] In this model, the termination of the chain represents the surface, where the potential attains the value V0 of the vacuum in
the form of a step function, figure 1. Within the crystal the potential is assumed periodic with the periodicity a of the lattice. The
Shockley states are then found as solutions to the one-dimensional single electron Schrdinger equation

with the periodic potential

where l is an integer, and P is the normalization factor. The solution must be obtained independently for the two domains z<0 and
z>0, where at the domain boundary (z=0) the usual conditions on continuity of the wave function and its derivatives are applied.
Since the potential is periodic deep inside the crystal, the electronic wave functions must be Bloch waves here. The solution in the
crystal is then a linear combination of an incoming wave and a wave reflected from the surface. For z>0 the solution will be required
to decrease exponentially into the vacuum

The wave function for a state at a metal surface is qualitatively shown in figure 2. It is an extended Bloch wave within the crystal
with an exponentially decaying tail outside the surface. The consequence of the tail is a deficiency of negative charge density just
inside the crystal and an increased negative charge density just outside the surface, leading to the formation of a dipole double layer.
The dipole perturbs the potential at the surface leading, for example, to a change of the metal
work function.

Surface states in semiconductors

The nearly free electron approximation can be used to derive the basic properties of surface states for narrow gap semiconductors.
The semi-infinite linear chain model is also useful in this case.[4] However, now the potential along the atomic chain is assumed to
vary as a cosine function

whereas at the surface the potential is modeled as a step function of height V0. The solutions to the Schrdinger equation must be
obtained separately for the two domains z < 0 and z > 0. In the sense of the nearly free electron approximation, the solutions obtained
for z < 0 will have plane wave character for wave vectors away from the Brillouin zone boundary , where the dispersion
relation will be parabolic, as shown in figure 4. At the Brillouin zone boundaries, Bragg reflection occurs resulting in a standing
wave consisting of a wave withwave vector and wave vector .
Here is a lattice vector of the reciprocal lattice (see
figure 4). Since the solutions of interest are close to the
Brillouin zone boundary, we set , where is
a small quantity. The arbitrary constants A,B are found by
substitution into the Schrdinger equation. This leads to the
following eigenvalues

Figure 4. Electronic band structure in the nearly free

electron picture. Away from the Brillouin zoneboundary
the electron wave function has plane wave character
and the dispersion relation is parabolic. At the Brillouin
zone boundary the wave function is a standing wave
composed of an incoming and a Bragg-reflected wave.
This ultimately leads to the creation of a band gap.

demonstrating the band splitting at the edges of the Brillouin zone, where the width of the forbidden gap is given by 2V. The
electronic wave functions deep inside the crystal, attributed to the dif
ferent bands are given by

Where C is a normalization constant. Near the surface at z = 0, the bulk solution has to be fitted to an exponentially decaying
solution, which is compatible with the constant potentialV0.

It can be shown that the matching conditions can be fulfilled for every possible energy eigenvalue which lies in the allowed band. As
in the case for metals, this type of solution represents standing Bloch waves extending into the crystal which spill over into the
vacuum at the surface. A qualitative plot of the wave function is shown in figure 2.

If imaginary values of are considered, i.e. = - iq for z 0 and one defines

one obtains solutions with a decaying amplitude into the crystal

The energy eigenvalues are given by

E is real for large negative z, as required. Also in the range all energies of the surface states fall into the
forbidden gap. The complete solution is again found by matching the bulk solution to the exponentially decaying vacuum solution.
The result is a state localized at the surface decaying both into the crystal and the vacuum. A qualitative plot is shown figure
in 3.

Surface states of a three-dimensional crystal

The results for surface states of a monatomic linear chain
can readily be generalized to the case of a three-
dimensional crystal. Because of the two-dimensional
periodicity of the surface lattice Bloch's theorem must hold
for translations parallel to the surface. As a result, the
surface states can be written as the product of a Bloch
waves with k-values parallel to the surface
and a function representing a one-dimensional surface state

Figure 5. Atomic like orbitals of a Pt-atom. The orbitals

shown are part of the double-zeta basis set used in density
functional calculations. The orbitals are indexed according
to the usual quantum numbers (n,l,m).

The energy of this state is increased by a term so that we have

where m* is the effective mass of the electron. The matching conditions at the crystal surface, i.e. at z=0, have to be satisfied for each
separately and for each a single, but generally different energy level for the surface state is obtained.

True surface states and surfaceresonances

A surface state is described by the energy and its wave vector parallel to the surface, while a bulk state is characterized by
both and wave numbers. In the two-dimensional Brillouin zone of the surface, for each value of therefore a rod of is
extending into the three-dimensional Brillouin zone of the Bulk. Bulk energy bands that are being cut by these rods allow states that
penetrate deep into the crystal. One therefore generally distinguishes between true surface states and surface resonances. True surface
states are characterized by energy bands that are not degenerate with bulk energy bands. These states exist in the forbidden energy
gap only and are therefore localized at the surface, similar to the picture given in 'figure 3. At energies where a surface and a bulk
state are degenerate, the surface and the bulk state can mix, forming a surface resonance. Such a state can propagate deep into the
bulk, similar to Bloch waves, while retaining an enhanced amplitude close to the surface.

Tamm states
Surface states that are calculated in the framework of a tight-binding model are often called Tamm states. In the tight binding
approach, the electronic wave functions are usually expressed as a linear combination of atomic orbitals(LCAO), see figure 5. In this
picture, it is easy to comprehend that the existence of a surface will give rise to surface states with energies different from the
energies of the bulk states: Since the atoms residing in the topmost surface layer are missing their bonding partners on one side, their
orbitals have less overlap with the orbitals of neighboring atoms. The splitting and shifting of energy levels of the atoms forming the
crystal is therefore smaller at the surface than in the bulk.

If a particular orbital is responsible for the chemical bonding, e.g. the sp3 hybrid in Si or Ge, it is strongly affected by the presence of
the surface, bonds are broken, and the remaining lobes of the orbital stick out from the surface. They are called dangling bonds. The
energy levels of such states are expected to significantly shift from the bulk values.

In contrast to the nearly free electron model used to describe the Shockley states, the Tamm states are suitable to describe also
transition metals and wide bandgap semiconductors.

Extrinsic surface states

Surface states originating from clean and well ordered surfaces are usually called intrinsic. These states include states originating
from reconstructed surfaces, where the two-dimensional translational symmetry gives rise to the band structure in the k space of the
surface.

Extrinsic surface states are usually defined as states not originating from a clean and well ordered surface. Surfaces that fit into the
category extrinsic are:[7]

1. Surfaces with defects, where the translational symmetry of the surface is broken.
2. Surfaces with adsorbates
3. Interfaces between two materials, such as a semiconductor-oxide or semiconductor-metal interface
4. Interfaces between solid and liquid phases.
Generally, extrinsic surface states cannot easily be characterized in terms of their chemical, physical or structural properties.

Angle resolved photoemission spectroscopy (ARPES)

An experimental technique to measure the dispersion of surface states is angle resolved photoemission spectroscopy (ARPES) or
angle resolved ultraviolet photoelectron spectroscopy(ARUPS).

References
1. Sidney G. Davison; Maria Steslicka (1992).Basic Theory of Surface States(https://books.google.com/books?id=rR-
PUXTHXIkC). Clarendon Press. ISBN 0-19-851990-7.
2. C. Kittel (1996). Introduction to Solid State Physics. Wiley. pp. 80150. ISBN 0-471-14286-7.
3. K. Oura; V.G. Lifshifts; A.A. Saranin; A. V. Zotov; M. Katayama (2003). "11".Surface Science. Springer-Verlag, Berlin
Heidelberg New York.
4. Feng Duan; Jin Guojin (2005). "7".Condensed Matter Physics:Volume 1. World Scientific. ISBN 981-256-070-X.
5. W. Shockley (1939). "On the Surface StatesAssociated with a Periodic Potential".Phys. Rev. 56 (4): 317.
Bibcode:1939PhRv...56..317S (http://adsabs.harvard.edu/abs/1939PhRv ...56..317S). doi:10.1103/PhysRev.56.317
(https://doi.org/10.1103%2FPhysRev.56.317).
6. I. Tamm (1932). "On the possible bound states of electrons on a crystal surface".Phys. Z. Soviet Union. 1: 733.
 7. Frederick Seitz; Henry Ehrenreich; David T
urnbull (1996). Solid State Physics. Academic Press. pp. 80150.
ISBN 0-12-607729-0.

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