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8. ENERGY BAND THEORY.

Aim: To understand the effects of the periodic potential in crystalline materials on the electronic states and electron dynamics. We also treat the physical basis of the difference between insulators, semiconductors and metals. In the previous Lecture we treated the outer electrons as freely moving in a box potential. In reality, however, the periodicity of the crystal leads to a periodic potential. The potential is lower close to the positive ions on the lattice (and in some cases basis) positions. The electrons experience a potential with the same periodicity as the lattice. This leads to some important consequences: 1. The reciprocal space can be divided into Brillouin zones. Physical properties related to the periodic potential can conveniently be described in the first Brillouin zone. 2. The continuous E(k) curve is split up into several energy bands separated by energy gaps. 1. Qualitative picture of energy bands. We give first an overview of the general idea of energy bands, starting from the energy levels of single atoms (H p. 84-86). In a two-atomic molecule (one electron per atom) the energy levels are split into a bonding and an antibonding one. The two electrons are shared between the two atoms and fill the lowest, bonding, molecular orbital. In a solid the upper energy levels are no longer discrete but the bonding and antibonding levels become broad energy bands. For a large number, N, atoms we obtain N closely spaced orbitals, giving rise to an energy band. Hoffman gives an example of the formation of Na. The outer atomic level is the 3s one which is occupied with one electron. In the solid state this gives rise to one 3s band that is half filled with electrons. It is easy for electrons to be excited into empty states, which leads to metallic properties. On the other hand a gap, where there are no electron states, may arise between bands arising from bonding and antibonding orbitals. As an example consider the elements with four valence electrons (one s and three p), i.e. C (diamond), Si, Ge. In these materials the atomic orbitals are hybridized and form sp3 hybrids. The overlap of orbitals lead to bonding and antibonding combinations which become bands when the number of atoms becomes large. If the overlap is not large enough, a band gap exists between the ”antibonding” and ”bonding” bands. In the group IV elements, the lower band is completely filled with four electrons per atom and the upper one is empty. Hence this is the origin of the semiconducting nature of these elements. There is a method to compute the electronic bandstructure that starts from the atomic energy levels. This so called tight binding model considers how they are broadened by the overlap of the atomic electron distributions in solids. Besides being applicable to materials with covalent bonds, the model is also useful for the d-electrons in transition metals and f-electrons in the rare earths. Basically the wave function ψk(r) is written as a linear combination of atomic orbitals. The coefficients are chosen to comply with the general form of the solution to the Schrödinger equation in a periodic potential (see below). The energy is obtained from the matrix elements of the Hamiltonian, by quantum mechanical procedures. There are two contributions: The interatomic one and the overlap energy arising from the overlap of electron distributions on neighbouring atoms. The computational procedure leads to relatively narrow bands.

We have one set of equations for each allowed value of k. 96) ψκ(r) = uk(r) exp (ikr). under a lattice translation. 95. G and take k to be within the first Brillouin zone by convention. p. 6. Huffman eq. We write ψk(r) = ∑ ck-G exp (i(k-G)r). higher zones will give equivalent information (but motion in higher zones is not unphysical as for phonons). H p. It is called the central equation.2. ψ(r) = ∑ ck exp (ikr). The energy eigenvalues are obtained from the determinant of the matrix of the coefficients multiplying the c’s.31. . To specify the state all the c’s have to be determined in principle. that are allowed by the periodic boundary conditions. The wave function is periodic in reciprocal space: From the series expansion for ψk(r). it can be easily shown that ψk+G(r) = ψk(r).The quantity (h/2π)k is called the crystal momentum of the electron. analogously to the case of phonons (but it is not the real momentum. 93-96). the wave vector is multiplied with the phase factor exp(ikT). We expand the periodic potential in a Fourier series over the reciprocal lattice vectors G. 3. Bloch’s theorem: The wave function can be written as a plane wave multiplied with a function with the periodicity of the lattice. k Substitution of these two series in the Schrödinger equation. p. 2. This means that we only need the solution in the first Brillouin zone. The Schrödinger equation is: [-(h2/4π22me) ∇2 + U(r)] ψ(r) = E ψ(r) We use the independent electron approximation: The equation describes the motion of one electron in the potential U(r). These allowed k-values are the same as in the case of the free electron model. Here we give a general treatment of the Schrödinger equation in a periodic potential and then we consider a few approximate models. For each k-state. For a given k. In real space. (H. transforms it to an infinite set of algebraic equations. but in practise a small number of ck-G will often be sufficient. 99. The wave function can be written as a superposition of plane waves with all wave vectors k. It enters into conservation laws for collision processes. 4. Some important properties of the wave function follows from this representation: 1. each root lies in a different energy band. Especially E(k±G) = E(k). the wave function is determined only by the coefficients ck-G. Wave equation in a periodic potential (H p.

and z-coordinates of the wave vector (We assume a cubic symmetry of the coordinate system). Each G will give rise to a different energy band.z). The free electron (“empty”) lattice. because of the periodicity. In the periodic zone scheme all bands are drawn in every zone. Note that G is unfortunately denoted K in the figure below. that is outside the first zone should be translated by an appropriate reciprocal lattice vector into the first zone. This is the simplest approximation that still gives a discernible band structure. y. however some may be degenerate (have the same energy).k. The direction is specified by k = 2π/a (x. In many cases we normalize the energy by dividing with the factor (h2/2mea2). Then the energy is immediately obtained as: E(k) = (h2/2mea2) [ (x+h)2 + (y+k)2 + (z+l)2 ]. where the numbers within parenthesis are the x-. 3. In the extended zone scheme one energy band is assigned to each Brillouin zone. but retain the periodicity of the lattice and reciprocal space. However. they refer to the cubic unit cell) as: G = 2π/a (h. Using the first zone only to depict the energy bands (the reduced zone scheme) is perhaps most common. . as used previously for the cubic structures. The contours of E(k) are determined first for G=0 and then using all the reciprocal lattice vectors pertaining to the structure under study. We obtain an infinite set of E(k)-contours in the first zone. Hence the part of the ”free electron parabola” E(k). In the case of a nonzero U.y.l). The reciprocal lattice vector can be written in terms of the Miller indices (Note that. The energy bands can be drawn in different directions in k-space. they will give rise to different energy bands in the solid. We assume that the periodic potential U->0.The periodicity of the energy and wave function in reciprocal space implies that they can be represented in different ways. In this limit the free electron model gives the relation E(k) ~ k2. only kvalues in the first Brillouin zone should be used.

0. e. The wave will not sense the periodicity in the potential.0). The model is good for the simple metals.. We write the periodic potential as a cosine term ~ cos (2πx/a). Use ALL G’s of all the types.l) equal to {110}. (011). However. 96-100).k. with (h. 1. Nearly free electron model (H p.k. The main differences in the real band structure are the occurrence of band gaps in the real structure and that degenerate bands are split up... Ex: Consider the bcc lattice in the [100]-direction. (101) and all combinations with one or two negative indices.. There are thus 12 different G’s of type 110! Do the calculation and check the figure below! Remember to include also the negative indices! 3. those of type 110 include (110). it is also instructive to see how the periodic potential affects the band structure. ..l). To obtain the energy bands take G=0 and G = 2π/a (h. For small k.Band structures from this approximation are able to give a good qualitative picture of the band structure of real simple metals. {200}. This means that we just keep the lowest term in the Fourier expansion for U..and so on. for example Al. This is the case of a weak periodic potential. Hence k = 2π/a (1. and consider the limiting cases. but only the average value. We consider some simple one-dimensional arguments. The free electron model is a good approximation here.g. the wavelength is much larger than 2a. as compared to the empty lattice.

For the ”+” solution. a standing wave (just as for the lattice vibrations). In one dimension k= n 2π/L. Start with the central equation connecting all Fourier coefficients c(k-G). then the number of primitive cells is N3 i. If L=Na. An energy gap.components of k. appears at the Brillouin zone boundaries.2. We now consider large values of k close to the boundary of the Brillouin zone. the ”-” solution has the largest electron density between the ions. . In three dimensions we have the same condition on the x-. The wave function is the sum of waves of equal amplitude. There are two possible linear combinations leading to standing waves and hence two solutions at the zone boundary. equal to the number of k-states in the first Brillouin zone. This can also be seen by keeping only the terms including k and k-G in the series expansion for ψk(x). Here k=±π/a=±G/2 and Bragg reflection takes place. Metals and Insulators. where n is an integer ≤ N/2 and > -N/2. the electron density is largest at the ion position. two electrons per primitive cell go into each energy band.and z. i. Hence the former solution will have a lower energy than the latter. The equation system has to be truncated in order to make it solvable. Huffman also makes a more formal treatment of the nearly free electron theory. The various models and types of energy bands from the case of free atoms to the case of free electrons in metals are illustrated in the scheme below: 4. moving to positive and negative x. equal to 2U1 (eq. Huffman presents computations for cases where only the first and/or second reciprocal lattice vectors and the first and/or second terms in the Fourier expansion for U are kept.37). From the periodic boundary conditions we obtain the allowed values of k. 6.e. y. Taking into account the electron spin the number of electrons is twice the number of k-states.e. Hence.

The first Brillouin zone is easily found to be also quadratic. Insulators and semiconductors have a completely filled valence band and an empty conduction band. the band gaps at the zone boundaries will distort the contours close to them. This is so also here for small values of k. there are two electrons per primitive cell in each zone. We take Ω to be the volume of the primitive cell. This is not so in higher dimensions since: a) Bands in different directions in the Brillouin zone may overlap in energy and b) hence more than one band may be partly filled. and those with even number are insulators. where we have included a factor of two due to the electron spin. compounds with odd number of outer electrons are metals. In one dimension. This is called the conduction band. . The reciprocal lattice is also quadratic with lattice constant 2π/a. When depicting constant energy contours in k-space. and the density of k-states becomes N(k) = V / 4π3. In this representation. Then the volume of the Brillouin zone is 8π3/Ω. This is illustrated close to the boundary between the first and second zone in the lower part of the second figure. The energy bands in the edge and diagonal directions in the first Brillouin zone are shown. The figure (after Myers) shows that bands in different directions overlap. However. Example: Two-dimensional quadratic lattice. we often use the extended zone scheme. In the free electron model these contours are circular. In three dimensions these features are qualitatively the same. Hence the second band occurs in the second Brillouin zone and so on. with one band of electron states in each zone.Metals have a partially filled upper band.

almost like atomic ones. It is thus higher close to the zone boundaries as illustrated for two dimensional lattices below (after Myers).The density of states can be obtained by an equation analogous to that derived for the phonon case: D(ε) = (V / 4π3) ∫ dSε / | ∇κε|. peaks due to van Hove singularities occur just as for the phonons. Link to applet on 2-dimensional lattice: http://solidstate.html 5. The bands are very narrow. Examples of real band structures.physics. . For alkali halides they are generally in the range 7-14 eV. KCl (after Elliott). A. Insulators We first depict the band structure of an ionic crystal.sunysb. The band gap is large around 9 eV. When the denominator in the integral is zero.edu/teach/intlearn/electrons/electrons. Flat bands give rise to a high density of states.

B. Semiconductors As an example of covalent crystals we treat semiconductors. as mentioned above. In the latter compounds there is an increasing amount of ionic binding. . The bands are quite wide. where hybridisation occurs (we have tetrahedral sp3 bonds). The materials become more like ionic compounds. It is seen that the bandgap increases and the bandwidth becomes smaller as we move to the right in the figure (after Elliott). We compare the bands of the elemental semiconductors (pure covalent bonds) with those of the III-V and II-VI compounds with the same number of valence electrons.

Ga and In show a very free-electron like behaviour. These are the alkali metals with bcc structure. c) Trivalent metals. These are connected to the p states but we do not go into this further. the Fermi surface is almost spherical. The most free-electron like metals are the alkali metals Na. Deviations from free electron behavior are also seen for Li unoccupied states. It has hcp structure.C. Metals We review the bandstructure of metals. as well as the Fermi surface and the density of states. The Fermi surface is in both the first and second Brillouin zone. but fcc is exhibited by Ca and Sr. b) Divalent metals. Due to the very free electron-like bandstructure of the occupied states. K … Also Mg and the group III elements Al. The volume enclosed by it is equal to the volume of a Brillouin zone. Al which has a fcc structure is the most common one. . Here Mg is the most free electron like one. In Na the conduction band contains 3s-electrons. It lies completely within the first Brillouin zone. Bands drawn adjacent to one another in the upper figure are in reality degenerate. a) Monovalent metals. In the picture below (after Myers) the empty lattice approximation is compared to a detailed band structure calculation.

The figures below illustrate this representation.and trivalent metals. Here we also use the representation in the first zone. third and in some cases even fourth Brillouin zones. This is to say. Remember that the reciprocal lattice of fcc is bcc. The Fermi surface in the higher zones is conveniently pictured in the first zone after translation by suitable reciprocal lattice vectors.It is seen that the bands are very free electron-like (remember we compared with the empty lattice) and the conduction bands are partly filled. Finally we show a figure of the Fermi surface in zones 1-4 for the di. . The Fermi surface is very complex and occurs in the second. we are going from the extended to the reduced zone scheme.

We finish with examples of the density of states (after Elliott).d) Transition metals. the d-bands are completely filled and are situated a few eV below the Fermi level. The last figure shows the DOS for the cases of a metal. As for an example of the density of states. The peaks are due to the d-bands. The outer electrons of these elements are 3d and 4s ones. The band-structure is schematically illustrated in the figure below (after Myers). They can qualitatively be described by tight binding calculations. Hence Cu. For Ge the valence and conduction bands are clearly seen. we depict it for Ni. In the noble metals.band peaks are seen superimposed on a background from the 4s-states. The d. upon which d-bands are superimposed. Cu. Copper has a free electron-like s-band.band is not completely filled. The d-bands are the more narrow ones and have consequently a higher density of states. Ag and Au are very free electron like up to energies of 2-4 eV. We concentrate on the first row of transition metals from Ti to Zn. Hence we have both 3d and 4s bands in the region around the Fermi level. It is seen that the d-bands fall in energy as we proceed from Ti onwards in the figure. . Here the d. and a semiconductor Ge.

tu-dresden.phy.Link to applet showing Fermi surfaces of metals: http://www.de/%7Efermisur/ .

which is inversely proportional to the second derivative of energy with respect to k. eq. The characteristic variation of the effective mass through a nearly-free-electron band is clearly displayed: .107.6. The figure below illustrates in one dimension: (a) a typical energy band (b) the velocity of the electron (which is proportional to derivative of energy with respect to k) and (c) the effective mass. and becomes negative close to the boundary of the Brillouin zone. The mass of the electron has now to be replaced by an effective mass. A. H. p. Effective mass We have earlier encountered effective electron masses used to reconcile free electron theory with experiments. This equation is the same in the present case. As k increases the effective mass increases. We determine the relation between the acceleration and force for electron motion in an energy band. (6. Electrons in bonds give rise to narrower energy bands than nearly free electrons.48). and hence to larger effective electron masses. but the existence of the reciprocal lattice and Brillouin zones necessitates a more detailed analysis. Here we find a physical basis of this concept. Electron dynamics (H p. The same holds for low k. 104-108) We have earlier treated the equation of motion of an electron within the free electron model. For free electrons it reduces to the usual electron mass.

in the same direction as the electrons.B. Electron and hole velocities are equal and hence also their accelerations. because there are no vacant states that the electrons can move to. even for nearly free electron ones like aluminium. We say that it is the holes that are responsible for electrical conduction in this case. They give additive contributions to the electrical conductivity of the material. However. 4. It follows for the effective masses that mh = -me. It is much easier to describe the dynamics in a nearly filled band with a small number of holes than by considering a macroscopic number of electrons. Hence. 1. electrons and holes move in opposite directions.e. Now remove one electron from state j. In certain cases we have electrons in one band and holes in another one. This means that the position of the hole is moving against the applied field. We can now understand the positive values of the Hall coefficient that were measured for some metals. By the same reasoning. This is so. 3. because the charges of electrons and holes have different sign. On the force side of the equation (see 6. in real space. For these metals conduction by holes in pockets at the top of partially filled bands is obviously dominating the dynamics.47) the sign is changed. A nearly filled band can however give rise to conduction. kh moves in the direction of the applied field. because the equation of motion for kh is just like the one for ke upon substitution of +e for -e. the position of the hole in k-space is at -kh. This follows because kh = -ke. We assign to the hole the sum of the k-vectors of the remaining electrons. J = ∑ (-evi) = evj. Consider the current density from the nearly filled band (for a filled band it has to be zero).46 and 6. A completely filled band cannot give rise to electrical conduction. Hence (h stands for hole and e for electron) kh = -ke. How do holes move in k-space? The equation of motion says that electrons move in a k-direction opposite to an applied E-field. The sum of all k-vectors in a filled band is zero. This is minus the kj=ke for the vacant state. Holes Empty orbitals in almost filled bands are called holes. . 2. The behaviour of the effective mass follows from the equation of motion in real space. i. i≠j The hole is considered to move with the same velocity as an electron in ”j” and to have a positive charge.