PHY583 Note 1d Band Theory of Solids

BAND THEORY OF SOLIDS

In general, there are 2 approaches to determine the electronic energies in solids: 1. Follow the behaviour of energy levels of isolated atoms as they are brought closer and closer to form a solid. 2. Show that the energy bands arise when the Schrodinger equation is solved for electrons subject to a periodic potential representing the lattice ions.

Isolated-Atom Approach to Band Theory

If 2 identical atoms are very far apart, they do not interact and their electronic energy levels can be considered to be those of isolated atoms. E.g. 2 sodium atoms, each having an outermost 3s electron with a specific energy. As the two sodium atoms are brought closer together, their wavefunction overlap, and the two degenerate, isolated 3s energy levels are split into 2 different levels, as shown in Fig. 12.16a.

The width of an energy band (

depend only on the number of

atoms close enough to interact strongly, which is always a small number. If the total number of atoms in solids (N 1023 atoms/cm3), we find a very large number of levels (determined by N) spaced within the width E, so the levels may be regarded as a continuous band of energy levels (Fig. 12.16c). *Two or more different quantum states are said to be degenerate if they are all at the same energy level. An energy level is said to be degenerate if it contains two or more different states. The number of different states at a particular energy level is called the levels degeneracy and this phenomenon is generally known as the quantum degeneracy. 1

PHY583 Note 1d Band Theory of Solids Degenerate state: a quantum state of a system, having the same energy level as another state of the system, but different wavefunction.

PHY583 Note 1d Band Theory of Solids For sodium, it is common to refer to the continuous distribution of allowed energy levels as the 3s band, because it originate from the 3s levels of individual sodium atoms. In general, a crystalline solid has numerous allowed energy bands, one band arising from each atomic energy level.

Electrical Conduction in Metals, Insulators & Semiconductors

The variation in the electrical conductivity of metals, insulator & semiconductors can be explained qualitatively in terms of energy bands. The position & the electronic occupation of the highest band, or at most, of the highest two bands determine the conductivity of solid.

PHY583 Note 1d Band Theory of Solids

Metals
Consider the half-filled 3s band of sodium. Fig. 12.19 shows this typical half-filled metallic band at T = 0 K, where the shaded region represents levels that are filled with electrons. Since electrons obey Fermi-Dirac statistics, all levels below the Fermi energy, E F, are filled with electrons, while all levels above EF are empty. In the case of sodium, the Fermi energy lied in the middle of the band. At temperature greater than 0 K, some electrons are thermally excited to levels above EF (as shown by the Fermi-Dirac distribution to the left of Fig. 12.19), but overall there is little change from the 0-K case.

If an electric field is applied to the metal, electrons with energies near the Fermi energy can gain a small amount of additional energy from the field and reach nearby empty energy state.
Thus, electrons are free to move with only a small applied field in a metal because there are many unoccupied energy states very close to occupied energy state.

Insulators
Consider: two highest-energy bands of a material having the lower band completely filled with electrons & the higher completely empty at 0 K (Fig.1220). 4

PHY583 Note 1d Band Theory of Solids The separation between the outermost filled and empty bands is commonly referred to as the energy gap, Eg, of the material. The lower band filled with electrons is called the valence band, and the upper empty band is the conduction band. The Fermi energy is at the midpoint of the energy gap, as shown in Fig. 12.20.

Since the energy gap for an insulator is large ( temperature

10 eV) compared to kBT at room

(kBT = 0.025 eV at 300 K), the Fermi-Dirac distribution predicts that very few electrons will be thermally excited into the upper band at normal temperatures, as can be seen by the smaller value of fFD at the bottom of the conduction band in Fig. 12.20. Although an insulator has many vacant states in the conduction band that can except electrons, there are so few electrons actually occupying conduction-band states at room temperature that the overall contribution to electrical conductivity is very small, resulting in a higher resistivity for insulators.

PHY583 Note 1d Band Theory of Solids

Semiconductors
Semiconductor: A material with much smaller energy gap Table 12.8 shows the energy gap for some semiconductors. 1 eV.

At T = 0 K, all electrons are in the valence band & no electrons in the conduction band. Hence, semiconductors are poor conductors at low temperatures.

Fig.12.20 An insulator at T = 0 K has a filled valance band and empty conduction band. The Fermi level lies midway between these bands. The Fermi-Dirac probability that an energy state E is occupied at T> 0 K is shown to the left.

PHY583 Note 1d Band Theory of Solids However, at ordinary temperature, the population of the valence & conduction bands are altered as shown in Fig. 12.21.

Fig. 12.21 The band structure of a semiconductor at ordinary temperatures (T 300 K). Note that the energy gap is much smaller than in an insulator & that many electrons occupy states in the conduction band. Because EF, is located the middle of the gap & Eg is small, appreciable number of electrons are thermally excited from the valance band to the conduction band. Since there are many empty nearby states in the conduction band, a small applied potential can easily raise the energy of the electrons in the conduction band, resulting in a moderate current. Because thermal excitation across the narrow gap is more probable at higher temperatures, the conductivity of semiconductors depend strongly on temperature & increases rapidly with temperature . This contrasts sharply with a metal, which decreases slowly with temperature. There are both positive & negative charge carriers in a semicondcutor. When an electron moves from the valence band into the conduction band, it leaves behind a vacant valence electron site, called hole, in the otherwise filled valence band. This hole (electron-deficient site) appears as a positive charge, +e. The hole acts as a charge carrier in the sense that a valence electron from the nearby site can transfer into the hole, thereby filling it & leaving a hole behind in the electrons original place.

Thus the hole migrates through the valence band. In a pure crystal, containing only one element or compound, 7

PHY583 Note 1d Band Theory of Solids number of conduction electrons = number of holes. These combinations of charges are electron-hole pairs, & a pure semiconductor that contains such pairs is called an intrinsic semiconductor as illustrated in Fig. 12.22.

In the presence of an electric field, the holes move in the direction of the field & the conduction electrons move opposite to the field. Energy Bands from Electron Wave Reflection This is a different approach to understand the origin of energy bands in solids. This approach involves modifying the free electron wavefunctions to take into account the scattering of electron waves by the periodic crystal lattice. A completely free electron moving in the +x direction, is represented by a travelling wave with wavenumber , described by:

According to de Broglie, the wave carries momentum . The energy of a free electron as a function of k is

and energy

A plot of E versus k is given in Fig.12.23. 8

PHY583 Note 1d Band Theory of Solids

Fig. 12.23 Energy versus wavenumber k for a free electron, where

Fig. 12.23 shows that allowed energy values are distributed continuously from zero to infinity, & there are no breaks or gaps in energy at particular k values. Consider what happen to a travelling electron wave when it passes through a one-dimensional crystal lattice with atomic spacing a. When the wavelength of the incident electron waves is very long (or small k) & low energy travelling to the right as in Fig. 12.24a, the waves reflected from successive atoms & travelling to the left are all slightly out of phase & on average cancel out.

PHY583 Note 1d Band Theory of Solids

Thus the electron does not get reflected, & the electron moves through the lattice like a free particle. However, if we make the electron wavelength shorter & shorter, when we reach the condition = 2a, waves reflected from adjacent atoms will be in phase as shown in Fig. 12.24b & there will be a strong reflected wave. This occurs because the path length difference is 2 a for a wave reflected to the left directly from atom 1 compared to a wave that travels from 1 to 2 & then is reflected back to 1, as shown in Fig. 12.24c. The longest wavelength at which constructive interference of reflected waves occurs is: 2a = . In general, constructive interference also occurs at other, shorter wavelengths: 2a = n n = 1,2,3,... ..............12.29

The negative sign arises from reflection from the atom to the left of atom 1.

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PHY583 Note 1d Band Theory of Solids In terms of wavenumber k, eqn. 12.29 predicts strong reflected electron waves when, ..................12.30

Thus for

the electron wavefunctions are not just wave travelling to the

right but are composed of equal parts of wave travelling to the right (incident) and to the left (reflected). Since the wave travelling to the right and left can be added or subtracted, we have two different possible standing wave types, denoted by ..................12.31 ....................12.32 Where describes a wave travelling to the right and a wave and :

travelling to the left.

Important point: has a slightly higher energy than than at . & has a slightly lower energy

This leads to a discontinuity in energy or the band gap, at 12.25.

as shown in Fig.

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PHY583 Note 1d Band Theory of Solids

Fig. 12.25 Energy versus wavenumber for a one dimensional lattice with atomic separation a. The E versus k curve for the free electron case is shown dashed. Note the forbidden bands corresponding to impossible energy states for the electron. state has higher energy than the kinetic energy of electron in potential energy of electron in state; total energy of electron in ) state > total energy of electron in state; (at state state;

state = kinetic energy of electron in

state > potential energy of electron in

i.e. total energy of electron in total energy of electron in

state is slightly above the free electron energy; state is slightly below the free electron energy.

Fig 12.25 also shows that the overall effect of the lattice is to introduce forbidden gaps in the free electron E versus k plot at values of .

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