‘RECIPROCAL SPACE OR WAVE VECTOR &-SPACE (b) Figure 5.11 idealized variation of electron energy E with wave vector k. The lower diagram shows the curvature of the electron energy band giving large effective mass at intermediate k, but srnall effective mass at low’ k as shown in the diagram. At k values close to t/a the effective mass of the electrons is negative ength. It tells us the spatial periodicity of the wavefunction, or if you prefer, the sember of cycles of the wave which occur in a given distance of 27 metres. We found that for free electrons the energy depended on.k?, and all values of k allowed. When the electrons are trapped, as in the square-well potential, ly certain values of & are allowed in order that the wavefunctions can meet their eundary conditions. in the last section we began to plot energy against & because this was useful in Serermining the effective mass of the electrons. We shall find that when it comes describing electrons in solids plotting E against k is a very useful way of epresenting the electronic properties. The plot of E against & is known as a seaprocal space plot because the dimensions of & are m~CHAPTER § BOUND ELECTRONS AND THE PERIODIC POTENTIAL When an electron is confined within a solid and experiences the periodicity of the lattice this periodicity affects the relationships between E and &. Another way of looking at this is that a wavefunction described by the wave vector & will have different energies depending on the presence and type of the crystal lattice ir encounters. We have already noticed, for example, that the interactions berween an electron and the lattice alter its effective mass and so distort the relationship between E and k. 5.5.1 Brillouin zones How can periodicity of the lattice be introduced into reciprocal space? We may think of the Brillouin zones [9] as a method for introducing the Periodicity of the crystal lattice into our model of the electronic structure of materials. The Brillouin zone is a region in reciprocal space. Before Saying more about exactly what this Brillouin zone is, let us consider the effects of a periodic Potential on the energy levels of “free electrons’. We know E = BR 2m for free electrons, bur when we add the presence of a periodic potential all of this changes. We know from the previous chapter that if the energies of the electrons are below the level of the periodic potential barriers the electrons will penetrate spatially into these potential barriers, but their wavefunctions will be attenuated the further they penetrate. If the potential barriers are much higher than the electron energy, then the wavefunction will be reflected at these barriers and the electron will be contained entirely within the potential box formed by the barriers. 5.5.2 Bragg reflection at the Brillouin zone boundaries What effect does the lattice have on the allowed electron wavefunctions and the relationship between energy E and wave vector k ? The solutions of the Schrédinger equation in the case of a Periodic potential with infinite energy barriers is simply (5.42) with integer values of n, as shown in Fig. 4.3. This means that only exact discrete values of the energy are allowed under these conditions, Ifa finite periodic potential exists at the lattice sites x = -twa, then this results in @ perturbation of the solutions of the wave equation compared with the free electron situation with the amount of Perturbation increasing as the height of the Potential barriers increases. In the simplest form of periodic potential v(x) = 0 for Wa + V(b). (5.46) (from above) So at the zone boundary, the energy states in the first zone are 2V(k = aja) slow the energy of the states in the second zone. This is the so-called ‘band zp’, whereby no electron states are available with energies in the range (h*/2m) x ~ a)" + Vk = n/a) because of the presence of the periodic potential. The magni- sade of the energy gap 2V(n/a) can, therefore, be found from the Fourier ssansform of the periodic potential of the lattice, Ar locations away from the zone boundary, the Fourier transform V(k) of the potential also has a finite value, which decreases with distance in k-space from che zone boundary. This means that the E versus & relationship is also distorted or eerturbed from the parabolic free-electron-like behaviour at values of k away from ene zone boundary, bur the farther from the zone boundary, the less the per- carbation. This is shown in Fig. 5.12. The distortion or perturbation of the electron wavefunction that occurs at zone coundaries of the periodic potential is known as Bragg reflection. The reason for “his terminology becomes clear if we consider what happens to the wavefunction. = the limiting case of an infinite potential at the atomic or ionic sites the elec ‘rons cannot stray into this region. Therefore, the electron wavefunctions must be completely contained within the local potential well between x = ta and the wavefunction must meet exact boundary conditions of D(a) = W(—a) = 0. This is equivalent to total reflection of the wave. tis clear, therefore, that an infinite periodic potential will give total reflection at *e zone boundaries. If the height of the potential is reduced then the reflection will