s due to interactions, ated by studying the nal space constructed. jin equation provides in Section 7.2. It also 1 as thermal conduc~ (7.28) 729) V7.1 and lead to (7.30) at) 7.32) cory for the electrical y. Indeed, when T is tron mean free path i energy dominate the sift velocity by many mal gradient is estab- . (7.28) predicts that a (7.33) in the absolute temper- K at room temperature. ‘THEGUANTUM THEORY OF SOLIDS 197 ‘The thermopower can be an order of magnitude larger in transition metas, due to the contribution of d electrons tothe conduction process. The sign and magnitude of S in a given metal are very sensitive to deviations from free-electron behavior. ‘The parameter x’ is related to the thermal conductivity, and Eq. (7.32) is known as the Wiedemann Franz law. When no electrical current flows, Eqs. (7.28) and (7.29) may be combined 10 give Jq= (OST —6/VT = «VT (734) where «is the thermal conductivity. To a good approximation, «’ ~ x. Equation (7.34) is Fourier’s heat conduction formula, Equation (7.32) shows that the thermal conduc tivity grows linearly with T at low 7. It also demonstrates why good electrical eonduc- tors will also be good thermal conductors. The same electrons responsible for trans- porting electrical charge also tranport thermal energy. The ratio L = x/aT = x*k3/3e called the Lorenz number, depends only on fundamental constants. ts numerical value is 244 x 10" W- 2/K>, The experimental values of L at T = 273 K for (Li, Na, K, Rb, Al, Ag, Au) are (2.22, 2.12, 2.23, 242, 2.14, 231, 2.32) x 10 W Q/K?, in reasonable agreement with theoretical prediction, For metals the thermal conductivity grows linearly with T at low T, peaks at inter- mediate T, and falls off at high T. The falloff at high T is due largely to the shortened mean free path of the electrons due to eleetron—phonon scattering, ‘THE QUANTUM THEORY OF SOLIDS In going beyond the Sommerfeld theory one attempts to describe all aspects of a solid in quantum-mechanical terms, The scattering from the lattice ions must be treated properly. The wave character of the electrons inevitably leads to interference effects, since typical wavelengths of the electrons are on the order of the Fermi wavelength, Ay =2z/ke and are comparable t0 interatomic spacings. In crystalline solids the ordered array of ions can produce Bragg diffraction effects, which block the prop- agation of electrons in certain directions andor with certain ranges of encrgies. In the following sections the quantum theory of solids is developed. 7.6 Bloch's Theorem ‘The treatment of a many-particle system such as a solid requires that a number of simplifying approximations be made before a concise mathematical description is possible. One begins with the independent-electron approximation, where it is assumed that each electron interacts with a potential V(r). This potential includes the effect of the ion cores as well as the other electrons in the solid. The result is that one need only solve @ one-electron Schrédinger equation to find a set of eigenvalues and eigenfunctions, In this section attention is focused on the solution of the Schrédinger equation for 4 periodic solid, where the potential has translation symmetry VE+R)=Vinj, (7.35)198 ELECTRONS NV SOLIDS: ELECTRICAL AND THERMAL PROPERTIES Where the set of vectors {R) defines the Bravais lattice. Fouricr-analyzing V(r) gives Vvir)= Vee", 7.36) c \whete (G) are the reciprocal lattice vectors. The reality of V(r) requires that the Fourier coefticients satisfy the “reality condition” Vf; = Vo, since Vr) =O Veer" = Do Vege = Vir) = Ve c c © The periodicity of V(r) is obvious: Vert R)= Vee") = Vee = V0, 738) c T where exp(iG » R) = 1 has been used. ‘The Schrédinger equation is tH - EI) [-Ee+vo-4 vir) =0. (739) Note that H is unchanged if a translation through vector R is mace. The wavefunction Wr +R) satisfies the same equation that yr) does, and so differs from it by at most, ‘a constant, that is, vir+R) = RVAe), (7.40) ‘The quantity 4x must have magnitude 1, If it were greater than 1, repeated translations would make the wavefunction grow in magnitude in an exponential fashion, that is, Wer + NR) = (tr) Wer), 4) ‘and it would not be possible to normalize the wavefunction in the infinite solid limit. Similarly, ifthe modulus were less than 1, y(r —NR) would not be normalizable as N= 00, Thus te = exp(ifa) with 6g real. By compounding translations, one has tate, = RAR: 742) a, + AR, = PRRs (7.43) which is satisfied by @ =k + R with k being a real vector, Thus wr +R) = e*F yr), ‘The function defined byalyzing V(r) gives (7.36) jres that the Fourier or, a3n n) 7.38) (7.39) e, The wavefunction from it by at most (7.40) repeated translations ial fashion, that is, al) ye infinite solid limit ot be normalizable as nslations, one has 7.42) 7.43) is 7.44) 7.45) THEQUANTUMITHEORY OF SOLIDS 199 is seen to be a periodic function, since te +R) = eM YEE ER) = EMR CR Ye) = u(t). (7.46) Enlarging the notation, Bloch’s theorem states that the solution of the Schrédinger equation may be factored into a plane wave multiplied by a periodic funetion u(r) with the Bravais lattice periodicity om, vale 'ug(P) (a) The acceptable values of k may be determined by imposing periodic boundary condi- tions (see Section 5.1). For a solid of size Ni by N2 by N3 atoms, a translation through ‘Nit should leave the wavefunction unchanged. Thus é 8) which has Ny independent solutions of the form b= fe A=Ob 8 749) where gi +; = 2, More generally, Berfer Be heOtum, 750) ‘where (g,) are the primitive reciprocal lattice vectors [see Eq. (3.8),] Thus k is a point in the first Brillouin zone, The total number of such points is NV = N\N2N3, which is the number of lattice cells in the crystal. Due to the periodicity of u(r) it may be expanded as a Fourier series: y(t) = SO ue lke)e'". (7.51) Inserting this into the Schrddinger equation gives 2 [ We Vv — | Vuctoes" = 0, (7.52) © Using Tenet =F Veucoe™, 733) oa oe this may be simplified to [Fuss ;| nat) + D> Veeck) = 0, (7.54) 7 o200 ELECTRONS INSOLIDS: ELECTRICAL AND THERMAL PROPERTIES where use has been made of the linear independence of the functions exp(iG +r) in removing the G sum. This infinite set of coupled linear algebraic equations for {ug(k)} may have many solutions, so the notation is expanded t0 {tn G(k)}, where = 1,2,3, is called the band-index. The energy eigenvalues will also be labeled by this index, £,(k). The relations in Eq. (7.54) are referred to as Bloch’s difference equations. ‘The condition for nontrivial solutions to Eq. (7.54) to exist is the vanishing of the determinant (called the Hill determinant): ® i | [Em +6) - ‘| fee" +Vo-e “The rool of this equation determine the eigenvalue spectrum (Ey (k)}. This spectrum is invariant under the transformation k — k+K, where K is a reciprocal lattice vector ‘Making this substitution into the Hill determinant and leting G’= G+ K and G” = K’—K yields “The condition remains invariant under the transformation above. Hence the first Bril- Iouin zone contains the entite energy spectrum. Other Brillouin zones simply contain replicas of this spectrum. Truncating the Hill determinant by employing a finite set of G vectors and solving the resulting secular determinant for the roots E = Eq(k) provides @ method, in prin- ciple, for ealelating band structures. Since the Foutier coefficients Vg fll off with increasing G for large G, the energy eigenvalue spectrum will converge as the size of the determinant is increased. More practical methods exist, such as the Green's function (Kertinga, Koha, and Rostoker (KKR)] method, the augmented plane wave (APW) method, and the pseudopotential method, but these are beyond the scope of the present book. The books by Fletcher (1971) and Asheroft and Mermin (1976) provide food introductions to modem band-structure computation techniques. Figure 7.5 presents the results of an electronic band-strcture calculation for Giamond along various directions in the first Brillouin zone. The lowest band corresponds to = 1, the next higher band to n = 2, and so on. One sees that there are two degenerate conduction bands and three degenerate valence bands at the T” point. Diamond is an insulator. The Fermi level lies at midgap, so all states with E <0 comprise the valence bands and are occupied. The conduction bands are empty. The bottom of the conduction band does not occur at the F point but rater, along the [100] direction, The bandgap is close to 6 eV, making diamond transparent co visible light. 7.7 Nearly Free Electron Approximation Jn analyzing some metals the free-electron approximation forms a suitable starting point for explaining the band structure. In these materials the ion cores are largely Sercened by the Valence electrons, leaving behind a weak potential that may be weated. using perturbation theory. Examples of such materials are the alkali metals (Li, Na, K, Rb, Cs), Mg, and Al.ctions exp(iG-r) raic equations for (y,6(k)}, where ill also be labeled Bloch’s difference vanishing of the 755) ). This spectrum is pocal lattice vector, =G+K and G” . 7.56) the first Bril simply contain 1s and solving + method, in prin- Veg fall off with serge as the size th as the Green's ed plane wave the scope of the (1976) provide calculation for The lowest band sees that there are at the T point. sates with E <0 are empty. The along the [100] to visible light. 2 suitable starting cores ate largely shat may be treated ‘metals (Li, Na, K, ‘THE QUANTUM THEORY OF SOLIDS 201 Wave vector E Figure 7.5. Electron band-structure calculation for diamond. (From J. R. Chelikowsky et al Phys, Rey. B, 29, 3470 (1984). Copyright 1984 by the American Physical Society.) Begin with Bloch’s difference equation [see Eq. (7.54)], (x46 ~ Eouctk) + > Vene-a(k asn c ‘where a free-electron kinetic energy is defined by are (7.58) fac In the case where the (Vc) all vanish, the solutions are B=. (7.59) In the extended-zone scheme the energy dispersion curve isa single parabola of revo- lution. In the reduced-zone scheme the information gets compressed into the first Brillouin zone (e.g., n/a < k < 7/a for the one-dimensional ease). In the periodic- zone scheme the information is repeated periodically in each Brillouin zone. Five pparabolas are illustrated in the respective schemes in Fig. 7.6. ‘There is one case for which the free-electron approximation fails badly, and that is when energy bands intersect each other. At such degeneracies any perturbation will have a large effect. To see this in detail, suppose that the bands described by reciprocal lattice vectors Gi and G2 cross each other. An example of this is seen in the periodic-zone scheme in Fig. 7.6. The one-dimensional bands with G = 0 and G = 2n/a intersect at k = 1/a. Other couplings beside those between the wo bands are neglected. Thus Eg, (7.57) becomes a pair of equations, (4G, + Vo ~ Blue, + Vo,-0.0 (exe; + Vo — Eluc, + Vo.-6,46, (7.602)202 ELECTRONS IN SOLIDS: ELECTRICAL AND THERMAL PROPERTIES Figure 7.6, Free-cleetron bands in the (a) periodic, (b) reduced, and (c)extended-rone schemes ‘The first Brillouin zone extends from —/a to 7a.ided-zone schemes THEQUANTUM THEORY OF SOLIDS 208 Here Vp describes a uniform background potential. The condition for the existence of solutions for this pair of linear equations is the vanishing of the secular determinant sug tVo-E Ven Bc eG, +VO~E G40, yielding EP Eleni, + 646; +2V0) + (xs, + VoNGuea, + Vo) —IVe,-cal? = 0, where Vo,-6, = Vé,c, has been used. The two roots are ve) Ba = Vo BG tec a\(* (7.63) 2 At the point of degeneracy the two e444 factors are equal and Vo + 2x+¢; + \Ve,-c.1- (7.64) ‘The condition for the equality of the free-electron energies reduces 10 G}+2k-G, = G3+2k- G>. 7.65) This i precisely the von Laue condition for Bragg scatering ofan electron, An energy gap is opened up between the two branches of the dispersion curve equal to twice the strength of the Fourier coefficient of the potential at that reciprocal lattice vector: E, = AE =E, -E_=21V6,-cil- (7.66) ‘Typical graphs for the two branches of the dispersion curves are presented in Fig. 7.7 in the reduced-zone scheme, AAs in the case of phonons, the spectral properties ofthe electronic states of a solid may be represented by the density of states, p(E}), the number of states per unit volume ° k 2 Figure 7.7. Typical dispersion curves for electrons in two interacting bands in the reduced-zone scheme,