8 Semiconductor Crystals [Absorption coefiient in em”! or 05 05 07 fo in Ve Figure 6 Optical absorption in pure indium antimonide, InSb. The transition is direct because both conduction and valence band edges are at the center of the Brillouin zone, k = 0. Notice the sharp threshold. (After G. W. Gobeli and H. Y. Fan.) ‘The band gap may also be deduced from the temperature dependence of the conductivity or of the carrier concentration in the intrinsic range. The carrier concentration is obtained from measurements of the Hall voltage (Chap- ter 6), sometimes supplemented by conductivity measurements. Optical meas- urements determine whether the gap is direct or indirect. The band edges in Ge and in Si are connected by indirect transitions; the band edges in InSb are connected by a direct transition (Fig. 6). The gap in @Sn is direct and is exactly zero; HgTe and HgSe are semimetals and have negative gaps—the bands overlap. EQUATIONS OF MOTION We derive the equation of motion of an electron in an energy band. We look at the motion of a wave packet in an applied electric field. Suppose that the wave packet is ma’ up of wavefunctions near a particular wavevector k. The 203204 ( group velocity is vg = da/dk. The frequency associated wit. a wavefunction of energy € is @ = e/fi, and so dddk or vai) Vuek) qd) The effects of the crystal on the electron motion are contained in the dispersion relation €(k). The work Se done on the electron by the electric field E in the interval ét is Ug= Be = —cE vg dt - ® We observe that Be = (deldk)8k = fivg Bk , @) using (1). On comparing (2) with @) we have 8k = —(cE/A)St , @ whence fdk/dt = —eE, the same relation as for free electrons. We may write (4) in terms of the external force F as dk ee © ‘This is an important relation: in a crystal fidk/dt is equal to the external force on the electron. In free space d(mv)/dt is equal to the force. We have not over- thrown Newton's second law of motion: the electron in the crystal is subject to forces from the crystal lattice as well as from external sources. The force term in (5) also includes the Lorentz force on an electron in a magnetic field, under ordinary conditions where the magnetic field is not so strong that it breaks down the band structure. Thus the equation of motion of an electron of group velocity v in a constant magnetic field B is (ccs) ate Sv xB SD) pen oy xB ; © where the right-hand side is the Lorentz force on the electron. With the group velocity fiv = grade, the rate of change of the wavevector is chy Sell dc (ccs) Vue x Bs where now both sides of the equation refer to the coordinates in k space. We sce from the vector cross-product in (7) that in a magnetic field an electron moves in k space in a direction normal to the direction of the gradient of the energy ¢, so that the electron moves on a surface of constant energy.8 Semiconductor Crystals The value of the jection kg of k on B is constant during the motion. The motion in k space is on a plane normal to the direction of B, and the orbit is defined by the intersection of this plane with a surface of constant energy. Physical Derivation of k= F We consider the Bloch eigenfunction y belonging to the energy eigen- value € and wavevector k: t= Chk + ©) explik + G)-r] . ® The expectation value of the momentum of an electron in the state k is Pa = (|i |k) = 2 lk + G)ICKk + PF = fk + 2 Glick + ©). © using 2ICk + 6)? = 1. We examine the transfer of momentum between the electron and the lat- tice when the state k of the electron is changed to k + Ak by the application of an external force. We imagine an insulating crystal electrostatically neutral except for a single electron in the state k of an otherwise empty band. We suppose that a weak external force is applied for a time interval such that the total impulse given to the entire crystal system is J = fF dt. If the conduction electron were free (m* = m), the total momentum imparted to the crystal system by the impulse would appear in the change of momentum of the conduction electron: J= Api = Apa = fidk . (10) The neutral crystal suffers no net interaction with the electric field, either directly or indirectly through the free electron. If the conduction electron interacts with the periodic potential of the crys- tal lattice, we must have J = Aptor = Apit + Apa - (11) From the result (9) for pa we have Apa = BAK + > AG[V IC + G)P) - Ak] (12) < The change Api: in the lattice momentum resulting from the change of state of the electron may be derived by an elementary physical consideration. An electron reflected by the lattice transfers momentum to the lattice. If an incident electron with plane wave component of momentum fik is reflected 205with momentum fi(k + G), the lattice acquires the momentum —fG, as re- quired by momentum conservation. The momentum transfer to the lattice when the state fi, goes over to Yyrak is Apr = “AD CLICK + GP Ak) (13) as the portion VilC(k + G)P «Ak (14) of each individual component of the initial state is reflected during the state change Ak. The total momentum change is therefore Apa + Ape = J = hdk (as) exactly as for free electrons, Eg. (10). Thus from the definition of J, we have fdk/dt =F , (16) derived in (5) by a different method. A rigorous derivation of (16) by an entirely different method is given in Appendix E. Holes The properties of vacant orbitals in an otherwise filled band are important in semiconductor physics and in solid state electronics. Vacant orbitals in a band are commonly called holes. A hole acts in applied clectric and magnetic fields as if it has a positive charge +e. The reason is given in five steps in the boxes that follow. 1. ky, = ke - ay The total wavevector of the electrons in a filled band is zero: 2k = 0. This result follows from the geometrical symmetry of the Brillouin zone: every fundamental lattice type has symmetry under the inversion operation r—> —r about any lattice point; it follows that the Brillouin zone of the lattice also has inversion symmetry. If the band is filled all pairs of orbitals k and —k are filled, and the total wavevector is zero. If an electron is missing from an orbital of wavevector k,, the total wavevector of the system is —k, and is attributed to the hole. This result is surpuising: the electron is missing from k, and the position of the hole is usually indicated graphically as situated at k,, as in Fig. 7. But the true wavevector ky, of the hole is —k,, which is the wavevector of the point G if the hole is at E. The wavevector —k, enters into selection rules for photon absorption.8 Semiconductor Crystals Figure 7 Absorption of a photon of energy fico and negligible wavevector takes an electron from E in the filled valence band to Q in the conduction band. If k, was the wavevector of the electron at E, it becomes the wavevector of the electron at Q. The total wavevector of the valence band after the absorption is ~k,, and this is the wavevector we must ascribe to the hole if we describe the valence band as occupied by one hole. Thus ky, = —k,; the wavevector of the hole is the same as the wavevector of the electron which remains at G. For the entire system the total wavevector after the absorption of the photon is k, + ky = 0, so that the total waveveetor is unchanged by the absorp- tion of the photon and the creation of a free electron and free hole. The hole is an alternate description of a band with one missing elec- tron, and we either say that the hole has wavevector —k, or that the band with one missing electron has total wavevector —k,. 2. enlkn) = elke) « (18) Let the zero of energy of the valence band be at the top of the band. The lower in the band the missing electron lies, the higher the energy of the system. The energy of the hole is opposite in sign to the energy of the missing electron, because it takes more work to remove an electron from a low orbital than from a high orbital. Thus if the band is symmetric,’ ke) = (ke) = —en(—ke) = — (1). We construct in Fig. 8 a band scheme to represent the properties of a hole. This-hole band is a helpful representation because it appears right side up. *Bands are always symmetric under the inversion k—> ~k if the spin-orbit interaction is ne- elected. Even with spin-orbit interaction, bands are always symmetric if the crystal structure Permits the inversion operation. Without a center of symmetry, but with spin-orbit interaction, the bands are symmetric if we compare subbands for which the spin direction is reversed: eh, 1) = ok, in © OTS, Chapter 9. sor‘wit lly) =~ (he, t0 imulate dynamics Hole band constructed =k, and of a hole. Figure 8 The upper halfof the figure shows the hole band thet simulates the dynamies of a hole, Fear ted by inversion ofthe valence band inthe origin. The waveveetor and enerBy of the hole sre equal, but opposite in sign, to the wavevector andl energy of the empty ‘electron orbital in the a eae el We do not show the disposition ofthe electron removed from the valence hand at ky. 3. Vn = Ve - (ag) ‘The velocity of the hole is equal to the velocity of the missing electron. From Fig. § we see that Vey(kn) = Vedk.), so that wplky) = velke)- =m, - (20) We show below that the effective mass is inversely proportional to the curvature d’e/dk’, and for the bole band this has the opposite sign to that for an electron in the valence band. Near the top of the valence band me is negative, so that m, is positive. 4. mr 5. pth = ee + ty xB) - 1) dt € This comes from the equation of motion (ccs) pte = ete + Lv, * B) (22) dt c that applies to the missing electron when we substitute —ky, for k, and va for ve. The equation of motion for a hole is that of a particle of positive charge e. The positive charge is consistent with the electric current car~ ried by the valence band of Fig. 9: the current is carried by the unpaired electron in the orbital G: j= (-ev(G) = (—e)[-v(E)] = ev(E) » (23) which is just the current of a positive charge moving with the velocity ascribed to the missing electron at E. ‘The current is shown in Fig. 10.8 Semiconductor Crystals 209 @ wo) © Figure 9 (@) At e= all states are filled except F at the top of the band; the velocity ois zero at F because de/dk, = 0. (b) An electric field E, is applied in the +x direction. The force on the electrons is in the k, direction and all electrons make transitions together in the —k,directipn, moving the hole to the state E. (c) Alter a further interval the electrons move farther along in k space and the hole is now at D. Figure 10 Motion of electrons in the conduction band and holes in the valence band in the electric field E. The hole and electron drift velocities are in opposite directions, but their electric eur- rents are in the same direction, the direction of the electric field. Effective Mass When we look at the energy-wavevector relation € = (f7/2m)k° for free electrons, we see that the coefficient of k* determines the curvature of € versus k. Turned about, we can say that L/m, the reciprocal mass, determines the curvature. For electrons in a band there can be regions of unusually high curva- ture near the band gap at the zone boundary, as we see from the solutions of the wave equation near the zone boundary. If the energy gap is small in comparison with the free electron energy A at the boundary, the curvature is enhanced by the factor A/E, and the reciprocal mass is enhanced by the same factor. In semiconductors the band width, which is like the free electron energy, is of the order of 20 eV, while the band gap is of the order of 0.2 to 2 eV. Thus the reciprocal mass is enhanced by a factor 10 to 100, and the effective mass is reduced to 0.1-0.01 of the free electron mass, These values apply near the band gap; as we go away from the gap the curvatures are likely to approach those of free electrons.