Chapter 11 Band Theory 11.1 BLOCH THEOREM In the case of free electron theory we assumed that the electrons move in a region of constant 2 one or three dimensional potential well. Although the free electron theory is jain the phenomena such as electrical conductivity, thermionic emission etc., it fails to explain why some materials are good electrical conductors while some are good electrical i and still some others are semiconductors? to understand the difference between the conductors and insulators, it is necessary to : ‘ariation of potential inside the crystal due to the presence of positive ion cores in the free electron model (Fig. 11.1a). It appears more realistic to assume the potential inside 2 metallic crystal to be periodic with the periodicity of the lattice, somewhat as shown in Fig. 11.1b. The potential is minimum at the positive ion sites and maximum between the two ions. The corresponding one dimensional Schrodinger equation can be written as: QD + \ sateen Ei=roa Setion sess LIN Fig. 11.1 One dimensional periodic potential in a crystal d@ 2, Se Set e-viniy=0 @ where the periodic potential V(x) may be defined by means of the lattice constant “a” as Vx) = Vix + a) Q)Band Theory 359 Employing the periodic potential, Bloch has sh — , ear inger equation takes the form shown that the one dimensional solution of the VAX) = exp (ikx) u(x) @ In three dimensions it is given by Vale) = exp (ik.r) u(r) The equation 3 (or 4) is known as Bloch function in one and three dimensions. They represent the free electron wave modulated by the periodic function 14(x) or u(r), where x(x) oF 14(0) is periodic with the periodicity of the lattice in one and three dimensions, respectively. Therefore, considering only the one dimensional case and suppose if we have N(N even) number of atoms in a linear chain of atoms of length L, then we can write (4) respectively. U(x) = u(x + Na) (5) and depends on the exact nature of the potential field. From eqs. 3 and 5, we have YACr + Na) = u(x + Na) exp [ik(x +'Na)] = exp (ikNa) ug(x) exp(ikx) = g(x) exp (ikNa) © This is frequently referred to as the Bloch condition. Similarly, the complex conjugate of eq. 6 can be written as ila + Na) = exp(-ikNa)yi(@z) * a” The eqs. 6 and 7 give us Veer + Na) ex + Na) = YX) YE) - @) This indicates that the probability of finding the electron is same everywhere in the whole chain of atoms, ie. itis not localized around any particular atom but is shared by all atoms in the chain (the whole crystal in three dimensions). Thus, eq. 6, gives us exp (ikNa) = 1 This will be true only if ' kNa = 21x integer = 2nn @) or where n = 0, +1, 42, ... and L is the length of chain of atoms. When n = N/2, we have k = n/a, which is the edge of the first Brillouin zone. When L is large (i.e. N is large), the allowed values of k would come close together and their distribution along k-axis becomes quasi-continuous. ‘The total number of allowed k-values in the first zone is Length of the first zone_ _ 2/a 10) Length of the unit spacing ~ 2x/L ao360 Solid State Physics This is equal to the total number of atoms in the chain of atoms (or in the unit cell in three dimensions). 11.2. THE KRONIG-PENNEY MODEL In the preceding section, we qualitatively discussed the behaviour of an electron in an undefined periodic potential. However, in order to know the exact E-k relationship it is necessary to consider a well defined one dimensional periodic [ potential. For the purpose, we shall consider Kronig-Penney model. They suggested asimpler Yo potential in the form of an array of square wells as shown in Fig. 11.2 The corresponding Schrodinger equations for the two regions I and I are of the form £¥ , 822 Fy =0 for O On simplifying this determinant, we obtain 2 2 cos k(a +b) = (Sap) a sinh Bb + cos aia cosh Bb en In order to simplify eq. 27 further, Kronig and Penney assumed that the potential energy is 2670 at lattice sites and equals Vp in between them, They further assumed that as the height of the potential barrier V tends to infinity and the width of the barrier b approaches zero in such a way a362 Solid State Physics that the product Vob remains finite, potential energies Vo r F-function spikes. Under these assumptions, sinh ib > Bb and cosh fb > 1 as b> 0 Hence, eq. 27 becomes pus . = B= By sin aa + cos a cos ka = Sag — Bb where B-a= 7 A Since, Vo >> E, s0 that 822m z Vo 2 gts 7 I Substituting this in eq. 28, we obtain 822m . cos ka = Vo Bb sin Ga + cos Ga 08 ka = 70g 2 . - saimaysy SiN 08 oo5 era Psin a = + cos aa ; _ 4n?ma where p= SiMe yyp ‘This assumption is equivalent to a Ditae 8-function tered by a distance a, the potential energy being zero inbetween ee (28) 2 a a sim qy, — p) - SME = SH (y, 28) 29) 30) Equation 29 is schematically represented in Fig. 11.3. The quantity on its right hand side is plotted as a function of az. The cosine term on the left hand side of the equation can only have SF sin aa cos wa aa Hell Psin aa ie M3 Plot of ES 4 cos aa vs aa aBand Theory 363 eee - and +1 as indicated by horizontal lines in the figure. A consequence of t rey ae tec y certain values of a (and hence E) are allowed. Further, from the left side Se eeyiaeeeee for a specific value of energy E (as in eq, 12), cos ka can have only one ue a ee = 4a is an even periodic function, it will have the same value whether pan neg itis increased by integral multiple of 27. Accordingly, the total energy a ctron is an even periodic function of k with a period of 2a/a. Fig. 11.4 shows a plot of energy as a function of A. If k is to be real, the magnitude of cos ka should be less than I (ie. cos ka | <1) which corresponds to the allowed energy band. On the other hand, those value of energy E for which | cos ka | >1, only the imaginary values of k are possible which correspond oe ae bands. The allowed and the forbidden energy bands are schematically shown in mn Allowed bands ert’ W N 1g, - Z = Allowed bands -Swla-2ria-na Wa Bria 3rd Fig. 11.4 Energy versus wave vector for a one dimensional lattice The analysis of eq. 29 leads us to the following inferences: 1. Allowed range of aa permits a wave mechanical solution to exist as shown in Fig. 11.5. Thus, the motion of electrons in a periodic lattice is characterized by the bands of allowed energy separated by forbidden regions. : 2. As the value of aaa increases, the width qa O24 oo ee of the allowed band also increases while y the width of the forbidden band decreases. This is because of the fact that the first term on the right side of eq. 29 on an average decreases with increasing a. 3. For further understanding, let us look at the influence of P on the energy spectrum, The quantity P is known to be a measure of the potential barrier strength. If P is large, means the potential barrier Vob is large (eq. 30), the function Psinaa described by the right hand side of eq. Fig: 115 A plot of with P = 32/2364 Solid State Physics =] region at a steeper angle as shown in Fig. 11.6. Thus, the atl ee sid the forbidden bands ae wider. Hence, the rato of the width ors forbidden band to that of the allowed band increases. let us take the case when the Forental bare strength is very large, i.e. P tends to infinity, However, a the right side Pr the eq, 29 has to stay within the limit +1, it follows from eq. 29 that poe S08 cos aa P40 ARE aa a ° aa a | : J @ ©) o Fig. 11.6 (a) Right side of eq. 29 for P = 6ras a function of aia (b) P —> % () P 0 BAe 40, ie. sin aa > 0 aq? = oa =+nmand o? = 2% a However, from eq. 12, we have 29? gq? 242 wr 82*mE nh = = or E= GB) a Po 8ma? This is equivalent to the case of discrete energy spectrum of a particle in a constant potential box of atomic dimensions. This is expected because for large P tunnelling through the barrier becomes almost improbable. If on the other hand, P is made equal to zero, then the eq. 29 leads to cos Ga = cos ka or @=k => =P = 82°mE 2 or 2 —_ (32) tin® : Substituting k = 2E, eq. 32 becomes =Band Theory 365 where A= hip and p = mv, This is equivalent to the case of a free particle, Hence, no energy level exists; allowed. Example: Prove that for the Kronig-Penney potential with P << 1 the energy of the lowest energy band at k = 0 is -_ ep 4x? ma? Solution: For k = 0, the eq, 29 reduces to Psin aa aT SE + 008 aa = or Pe cos aa aa ~~ sina (aa)? aa? where - Sasa a and P_(aa) aa? Thus b- Sea ee But 8n?mE y a? OP Therefore, Pate a % B= Gnat 11.3 CONSTRUCTION OF BRILLOUIN ZONES ‘The Brillouin zone is a representation of permissive values of k of the electrons in one, two or three dimensions. The concept of Brillouin zone provides a way to understand the origin of allowed and forbidden bands in solids. Let us follow an intuitive approach to discuss the construction of BZ in one, two and three dimensional lattices. In One-dimension Let us consider the motion of an electron along a one dimensional periodic latice. A direct consequence of the periodicity is that the energy spectrum consists of allowed and forbidden regions as shown in Fig. 11.4. Let us now consider the values of k at which the discontiuities in E occur. They occur whenever the left side of the eq. 29 reaches its maximum value, i.e. whenvalue of energy at points (Jy, V2 ana {43 SttvurE ve a oti we 115 EXTENDED, REDUCED AND PERIODIC ZONE SCHEME ‘The wave vector representation of a plane wave eigenstate is simple and unambiguous while the——— 372. Solid State Physics representation of Bloch states are not so because the Bloch function isnot a simple buta modulated plane wave, To represent such sates, three different schemes are cons used. They are iled the extended zone scheme (or the Brillouin zone scheme), the rey zone scheme andthe periodic zoe scheme (ot the repeated zone scheme). Al he three sehea’ represent the identical physical behaviour and any of these can be used for convenience." Plane waye Extended Zone Scheme Let us consider a one dimensional lattice in which the energy of an electron is being slow increased so that the value of k is also increased. y When the value of & becomes large enough, \ the wavelength becomes small enough as k = 2n/A. the electron will suffer a Bragg reflection : following the Bragg’s condition 2d sind = nd. ' Fora one dimensional lattice, d =a (the spacing { \ 1 ' ' 1 4 2Weyt 1 between the atoms), so that the Bragg reflections will occur at BE where n= #1, 42,... Asa result of these reflections, energy gaps are developed in the free electron parabola as shown. in Fig. 11.12. This representation of energy as a function of k is known as extended zone scheme. Physically, this scheme is very close to the free electron scheme and differ only at the zone boundaries. However, like free electon case, the k-space is infinite in the extended zone scheme but is dissected by the planes of energy discountinuity into segments called Brillouin zones. The first BZ is that part of the k-space which is located in the neighbourhood of the origin and is bounded by the first set of planes. Similarly, the nth zone is reached after crossing (n-1) such planes and is bounded by the nth planes, where the nth zone is represented by composite segments of k-space between (n — 1)th planes and the nth planes. The extended zone scheme represents various Brillouin zones in k-space. Reduced Zone Scheme ©) “rla-trtacnla 0 nla Inia 3m Ineq. 3, itis observed that the wave vector k is not uniquely defined since we may write the same as Fig. 11.12 Energy as.a function of wave vector for ‘atone dimensional lattice in (a) ext (b) reduced, (c) periodic zone schem*Band Theory 373 402) explikx) = ox (4 + 2), evn(- Brine a re) (43) where n is an integer. The second exponential on the right hand side of eq. 43, exp(-2ninx/a) = exp(ings) contains the necessary lattice periodicity. It is therefore possible to restrict the value of k to an interval of length 27/a without loss of information. For simplicity, let us start with a free electron case, We know that an ordinary free electron wave is given by yx) = explikx) a and the corresponding energy expression is hk? E(k) = (45) tk) 8x?m ed A plot between E versus k gives a famous free electron parabola as shown in Fig. 11.13a. Let us now write eq. 44 as Vix) = exp(ikx) = expi(k + g) exp(-igx) = explik’x) exp(-igx) (46) where K’ (= k + g) is the reduced value of the original wave vector k. Since, the second term on the right hand side of eq. 46 is periodic function in the lattice, this has the form of eq. 3. But it is extremely artificial representation of a plane wave. Actually, it is the limiting case of a vanishingly small periodic potential. Under this assumpsion, one must take into account the symmetry requirement of the periodicity. The general demand of the pereodicity implies that the possible electron states are not restricted to a single parabola in k-space, but can be found equally well on parabolas shifted by a vector g = 2n/a (Fig. 11.13b). The energy expression in the reduced zone scheme becomes a _ he 2nn\ E(®) = E(k + g) = im (« + 2a) (47) where n= 0, #1, #2, .. Since, the behaviour of E(X) is periodic in k-space and hence follows the symmetry properties, it is sufficient to represent this in the first zone only. In order to achieve this, let us displace the part of the parabola of interest linearly by the appropriate multiple of g = 2nz/a as shown by arrows in Fig, 11.13b. The E versus k curves for several values of n reduced into the first zone for a simple cubic lattice with vanishing potential are shown in Fig. 11,13c. Each value of n defines a Brillouin zone in the reduced zone scheme representation, Let us consider the Bloch function give by eq. 3 and try to choose k such that 1(x) is as constant as possible and the electron wave function for a given k look as much as possible like a free electron wave. Therefore, writing eq. 43 in vector notation, we have yx) = a(x) exp (ikx) = exp i (kK + g)x [exp(-igx) u(x) = exp (ik’x)uk(x) (48) where K’ =k + g, and g is some geometrical reciprocal lattice vector, The new function ug (x)374. Solid State Physics “Sala -Wa 0 a 2na Ila @ — ‘2nd = Ist zone 2nd : 1 st zone. © Fig.11.13(a)_Energyasafunction of wave vector fora free electron (b) Dispersion curve with thetranslational symmetry and the various bands (c) The same disperson curve in the first zone only has the same periodicity as u(x), so that k’ is as good a wave vector as the original vector k. Although every electron state is characterized by a wave vector, but it is not unique. They differ from one another by a reciprocal lattice vector. This nonuniqueness allows us to bring all wave vectors into the first Brillouin zone following above discussed procedure. Thus, the Fig. 11.13b showing the dispersion curve in the extended zone scheme is transferred into the reduced zone using suitable translational symmetry. This is shown in Fig. 11.13c. Periodic Zone Scheme In the preceding section, we obtained the E versus k plot in reduced zone scheme by translating the desired portion of the neighbouring parabolas into the first zone as the energies obey translational symmetry. A reverse process is equally probable. Accordingly, we can translate the desired portion of the first zone to any or every other zone, we can obtain a periodically repeated zone as shown in Fig. 11.12c. This construction is known as periodic or repeated zone scheme. This representation leads us to a very important result that the electrons in a crystal behave like free electrons for most of the k values except when k approaches n/a. 11.6 EFFECTIVE MASS OF AN ELECTRON ‘As we know that the free electron energy in terms of kis given by Wk? ~ 8mBand Theory 375 where m is the mass of the electron. Differentiating this expression, we get dE _ Wk @E_ Ww (49) ak atm a Tam so that fi (8) (50) 4n? (dk? For a free electron model, where E versus k has a parabolic relationship. As the mass of the electron is considered to be constant therefore dE/di2 can also be taken as constant (¢q. 49). However, when the electrons move in a periodic potential of the crystal lattice the parabolic relationship between E and k no longer exists. There is a breakup in the curve at various Zone boundaries leading to the origin of allowed and forbidden bands. Near the forbidden band, the curvature of E versus k curve changes, and can become negative (since as k approaches the zone boundary d?E/di? first reduces to zero and then becomes negative). Therefore, dE/dk° is no longer a constant as also the mass of the electron, actually both of them are a function of k. Thus, under periodic potential, the mass of the electron given by eq. 50 is known as effective mass and is represented by the symbol m*. So that =? (dE)" ES a? (42) 6) The effective mass is a new concept and arises because of the interaction of the electron wave packet with the periodic lattice. Ifthe interaction between them is very large or in other words if there is a strong binding force between the electron and the lattice, it will be difficult for the electrons to move, meaning thereby that the electron has acquired a large (or even infinite) effective mass. To explain a negative effective mass, let us suppose that there is an electron with k value just less than 7/a at the boundary. It will manage to move through the crystal. But then suppose that a field is applied which should accelerate it and increase k. As the electron responds to the field, it will meet the condition for Bragg reflection and will be scattered back in the opposite direction. In this way, it will behave like a particle with a negative charge and negative mass(strictly speaking the situation in a real crystal is more complicated than this). A force applied in one direction may cause acceleration in other not necessarily just the opposite direction. The effective mass of Fig. 11.14 The effective mass, energy and the first an electron may be positive or negative and is and the second derivatives of energy as shown in Fig. 11.14 by plotting a curve between a function of k— 376 Solid State Physics ‘m* and k inthe first Brillouin zone for one-dimensional lattice, I is clear that the effective is postive in the lower part of the band (lower k value) and negative close tothe zone boas (near k ~ 7/a), The figure also shows the curves E versus k, dE/dk versus k and d2E/aj2 oa k in qualitative form, us The effective mass m* may be equal to m(m" = m) only when the energy is not near the ed of aband and E versus k curve is parabolic (ic. only under the free electron approximation most conductors, m* = m as the band is only partially filed. In semiconductors, insulators, en certain conductors (e.g. bismuth) where full or almost full valence bands are involved, the effective mass differs from m, 11.7. THE NEARLY FREE ELECTRON MODEL In this model, the crystal potential is assumed to be very weak as compared to the electron Kinetic energy so that the electrons behave essentially like free particles. The weak periodic potential introduces only a small amount of perturbing effect on the free electrons in the solid, ‘Therefore, this model demands the application of very elementary perturbation theory. For simplicity, only the one dimensional case is discussed. It is convenient to choose the zero of energy so that the mean value of the potential function is zero, i.e. j V(x)dx = 0 (52) where a is the periodicity of the lattice. The unperturbed wave functions corresponding to V= O are the plane waves -—L “ (2) = Tye exp (ier) (53) where the wave functions are normalized over a microcrystal containing N atoms. The unperturbed electron energies are E(k) = Hk? 54) (k) 827m (4) This is free electron case where k can take any value, Now suppose, we take into account the periodicity of the lattice keeping V = 0 and restricting & to lie in the first Brillouin zone only. Then, we have Valx) exp (ik’x) where =k+g=k+ 12%, and E(k : 2 iim (« * 2) ey where k< % and n =0, #1, #2,....Nand Theory 377 As we introduce the periodic potential, the real wave function becomes Wa 0D ACD EB Ane Oe (56) where AA) are constants and are found to be small from perturbation theory. ‘Their values corrected to first oner are given by Auth) = kk 67) MD Ta) = BOR where = JOtV Qyde (58) ‘The perturbed energy, corrected to second order is avieott Et) = 5° lekIVIk>I (59) (k) = BOA) +E apy = BOR) Because of eq. 52, the first order term is zero, Now, let us take into account the real periodic potential which may have the same periodicity as that of the lattice, In terms of the Fourier series, it can be expressed as V(x) = yoYa exp(-igx) and Vy = Vi ‘Then the integral 58 becomes =Vq ifk-k = 0 otherwise (60) Consequently, the wave function becomes = exp(ikxy | -i ya(x) = exp(ikx) (se Dyn (k) expt ie) 1) with Ag = 1 and Ay = where n #0 E(k) -E ‘The perturbed energy is, 7 ‘0 WAP E(k) = E°(k) + 2 ae E%(k) = e(k - wt) (62) ‘The energy is either decreased or increased slightly with respect to £°(k) depending on the difference E°(k) — E°(K’), which is given byARR REE AS a Ae Se i ae 378 Solid State Physics = eet 9) ER) - EW) = a, H kee 2 [ya _(aand#) |= hea (2a am (P Ua) | eat E ta Ma (63) where mis an integer. The perturbation theory therefore breaks down whenever the wave vector is an integral multiple of tnz/a and the wave is reflected (k = ~K). Near a zone boundary, it jg necessary to write Vi(2) = Ap explikx) + Ay exp i(k + g)x ) where Ag and A, are constants. The eq. 64 means that one Fourier coefficient V, will be large near the boundary k = v/a. Substituting eq. 64 in eq. 1, we obtain [E°(k) — E(K) + V,(2)]4o exp(ikx) + [E(k + g) — ER) + VO)IAn exp i(k + 9)x=0 (65) If we multiply eq. 65 either by exp(ikx) or by exp[-i(k + g )x] and integrate, we obtain the following simultaneous equations, i.e. [E(B - EWA + Va An Va Ao+ [E%Ck + g) - ERA, (6) For a non-trivial solution, the determinant of coefficients must vanish. The resulting quadratic equation has two solutions 2E(R) = [E%Ck + g)] + [(E%(k) - B%(k + g)}? + 4lV,P)? (6) At the zone boundary, k = tn/a and E(k) = E%Ck + g). Therefore, the two energies are e*(22) = (2) + Val e-(*2) =2°(at) -IWal Thus, the energy gap at the first zone boundary (n = 1) is AE = Et - E-=2V Fig. 11.15 shows the energy gap at the first and the second zone boundaries in extended and reduced zone schemes. Also, in this case, |A,/Agl = 1, so that at k = n/a the wave function is *Band Theory 379 ' ce —The free electron! 4 parabola ‘Allowed energy band @ the NFE model, (a) the extended zone scheme, (b) the reduced zone scheme Fig. 11.15 Energy banc superposition of two plane waves traveling in opposite directions and thus represents a standing wave. Near k = 0, the difference in the unperturbed energies is so large that the perturbation effect is negligible and hence there is no effect on the curve in this region. ‘When E%k) — E%(k+ g) >> Vos then E(k) = E%k) or E(k + g), i.e. away from Bragg reflection, the energy values are practically plane waves, the same as that of the free electrons. 11.8 TIGHT BINDING APPROXIMATION Itis another extreme view point to see the electrons in a periodic potential. In the NFE case, we ‘observed that the electron wave functions outside the ion core look very nearly as plane waves. However, near the ion cores they look like atomic orbitals. This suggests an entirely different scheme for the construction of wave functions. In 1928 , Bloch suggested that the crystal wave function with the correct symmetry could be constructed from the linear combination of atomic orbitals (LCAO). Let us start from an electron in a free atom and then suppose that a number of such atoms are brought together to form a crystal. For simplicity, a two dimensional arrangement of atoms on a vo) square lattice is shown in Fig. 11.16, Let rand R, be the position vector of the electron (at p) and nth atom in the crystal. The potential of an electron in a free atoms is V(r - Ry) and that in a crystal is V(r). In Fig. 11.17, they are represented by dashed and the solid curves, respectively. In tight binding approximation, is assumed that the electron wave function is influenced by the nearest atom and is unaffected by other atoms of the lattice. The wave function of an electron for a free atom is then Fig. 11.16 An atom in the tight binding approach = Wolr— RD= 380 Solid State Physics N 1 Yar= Ry) | Atomic potentat Mn) Crystal ponential | 1 | ! ! | Fig. 11.17 Atomic and crystal potentials Spproximated as y (r— Ry), 80 that in general, the erystal wave function may be writen as» linear combination of the form Yur) = E explik-Ry Wo(r ~ Ry) (68) the crystal, which for simiplicity we assume is clrons are in a periodic potential, ys(r) must be ¢ summation in eq. 68 is over all atoms of infinite. Since, we have considered that the ele 2 Bloch function because it can be shown that Yule + Rey) = Z explileRy Wo (r — Ry + Ry) = explik-Ry ) z explik-(Ry~ Rn Wolr = (Ry = Ry )) = explik-Rn) Wi(r) (69) ‘This shows that the Bloch condition (eq. 3) is satisfied. ys(r) given by eq, 68 is a solution of the Schrodinger equation for the whole crystal: AYAr) = Ey(r) (70) The crystal Hamiltonian £7 may be written as the sum of the Hamiltonian for a free atom He Hy +I; ay ; We with My =~ tem V? + Vo(r~ Ry) ™) and My = Vir) ~ Volr~ Ry) @) where Volr ~ R,) is the potential due to nt th ground state atom ‘on the electron at r. ‘The energy of the electron in the crystal 41k) can be found by evaluatingBand Theory 381 f Wi CPLA + Hi lwe(r)dr (74) J vicowndr where the denominator J wicovscnar= EE exptit nt, Radlf Vir Ra Wor Bo) Neglecting the overlap of electron wave functions between the neighbouring atoms such that Jvie- Re Wolr — Ra )dr = Sam (75) and J vicoyetnnar =w 6) where N is the total number of electrons (atoms) in the crystal. Therefore, eq. 74 becomes £0) = 4 f vicntite + ws(ndr aie =H [ vicn(- Eg? + oer- Ro) )aenar + J vicar - Wer- Rolvairer = [ vitrwstondrs fp BB cette Re Ref vir Rad x UV¢e) = Volr= Ra Wolr = Ba) dr = Ey + 1, EZ explik(Ry~ Ralf VEC ~ Re) x [V(r) - Vor — Rn) Yolr - Ra) ar (77) Here, we expect that every term in the summation from n= 0 ton =N-1 to contain N identical terms, which may be evaluated most easily by substituting n = 0. Hence, eq. 77 reduces to Ett) = By + % xpi) f yS(r~ Ra) (VO) = Volo] vol dr 18) Further, if we make an approximation that Yo is spherically symmetric (i.e. to consider alkali metals for which the ground electronic state is an s-state) so that the contributions due to all nearest neighbours may be assumed to be identical. For m= 0, the integral in eq. 78 givesa ee 382 Solid State Physics J vice 1109 - Yao won dr=— a oy and for the nearest neighbour atoms. J vi We - Vo Wo ar=— B (in where rand B are constants and are known as overlap integrals. Since V(r) ~ Vo(r) is negative therefore ax and B are positive. Consequently, the eq. 78 can be written in a simplified form ag E(k) = Ey - &- B EZ exp(-ik-Rm) (81) where the summation is to be carried out over the nearest neighbours only. It is observed that the eq. 81 consists of a constant term Ep ~ a together with the term dependent on k. Iti the latter term which transforms the discrete atomic levels into the energy bands in the solid. In order to demonstrate the application of the above method, let us take the case of a simple cubic crystal and consider only the nearest neighbout interaction. For an atom which is taken as the origin, there are six nearest neighbours whose lattice vectors are: Rm = (ta, 0, 0), (0, ta, 0), (0, 0, +a) (82) Substituting this in eq. 81, we obtain E(k) = Ey ~ @- 2 (cosk, a + cosk, a + cosk, a) (83) For small value of k, we may expand the cosines and retaining upto the second term, eq, 83 becomes Ka? kya? Kia? 1 =6)-«-28|(1- s }«(- -|+( 1-2 = Ey- a 6B + a? (k? +k} +k?) - 8h Since, the last term on the right hand side of eq. 83 is periodic and hence E(k) is also periodic with the periodicity 27/4, Thus, the first Brillouin zone is defined as —m/a < k< nla. The resulting Brillouin zone is a cube. Further, along a cube axis, the energy is minimum at kx = 0. Thus, the bottom of the band is given by Emin = E)poxom = Eo - ot 68 (85) Similarly, the energy is maximum at ky = ky = ky will be given by na, and hence the top of the energy band Emax = E(®iop = Ey - + 6B (86) ‘rhe constant energy surfaces near the bottom and top of the band for simple cubic are shown in Fig. 11.18. The width of the energy band isBand Theory 383 (a) near bottom of band Fig. 11.18 Constant energy surfaces for simple cubie lattice in tight binding mode! (6) near top of band E(®hop - E(®vouom = 128 (87) cubic case for tight binding and free The two dimensional view of the energy contours for simple del, the Brillouin zone of a simple electron model are shown in Fig. 11.19. In tight binding mot wa wa & ’ 1 i wa na -ra| ont eae™ is wa -Wa (@) tight binding approximation _(b)neary-free electron approximation Fig. 11.19 Electron energy contours for simple cubic lattice cubic lattice and the E versus k curve along a cube axis are shown in Fig. 11.20. Further, from eq, 80, it follows thatthe energy width of the band becomes greater asthe overlap of the wave Feretions on the neighbouring atoms increases, Thus, the inner electronic levels of the free atoms give rise to narrow bands in the solids and increase as we proceed 10 the outer levels. 11.9 ORTHOGONALIZED PLANE WAVE (OPW) METHOD es in the NFE and the tight binding models, in 1940 Herring Jane wave (OPW) method for energy band calculation. ake a clear cut distinction between the core state and im the core states are associated with 1s? 2s? 2p® ed with 3s? 3p shells. Further, the core wave -d about the lattice sites. On the other hand, the After noticing some inadequacit introduced the orthogonalized pl In the OPW method, it is necessary to m the valence state. For example, in aluminiui atomic shells, while valence states are associat functions rapidly oscillate and are highly localize