CHAPTER 13 Banp Tueory OF SOLIDS 13.1, INTRODUCTION Inall solids, building blocks, locked into their positions. Crystalline solids, amorphous solids, such as glasses and plastics, blocks. Their atomic or molecular building blo regard metals and other crystalline solids as giant mo places according to a well-defined plan, just as in an polymers, but they are three-dimensional polymers rather than polymers The bonds that hold the atoms in their places within a crystalline solids are essentially te same as the bonds that hold the atoms within an ordinary molecule. Ultimately, these bonds arse from the Coulomb interactions among the negatively charged electrons and the positively charged nuclei, Whenever two atoms are in close contact, the electron distribution of each is disturbed by the presence of the other. This redistribution of the electrons usually leads to binding force betwees the atoms. Depending on just how the electrons are redistributed, we speak of ionic bonds, covalent bonds, van der Waals bonds, hydrogen bonds, or metallic bonds. All of these kinds of bonds, wh the exception of metallic bonds, occur in ordinary molecules as well as in solids, The characteristic feature of metals is the presence of an abundance of free elec the atoms of a metal join in a crystal, the outermost or valence electrons become detached fo their atoms, These electrons are then more or less free to roam through the entire volume of the metal_—they form a “gas” of free electrons which fills the entire volume of the metal. As ne * see, this gas is not only responsible for the bonds that hold the ions in their places in the lat but it is also responsible for the electrical properties of metals. A similar gas of free eles ® responsible for the remarkable electrical properties of semiconductors, which form the beckboot of modem electronic technology. 13.2. BONDS BETWEEN ATOMS We will now briefly discuss the kinds of bonds that hold the atoms in solid. Our discussion will be.) + quantitative because quantitative treatment of the theory “® of bonds requires the full machinery of wave mechanics ane s = ito cae ies had better keep in mind are ofan intermediate kind, partially ionie Sa , ly ionic and partially covalent. to las loans cay tons ae ea 1 acquire extacleerons, When sons ofthese too kinds interact, the rearrang Seat eae we erent of distribution ia very sim gement of the electron Fig. 19.1 Amangen’ cy ative ple: an electron from an atom of ions int! whether molecules or atoms, are permanently and almost rig ‘such as metals and minerals, are distinguished frog by the regularity of the arrangement of their buldng .cks form an orderly, repetitive lattice. Thus, we can ecules in which the atoms are held in specif ordinary molecule. These giant molecules ae ordinary, stringlike, one-dimensional trons. Whe Nat, -qires tha ast be for higher er ease of c {panial ov samplicated sinimate | Figure sential eng inction ¢ “By has b Sshanical y ‘i Potenti ihe to ‘ther ene, athe ex “lygand ThEOTY of Solids pe ist kind becomes attached yo xd negative ions, such as Na eaten re nb alaction between the Positive id iespherically symmetric electron © and the ne isthat of two point charges, ae guration ie sh imerse-squate force. This Coulomb jeri! MEtgy Ue eB their Coulonge the NaCl lattice (See Fig. 13,1), MTaction is Tesponsibt: , comesponding oan ease However, ifthe distance between th ot helding te Ne ona inner electrons of the two atoms Overlap, th 5 ising from the Exclusion Principle, Tris no" tM Potential This ¢ energy is modifi fr : morte | oct ty btn te aman ry ema tice, yet big vfiguations unchanged since hae we bviously impossible ie nd fo some form a TC held jg | at any state occupied in each of the seane cep their electron ant molepye | snms would be doubly occupied in the ‘combined am. Consequently, the Exclusion Principle squires that whenever atoms overlap, electron aust be forced into formerly unoccupied states othigher energy. This effect occurs not only in se tiecase of complete overlap, but also in the case ' chs | ofpartial overlap (the latter case is rather more ich is isu | ompicated because the wave functions of atome ding force ener | in intimate contact are strongly distorted) nic bonds,coulkt | Figure 13.2 shows a plot of the mutual inds of bond, | puential energy of a Na” ion and a CI- ion as lids. function of their separation (this potential ee electrons Vie | ergy has been calculated from the quantum- | tichanical wave function). The sharp increase “lite potential energy at distances shorter than 2Aisdue to electrons that are forced into states ‘tgher energy. At a distance larger than about Fig. 43.9 protential energy of interacting Na” : the exclusion effect disappears, and the and CI’ as a function of distance. Callomb interaction takes over. From this plot ‘Ese that at large distances the force between the ions is attractive, but mie Ata distance of 2.4 these attractive and repulsive forces cancels, Sulibrium joint. i This The ceplsive contribution to the force at the short distance is called the repulsive core. I atoms and itis ‘ of atoms—it is found in al Rive core is a general feature of the ior toad ‘Thus we see that the Exclusion Principle is o ‘ally the same for all the different kind "“ponsible for the resistance that all atoms o yl Covatent Bonds: Atoms that are not very wil | jg’ Willing to share electrons with their neighbow “810 between the atoms. Usually the s are €ssentaly these bonis ns =a > & ge 2F 2 F Pe 3 - zz ofa but at short distances it is giving a (classical) to interpenetration. 7 rn to give up electrons or to accept electrons ‘The shared electrons tend to concentrate osite spins, each secur in pairs of oppe shared electron’ rons gives rise 10 a bond between positive charges in the the carbon atom likes to ces, For instane ‘ni 1 preferences Fo he atom (see Fig. 13.3). ee centered on the “net bonds exhibit strong directions Pre Tyrone esgteona 3, ovale cor re The puilentbonds directed toward the comet asin scl tthe 7 é big fing of carbon atoms with other Ce rig. diamond, the hardest of all crys!Fig.13.4 Waal aes and most molecules dono hy : The atoms of the noble gases ani ; . oo east ne eto share. The interaction between two such toms wil en ae aoe ae erp cal redistribution of electrons, but merely 10 a corelation ofthe totem, yy dow ale redist not lead to any large-se: lectron pity of at e1CC and jtion ©! . We can roughly understa Sona a le of the electrons in the Simple clastcal Bohr model. Imagine ee i wero ae ees i casalar abt On the vera he x eos) Satie See It ofthe atom is zero, since each electron ion i8 eh isjnt os ely to be foond on one sie ofthe noleas as on ron ha, th ame a re er, at each instant of time, the dipole moment the other, However, sravelength, for « instantane ’ math, At \ding on the instantaneous Fig. 13.5 fotin their p has some nonzero value depenc eee ipa — 1B CIpole P ite wavelength, ee a ear esa to polarize the charge distribution in neighbouring Pipe potatial —— ST eiearnael dipole moment, As we know from sler-nagn rn ef aialeaate ee is " i electrons, bemeen aligned dipole moments is attractive. (In terms of the motions of ia Se its neighbouring atoms tend to be correlated in such a way a ee Speers Cara charge distributions of We can readil roid coming near each other and, therefore, the net force between the charg mote ee i atoms is attractive). This force between neighbouring atoms is called the van dec cot he n gas, ee ate bonds Produced by the van der Waals forces are much weaker than ionic or ae itty of meta bonds. Hence the noble gases only crystallize at very low temperatures or at very high pr ist calculatic a forces NNote that since the mechanism underlying the van der Waals forces is quite general, these "Drude treated act between all kinds of atoms and ‘molecules but they are only important when the ionic or covalent forces are absent. The cohesive forces in liquids ‘are van der Waals forces, (iv) Hydrogen Bonds: The hydrogen atom can lose its electron to neighbouring atoms, leaving the hydrogen witha postive charge. This Positive charge placed between two adjacent Negative ions Produces a bond between the i this bond is some covalent bond, wit What similar to a ith the positively Fig. 13.6ee a Theory of Solids, wo | | © ecdhydrogen playin | seed by the role g | Zsa molecules in ice crystal, pe leet | ssa aa Se ee ws 5: The e1 Molectle © also responsible fo cowhal letra peg nue of Dv efor jonny the two ,ecalis somewhat similar to that Sten perel ie ape clectron with eight be ‘ne ‘Pall of the other atom: i atoms shave electron “one ofthe esa they fon cP The each mo parece 8 Of fire Clectrons are sesembedded in an interpenetrating soe O08. Thus the meg 2 MV through the entire apes. The Coulomb attraction bere, 4 of Negative Consists ofa lattice of positive joi negative charges holds the iong 1. MS positive ‘Although the “free” electy, i places ‘ons go:bed t0 any particular atom, they oe Metal are not + + e a | zx of forces. When an electron passes nn ompletely aperiences a StIONg, attractive Coulomb fan em it Olea, 4 x of all the ions on an electron can be dea The net SUCh 3 penodically repeating potential-energy free by || tg | Fg 13.7). Classically, an electron merino (ee tbe a, potential would simply ee I speed up near each ion séslow down inthe spaces between. Wave-mechaniain FIO 13:7 Potential energy of a “ree #e motion of an electron is rather mo * electron moving through a metal re complicated | jxcenain ranges of wavelength the motion w actaslly along a straight line (x-axis) _ 258 1 et HyScogen bonds ace responsible fc onsible for joing 1Ons in th «~ ; ible (forbidden e Tey bands). However, for an electron of long wavelength, or low momentum, N fee particle i.e, the periodic potential produces no effect on the motion, UT ‘© 1 insensitive to any disturbance whose size is small ‘compared g. 135 length; for ex in waves of long wavelength (swells) are unaffected by a small in their path. Ane only senses the potential averaged over toughly of wavelength tion in niga} ie wavelength ludes several of paths and valleys shown in Fig. 13.7 then erage potenti ch is equivalent to zero force. Under these conditions the electrons in the metal will behave like free panicles 123. THE FREE-ELECTRON GAS We can readily explain several of the imponant physical properties of metals in terms of electron gas. For instance, the motion ofthe free electrons is responsible forthe high electric ty of metals. Accordingly, the free electrons are often called conduction electrons. One *ftke first calculations of the conductivity of a free-electron gas was made by P. Drude around 4) Drude treated the electrons in a piece of metal as classical particles, salar femal eos tnd These Jectrons do not bring about @ nadom directions. These thermal velocities of Lat Oa ee en deren hee eras 2 ct i e, for every el ne hare Seo he ene oe it ce ea ed vm or generator, an electric field £ willbe produced within See nae of the electric force, the electrons will accel es i _ of metal and, under the es er vi reco Tso ve sn el ge ort rhoae me mai or in collisions with ed the drift Seis ed by rors ht the lcs ue in ols WS fa frictional fore aa fein Jay the role of speeds. Under typical conditions, §) [£5 of the lattice. These collisions P ‘i the random 5 to ‘small compare f perhaps 10° m/s. But Te if speed always au Trent bas 4S Pe of anelectoncomis tear oa sin ae wie eed of about 10 vn dif mosion along the wi: qualitatively, Le electron have randot lows ed a much si 2gzags on which is superumt . jal is a constant, wi260 the motion resembles that shown in Fig. 13.8 but the amount of drift per zigzag is much less than shown in this figure. The number of collisions per second that an electron makes with the ions of the lattice is proportional to its speed. Since the drift speed is negligible compared to the random speed, the drift speed has next to no effect on the collisions rate. This means we can regard the collision rate as a constant, independent of the drift speed and of the electric field. We will designate the collision rate by 1. The quantity tis called the relaxation time; roughly, iti the time interval between successive collisions of an electron The drift motion of the electrons determines the net, macroscopic current ca ‘We can calculate the drift speed by examining the losses and gains of momentum of this electron, If the drift speed of an electron is v,, then the momentum is m,vd. We expect that, on the average, @ collision will absorb all of this momentum, i.e., a collision will destroy the forward motion and leave the electron with only the random thermal motion. This means that, in each collision, the clectron, loses momentum m,v,, The average rate at which the electron loses momentum in collisions is therefor mv, a2) mM (a). *% ‘ On the other hand, the rate at which the electron gains momentum by the action of the electric field is 22) — -eE (3 ° ®) Under steady-state conditions, the rate of loss of momentum must match the rate of gain, By setting the right sides of Equations (1) and (2) equal, we get Ex ™, Tied by the wir 3) This is the speed with which the electron gas flows along the wire. The negative signin Equation (3) indicates that the direction of flow is opposite to the direction of the electric field, To find the electric current carried by this flow of the electron gas, we need to take into account the number of free electrons. Suppose that the metal of the wire has n free electrons per unit volume. In metals, the number of free electrons is usually one per atom; typically, this amounts to 10 or 10 electrons per m’, If the wire has a cross-sectional area A and a length /, then its total number of free electrons is n x (volume) = nA/ and the total charge associated with these electrons is Aq =~endl (a) Within a time interval 4 =1| v4 all of these electrons emerge at one end of the wire, Hence the current in the wire is ) at thy om, f'we express this in terms of the potential difference AV’ = El across the ends of the Wi we get (ent A) . r=) SA lay @ m1) ‘This is Ohm’s law: the current is proportional to the potential difference. Accord © Equation (6) resistance of the wire is Rad _ im | t geri al motions ¥ sry disagrees nhctivity on te ieelctron gas | ste heat eapaci sntnoticeably | ite free electrc ‘awat the Exclu ‘ston gas beca ‘slessical then Aas of qu ules of half {Femi gas she ‘raticles of ‘Quantum me Svoutd me eeatldmeantheory of Solids god je conductivity is os ° o = Lent a Example 1. The conductivity of silver is 5 (8) oluume is 5.8% 10 poo co, liver is 6.2% 197 os ina silver wire of ‘omen ate the relaxation ume jhe number of free electrons alee i : s lime. Calculate the dri Solution: From Equation (gy “™*/€eted to a potential ‘ference of 1) aot of the om, (62107 Qm) 9.110" ky | en (LexloFG? <8 =3.8 x10" ; | | CP x 5.810" ‘ ay | Theelectric field inthe wireis E= 4 Vid=40 Ving noun, Hence, fom Equation to j . - ence, from Equation (3), The ft gat vg = EEE _ 16107 20Vim «3.8 110s ON the grt m, 9.1%10 forward mae 4 =-0.13m/s i Collision, the Many Such a low drift speed typical for the motion of the free electrons in metals. (In contrast, the tty | pandom speed of these free el colin wa a ied ot lectrons is much larger; the typical value of the random speed is | 134. FERMI GAS acto otee Although Drude’s simple classical calculation leads othe correct form of Ohm's law, the attempts clsiy | atdetermining the relaxation time t from the atomic parameters and the classical theory of random thermal motions were a complete failure—the value of the relaxation time calculated from classical theory disagrees with experiment, and also fails to reproduce the observed dependence of the ) | conductivity on temperature. Furthermore, according to classical theory we would expect that the | feeelectron gas has a heat capacity of its own amounting to 3 cal/K mole, which has to be added ch the rate of gin}! | io the heat capacity of the crystal lattice. But experiment shows that the heat capacity of metals isnot noticeably different from that of other crystals. All these difficulties of the classical theory ofthe free electron gas disappear when we treat the electrons by wave mechanics and take into aicount the Exclusion Principle, which plays crucial role in determining the properties of the free- eketion gas because it forces electrons into states of very high kinetic energy, much higher than : Thi ja | tte classical thermal kinetic energy 3/2 kT. si i 1 of the cert ‘A gas of quantum-mechanical particles obeying the Exclusion Prinses or ates eed 10 akc sist | Mricles of half-integer spin—is called a Fermi as The a been an a th consider the simple - actrons Pera ht] Femi gas shows up drastically if we comity K) all have zero kinetic energy—they al are at . ature (T= ~ amoutis'? 4e| the particles of a gas at zero temper this ‘ol ‘®t. Quantum mechanically, electrons at 2er0| temperature ean ke would mean that they all are in the ground state, ere conta i i rae atzero temperature the electrons Ea ‘occupy opposite spins in each orbital sta vaste We can roughly regard the free electrons in! al pets Pails in box, The available states ae then describes "9S | fait’ and the energies of the available states are 8 “| “lowing three-dimensional equation. 3,2 aa pty ene BE a(t)” om box is a cubes ‘ot all have zero Kinetic energy because (dcontradict the Exclusion Principle. vest energy, two electror Al) measuring 1, Here, we have assumed that the gt Posing his assumption is convene + eget as pst i 1) tegen tes OF tae My» and me a yith Me My 8 Figyettimensional space labelled’ W 13.9 shows some of these points:‘262 . fodem p intervals between adjacent points are one unit, and that 7 (> 0, m, > 0, n, > 0). We can use this figure to count the mn given energy E. The origin is all the points are in the fin tumber Of available sure, We can express the energy in terms of this radius, &% sa 6) and conversely we can express the radius in terms of the given energy E anf wh 4) The number of available orbital states of energy less than E is sim within the radius R. Each point is associated with a volume element of one u ie elements can be regarded as infinitesimal provided R is a large number. The Tumberof points within the rane Ris, therefore, simply the volume within the first octant, ie., 4) (4n/3) R. Taking into account the two spin states per orbital state, we find thatthe number of states of energy les thay Eis PY the numbe of nit these Volume elena mse 14x ( 2m, ’) a =2x—5| See) gt Nee (5) Since the volume of our box is V = L?, this reduces to N= Be Oo In crystal at zero temperature, the electrons fill the available states of lowest energy. Hence if we set the number of states in Equation (6) equal to the number of electrons, the energy E vill equal the energy of the highest occupied state, or Fermi level. Solving for this energy F. we obtin apn (NY? Ep = (Bn?) H(4) 0 ip = 3r'y 2m, of the electron gas. Note that this energy depends only on This is called the Fermi energ} the density of the electron gas’, Electron velocity at Fermi surface is given by ® (3Nn?)?? dav? = E, d ( ) 2 2m, Ah ( Baa : ® m, OV which is ~ 10° cm s"! E, has a magnitude of § eV. So at absolute zero, the conduction electrons in a metal a not Condensed to zero ener, 2) Stale as in classical mechanics but they fill all energy levels ove"® Tange of about 5 eV above the ground state Ifthe temperature is raised, what happens to the increases, some levels which were vacant absolute “ere occupied at absolute zero become vecan, stron 38 energy levels? As the KE of eect Zero get occupied and some others ® *E ‘quation (7) gives the. tthe energy ofthe lev the density ol cis defi gy for non-zero temperatures pied; it depends on the tempera! 18) oo2 rm ite BBM op points een Points within pet iy TakIDg int seus TRY less thn R? fF en 5) 6) s of lowest energy. Hee trons, the energy £ il r this energy E, weobat ye 5 energy depends ea Fermi gave the probabi a i ty function « icles which obey the Pauli's exert" “scribing the thermal behavi . prt exclusion Principle. This race a aviour of a group o' (9) State hi ,sinthermal equilibrium at a temperat Fre “nergy E is occupied by an electron in an ideal sre possible states which is occupied,” Mermi Energy and /(E) represents the faction Figure 13.10 (a) gives the plot of th yaslte zero, =O the Fert Fe fiction f(E) against E for T= 0 and T>> 0 SEV=1 for EE, Soat absolute zero E, gives the cut off ene mplet "gy. All the states with energy E E, are vacant. Asthe temperature increases the dicebucen ee, affas shown in Fig. 13.10 (6). States with energy less than E, by an amount of the onder of Lt being partly occupied. The value of E, depends on the temperature but for KTIE, << 1, E, (1) is closely equal to its value at T= 0. At any temperature the Fermi function f(E) u for E = £, So, the physical meaning of E, may be stated as that at the Fermi level (ie, whea E = E,), tke probability that the particular energy state may be occupied is 1 E, (which is of the onler of5eV for many metals) s HE) ne) oO E Ey se Te Fig. 13.10 (a) Plot of Fermi function f (E) for two temperatures. This gives us a significant difference between classical statistics (Maxwell-Boltzmann’s statistics) ‘sd Fermi Dirac Statistics. ° ill have zero energy at absolute According to Maxwell-Boltzmann's distribution, all electrons wil T= OK, while scocrding 0 Fermi-Dirac distribution, there are some aa having energy ‘P05 eV. If we assume the electrons to obey Manwell-Boliemann’s law, then to have energy TTY the te be ~ 5000 K Fore er = E, >> KT the term 1 may be neglected in the denominator of the ession (9) for f (E) and the Fermi function becomes uo eet SE) = 0 in the region E - Ep >> AT, the SitengttOR and we get a Boltzmann tail Say <2 "© high values. It may also be ‘ompared with E, (kT << Ep): ;stribution becomes identical to the Boltzmann re will be few electrons having energies the melting point of metals AT js much Fermi dis 1. In this case thet noted that belowid | om" 264 wo " why Moa ect" Fermi level at a temperature is given by the relation Metom ing Fatt sect w(K yy Oc Be = EnV 95 F } Powe ne ERS L, este yl | ty pene where E,, is the Fermi enengy a absolute 22701, T= 0-A% Tncrease terms jy wu Fagot ener nant ni level bg 78 at (ary . . Serene, — Fah neat but the decrease is very small as [7--J 18 0F the order Of 2+ 10 at room temperiy, J n set || 4asDyo 0a a+b x suth states are occupied, how can the ékctrons make the transitions? The answer that the electric field acts also on the electrons in the higher states; it increases the momentum il the electrons at the same rate. The electric field removes electrons from the higher states lifting feminto even higher, unoccupied states, and creates vacancies at just the rate needed to accommodate ‘eclectrons arriving from the lower states. Hence the Exclusion Principle does not interfere vith the acceleration process, which proceeds pretty much as in ike classical case. Only in the ‘eceleration process does the Exclusion principle makes a difference, most collisions are forbidden because the final state is occupied. Density of States. /1 is defined as the number of electronic states per unit energy range and “ denoted by D(E) We have from the Equation (3) Fig. 13.12 (2) (16) ‘here we have replaced R by NV k “Ss than E within the radius R. . Differentiating Equation (16) wart. N. We dE aN get oe IN t (17) di az Wives number of energy levels “Ct result is C, = V2m (KTIE,) Nok2 66 Mem As there are two quantum states for each energy level, one of spin up and other so we have the density of states of a free electron gas in one demension Of spi ‘Also from Equation (3), we have, re 1 _an(_1 ) - Als) WN LAME, L\2m,E. <. Equation (17) may be written as | Eq sea 1 : sa? DO =e * ame. a i0 _4L(m\" a9) | sole h(E DE) We hav ‘Variation of density of states D (£) with energy Eis shown in Fig. 13.12 (6). Eis the Fermi energy. From the above curves it is evident that the energy states are full upto Fermi level which corresponds to topmost filled energy level le, beyond which all states are empty. 0 fe This is Example 2, What is the Fermi energy for the FI > ie {free electron gas in silver? What is the speed of an Ig. 13.12 (b) electron with this enrgy? [N/V = 5.8 x 10” /m*] Solution: With N/V = 5.8 x 10°8 /m°, Equation (7) becomes ys (1.05 x 10™Js)? 2x9.1x10"'kg ‘The electron with this energy have the speed We car E, = (3n? (5.8 x 107 /m?)?? dl) .4x10° m/s Ans. (2) ‘Thus the typical speeds of the electrons in the Fermi gas are quite large. For comparisot, note that if we wanted to give the molecules of a classical gas Tet eecisot ieererctmapsa Exam we would have to heat the gas to a temperature of 6 x 10" K and this is a striking illustration f “(Give the difference between the clasical gas and the Fermi gas, Sotuti pa Braye 3. Consider silver in the metallic state, with one free electron/atom. Calculate the ergy. Given density of silver = 10.5 gm/cm’ and its atomic weight = 108. Solution: We have Y. _ Atoms _ (Atoms/mole) x (mass/volume) _ No XP Fi Vol a Wh ‘olume mi an mass/mole ) 'o = Avogadro number = 6.02 x10” Atoms/mole. ® = density of Silver = 10.5 g/cm’. a poe mass of Silver = 108 gm/mole. M - S@x 10? atom/mole x 10.5 gm/em? L 108 gm/mole “Cae ; = 59x10" “yer Now Fermi energy is es ol” Me electonsem? = 5.9510! free electors! wer i Ep ze 2 ‘" 8m.\ nV,OE ey jong 08 2 108 xe 0 we! € a P po <3 Theory of Solids os se 267 = 8510s (3,5 2 5.9.10" im! 91610 -(2282e10% my gxample 4. If the Fermin? " Joule = 5.4 eV Ans. ee SPR OF a metal is 10 e¥, what isthe corresponding classical 3 pa 2k 2 (10x 1.602 x 10°"cy Sk = 4.64 x 108 Sx (381x105) > 464 * 10" K Ans, Example 5. There are about 2 cg. Fermi velocity and Fe N Solution: TF >No. of fie We have the relation 5 * 10" free electrons/ min sodium. Calculate its Fermi mi temperature (h = 6.62 10 J-s) electrons/unit volume of metal 2.5 10°%/m? (3 NV? _ (62x10) (3 5B (2a)" emo (35, Im 8x 7 25 (9.110) 8x sx10” sx1o" =e" @ rey 6x10 the max. K.E. of free electrons at absolute zero. Let v, be the Fermi velocity, so we tne 047 ms We can define Fermi temperature 7, from the relation p= AT 5x10" 623 10'K Ans. T= & 138x10 Example 6, Calculate the Fermi energy of sodium assuming that metal has one fee electron ston. Given density of sodium = 970 kg/m). Solution: In this case . LN _ 6.02 x10" _ 9 54 x10* Vv ~Mp 23/970 Fermi energy is given by the relation (3 xy" (6.625 x10 Iman Vv) rari” N y= SLID ey a9 eV Ans. =5.11x10" Tex10™ etween F (E) = 0.9 and F (E) = 01 a Example 7. Calculate the extent of the energy fae between which is 3 eV “erature of 200 K and express it-as a function of Ep ‘lution: We have the relation 1 1 P(E) = emer = Tew Oar FE) = ge ive268 Ey - 09 (a) In this case F(E) = 0.9 and let CE, EMT ao “ sin8 om 096 09e!' or ove" et 9 ing log on both side Taking log on, both ex? = log, 9 = 2.3026 » log, 9 = 2.198 = 2.198 oF 2.198% ky -T , -E or a Ni 7 = 1384107 4200 oy _ oor ev. ow 1.6710 gy, ~ E = 2198 + 0.017 = 0.037eV So E = E, ~ 0.037 = 3 - 0.037 = 2.963 eV (b) In this case F(E) =0.1 So Ol = TB Ep hy 7 1420" = ut x = Ain Be “Tre (Pex or) Now Fermi E or 1=0140.1e e=9 Taking log both sides x = 2.3026 log,, 9 = 2.3026 x or 0017 3 0.954 E, ~ Ey = 0.017 » 2.3026 x 0.954 = 0.037 eV ~ ;, ~ E = 0.037 ~ 2.963 = 0.074 eV AE _ 0.074 o <= == =25% ; Ep 7 0025 = 2.5% Ans. Lampie 1 on ome ‘ ee a femperature at which there is one per cent probability that 95" +“ Coppep “ i, above Fermi energy will be 8 en Solution: We have the relation °* Oceupied by an electron. timate 1 “10% ¢ Mion: In the case ig 9M: In 4 02g ye “2 coy} by feyd Te01y oF Solids 269 0.01 + 0.01 g ~ 0.01 e Taking log on both sides * = 23026 log,, 9 7 log, 99 os : Fy T= 23026 tog, 99 hy T = 05 "23026 tog, 95 = 0109eV 7 = 2:109 1.6 «10° _ _ 138x10= Hence T = 1264 kelvin Ans, Example 9. Find the fermi energy in copper on the ‘per on the assumption that each copper atom contributes xe fee electron to the electron gas. The per O40 Ga ead le ee density of copper is 8.94 x 10° ke/m! and its atomi pss = 63.5 u. Given w= 1.66 © 107? fo nn COPPe IS 8.94 % 10! kg/m! and its atomic = 1264 K Solution: In this caseP = 8.94 x 10° Agim’, mass of atom = 63.5 w Number of free electrons/unit volume, n=. y so nN. atoms __mass/m? Vm ~ mass/atoms = B10" Kale 9 45 10% stomsin? (519(1,66x10 gin = 8.48 x 10° electronsim? Now Fermi Energy is given by Z£eay-2ey F 8m, (nV) 8m, re) coasei0y (ants F8x9.11x1 3.14 = 0,603 * 1077 * (8.10 x 10°? = 1.13 « 10% — LIS 10 oy = 7.04eV Ans. 1.610" _ ean collision time in copper at 20°C, assuming one free Example 10. (a) Estimate the mean collision time i Hears pepo tem el 8.48 * 10" electrons m? and {ron/eopper atom. (b) Assuming that the average speed 0 Ms estimate the mean free path in copper atom. (Given n 1673 « 10% Om), Solution: In this case average velocity is given by y <> = 10 mis, P = 1.673 x 10° Om, 8 3 48 © 1028 electrons/m () Mean collision time . we 9.1L © = Ggant0) x (6x10) (1.673% 10") = 251 x 10's y>e 6) ') We have the mean free path 2 = # = 2.51 x 10% m Ans. = 10! 6 2.51 x 10"eT 5 a“ Moder Prac, 270 i Example 1. A metallic wire has a resistivity of 1.92 * 10-8 Om. For an electrie 8.14 Vim, find (a) average drift velocity of electrons and (b) mean collision wn coe ld of 7 Ming there are 6 x 10° electrons/m’. ‘ reo "8 thay ave? x = 0. = 6 « 102 Solution; In this case P = 1.42 10 ot 4 Vim, n = 6 x 10% Clecttonm? yO! (a) Resistivity of a metal is given by the relation m. ie net ; m, gestion 2. Mean collision time, tp ’ 911x107" (6x 10")(1.6x 10") (1.4210) ple 15. t = 4.236 x 10s Ans. mom, J Example 12. (a) Determine the mumber density of carriers ina copper wire assuming he! ay is one carrier ‘encuen) per copper atom. (b) The maximum recommended current ina 14 guige iti? copper wire (radius = 081 mm, A = 2.1 * 106 m’) used in household circuits is 15 Determine sastvity of the drift speed of the electrons in such a case. (Give P= 8.95 * es kg/m and M = 63.5 gino), 35% Solution: Given 1= 15 A, A= 2.1 * 10° m?, P = 8.95 * 10° kg/m? and M = 63.5 pmo, axation tir . Nap save (a) Number of free electrons/unit volume, n = —_ (6.02 x 10” mol") (8.95 x 10° g/m’) rs (63.5 g/mol) = 8.48 x 108 electrons/m’ (6) Drift velocity of the electrons may be written as ample 16. ( mee ‘welectron fo "nde 896 | = eS lution: G © 8.48 x10" x 2.110 x16 x10" 45 « 1933, = 5.3 10“ m/s Ans. Example 13. Find the drift velocity of the free electrons in a copper wire whose cross sectional , Mee ¢| area is 1.0 mm? when the wire carries a current of 1.0 A. Assume that each copper atom conrtues ™ctrons one electron to the electron gas. (Given n = 8.5 x 10°% electrons/m). Solution: In this case 4 = 10 mm? = 1.0 x 10° m,1=104 Drift velocity of the free electrons is given by the relation Jt as ple oe nde Patan Lo vais 4 x10") (1.010%) (16x10 Mion: ot = 7.4 * 10% m/s Ans, yin Example 14,4 uniform silver hasa y My Wily of 154 » 10° om at room tempera Ea Nyl? » calculate (a) the drift velocity (b) the mobil “nn ming that there are 5.8 x 1078 electrons/m’ of the rat oh 0" Om, E = 100 Vim, n= 5.8 x 10 electrons! 4 (@) Mean collision time may be written as t=Vy ay , m f Solids Yn pa EO Of trig an ei ing ore 9.11107! My 8x10") (6x10) = Stop, = 3.98 x 19 ONO (1.5410) Ore | s Ans, (b) Drift velocity, is given by », ={ ££ 7 m = 6.610") (100) 3.98 10") 99 = OT m/s Ans, (@) Relation for mobility ist ge = 7*10-3m'/Vs Ans. 15. Fi si Eaample ; au the relaxation lime of conduction electrons in a metal of resistivity nating 4 10*Qm, ithe metal has 5.8 x 10° electrons/m, A.Detenig Solution: In this case P = 1.54 x 10° Om, n= 5.8 x 10% electrons/m? and t =? ~ 63:5) | Resistivity of the metal, P =, so we have = 635 ph nee Relaxation time, toe e*p 9.11 x10" (5.8 x10) (1.6 x10") (1.54 10) = 3.97 x 10 5 Ans. Example 16. Calculate the mobility of electrons in copper assuming that each atom contributes ‘w fee electron for conduction. Resistivity of copper = 1.7 * 10*Qm. Atomic weight = 63.54. lasity = 8.96 x 10° kg/m! and Avogadro's number 6.025 * 10"/mole. Solution: Given that P = 1.7 x 10° Qm, M = 63.54, D = 8.96 x 10° kg/m’, = 6025 x 10/ mole, Number of free electrons/atom = I and # t ss, Fre elecrons/unit volume, = 97 = Navy ge C708 rom oo 025x10*)(8.96x10°) | = 63.54 = 8.50 x 10°%m? Ans. Example 17. Calcul i ‘nd thermal velocity of free electrons‘in copper at ‘ . te the drift velocity a | 'emerature, (300 1), when 2 a wire of length 3 m and resistance 0022 2 carries a 115 A. Given y= 4.3 x 10? ms. ‘Solution: In this case 1 = 3 m, R= 0.022 9, 1= Net y= 15 A, T= 300 K, Hy = 4.3 x 10> m/Vs, Von ? “Mage drop across the copper wire fs siven bY oo = 033 V x El 3 Hlectric feta, = 0.11 V/m Dri Th . velocity, ‘mal velocity is written as,272 5 x1,387 x10 «300 “ 9.11%10" = 1.17 « 105 m/s Ans. Example 18. Calculate the Fermi energy in eV for silver at 0 K, given that th e dens silver = 10500 kg/m?, atomic weight = 107.9 and it has one conduction per atom.” Solution: Given T= 0 K, D = 10500 kg/m’, M = 107.9 and E, =? au Pp Number of free electrons/unit volume, n= ave N, 7 (6.025 x 10°*) (10500) me 107.9 = 5.863 * 10"%/m? Ans, R a)" sal sey eye 6.6310) (35.863 x10" sop 2) “3x9.11x1 3.14 Giver e4 = (0.603 x 1077) (5.60 x 10°8)73 = 8.83 x 10°9y solution 19 = 283x107 = 5.518 eV Ans. . 1.60x10"" goFemi ¥¢ Fermi energy for silver is 5.518 eV which corresponds to Ey (0). x E, (0) = 5.518 eV Example 19. Energy over which probability f (E) falls from 0.9 to 0.1%. Over what range of energy, expressed in terms of KT, does the Fermi-Dirac distribution function change from 0.90 to 0.10? Solution: F—D function is given by, f(E) = +1 ii temper Lumple 2 “probability 0K) Suton; if Probab or wy “ee or = log, 0. log, 0.11 = 2,303 lo; On MH Big ON Subtracting Equati g a ion (2) from Equation (1), we have at a 2.303 (logy) 9 logig 0.11) = 2.303 logy, a) 2.303 * logis (81.818) = 2303 « 1.91 = 4 Ams,“10% "im? 8.83 x 10h, 1.1%, Over what ry ction change fon! 4 theory of Solids ot go the probability that p44 KT, 40 this is the Example 20. The specific rok FD fut e207 rave ich ion changes in terms of KT. re are (w0 electrons pr ey Wate ie es and fom. Cale a Maton Speci pay 2M. Coleus te non 273 4 state occupied Fange over which [io 90% 10 10% over an energy range values of n and E ih ct C1 la 7 = 184 F Number of electrons/atom = 2 N= and B= Number of fee cletronvunit volume,» = = y ») Molecules ae n= 602 «19 SS, Lmole , _g electrons x1 atom 7 184g cm "~~ atom.molecule n= 1.23 « 19° , the allowed energy bands are infinitely amo M1 Partic and are independent of K. We sh “tien Let us now consider the impact of varying P which is measure of Potential barrier strengt® mente The 4 pr i r when P is very large, the barrier are strong and in the limit P -»c0, the electron can be consiet 'Salong as confined to a potential well, this case applies to the crystals where electrons are tightly bow! "Sent egg with the nuclei. [ Vea to clas ; a In case, P is small, the barrier strength is also small and in the limit P > 0(no bat”, "3 equi is the electron can be considered as moving freely through potential well. This is the case of ¢F9S™ Naor 3 in which electrons are free to move around. Seatve BRILLOUIN ZONES Wenge / i ; ait lene We have seen in the Kronig-Penny model that the energy discontinuities in a mone#™ hig My are dimensional lattice occur when K = n/a, Where n is integer, positive or negative a dimensional monoatomic lattice, a ive representing the value of Kis divided by energy disco™™ into segments of length n/a, as shown Fig. 13.14function cing ite quantity th Ay 13.13, forthe ae ote the energy ion isthe inprat bands sept regions os ka*#! he wien 07 owet arr ond Theory of Solids These line segm ipesegment —1/a SK The segments -2n/ac x r/a that do not fit ito ihe. 2° Hee fst one yet which have sufficiently small wave tunbers to avoid diffraction by diagonal atomic planes Fig. 13.15 (Fig. 13.15), The second Zone consists of electr sovingin +x andy directions, with the ane approached. Further Brillouin Zon 136. SPECIFIC HEATS OF SOLIDS Failure of classi fons with & varying from n/a to 2nla for electrons Possible range of k values narrowing as the diagonal directions can be constructed in the same manner. 1 theory: Blackbody radiation is not the only familiar phenomenon whose ‘planation requires quantum statistical mechanics. Another is the way in which the internal energy ofa solid varies with temperature Molar specific heat. Let us consider the molar specific heat of a solid at constant volume, C,which is the energy that must be added to one 1 K mol of it, whose volume is held fixed, to ‘ase its temperature by 1 K. The specific heat at 99 ‘mistant pressure C, is 3 to 5 per cent higher than C, insolids because it includes the work associated with volume change as well as the change in internal ey et Classical theory of heat. The internal heat 8 ®rrBy of a solid resides in the vibrations of its & “stiuent particles which may be atoms, ions or 49 Ileeules; we shall refer to them as atoms here for § Gnenience. These vibrations may be resolved into. = ‘RrPonents along three perpendicular axes, so that we 1 resent each atom by three harmonic oscillators. “erding to classical physics a harmonic oscillator cal equilibrium at the temperature T has an wit ergy of KT. On this basis each atom in ag a img uldhave 3 £7 of energy. kilomole of solid : Fig. 15.16 tun Avogadro's number N, of atoms, and its total 9 ‘jr l ergy E at the temperature T accordingly H to be m E =3N, kT = RT * R = Ny k = 3.31% 10'J/mol K 71.99 Kean sample of n kilomoles, PV = nRT) “versal gas constant, (We know that in an ideal““ Modern Physi, 13.7, DULONG PETIT LAW s The specific heat at constant volume is given in terms of E by (3 ae ea (1) we ast and so here C, == 3R = 5.97 Keal/kmol K a eit ee ‘About 100 years back, Dulong and Petit found that, indeed C, = 32 for most solids at me (st inf temperature and above, and Equation (2) is known as the Dulong-Petit law in their honoue i, Ke ie mr 13.8. LIMITATIONS OF DULONG-PETIT LAW ‘at if However, the Dulong-Petit law fils for such ight elements as boron, beryllium, and cation, fyi! (as diamond), for which C, = 334, 3.85 and 1.46 Keal/kmol K respectively at 20°C. Even wore, (yy fF the specific heats of all solids drop sharply at low temperatures and approach 0 as 7 approaches fois G OK Figure 13.17 shows how C, varies with T for several elements. Clearly something is wrong. gst ™ st with the analysis leading up to Equation (2) and it must be something quite fundamental because jg it t yi the curves of Fig. 13.17 share the same general character. i ite « oillat© a point ¢ joe 6 ‘Aluminium go find Cy 7 Silicon : peBYE" : ‘Carbon (Diamond) aihough I iz sproach 3 sauues led §, ons a andere a 2 ste inten 1. PHONO Teelastic : ; ‘Voama °o 200 700 600 300 7,000 720° ahs an Absolute Temperature Sa star Figure 13.17 wile elec (tt soli 13.9. EINSTEIN'S SPECIFIC HEAT FORMULA ‘ay In 1907 Einstein announced that the basic flaw in the derivation of Equation (2) lies in 8 ig figure of KT for the average energy per oscillator in a solid. This flaw is the same as that responsi ve fi forthe incorrect Rayleigh-Jeans formula for blackbody radiation. According to Einstein, the probsb0)” yo Jv) that an oscillator has the frequency v is given by /(v) = 1 (é”*" ~ 1), Hence the average ee ty, for an oscillator whose frequency of vibration is v is Seg - hy OV b= AYO) = a L and not ¢ = kT. The total internal energy of a kilomole of a solid, therefore, becomes \ -_ 3Nyhv A) EI e= wy and its molar specific heat is 2 pat 3 \ ¥ sr(4¥) ad Soe a Wt) Py\ peony of SONGS 279 "is in the right track, At high temperatures, Av << AT, and an seat once that his approac | ons | erly tye, (6) : 2h y ace Fquation (3) becomes © = hv/(hWAT) = AT’ which leads to C, = 3R, the Dulong- - x a8 should. At high temperatures the spacing hv between possible energies is small a . > AF So € is effectively continuous and clasical physics hole . CASE OF FAILURE OF CLASSICAL THEORY ef Pc me temper the value of by Equation (5) decreases. The reason lassical behaviours that now the spacing between possible energies is becoming 0 AT. which inhibits the possesion of energies above the zero-point energy. The natural = coon) v fora particular solid can be determined by comparing Equation (5) with an empirical Sag) jae ofits C, versus 7. The result in the case of aluminium is v= 6.4 * 10” Hz, which agrees Ssamates made in other ways, for instance on the bass of elastic moduli. ‘iy i thatthe zero-point energy of a harmonic oscillator docs not enter this analysis? We de rmited energies ofa harmonic oscillator as (n + 12) hv. nO, 1,2. the ground state sillstor in solid is, therefre, ¢y = 1/2 hy, the zero point value, and not ¢, ~ 0. But int energy merely adds a constant, temperature-independent term of £, ~ (3N,) he molar energy of solid, and this term vanishes when the partial derivative (AE/OT), is DEBYE'S THEORY OF SPECIFIC HEAT igh Einstein's formula predicts that C, > 0 roach does not ag 1s T — 0, as observed, the precise manner ee foo well with the data, The inadequacy of Equation (5) at low led Peter Debye to look atthe problem in different way in 1912, In Einstein's model, “garded as vibrating independently of ts neighbours. Debye went to the opposite extreme red solid as a continuous elastic body. Instead of residing in the vi the intemal energy of a solid according to the new model resides in el PHONONS ARE QUANTA OF ACOUSTIC ENERGY clastic waves in a solid are of two kinds, longitudinal and transverse, stic standing waves, and range in frequency (The interatomic spacing in a solid sets a lower limit to the possible and hence an upper limit to the frequencies). Debye assumed that the total number x1.6x10ex1.0x10°m = 2.210 volt =22 pV. Example 28. 4 copper strip 4.0 cm wide and 0.55 mm. thick carries a current of 100 A. If {gidinamagnetic field of induction 2 weber m” acting at right angles to the strip, a Hall potential | rence 29.7 x 10 © V appears across its edge. Find (i) Hall electric field (it) the number of 7 carriers/m? in the strip. lution: (i) We have Vy _ 29.7 x 10% 5, == 5 ong 4x10" () Charge carriers/unit volume can be had from the relation B__1B e "=7E, AeEy "the current and A the area of cross-section of the conductor. 100 x2 =Su0? w16x 10 x 7425x107 = TH 107 x 1.6 x 10” x 7.425 x 10" 10” © 1.6% 7.425 5 = 8.410" chargecarriersm”. Me‘282 ; Modern Physics , Example 29. An electric field of 100 v/m is applied to a sample of n-type sem . whose Hall coeff. is 0.0125 m'/coulomb. Determine the current density in H, = 0.35 mo vig, Solution: Hall coeff. is given by conductor ‘he sample assuming In this case e eo 10? "=Texio™x00l5 ™ Again we have the relations nest, and oak E J=o-E=nep,E Putting the various values J = 5x10" x 1.6 x10" x 0.36 x 100 2880 A/m? QUESTIONS AND PROBLEMS 1. Describe the formation of Bonds in solids on the basis of electronic configuration. 2. Name the types of Bonds in solids, and explain the qualitative difference between them. 3. What do you mean by Ionic Bonds? What types of solids contain ionic bonds? Give examples in supports of your answer. 4. Explain the stability of ionic bonds in solids. What are their characteristics? 5. Explain in brief the Hydrogen Bond, lonic Bond and Metallic Bonds in solids. 6. What do you mean by Covalent bonds. What type of solids contain covalent bonds? Explain the ‘answer giving examples. 7. Explain the stability of Covalent bonds in solids. What are their characteristics? 8. Distinguish between Covalent and Ionic Bonds in solids. Iustrate with examples. 9. Explain the formation of Metallic bonds in Sodium metal. 10. What is Metallic bond in metals? Explain their stability and characteristics. Why the solids having molecular bonds are poor conductors of electricity? 11. Write brief essay on molecular bonds, their stability and characteristics. Why the solids having molecu bonds are poor conductors of electricity? 12. Explain the bond formation in diamond as a rigid crystalline solid while graphite is an amorphous non-crystalline solid. 13. Write notes on the following: (a) Hydrogen Bonding (b) van der Walls forces in solids (6) Sp. heat of solids (d) Concept of Phonons. 14, Give ideas about the free electron theory of solids. 15. What is fermi energy? Show how this energy depends on the density of electrons gas: 16. Give Kronig-Penney model of solids. 17, Explain the significance and importance of Hall effect. How Hall coefficient c 18. What do you understand by sp. heat of solids? How the concept of Phonons an be determined! bbe explained?v Sy pls vin and rroory of Sots 283: H gwiat is Hall effect? How the Hall vottge is related to Hall coefficient? tp mobilities of electrons and holes in a sample op intrinsic germanium at 300 K are 0.36 m’v 's | © and 0.1 mvs FesPectively. I the conductivity of spe men is 2.12 O'm ! corns be forbidden eneray B9P : : yy The following data are — for intrinsic Bermanium at 300 K. n= 2.4 « ane wanes vty {smn = 0.39 miv'' 5"! Calculate the conductivin ar as sample. [Ans. 232 O'm'] yy, Theband gap of an alloy semiconductor gallium arsenide phosphate is 1.98 eV. Calculate the wavelength © of radiation emitted when the electrons and holes in the material combine directly. Mention the colour of rad ation. : [Ans, 2 = 625 nm; Red colour] x3.Compare the densities of charge carries in a pure silicon erystalat the rwo temperatures 27°C and * s79¢. Eg for Si is 1.1 eV. [Ans. 0.12] u.Ina semiconductor the effective mass of an electron is 0,07 m and that of hole is 0.4 mg, where m, is free electron mass. Assume the average relaxation time of holes to be half that of electrons, Find the nobility of the holes when the mobility of electrons is 0.8 m?v"' sec, [Ans. Hy = 0.7 mvs!) 8.1 sample of silicon is doped with 3 x 10 Arsenic atoms and 5 x 102 Boron atoms. Find the clectron and hole concentration if the intrinsic charge carriers are 2 x 10°/m’. [Ans. 2 « 10%m?; 2 « 10/m?] ny,