Lecture notes CVR College of Engineering Dr VSeetha Rama Raju mo Band theory of solids Electrons in a periodic potential: Bloch theorem: The free electron theory of metals assumes that a conduction electron in a metal experiences a constant (or zero) potential and so is completely free to move about in the crystal. This theory explains successfully the phenomenon of specific heat, electrical conductivity, thermal conductivity and paramagnetism, but fails to explain why some solids are good conductors of electricity, some are semiconductors and others are insulators. According to band theory, metals and alloys are crystalline in nature. A crystal is considered as an infinite array of | [>> lattice points. Inside a real |, © ©°O © crystal, there is . arrangement of charged ions through which the electrons move. The motion of |: * + -, electron in a metallic crystal is shown in figure. The potential of the electron at the positive ion site is zero and is maximum centre between two ions. The motion of electron in periodic potential can be explained by using Bloch theorem. The Schridinger wave equation for the motion of electron in one-dimensional potential is given by 2 | am ait wE-V) 0 a According to Bloch theorem, the solution for the above equation would be of the form ix) = U(x) . et where Ux(x) has the periodicity of the lattice and is given by Ux(x) = Ux (x+a) GB) where ‘a’ is crystal translational vector, ‘k’ is wave vector. Equations (2) and (3) are called Bloch functions. Band theory of solidsLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo ‘The Bloch function of type (2) has a property vy (x+a) = U(xta) . eke) = Uns). e#!, etka y (xta) = y 0). eR 4) Equation (4) referred to as Bloch condition. Kronig — Penny model of periodic potenti According to Kronig-Penny model, the electrons move in periodic potential field provided by the lattice. The potential of the electron varies periodically with the periodicity of lattice. The potential energy of electron is zero near the nucleus of the positive ion in the lattice and ‘maximum when it is half way between the adjacent nuclei which are separated by interatomic spacing ‘a’ 7) " 1 a Oo sa The regions denoted II correspond to the positively charged ions of the crystal lattice. The regions denoted I represent the empty spaces between the ions. The lattice parameter is a=b +s. The periodic motion can be described using Schridinger time-independent wave equation for the two types of regions and are given as ot, BEy=o forV=0 a oY, Evy y=0 for V = Vo @) Let 2 i) f? == (Vo-B) @ + Equations (1) and (2) become Band theory of solidsLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo ey ote atws0 6) ah pe a B’yw=0 (6) According to Bloch theorem, the solution for the Schridinger wave equations of the form (5) and (is w(x) = Unix). ef a ‘Where Ux(x) is periodic function and *k’ is wave vector Differentiating equation (7) twice w. r. to *x’ and substituting in equations (5) and (6) and solving then we get ace] Se + cos ua = cos ka (8) pSESt + cos aa =cos ka 0) Where P= 2"? called strength of the barrier Equation (9) can be understood by plotting a graph between aa along x-axis and P=2"" + cos oa along y-axi + cosa, From the graph the following conclusions can be drawn 1. During the periodic motion of electron, it is moving interms of few allowed bands and forbidden bands of energy. The allowed energy bands are represented by shaded parts which are separated by forbidden regions. 3. As energy of electron (aa) increases, the width of allowed energy band also increases. This is because of first term in equation (9) n Band theory of solidsLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo 4. If 'P* is large ice. large potential barrier, the wi and width of forbidden band increases. th of an allowed energy band decreases As Pa, the allowed energy region becomes infinitely narrow i.e. as Pr then equation (9) has only solution - joe sin aa =0 | a= tne ° . “nce @? = 2 [since a? = 7B _ Energy levels are discrete i.e. energy levels are quantized. - Pad” 5. As P40 equation (9) becomes cos aa = coska and ke = dime? Em am = am = mY ‘This means that as binding energy tends to zero, the electron behaves as free electron. Brilliouin — Zones (or) E ~ K diagram: Brilliouin — zones are the boundaries that are marked by the values of propagation wave vector “‘k’ in which the electron can have allowed values without diffraction. Since ‘k’ is a vector, it has different values in different directions. The relation between the wave vector and the energy of the electron in a potential field can be obtained as follows. = - (1) where ‘a’ is length of potential box and = aint Kary Qo wae 8) Band theory of solids 10Lecture notes CVR College of Engineering Dr VSeetha Rama Raju mo substituting equation (3) in equation (1) we get Boy Ee (4) ame br A plot is made between the total energy “E’ and the wave vector *k’ for various values of k with n=+4l, 42,43 ieforn=41, k =4" for (Fae trend] second towed bond For the above values of the curve obtained as shown in the figure, which is in the form of a parabola with discontinuities. a ¥ ° y F ¥ It is clear from the figure that the energy of electron is continuously increases from k =0 to +5, Then the electron meets the wall and is reflected. This range of allowed energy values in the region between — to is called first Brillouin zone. Afier a discontinuity in ermagy cae farbidden region, aoter allowed region tended from =25t0 2 and Zoo 2 This is known as second Brillouin zone. In the same way further Brillouin zones will be continued. ‘The free electrons moving in periodic potential of lattice can have energy values only in the allowed regions or zones, Therefore, we can conclude that the electron can go from one Brillouin zone to the other only if it is supplied with energy equal to forbidden gap energy. Thus the forbidden gap is the one which decides whether the solid is a conductor or insulator or semiconductor. Effective mass of electron (m’): When an electron of mass ‘m’ is placed in a periodic potential and if it is accelerated with the help of an electric (or) magnetic field, then the mass of the electron will not be a constant, rather it varies with respect to the field applied. That varying mass is called effective mass (m’). ul Band theory of solidsLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo Let us consider an electron of charge ‘e” and mass ‘m’ moving in a erystal la electric field “E’. eof The force exerted on the electron is F = -eE Wehave = F=ma on) ‘The acceleration ‘a’ is not a constant in the periodic lattice of the crystal. Its variation can be considered to be caused by the variation of the electrons ma ss when it moves in the crystal lattice. So the mass of the electron is replace by its effective mass m’, @) and Fema - @) Consider the free electron as a wave packet where the group velocity ‘v," corresponds to the particle velocity, “4 =2a%t t = 2m] =n since @ = 6) Where theenergyE=hv and ha Accelerat y= Se 6 ceeleration ‘a’ = ) Lae _1ate ae “hdkde ~ har ae Since bk =P and a Then i= 7) (8) 2 Band theory of solidsLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo Comparing equati ms (3) and (8) we get -_w m= aE ae 0) :- mass is not constant for an electron moving in a periodic lattice but it is a function of “’ as it @E depends on —S Variation of E with K: The variation of E with k is shown in figure. Since E ak, ask’ increases “E’ also increases. “From this graph velocity of electron (v) can be calculated. Variation of ‘v’ with *k’: ‘The variation of velocity ‘v’ with K is shown in figure. (At k=0 0. (ii) As the value of “k’ increases, ‘v" also increases and reaches its maximum value at k= kp. where —_ko= point of inflection (iii) At k > ko : As the k value increases beyond ko, the velocity begins to decrease and finally reaches to zero at k = w/a. The —ve values of k also exhibit similar behavior. Variation of m* with k: of m* with 4 is shown in figure. = (i) Atk=0, —m* =m, electron acts as a free electron. (ii) As the value of *k’ increases m" increases, reaches its maximum value at k = ko on the E-K curve. Therefore, m* is +ve in upper region (at the bottom of energy band). Atk > ko: As: value increases beyond ko, m* starts decreases and reaches to a small negative value at k= ra. Therefore, _m* is ve in lower region (at the top of energy band). It means, in lower region electron behaves as a +ve charged particle called as a hole. i.e, electron with -ve effective mass is called as Hole. Band theory of solids BLecture notes CVR College of Engineering Dr VSeetha Rama Raju mo Concept of Hok led into two bands In the E ~k curve, the band (first Brillouin zone) can be di 2, upper band and lower band with respect to a point (ko) called as point of inflection. From E — k curve we can say that i) Inthe lower band the value of $= is a decreasing function from the point of inflection ‘Therefore “is +ve and hence m’ should T be +ve in the lower band. | | tower band £2 24 ye ii) Inthe upper band of Bk curvethe value |.) SY kg axe of Sis found to be an increasing function T from the point of inflection. | i Upper band Therefore £4 is ve and hence m” should 5” pep pn be -ve in the upper band. ? m’-k iii) At the point of inflection <= plot effective mass goes to co as shown in figure ‘The electron with the negative effective mas is called Hole, in other words the electron in the upper band which behaves as a positively charged particle is called Hole. It has the same mass as that of an electron but with positive charge. Formation of energy bands in soli EE cor tction ane The atoms in solids are held together by interatomic £ (am eocetans forces or bonds. The attractive forces between e+ : i——; atoms bring them closer until the individual 3 au leeecanayieaas electron clouds begin to overlap. A strong repulsive = mi force arises to comply with Pauli’s exclusion lerengy ives) energy tands principle. When the attractive force and repulsive ina ve son inasoie force between any two atoms are equal, the two atoms occupy a stable position with a minimum. potential energy. The spacing between the atoms is called equilibrium spacing. ‘The electrons of a single atom occupy atomic orbitals, which form a discrete set of energy levels. If several atoms are brought together to form a molecule, their atomic orbitals split due to the Pauli’s exclusion principle. This produces a number of molecular orbitals proportional to the number of atoms. When a large number of atoms are brought together to form i : ion (ar. uni) Band theory of solids 4Lecture notes CVR College of Engineering Dr VSeetha Rama Raju mo a solid, the number of orbitals becomes exceet them is shown in the figure for sodium metal. ily large with forbidden energy gap between The Na atom contains 11 electrons having the electronic configuration 1s? 2s? 2p® 3s! 3p". AL Ok, the lower band is partially filled with one electron known as valence band. The upper band is empty and is known as conduction band. The gap between the two is called forbidden energy gap, which distinguish the metals, semiconductors and insulators. Classification of materials into metals, semiconductors and insulators on the basis of Band theory: Insulators: In case of insulators, the | £ne"y of electrons forbidden energy band is very wide. Due to | this fact electrons cannot jump from valence band to conduction band. For | neue aa example, in case of materials like glass, the | °"S=="™"* pe A) ae valence band is completely full at ok and [seme] [aml [ome the eneray gap between valence band and | a comune conduction band is of the order of 10eV. Even in the presence of high electric field, the electrons do not move from valence band to conduction band, The resistivity of insulators at room temperature is of the order of 10” Q-m. Semiconductors: In semiconductors, the forbidden band is very small. Ge and Si are examples of semiconductors. In Ge the forbidden band is of the order of 0.7eV while, in case of Si the forbidden band is 1.leV. When a small amount of energy is supplied, the electrons can easily jump from valence band to conduction band. In semiconductors, the conductivities are of the order of 10° U-m. Conductors: In case of conductors, there is no forbidden band and the valence band and conduction band overlap each other. Hence plenty of free electrons are available for electric conduction. The electrons from valence band freely enter in to the conduction band. Due to the overlapping of valence band and conduction band, a slight potential difference across the conductor cause the free electrons to constitute electric current, In metals the conductivities are of the order of 10” U-m. Band theory of solids