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Band theory of the electronic properties of solids

W hat is the the ory of band? Solution to the Schrdinger equation for a periodic potential The W ave Prope rtie s of the ve ctor k The e ne rgy spe ctrum of e le ctrons Populating bands by e le ctrons. m e tals and non-m e tals C om pute r calculations ab initio band structure The e volution of the e le ctronic structure of the pe riodic table of e le m e nts in the crystalline state . Sum m ary: possibilitie s and lim its of band the ory

Second SOLUTION FOR POTENTIAL Schrdinger equation periodic

2.1. Wave function

a) Bloch theorem Determines the general form of the wave function as (2.1) which can be expressed in words, which are the wave functions solution of Schrdinger equation with periodic potential U ( r ) are the product of a complex plane wave exp (i k r ) and a periodic function u n k ( r ).

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De signe d by: R afa Kosture k

Figure 2.1. periodic potential U ( x ), Bloch function , and create a function that factors in n k ( r ) and exp (i k r ) . (For complex functions and exp (i k r ) shows the real part.)

Symbol u n k ( r ) can not be confused with the potential U ( r ) and is not a single function, but a set of different functions, changing with the change of quantum numbers wskanikujcych them n and k . Bloch theorem is presented on the basis of band theory analysis, so be sure to deepen his understanding of the trace evidence . He points out that the form of the wave function is a consequence of the discrete translational symmetry of the potential U ( r ).
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Band theory of the electronic properties of solids

consequence of the discrete translational symmetry of the potential U ( r ). analogy: the potential of wave functions kulistosymetrycznego

b) the nature of the wave function delocalized According to Born's interpretation of the wave function, the product of dV determines the probability of finding the electron in the volume element dV. Scakujmy the probability of the unit cell volume:

(2.2)

The product of u ( r ) u * ( r ) is a periodic function, so the probability of finding the electron in each unit cell is the same. The electron is therefore "present" in the whole volume of the crystal. We say that the Bloch wave functions are delocalized . c) The Bloch as the wave runs Delocalized electrons is not fixed. In analogy to the free electron wave function Ae and k r , Bloch function u ( r ) e and k r represents the electrons running through the crystal without scattering. Experimental consequence is that the resistance of the metal, the perfect crystal at absolute zero is zero. fact that the electron scatters on the potential of a single atom, and the periodic collection of these potentials is not scattered electron, is one of the paradoxes of quantum mechanics.

2.2. PROPERTIES OF VECTOR k

a) k as the number of quantum The real wave vector k and the integer n is an indicator function with and , therefore, act as quantum numbers. As we shall see, the energy eigenvalues are functions of k and n . b) The ambiguity vector k Brillouin zone. Bloch functions are surprising at first, property: as the same functions the corresponding energy eigenvalues calculated for k and k + E identical: and G are

(2.3) G is a reciprocal lattice vector, defined as G = h A + k B + l C, where A , B , C are the reciprocal lattice vectors of base and h, k, l integers indicators numerujcymi points of the network. Solution for k + G is a "duplicate "solutions for k . proof of formula (2.3) shows that it is a consequence of the discrete translational symmetry of the crystal. all significantly different Bloch functions correspond to the values restricted to a single cell primitive k reciprocal lattice. It was assumed that in one dimension will stretch from , and in three-dimensional space will reverse block with center k = 0 limited set routed walls at right angles by means of segments connecting the center of the cell with the closest reciprocal lattice points. As defined polyhedron, a volume equal to the volume of reciprocal lattice primitive cell is called the Brillouin zone .

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Figure 2.2a. Brillouin zone in the space of 1-dimensional

Figure 2.2b. Brillouin zone structure in the space of 2-dimensional oblique network.

Figure 2.2c. Brillouin zone for the network-centered cubic surface (fcc). Limiting wall zone square and hexagonal derived, respectively, from the reciprocal lattice points of the type (2,0,0) and (1,1,1).
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Band theory of the electronic properties of solids

c) The product of

the electron kwazipd.

To determine the relationship of the product of the electron momentum operator act on the function of Bloch momentum. For the case of 1-dimensional direct account

shows that the Bloch functions are not eigenfunctions of the momentum operator. Thus, it is not momentum. properties in analogy to phonons say that is a vector kwazipdu electron. This means that the interaction with other kwaziczstkami (electrons, phonons, magnony) trapped in the crystal and the "real" particles penetrating through the crystal (photons, neutrons) law of conservation of momentum to replace the offending conduct kwazipdu,

(2.4) proclaiming that the sum kwazipdw and shoot P before the collision is equal to the sum kwazipdw and shoots after a collision plus any reciprocal lattice vector. However, the law of conservation of energy, (2.5) in the crystal does not change. proof There is no simple equation (2.4). Heuristic justification is the claim (2.3) that the Bloch functions for k and k + G are identical. Hence the law of conservation of force can only kwazipdu accuracy of component G . rationale pseudopdu conservation laws is also connected with the symmetry conservation laws (Noether's theorem). Potential constant (empty space) is invariant relative to the continuous shifts as time and space. The consequence of this symmetry is the law of conservation of energy and momentum. Periodic potential (crystal) is invariant relative to any shift in time, so the law of conservation of energy remains unchanged. However, in the space can be offset only by a discrete set of network vectors { R }. Spatial symmetry is reduced to modify the law of conservation of momentum in the direction of his weakness. Kwazipdu conservation law allows, in particular, the occurrence of collisions "of metastasis", impossible in empty space.

Figure 2.3. collision kwaziczstek two: (a) normal and (b) of metastasis,

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d) Periodic boundary conditions. K & Kwazicigo variable number of states

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states Also, in full analogy with phonons apply the periodic boundary conditions to "cut out" of an infinite crystal safer parts of a finite volume, which allows the counting of the volume per state. The advantage of such a finite imaginary crystal is that it has no surface atoms. start with a one-dimensional "crystal" containing the N cells of the lattice constant a . Periodic boundary condition is equality of Bloch functions in end points x = 0 and x = In , u (0) exp (i k 0) = u ( N a ) exp (i k a N )

Figure 2.4. illustration of periodic boundary conditions and variable nature kwazicigego k in one dimension

The periodicity function of apparent u (0) = u ( N a ), further exp (i k 0) = 1 Thus, these factors can be simplified, is equal 1 = exp (i k N a ), which occurs when the product of N and k is an integer multiple the allowed values k of . Hence

(2.6) ( m - integer) are at equal distances Because the length of the

"crystal" on a macroscopic, the values k are so thick that the experimentally of that grain can not be seen. We say that the variable k is kwaziciga. calculate the number of allowed values k is in the Brillouin zone. If this is a oneof dimensional section of the Divide-dimensional "volume" of the scope of the Brillouin zone k attributable to one state receive

(2.7a)

The resulting model can be expressed in words: The number of allowable wave vectors in the Brillouin zone is equal to the number of primitive cells in the crystal volume (2.7b)

This claim is true also in three-dimensional space. It has a great importance in determining the full states of the electrons. e) An electron in a crystal as kwaziczastka Properties b) - d) vector k of the electron are exactly the same as the vector k phonon. The electron and phonon belong to the category that is quantized kwaziczstek "objects" whose growth is dependent on the existence of the crystal lattice. In particular, the law of conservation of momentum usually is replaced by the right kwaziczstek kwazipdu behavior. physics solid yet know the other kwaziczstki (Magnon, plazmon, Polaron, exciton). In analogy to kwaziczstki elementary particles can be:
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Band theory of the electronic properties of solids

- bosonami by a Bose-Einstein decomposition (such as phonon) - fermions, for which the Fermi-Dirac distribution (such as an electron) In analogy with the particle can have zero kwaziczstki (as phonon) or finite (electron) mass. We will see that the electron in the crystal behaves like to have an effective mass, which is different from the mass of the electron in vacuum.

2.3. ELECTRON ENERGY SPECTRUM.

a) Effective Schrdinger equation. Bloch us substitute the function ( 2.1 ) into the Schrdinger equation with periodic potential ( 1.2 ). Performing calculations we find that the factor exp (i k r ) is simplified, and the other components can be collected into a

(2.8)

It is effective Schrdinger equation . Analogy: effective Schrdinger equation for the potential kulistosymetrycznego b) The solution of the Schrdinger equation for the effective onedimensional crystal: the origin of band structure. The principal advantage of the introduction of the Schrdinger equation is effective in that the periodic function is unknown u n , k ( r ), and the eigenvalues n, k are the same as the output equation. This means that it is E sufficient to solve them - typically numerically - for a single cell. Output Schrdinger equation must be solved for the whole crystal. discuss properties of solutions of Schrdinger equation for the effective one-dimensional example. The solution u n , k ( x ) is a periodic function, so the boundary condition is valid: the value of the function u and the derivative u '= d u / d x are the same in the two points at the network period and , for example, u (0) = u ( a ), u '(0) = u '( a ) Figure 2.5 shows the imaginary numerical solution, taking off from the point at (0) . This curve for the selected at random energy values not meet the do boundary condition. Satisfy the boundary condition only certain energy values which form a sequence of discrete solutions, E 1 , E 2 ... which numbers the quantum number n .

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Figure 2.5. imaginary effective integration of the Schrdinger equation for the three sample values the energy E . E n is the energy of its own, for which the function of u ( x ) satisfies the boundary condition.

For k = 0, we obtained a sequence discrete energy levels, such as the potential of the particles in the cavity. But the wave number k is a parameter of effective Schrdinger equation. The change k eigenfunctions and energies are continuously changing (Figure 2.5). Dependence of E ( k ) is called, as the phonons, the dispersion relation. Outside the area function E ( k ) is repeated periodically, as a consequence of the ambiguity of the wave vector ( formula 2.3 ). significant changes in the parameter range of k is restricted to a finite area Brillouin zone, therefore, the corresponding values E form a band of of finite width. Hence the name "band theory".

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Figure 2.6. example of the dispersion relation E (k) in one dimension. The upper band is composed of two subbands n = 3 and n = 4

c) The terms of bandwidth, and sub-band energy gap Kwazicigy energy for a fixed set of n is called subbands , quantum number n is the number of subbands. further sub-band can overlap, creating a set of energy allowed kwazicigy called bandwidth . For example, for silicon (Fig. 2.7) the four lower sub-band combine to one band, called the valence band. Above we find the energy range for which the effective Schrdinger equation has no solutions for any k . This range of energy is the energy gap . subbands overlap each other can lead to their merger into one big band, for which there is only a lower bound. So for example for copper, see Figure 4.5 . Finally, note: where it does not lead to confusion subbands are also called strips.

d) Examples of the dispersion relation E (k) for the three-dimensional crystals. Relation dispersion E n ( k ), that is, the energy dependence of the quantum numbers n and k has full information on the energy spectrum. Draw a complete graph E n ( k ) requires a 4-dimensional space. Assumed energy dependence plot of the characteristic wave vector along the Brillouin zone sections. Shown in Figure 2.7 silicon band structure is the basis for understanding the most important information of material civilization.

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Figure 2.7. example of the real band structure: the curves E ( k ) for silicon plotted along sections of L , X, XK and K the reverse. The positions of points , K, L, X explains Figure 2.2c

e) energy bands Degeneration Word of degeneracy in quantum mechanics means that the different states correspond to the same energy value. As the degeneration of the whole quantum mechanics has to do with the symmetry of the system. An example illustrates the characteristic manifestations of Si in the band theory of degeneration. One of the symptoms of degeneration is to connect with each other subbands in the high-symmetry points . In Figure 2.7 there is for points , X. Second, degeneration can affect the entire line of high symmetry . For example, the individual subbands n = 3 and n = 4 in sections K and KX merge in sections X and L, one branch contains twice the number of states. It has to do with the fact that the lines X and L are high-symmetry axes (axis 3 and 4fold), while the line symmetry XK and K is lower (Check yourself on Figure 2.2c ) degeneration type band structure for a given crystal symmetry You can clearly predict - without solving the Schrdinger equation - using theoretical methods using group theory.

f) Effective mass Dispersion relations E ( k ) create analytical extreme bottom or top of the band. This means that the dependence of E ( k - k 0 ), where the vector k 0 determines the position of the extreme, can be developed in a power series of linear expression equal to zero. In one dimension (2.9)

Comparison of the development of such functional relationship similar to the free electrons, leading to the conclusion that local extremum function E ( k ) is mathematically the same as the electron effective mass equal

(2.10)

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Introduced the effective mass as a formal parameter describing the curvature of the band. This concept, however, has physical meaning because it expresses the periodic potential of the network effect on the dynamics of the electron. The value of m * can be just greater than and less than the mass of the electron in a vacuum. the multidimensional space may appear effective mass dependence of the direction - it becomes effective mass in general tensor of order 2. The high-symmetry points, such as Brillouin zone center (point )

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order 2. The high-symmetry points, such as Brillouin zone center (point ) networks cubic tensor reduces to a scalar because it forces the symmetry of d 2 E / d k x 2 = d 2 E / d k y 2 = d 2 E / d k of 2 . it takes for the Si valence band to the top. However, a minimum of E (k) of the conduction band of silicon is at a point of the section X ( Figure 2.7 ). The derivative d 2 E / d k 2 is different along and perpendicular to the X, the corresponding values equal are to the effective mass of 0.98 and 0.19 on the free electron mass.

g) The density of states. As in the case of free electrons and phonons can define the function of density of states as the limit ratio of electron states in the range E , E + E to the width of the range E. (2.11) Thus defined, D (E) is an extensive quantity proportional to the volume of the crystal, so it was assumed normalized by dividing by the number of primitive cells or the number of atoms. band structure for the E n ( k ) function of the density of states is calculated numerically. Electron density of states curve has, however, some general characteristics (Figure 2.8):

Figure 2.8. characteristic features of the density of states for d = 3

(I) energy in the interval D ( E ) = 0 (Ii) the fact that the bottom and top of the band relationship E n ( k ) is a parabolic that the functional form of D ( E ) is the same as that of free electrons. For d = 3, (2.12)

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Band theory of the electronic properties of solids

(2.12)

proportionality factor const depends on the effective mass. (Iii) in-band curve D ( E ) is nieanalityczna - there may be sharp van Hove singularities .

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