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U =

n= 3 n= 2

n= 1 x U=0 For electrons in a quantum well, the energy has discrete levels as h2 n2 E= (n=1,2,) 8m D 2 For wavefunction n ,s , we have degeneracy g(n)=2 due to the spin. (2) Harmonic oscillator The energy is 1 K (n=0,1,2) En = h (n +1/ 2); = 2 m The wavefunction is n , and the degeneracy is g(n)=1. (3) Rigid rotation The energy eigenvalues are

=2 A(A + 1) = hBA(A + 1) (for |m| A , A =0,1,2, ). 2I For wavefunction nlm , the degeneracy is g(l)=2l+1. (4) Hydrogen atom Mc 2 13.6 eV En el = 2 1 2 = ( n 1, n A + 1 and m A , A =0, 1, 2, ) 2= n n2 The wavefunction nlms corresponds to degeneracy g(n)=2n2. El =

Now let us consider electrons in a solid. The parabolic approximation at the band edge gives 2 2 2 2 = 2 k 2 = (k x + k y + k z ) E Ec = = , 2m* 2m*

where k x , k y , k z =

2 na . In different directions, n values can be different. For L wavefunction (k x , k y , k z ) , we have three quantum numbers.

15

10

Debye

5

k /a

0 -1

0 k / (/a)

= vk = v k x 2 + k y 2 + k z 2 ; E

= h (n +

)

,

n 2

where v is sound velocity.

(a) Electron ky Volume of One Unit Cell

kz

4 L 2 L 0

k+dk dk 2 L 4 L

6 L

k kx ky

kx

In above figure, we can find the volume of one state is V1 = (2 / L)3 . In the above sphere, the number of states within k and k+dk is 4 k 2 k Vk 2 k , N = = 2 2 V1 in which V=L3 is the crystal volume.

The density of states is defined as the number of quantum states per unit interval of energy and per unit volume 1 N k 2 k k 2 dk D( E ) = . = 2 = 2 V E 2 E 2 dE At the band edges, the electrons have energy = 2 (k x 2 + k y 2 + k z 2 ) =2k 2 , E = Ec + = Ec + 2m* 2m* thus 2m* ( E Ec ) . =2 Considering spin, the density of states is k 2 dk 1 2m* D( E ) = 2 2 = 2 ( 2 )3/ 2 (E Ec )1/ 2 . 2 dE 2 = k=

Electron Density of States

Ec EF E

(b) Phonon According to the Debye model that assumes three modes (two transverse, one longitudinal) are identical, we have

3 3 2 N dk = 2 k2 = 2 3 ; = vk . V 2 d 2 v (c) Photon For electromagnetic waves, we only have two transverse modes. The density of states is D( ) = 3 D( ) =

2 .

3 2 c

The density of states is a purely mathematical convenience but is central to correct counting of the number of electrons and the energy (or charge and momentum) that they carry. As a simple example of how the density of states is needed, lets evaluate the energy of the topmost level at T=0, i.e., the Fermi level, Ef. At zero Kelvin, the filling of the electron quantum states starts from the lowest energy level and moves up from one energy level to the next until all electrons are placed into distinct quantum states. The number of electrons per unit volume at T=0 is

1 2m * (E f E c )3 / 2 , n = D(E )dE = 2 2 3 = Ec in which the electron density n=N/V.

Ef 3/ 2

= 2 k xy 2 2m *

+ n2

= 22 2m *d 2

(n=1,2,)

2 ja , L while the z direction is quantized by number n. For a given energy E, we have solutions for kx, ky when En<E. A constant energy surface is drawn in the following figure. Here we can nondimensionalize the coordinates to maintain the surface as a sphere. The solutions lie on the sketched circle determined by E-En, i.e.

| k xy |= E ( k x , k y , n ) En 2m* . =

higher E is required to find solutions for kx, ky.

The calculated density of states is presented in the following figure, which is staircase for

one-dimensional constraint. For two-dimensional constraint (quantum wire in HW, n, l as

the quantum numbers), we have D( E ) (E Enl

) 1/ 2 . If all three dimensions are under

constraint (quantum dot, n, l, k as the quantum numbers), the density of states is just like

jumps at different Enl k .

kz (n)

bulk (3D) D(E ) n=3

kx

quantum well (2D)

n=2 n=1

ky

Chapter 4 Statistical thermal & energy storage In Lecture 2, we have mentioned that matter tends to occupy the lowest energy levels. For an energy level Ei, we have given the Boltzmann factor for its occupying probability as P ( Ei ) = Aexp(Ei / k BT ) , in which the constant A can be determined by normalization over all quantum states P( Ei ) = 1.

All QS

For monatomic atom, we have m E = (vx 2 + v y 2 + vz 2 ) . 2 Normalization gives 2 2 m ( vx + v y + vz2 ) dvx dv y dvz = 1 A exp 2 BT m 3/ 2 A=( ) . 2 k BT The average number of particles is

2 2 m vx + v y + vz2 m 3/ 2 . f =< n >= n( ) exp 2 BT 2 k BT where n is the particle number density. The Boltzmann factor can only be applied to closed systems, while for an open system exchanging energy with the outside, the probability becomes P ( Ei , N i ) = A exp[( Ei N i ) / k BT ] , where Ni is the particle number, chemical potential is the criteria for the equilibrium state of mass exchanging process with the outside, just as pressure for mechanical equilibrium and temperature for thermal equilibrium.

Now consider electrons at energy Ei. Ignoring the spin, we have two possibilities: Electron number 0 1 Ni 0 1 Energy Ei 0 Ei

Normalization gives P (0, 0) + P( Ei ,1) = 1 or A + A exp[( Ei ) / k BT ] = 1. Therefore 1 A= . ( Ei ) / k BT 1+ e The average number of occupancy of this quantum state is thus f =< n >= 0 P(0, 0) + 1 P( Ei ,1) 1 = e ( Ei ) / kBT ( Ei ) / k BT 1+ e

1

. = ( Ei ) / k BT 1+ e This is called the Fermi-Dirac distribution. f 1

1/2

exp( h h n ) Aexp( ) =1 2k BT n =0 k BT

h 1 = 1. )A 2k BT 1 exp( h ) k BT h h A = exp( )(1 exp( )) . k BT 2k BT And nh h P ( E) = exp( )[1 exp( )] . k BT k BT Then the average number of the phonons, or the occupancy of the quantum state is exp(

) ,

n=0

= [1 exp(

h

)] n exp(nh / k BT ) k BT n=0

= [1 exp( = 1

h / k BT

h d )] exp(nx) k BT dx n =0

(x=h/kBT)

1 e which is the Bose-Einstein distribution. Note: The differentiation is a mathematical trick that leads to the same results as the original summation.

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