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Fermi-Dirac Distribution Lecture 11 Band structure: A quantum theory of metals and semiconductors Reminder: Homework 4 ppy,osted today, due next Thursday Recall from last class: Band theory of solids As atoms are brought together from infinity, the atomic orbitals overlap and give rise to bands. Outer orbitals overlap first. The 3s orbitals give rise to the 3s band, 2p orbitals to the 2p band, etc. The various bands overlappp to produce a sing le band in which the ener gy is nearly continuous. Note: We can no longer consider the electrons as belonging to specific atoms – they are shared among the entire solid. Band theory of solids In a metal, the various energy bands overlap to give a single energy band that is only partially full of electrons. There are states with energies up to the vacuum level, where the electron is free. Band theory of solids: The Fermi Level TilTypical elltectron energy bbdand diagram for a mettlal. All the valence elect rons are in an energy band, which they only partially fill. The top of the band is the vacuum level, where the electron is free from the solid (PE = 0). Band diagram of a metal: ‘free’ electrons Electron Energy E= KE=p2/2m Energy band diagram of a metal. In the absence of a field, there are as many electrons moving right as there are moving left. The motions of two electrons at each energy cancel each other (as for a and b). Band diagram of a metal: applying an E-field Elec tr ic Field , E-x EFo In the presence of an electric field in the −x direction, the electron accelerates and gains energy to a’. The average of all momenta values is along the +x direction and results in a net electrical current. Band diagram of a metal: only electrons near EF contribute to conduction!! Electric Field, E-x EFo Lattice scattering abruptly changes the momentum of an electron, but conserves energy. Therefore, an electron is scattered to an empty state near EFO but moving in the -x direction. In vacuum, the electron has mass, m (a) An external force Fext applied to an electron in a vacuum results in an accelileration avac = Fext / me. In a band, the electron has an effective mass, m* (a) An external force Fext applied to an electron in a vacuum results in an accelileration avac = Fext / me. (b) An external force Fext applied to an electron in a crystal results in an acceleration acryst = Fcryst / me* In a band, the electron has an effective mass, m* Semiconductors: Silicon The electronic structure of Si: 1s2 2s2 2p6 3s2 3p2 The crystal structure of Si: diamond cubic Why does Si bond with 4 neighbors, since there are only 2 unpaired electrons? Hybridization of Si orbitals When Si is about to bond, the one 3s orbital and the three 3p orbitals become perturbed and 3 mixed to form four hybridized orbitals, hyb, called sp orbitals, which are directed toward the corners of a tetrahedron. The hyb orbital has a large major lobe and a small back lobe. Each hyb orbital takes one of the four valence electrons. Hybridization of Si orbitals Formation ofbdhlflf energy bands in the Si crystal first involves hybridization of 3s and 3p orbitals to four identical hyb orbitals which make 109.5o with each other. hyb orbitals on two neighboring Si atoms can overlap to form B or A. The first is a bonding orbital (full) and the second is an antibonding orbital (empty). In the crystal B overlap to give the valence band (full) and A overlap to give the conduction band (empty). Energy bands arise from bonding & antibonding wavefunctions Left: potential energy versus atomic separation. At the equilibrium distance for Si, a bandgap is formed. Right: Simple energy band diagram of a semiconductor. CB is the conduction band and VB is the valence band. AT 0 K, the VB is full with all the valence electrons. Determining the number of electrons in a band, n Why? n conductivity Analogy: Calculate the population of San Francisco 1.Find the density of houses in the city (# houses/area): g(A) 2.Multiply g(A) by the probability of finding a person in the house: f(A) 3.Integrate over thfhhe area of the city Distribution function n f (E )g (E )dE Density of states band Density of States, g(E) How are the energies of the electrons distributed in a band? 1 state with the highest energy Many states with comparable intermediate energies (given by the # of nodes) 1 state withhh the lowest energy Density of States, g(E) g(E) is the number of states (wavefunctions) in the energy interval E to (E+dE) per unit volume of the samppgple. It is crucial for determining the electron concentration per unit energy in a sample. The total number of states per unit volume up to some energy E’ is: S E ' (E ) g (E )dE V 0 Deriving the density of states in 2D -- metal Let’ s consider the electrons in the sosolilidd to be in a 3D potential well of volume V, with sides L. The energy of the electrons is: h2 E n2 n2 n2 n1n2n3 8mL2 1 2 3 In 2D, we only have n1 and n2. Each state, or electron wavefunctions in the crystal, can be represented by a box at n1, n2. How many combinations of n1 and n2 hav e an energy less than E’? Deriving the density of states in 2D -- metal Let’ s consider the electrons in the solid to be in a 3D potential well of volume V, with sides L. The energy of the electrons is: h2 E n2 n2 n2 n1n2n3 8mL2 1 2 3 In 2D, we only have n1 and n2. Each state, or electron wavefunctions in the crystal, can be represented by a box at n1, n2. The area contained by n1 and n2 approximates a circle with area ¼(πn’2) Deriving the density of states in 3D -- metal In three dimensions, the volume defined by a sphere of radius n' and the positive axes n1, n2, and n3, contains all the possible combinations of positive n1, 2 2 2 2 n2, and n3 values that satisfy n1 n2 n3 n 1 V n'3 sphere 6 Each orbital can hold two electrons, so the total number of states up to some quantum number n’ is: 1 S (n) 2V n'3 sphere 3 Deriving the density of states in 3D -- metal 1 S (n) 2V n'3 sphere 3 h2 h2n2 8mL2E' E n2 n2 n2 n'2 n1n2n3 8mL2 1 2 3 8mL2 h2 L3 (8mE ')3 / 2 S (E ') 3h 3 Since L3 is the volume of the solid, the total number of states per unit volume is: (8mE ')3 / 2 S (E ') V 3h 3 3 / 2 g dS m (E ) V 8 21/ 2 e E 1/ 2 dE h 2 Determining the number of electrons in a band, n Distribution function n f (E )g (E )dE Density of states band Knowing how the energies of the electrons are distributed in a band (g(E)), we seek thffdhhe probability of finding a particle with an energy E (i.e., the “distribution function,” f(E)). The Distribution Function f(E) & Particle Statistics The probability of finding a particle with a given energy will depend on whether or not multippple particles can occupy the same energy state. Formally, particles are called “bosons” if they can occupy the same energy state or “fermions” if they cannot. Ex: Bose-Einstein Condensation (Nobel Prize, 2001) Rubidium gas Boltzmann Statistics Two particles with initial wavefunctions 1 and 2 at E1 and E2 in terac t and end up at different energies E3 and E4. The ir corresponding wavefunctions are 3 and 4. Here, let’s assume it doesn’t matter if E3 and E4 are already occupied by other particles. Boltzmann Statistics P(E)=probability of an particle having energy E The probability of an particle with energy E1 interacting with an ppgyarticle of energy E2 is: P(E1))(P(E2) The probability of the reverse process is P(E3)P(E4) In thermal equilibrium, the forward process will be just as likely as the reverse process: P(E1)P(E2)P(E)=P(E3)P(E4) Also: E1+E2=E3+E4 (conservation of energy) Boltzmann Statistics The only function that satisfies: P(E1)P(E2)=P(E3)P(E4) E1+E2=E3+E4 Is the Boltzmann function: E P ( E ) A exp kT Boltzmann Distribution Boltzmann Statistics for two energy levels N E E 2 exp 2 1 N1 kT *as T increases, N2/N1 increases* The Boltzmann energy distribution describes the statistics of boson particles, which are not restricted byyyppygy how many particles can occupy an energy level. The distribution also holds for electrons (fermions) when there are many more available states than the number of particles. Fermi-Dirac Statistics Now, consider particles that cannot occupy identical energy levels ((,i.e., electrons obey yging the Pauli exclusion p rincip p)le) When particles 1 and 2 interact, they can only enter new energy levels that are not already occupied The probability of interaction between particles 1 and 2 to yield energies 3 and4d 4 is: P (E1)()P(E2)[1-P(E3)][1-P(E4)] In thermal eqq,uilibrium, the forward p rocess will be just as likel y as the reverse process: Also: E1+E2=E3+E4 (conservation of energy) Fermi-Dirac Statistics The only function that satisfies: P(E1)P(E2)[1-P(E3)][1-P(E4)] = P(E3)P(E4)[1-P(E1)][1-P(E2)] E1+E2=E3+E4 Is the Fermi-Dirac function: 1 P(E) E E 1 exp F kT where EF is the Fermi energy.
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