Lecture notes in Solid State 3 Eytan Grosfeld Physics Department, Ben-Gurion University of the Negev Classical free electron model for metals: The Drude model Recommended reading: • Chapter 1, Ashcroft & Mermin. The conductivity of metals is described very well by the classical Drude formula, ne2τ σ = (1.1) D m where m is the electronic mass (as decided by the band-structure) and e is the electronic charge. The conductivity is directly proportional to the electronic density n; and, to τ, the mean free time between collisions of the conducting electrons with defects that are generically present in the system: • Static defects that scatter the electron elastically, including: static impu- rities and structural defects. One can dene the elastic mean free time τe. • Dynamical defects which scatter the electron inelastically (as they can carry o energy) including: photons, other electrons, other excitations (such as plasmons). One can accordingly dene the inelastic mean free time τ'. The eciency of the latter processes depends on the temperature T : we expect it to increase as T is increased. At very low temperatures the dominant scattering is elastic, and then τ does not depend strongly on temperature but instead it depends on the amount of disorder (realized as random static impurities). We expect τ to decrease as the temperature or the amount of disorder in the system are increased. The Drude model 1897 - discovery of the electron (J. J. Thomson). 1900 - only three years later, Drude applied the kinetic theory of gases to a metal - considering it to be a gas of electrons. Assumptions: 1. Electrons are classical objects: solid spheres of identical shape. 2. There is a compensating positive charge attached to immobile particles, to ensure overall charge neutrality: 1 2 (a) Each isolated atom of the metallic element has a nucleus of charge −19 eZa (0 < e = 1:60 × 10 C, Za is the atomic number). (b) Surrounding the nucleus are Za electrons of total charge −eZa, com- posed of Z weakly bound valence electrons, and Za −Z tightly bound electrons, the core electrons. In a metal, the core electrons remain bound to the nucleus and form the (immobile, positively charged) metallic ion, while the (mobile, negatively charged) valence electrons are allowed to wander far away from the parent atom. In this context they are called the conduction electrons. 3. Electrons are almost free (no forces act between electrons), except elec- trons can collide with ions (more generally, and more correctly, we need only assume that there is some scattering mechanism, as modern theories show that static ions on a perfectly ordered lattice do not lead to scatter- ing. We will see that later when we discuss Bloch theorem). Between colli- sions they move as dictated by Newton's laws of motion. Electron-electron interactions are neglected between collisions (independent electron approximation). Electron-ion interactions are neglected as well (free electron approximation). Many of the properties of metals can be described using the classical Drude theory, including • Conductivity, • Conductivity at nite magnetic eld and Hall conductivity, • Thermal conductivity (and the historic explanation of the Wiedemann- Franz law which agrees with experimental results: only about a factor of 2 too small compared to them), • Thermoelectric eects (Seebeck eect), • AC conductivity, • Interaction with the electromagnetic eld (reection below the plasma frequency, transmission above the plasma frequency, plasma oscillations at the plasma frequency). While many of the results turn out to be inaccurate and the mechanism for scattering remains unexplained, the basic assumption of a free electrons gas that undergoes scattering remains essentially the same in modern theories. The modied Newton-like equation describing the average momentum for an electron can be derived in the following way. An electron experiences a collision with a probability per unit time of 1/τ, where τ is known as the relaxation time or the mean free time. So the probability for a collision in a time interval dt is dt/τ, and this is also the fraction of electrons that collided during that time. For a macroscopic number of electrons that have collided, the average momentum immediately following the collision is zero. The average momentum for the electrons at time t + dt is therefore dt dt p(t + dt) = [0 + F(t)dt] + 1 − [p(t) + F(t)dt] ;(1.2) τ τ | {z } | {z } electrons that collided electrons that did not collide 3 where p(t) is the momentum per electron, F(t) is the external force per electron. Therefore, p(t) p(t + dt) − p(t) = F(t)dt − dt + O(dt)2; (1.3) τ and we get the central equation of motion for the Drude model dp p(t) = − + F(t): (1.4) dt τ Hence the eect of individual electron collisions is to introduce a frictional damp- ing term to the equation of motion. In more technical terms, following a collision, we will use the Boltzmann distribution to generate a velocity for the electrons m 3=2 mv2 f(v) = exp − (1.5) 2πkBT 2kBT so the electrons have an averge speed which is controlled by the (local) temper- ature, but the average velocity is zero due to the angular averaging. Conductivity Ohm's law: the current I owing in a wire is proportional to the potential drop V along the wire V = IR; (1.6) where R is the resistance (measured in Ohms) which depends on the shape of the wire. One can dene the resistivity ρ according to E = ρj; (1.7) where E is the electric eld and j is the current density. The quantities are related in the following way. For a current owing in a wire of length L and cross-sectional area A the current density along the wire is j = I=A. Since V = EL, we get V = (ρI=A) L hence R = ρL/A: (1.8) All the dependence of R on the dimensions of the wire is now explicit, hence ρ is a material property. The inverse resistivity is the conductivity σ = ρ−1. The inverse resistance is the conductance G (measured in 1/Ohms). In the framework of the Drude model, we can solve explicitly the dierential equation with F = −eE, to get −t/τ p(t) = −eτE + (p0 + eτE)e (1.9) when t ! 1 we reach steady state, for which we get a drift velocity eEτ v = − ; (1.10) m and a corresponding current density is ne2τ ne2τ j = −nev = E; σ = ; (1.11) m D m justifying Eq. (1.1). 4 Thermal conductivity The Drude model was able to give an explanation to the empirical law of Wiede- mann and Franz (1853), that the ratio of the thermal to electrical conductivity is directly proportional to the temperature, with a proportionality constant which is more or less the same for all metals. Hence, one denes the ratio κ/σT , known as the Lorenz number. To estimate the thermal conducitivity of electrons one considers a metal bar along which the temperature varies slowly. Fourier's law states that jq = −κrT (1.12) where jq is the thermal current density (its magnitude is the thermal energy per unit time crossing a unit area perpendicular to the ow). Electrons arriving at point r with velocity v have on average underwent a collision at r − vτ and will carry thermal energy E[T (r − vτ)], hence 1 j = − nv fE[T (x − vτ)] − E[T (x + vτ)]g (1.13) q 2 @E ' −τvn v · (rT ) (1.14) @T Averaging, we get 1 hvvi = hv2iI (1.15) 3 and dening dE 3 c = n = nk (1.16) V dT 2 B we arrive at the result 1 κ = c τhv2i (1.17) 3 V The Lorenz number is κ 1 c hmv2i L = = V (1.18) σT 3 ne2T 2 with hmv i = 3kBT one gets 3 k 2 L = B = 1:11 × 10−8 (J/CK)2 (1.19) 2 e Quantum free electron model for metals: The Sommerfeld model Recommended reading: • Chapter 2, Aschroft & Mermin. A quantum model: a free electron gas. At thermal equilibrium, the number of electrons having energy E is given by the Fermi distribution 1 f(E) = ; (1.20) eβ(E−µ) + 1 in which β = 1=(kBT ) is the inverse temperature (kB is the Boltzmann constant) and µ is the chemical potential. At zero temperature (β ! 1) the chemical 5 potential is equal to the Fermi energy, EF , and the Fermi function describes a step-function, such that all states with energy E ≤ EF are full and all states with energy about EF are empty. In the grand-canonical ensemble, where the chemical potential is xed, the number of electrons is temperature-dependent. The electronic density (number of electrons per unit volume) is given by 1 n = dEN (E)f(E); (1.21) ˆ−∞ where N (E) is the density of states (number of states having energy E per unit volume). We can straightforwardly adopt the results of the Drude model for this case, however, we need to correct the following points: • The typical velocity squared for the electrons, hv2i, is set by the Fermi energy and not by the temperature mv2 = E ; (1.22) 2 F D 2 E (compare with mv 3 for the Boltzmann distribution). 2 = 2 kBT • The electronic heat capacity is proportional to the temperature and is not a constant. The reason is that at nite temperature T there are ∼ Ω(EF )kBT electrons which become excited (here Ω(EF ) ∼ n=EF is the density of states at the Fermi energy), and they each typically carry additional energy kBT , leading to an increase in energy of about E ∼ 2 compared to the ground state; Hence dE .