Electronic Properties of Solids

Electronic Conductivity
Electron/hole, e.g. metal, conjugated polymer Electrical conduction Ions, e.g. melts, electrolyte, vacancies in solids

Resistivity () = resistance () x [area (cm2)/thickness (cm)] Conductivity (-1cm-1) = 1/

Electronic Conductivity

Metallic Conductivity
1. Delocalized valence electrons 2. Collision between free electrons and phonons are responsible for the residue resistance to current flow and associate heat loss 3. Band theory, overlapping of valence orbitals 4. Metallic conductivity occurs: Metals Metal alloys A variety of inorganic solids, e.g. TiO Conjugated organic systems, e.g. doped polyacetylene

Metallic Conductivity in Metals and Inorganic Solids

Metals: Inorganic solids: TiO

Conjugated Organic System

Conjugated system: a skeleton of alternate double and single C-C bonds Polyacetylene:

10-5 -1cm-1 Existence of bandgap 10-9 -1cm-1

Doped polyacetylene (Nobel Prize of Chemistry 2000) Electron acceptor (p-dopant): Br2, I2 and AsF5 Electron donor (n-dopant): alkali metals Conductivity as high as 103 -1cm-1 in trans doped polyacetylene!

Organic Charge Transfer Complexes

Two component organic systems ( electron donor and acceptor)

electron acceptor

electron donor

Partially occupied delocalized -electron system

Superconductivity

1. Zero Resistivity (No electron-phonon collision occur, no heat loss) 2. Perfect Diamagnetism ( = -1) 3. Confined to low temperature (critical temperature Tc) Conventional superconductor High temperature superconductor

Discovery of Superconductors

Hoffman Lab (Harvard University)

Dr. Kamerlingh-Onnes (Nobel Prize of Physics 1913) Superconductivity in mercury at liquid helium temperature (~4K)

Drs. Johannes G. Bednorz and Karl A. Mller (Nobel Prize of Physics 1987) Ceramic superconductors e.g. La2xBaxCuO4-x; YBa2Cu3O7 Critical temperature 35K

Zero Resistivity

BCS theory (for conventional superconductor) Prof. Bardeen, Cooper and Schrieffer; Nobel prize of physics in 1972 Cooper pairs (strong electron-phonon interaction) Weakly bound, with a typical separation of hundreds nanometers Pairing only occurs at low temperature

Perfect Diamagnetism
Perfect diamagnetism: complete absence of magnetic permeability

Eddy currents (will not decay) created in superconducting materials inside a magnetic field Screening currents flow at the surface of the superconductor exactly cancels the externally applied magnetic field (below critical field strength)

Type I and Type II Superconductors

Magnetic line of force are NOT completely expelled in the vortex state Flux pinning due to crystal defects or impurities Levitation and suspension

Superconducting Materials

Family of cuprates are known to be high temperature superconductor!

e.g. YBa2Cu3O7, NdBa2Cu3O7 Bi2Sr2CaCu2O8+d HgBaCaCuO High Hc2 High Jc highest Tc

Crystal Structure of Cuprate Perovskites

Ideal Perovskites

Perovskites: ABO3 compound Oxygen-deficient structure Cu can have various coordination and valence states (+1, +2 and +3)

Crystal Structure of YBa2Cu3O7

YBa2Cu3O7 YBa2Cu3O6 YBa2Cu3O7
BaCuO2.5: Cu2+ (square pyramid) YCuO2: Cu3+ (square planar)

YBa2Cu3Od
decrease, Tc decrease < 6.4, no superconductivity

YBa2Cu3O6
Cu3+ Cu+ (linear)

Oxygen Content in YBa2Cu3O7

Vary easily over the range 6 < d < 7 simply be heating the material at different temperature and different oxygen partial pressure

Determination of oxygen content in YBa2Cu3O7 hydrogen reduction TG

YBa2Cu3O7(s) + (-3.5)H2(g) Y2O3(s) + 2BaO(s) + 3Cu(s) + (-3.5)H2O(g)

Iodometry

Fullerides

A3C60 compound, high Tc M+ alkali cations are merely packing ion Tc increase as the C603- anions are pushed apart

Importance of Superconductors
Zero resistance Efficient power transmission Miniaturization of circuit boards and electronic components (heating dissipation will be solved)

Perfect diamagnetism Detect minute magnetic field (application in medicine) Levitation, such as Maglev trains

Semiconductivity

1. Limited degree of electronic conduction, between metallic conduction and insulating behavior 2. Band theory (band gap) 3. Number of electron depends on temperature and impurity level 4. Basis of the microelectronic industry

Semiconductors

Semiconductors: Si, Ge, III-V, II-VI materials and their alloys

Carrier Numbers in Intrinsic Materials

Intrinsic: extremely pure semiconductor with insignificant amount of impurities
electron

EF hole

n = n0exp(-E/kT)

n=p

n0: total # of electrons k: Boltzmanns constant E: activation energy T: temperature

conductivity

= ne

mobility

number of carriers

Manipulation of Carrier Numbers-Doping

Controlled amount of specific impurities can increase either the electron or the hole concentration

p-type semiconductor

n-type semiconductor

Density of States

Available energy states at a given energy level

Fermi Function

It specifies, under equilibrium condition, the probability that an available state at an energy E will be occupied by an electron

Carrier Distribution

n-type

Intrinsic

p-type

p-n Junction

VA = 0

VA > 0

VA < 0

Rectifier: current pass in one direction (convert a.c. to d.c. electricity) More complex arrangement such as pnp or npn junction, which acts as a current/voltage amplifier

p-n Junction Optoelectronic Diode

1. Light-emitting diode

3. p-n solid state solar cells

(Forward bias) 2. Photodiode

(Zero bias)

(Reverse bias)

Field-Effect Transistors (FETs)

First FET

Metal-Oxide Semiconductor FET (MOSFET)

Source-Drain: provide a potential difference Gates: control the charge induced into the channel (depletion mode or enhancement mode)

Inorganic Oxide Semiconductors

Mixed valency semiconductors, for example: Ni1-3x2+Ni2x3+VxO (V: vacancy)

Conductivity arises because electron can transfer from Ni2+ to Ni3+ ions Highly temperature dependent Very difficult to control the conductivity Controlled valency semiconductor, for example : Li+xNi1-3x2+Ni2x3+O

Ionic Conductivity
Occurs in materials known as solid electrolytes, superionic conductors or fast ion conductors Rigid framework structure with mobile lattice Conductivity as high as 1 -1cm-1 Structural requirements: Available empty sites for ions hopping (existence of defect vacancy) Energy barrier for ion hopping is small (high temperature)

Alkali Halides: Vacancy Conduction

Vacancy Conduction Creation of Cation Vacancy

Anions are less mobile than cations Movement of cation vacancy

1. Heating (intrinsic) Number of vacancies increase exponentially with temperature, and the number is intrinsic the material 2. Addition of aliovalent impurities (extrinsic) Na1-2xMnxVxCl

Ionic conductivity = exp(-E/RT) Cation mobility = 0exp(-Em/RT)

Activation Energy for Ion Hopping

Triangular interstice ~0.45; tetrahedral interstitial site ~0.59 Extrinsic: = ne0exp(-Em /RT) Intrinsic: n = Nexp(-Ef / 2RT)

= e0exp(-Em /RT)Nexp(-Ef/2RT) = Aexp[(-Em+Ef /2)/RT]

Ef/2 is the activation energy for formation of one mole of cation vacancies

Silver Chloride: Interstitial Conduction

Direct interstitial mechanism Indirect interstitialcy mechanism Interstitial Ag+ ions are more mobile than the Ag+ vacancies

Extrinsic Doping in AgCl

The presence of aliocation, e.g. Cd2+, will increase the number of cation vacancies The product of the concentration of cation vacancies and Ag+ interstitials is constant

Solid Electrolyte
Intermediate between normal crystalline solids and liquid electrolytes (0.1-10 -1cm-1) Only one species mobile Occurs in glasses, ceramics, crytals and gels Occurs mainly with M+, F-, O2ions Good solid electrolyte: -alumina, yttria-stabilized zirconia Good solid electrolyte:
Large number of carriers and empty sites Lower activation energy for hopping Framework structure, preferable 3D Anion framework is highly polarizable

Solid Electrolyte

-Alumina
General formula: M2O . nX2O3 Na2O . nAl2O3 Na+ mobile at r.t. M: monovalent cation X: trivalent cation

The presence of oxygen deficient layers 2D conductors (alkali ions can move freely within the conduction plane)

AgI
For example AgI: transition: (quasi-melting) Melting: disordering of both cations and anions disordering of Ag+ ion

-AgI: bcc structure RbAg4I5: 0.25 Scm-1 at r.t.

Anion Conductors
For example: PbF2 with fluorite structure

Stabilized Zirconia
High temperature cubic polymorph of Zirconia (fluorite structure) can be stabilized to room temperature by formation of solid solution with CaO or Y2O3 Each Ca2+ ion that is introduced one O2- ion vacancy is created Yttria-Stabilized Zirconia (YSZ) Good O2- ion conductors at very high temperature e.g. 1500C

Crystalline Li+ Ion Conductors

-Li2SO4: phase transition at 5720C and has ~1Scm-1 Li4SiO4: doped to create either Li+ vacancies or Li+ interstitials Li3N: layer structure, Li3-xNHx (Li vacancy mechanism) Li-containing Perovskites (10-3 Scm-1 at 250C)

Mixed Ionic/Electronic Conductors

The time between successful hopping of ions (site residence time) may be reduced in the presence of electronic conduction Transition between ionic conduction and mixed conduction can be induced in the same material, such as oxide ion conductor

Applications of Solid Electrolytes

Thermodynamic measurements:

Determine emf of a cell reaction using Nernst equation: M M+ + e X + e XM + X MX E1 = E0M/M+ + (RT/F) loge[M+]/[M] E2 = E0X-/X + (RT/F) loge[X]/[X-] G = -nEF

Sodium-Sulphur and Zebra Batteries

Operates at 300 to 350 0C 100 to 200 Wh kg-1

Cell discharge reaction: 2Na + xS Na2Sx Solid electrolyte: -alumina, which is a good conductor of sodium ions but a bad conductor of electrons

Lithium Battery
Anodes: Li metal

Electrolyte: Current: liquid electrolyte, Li salt dissolve in non-aqueous solvent such as propylene carbonate Next generation: polymer electrolyte, Li salt dissolve in polar polymer such as poly(ethylene oxide) Longer term future: solid electrolyte Cathodes: Intercalation host structures which allow conduction by both electron and the mobile ions of the electrolyte (reversible electrodes)

Oxygen Sensor

E = (RT/F)loge[PO2]/[PO2] The difference in oxygen partial pressure can be related to the cell voltage Able to measure partial pressure as low as 10-16 atm

Dielectric Materials
Zero electrical conductivity and are used as capacitors, substrates and electrical insulators Potential difference across a dielectric leads to polarization of charge

C0 = 0A/d Q = C 0V = C1/C0

Ferroelectricity
Extremely large permittivities Possibility of retaining some residual electrical polarization after an applied voltage has been switched off

Perovskite Structure
For example: BaTiO3

Below 120 0C Structural distortion Net polarization (spontaneous polarization) Ferroelectric Curie temperature Tc

Above 120 0C Charges are symmetrically positioned No net dipole moment

Perovskite Structure
Application of an electric field across a ferroelectric lead to a net change of dipole polarization Direction of polarization Magnitude of polarization Domain wall migration

Antiferroelectric Materials
Dipoles arrange antiparallel to adjacent dipoles Net spontaneous polarization is zero Non-polar and non hysteresis loop antiferroelectric state is only marginally stable than ferroelectric state ferrielectric

Applications of Ferroelectric Materials

1. Capacitors (: 102 to 104) 2. Thermistors (thermally sensitive resistors) Show an anomalous and large increase in resistivity as the temperature approaches Tc Thermal and current overload protection devices, such as reusable fuse and time delay fuse

Pyroelectricity
Exhibit net spontaneous polarization Ps The direction of polarization is irreversible by an applied field Example: ZnO

Ps is temperature dependent Ps = T : pyroelectric coefficient

Piezoelectricity
Under the action of an applied mechanical stress, piezoelectric crystals polarize and develop electrical charges on opposite crystals face P = d : stress; P: polarization d: piezoelectric coefficient PZT: Lead Ziconate Titanate

crystal structure direction of applied stress