MSE 156/256 - Solar Cells, Fuel Cells and Batteries: Materials for the Energy Solution Stanford University

Autumn 2012 Unit 2: Semiconductors

Crystalline structure Electrical transport Resistance, resistivity and conductance Materials classification Metals, insulators, semiconductors Conductivity: mobility and carrier density Electronic states Energy, occupancy and bands Free electron picture Electron energy and momentum Density of electron states Filling of electronic states Semiconductors and band gap Electrons and holes

Crystallographic Structure
Many semiconductor elements and compounds are: Group 4 elements or average of group 4 (i.e. III-V, II-VI) Covalently bonded Have structure with tetravalent units with 4 nearest neighbors
Diamond cubic crystal lattice

Example: Diamond Cubic Structure The structure for C, Si, Ge, Sn (grey tin) May be visualized as 2 fcc s with one translated along the body diagonal Lattice is relatively loosely packed Atomic packing factor = 34% Compound semiconductors, often have a variation of diamond cubic called zincblende (named after ZnS) where the III-V (e.g. Ga-As) atoms alternate

H.K.D.H. Bhadeshia: Yes, anyone can use it, I created it and am happy with this... and there is no need for acknowledgement.

Electrical Properties of Solids

Ohm s Law Current I Voltage Resistance L Resistance R ~ ohm = volt/amp Resistance is a device property (depends on what the device is made of and its physical dimensions) We can relate this to a material property Length Resistivity ~ ohm-length Cross section area A V

Electrical Properties of Solids

Ohm s Law Current Resistance I L A V Length

Voltage

Microscopic Ohm s Law

Cross section area

Current density

Electric field ~ (Volts/meter)

More generally

Conductivity = 1/

Materials Classified by Conductivity

Polystyrene teflon Nylon SiO2 Germanium Silicon Graphite Cu Ag Au 105 Metals 1010

Conductivity

10-20

10-15 Insulators

10-10 10-5

100

Semiconductors

Semiconductors: The conductivity is controllable by addition of impurities called dopants The conductivity is strongly temperature dependent and increases as the temperature increases

Conductivity: A Closer Look

Current density ~(A/m2) Electric field ~ (V/m) Conductivity ~ (A/Vm) or (m)-1 Physics of conductivity in solids V Charge carrier number density L Application of field E = V/L produces force on carriers

Charge per carrier (q = - e for electrons)

Motion of electrons is responsible for electrical current in conventional metals and semiconductors

Conductivity: A Closer Look

Physics of conductivity in solids V Application of field E = V/L produces force on carriers

L Force results in a drift velocity Drifting charges Current density Important material property Carrier mobility

Recall microscopic Ohms Law

Relationship between material properties Conductivity related to: Carrier density Carrier mobility Units on mobility

Describing Electrons in Solids

Electrons are described by quantum mechanical states These states describe - the energy of the electron - its momentum (more on this later) - the probability of finding it at a given location - the property of an electron known as spin (its either up or down)

Electron states in a quantum corral made of Fe atoms on a Cu surface. This depiction is a picture of a gilded wooden block carved by artist-physicist Julian Voss-Andreae from data taken in 1993 by Lutz et al. Creative Commons Attribution-ShareAlike License. http://en.wikipedia.org/wiki/File:The_Well_ %28Quantum_Corral%29.jpg

Important characteristics of electron states: Energy This gives the energy of the electron that occupies a given state Occupancy Each state can be occupied by either zero or one electron Electron with different spin are different states States with a given energy can have a fractional average occupancy between zero and one

Energy

Electron Energy Bands: Isolated Atoms to Crystals

Two atoms Energy Bring atoms together Atomic electron Anti bonding states split (and sometimes bonding hybridize)

Isolated atom Isolated atom Four atoms Energy Bring atoms together

A lot of atoms Energy

Bring atoms together

Conduction

Valence As many atoms are brought together to make a crystal Atomic electron states are split to have different energies New crystal electron levels are grouped into bands of narrowly-spaced energy levels Anti bonding states become the conduction band Bonding states become the valence band

Band theory of solids

Free Electron Picture

Atoms give up outer electrons, creating electron sea and charged remaining atom cores Electrons behave as though they are particles in a box, - Must each occupy its own quantum state (electrons are fermions) - Interactions with positive atom cores and with each other Free electron model No interaction between electrons and ion cores Electron have only kinetic energy
+ + + + +
Electron Cloud

+ +

+ -

Positive Ion Cores

Classically, Momentum Quantum Mechanically: de Broglie wavelength

Band theory of solids Free electrons

Free Electron Picture

Electron (kinetic) energy

Classically, Momentum

Quantum Mechanically: de Broglie wavelength

5 4 3

wavenumber Free electron energy

2 1 0 -2 -1 0 1 2

a = Lattice parameter

Density of States in a Band

Bands can have different number of states per energy We call this density of states Energy Energy Density of states (DOS) is the number of electron quantum mechanical states per volume per energy = number of states between and

For free-electron bands in solids, the density of states varies with energy within the band Density of states Energy

Low DOS

High DOS

Electron mass

Energy Free electron density of states

Filling of Free Electron States: T = 0 K

For T=0 K Fill states in order of energy (lowest energy first) Density of states

Energy

Imagine we put in n electrons per volume electrons fill states in order of energy What is energy of highest filled state?

Energy

Invert to find Fermi energy

Cu example: One electron per atom

Filling of Free Electron States: T 0 K

For T0 K Electron states are occupied according to the Fermi-Dirac Distribution
1.0 0.8 0.6

- Electron chemical potential also called Fermi level (T dependent) (T=0) Fermi energy

0.4 0.2 0.0 -1.12 0.00 1.12

0K 300 K 600 K 1000 K 1500 K 2000 K 2.24

kBT Density of states

f ( T )D ( )

Energy

Material Classification
Electron Energy
Conduction Band Conduction Band

Semiconductors

Conduction Band

Eg
Valence Band Valence Band

Fermi Level

Metal Semiconductor

Valence Band

So for any practical temperatures

Insulator

Semiconductors, insulators have a gap between valence band and conduction band The Fermi level lies in the gap between these bands At T = 0 K the electronic levels in the valence band are completely occupied by electrons At T = 0 K the electron levels in the conduction band are completely unoccupied At T > 0 K the some electrons are promoted from the valence band to the conduction band

Band Gaps of Common PV Materials

Material Crystalline Si Amorphous Si CdTe CuInSe2 (CIS) Cu2InGaSe4 (CIGS) GaAs InP Band Gap (eV) Type of Gap 1.12 1.75 1.45 1.05 1.0 1.7 1.42 1.34
4 3
21

Indirect Direct Direct Direct DIrect Direct Direct Direct Electron Energy Ec
Ev

Conduction Band Eg Valence Band

Cu2ZnSn(SSe)4 (CZTS) 1.0 1.5

Photons with energy above the band gap can excite carriers from valance to conduction band

AM1.5 5960 K Spectra

x10

2 1 0 0

MSE 156/256 - Solar Cells, Fuel Cells and Batteries: Materials for the Energy Solution Stanford University Autumn 2012 Unit 2: Semiconductors Coming Up:

Crystalline structure Unit 3: Transport and Electrical transport Resistance, resistivity and conductance concentration in Materials classification semiconductors Metals, insulators, semiconductors Conductivity: mobility and carrier density Electronic states Energy, occupancy and bands Free electron picture Electron energy and momentum Density of electron states Filling of electronic states Semiconductors and band gap Electrons and holes

carrier