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# Introduction To Materials Science FOR ENGINEERS, Ch.

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Electrical Properties

## Outline of this Topic

1. Basic laws and electrical properties of metals 2. Band theory of solids: metals, semiconductors and insulators 3. Electrical properties of semiconductors 4. Electrical properties of ceramics and polymers 5. Semiconductor devices

## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Goals of this topic: Understand how electrons move in materials: electrical conduction How many moveable electrons are there in a material (carrier density), how easily do they move (mobility) Metals, semiconductors and insulators Electrons and holes Intrinsic and Extrinsic Carriers Semiconductor devices: p-n junctions and transistors Ionic conduction Electronic Properties of Ceramics: Dielectrics, Ferroelectrics and Piezoelectrics
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## 1. Basic laws and electrical properties of metals

Ohms Law V = IR E = V/L where E is electric field intensity = / E where = the mobility = the drift velocity Resistivity = RA / L (.m) Conductivity = 1 / (.m)-1
University of Tennessee, Dept. of Materials Science and Engineering

## Materials Choices for Metal Conductors

Electrical conductivity between different materials varies by over 27 orders of magnitude, the greatest variation of any physical property

Metals: > 105 (.m)-1 Semiconductors: 10-6 < < 105 (.m)-1 Insulators: < 10-6 (.m)-1
University of Tennessee, Dept. of Materials Science and Engineering

Most widely used conductor is copper: inexpensive, abundant, very high Silver has highest of metals, but use restricted due to cost Aluminum main material for electronic circuits, transition to electrodeposited Cu (main problem was chemical etching, now done by Chemical-Mechanical Polishing) Remember deformation reduces conductivity, so high strength generally means lower : trade-off. Precipitation hardening may be best choice: e.g. Cu-Be. Heating elements require low (high R), and resistance to high temperature oxidation: nichrome.

## Conductivity / Resistivity of Metals

High number of free (valence) electrons high Defects scatter electrons, therefore they increase (lower ). total = thermal+impurity+deformation

thermal

## impurity from impurities

Resistivity increases with temperature (increased thermal vibrations and point defect densities) T = o + aT Additions of impurities that form solid sol: I = Aci(1-ci) (increases ) Two phases, , : i = V + V
University of Tennessee, Dept. of Materials Science and Engineering

Electric field causes electrons to accelerate in direction opposite to field Velocity very quickly reaches average value, and then remains constant Electron motion is not impeded by periodic crystal lattice Scattering occurs from defects, surfaces, and atomic thermal vibrations These scattering events constitute a frictional force that causes the velocity to maintain a constant mean value: vd, the electron drift velocity The drift velocity is proportional to the electric field, the constant of proportionality is the mobility, . This is a measure of how easily the electron moves in response to an electric field. The conductivity depends on how many free electrons there are, n, and how easily they move
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University of Tennessee, Dept. of Materials Science and Engineering

## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Scattering events

2. Band theory of solids: metals, semiconductors and insulators Band Theory of Solids Schroedingers eqn (quantum mechanical equation for behavior of an electron)

## Net electron motion

K + V = E
2 (-h2/2m) + V = ih x2 t

vd = eE = n|e| e
n : number of free or conduction electrons per unit volume
University of Tennessee, Dept. of Materials Science and Engineering

Solve it for a periodic crystal potential, and you will find that electrons have allowed ranges of energy (energy bands) and forbidden ranges of energy (band-gaps).
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University of Tennessee, Dept. of Materials Science and Engineering

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## Electrons in an Isolated atom (Bohr Model)

(m) = Metal (s) = Semicon Na (m) Ag (m) Al (m) Si (s) GaAs (s) InSb (s) Mobility (RT) (m2V-1s-1) 0.0053 0.0057 0.0013 0.15 0.85 8.00 Carrier Density Ne (m-3) 2.6 x 1028 5.9 x 1028 1.8 x 1029 1.5 x 1010 1.8 x 106

Electron orbits defined by requirement that they contain integral number of wavelengths: quantize angular momentum, energy, radius of orbit

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

When N atoms in a solid are relatively far apart, they do not interact, so electrons in a given shell in different atoms have same energy As atoms come closer together, they interact, perturbing electron energy levels Electrons from each atom then have slightly different energies, producing a band of allowed energies

Each band can contain certain number of electrons (xN, where N is the number of the atoms and x is the number of electrons in a given atomic shell, i.e. 2 for s, 6 for p etc.). Note: it can get more complicated than this! Electrons in a filled band cannot conduct In metals, highest occupied band is partially filled or bands overlap Highest filled state at 0 Kelvin is the Fermi Energy, EF Semiconductors, insulators: highest occupied band filled at 0 Kelvin: electronic conduction requires thermal excitation across bandgap; T (At 0 Kelvin) highest filled band: valence band; lowest empty band: conduction band. Ef is in the bandgap

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Metals, Semiconductors, Insulators At 0 Kelvin all available electron states below Fermi energy are filled, all those above are vacant Only electrons with energies above the Fermi energy can conduct:
Remember Pauli Exclusion Principle that only two electrons (spin up, spin down) can occupy a given state defined by quantum numbers n, l, ml So to conduct, electrons need empty states to scatter into, i.e. states above the Fermi energy

Metals

## Insulators Eg > 2 eV Empty conduction band Ef

Semiconductors Eg < 2 eV

Empty band

Band gap

## Filled valence band

When an electron is promoted above the Fermi level (and can thus conduct) it leaves behind a hole (empty electron state)
A hole can also move and thus conduct current: it acts as a positive electron) Holes can and do exist in metals, but are more important in semiconductors and insulators

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

The Fermi Function This equation represents the probability that an energy level, E, is occupied by an electron and can have values between 0 and 1 . At 0K, the f (E) is equal to 1 up to Ef and equal to 0 above Ef
Empty states

Metals

Energy

## f (E) =  / [e(E - Ef) / kT +1]

EF

EF
Electron excitation

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(b)
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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Semiconductors, Insulators
In metals, electrons near the Fermi energy see empty states a very small energy jump away, and can thus be promoted into conducting states above Ef very easily (temp or electric field) High conductivity Atomistically: weak metallic bonding of electrons In semiconductors, insulators, electrons have to jump across band gap into conduction band to find conducting states above Ef : requires jump >> kT No. of electrons in CB decreases with higher band gap, lower T Relatively low conductivity An electron in the conduction band leaves a hole in the valence band, that can also conduct Atomistically: strong covalent or ionic bonding of electrons
Conduction band Conduction band

Free electron

Energy

Band Gap

EF

## Electron excitation Hole in valence band (b)

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Valence band

(a)
University of Tennessee, Dept. of Materials Science and Engineering

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Valence band

## Introduction To Materials Science FOR ENGINEERS, Ch. 19

E field
Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si
hole free electron

Si Si Si

Si Si

## Both electrons and holes conduct: = n|e|e + p|e|h

n: number of conduction electrons per unit volume p: number of holes in VB per unit volume

Si

(a)

E field
Si Si Si Si Si Si Si Si
hole

(b)

In intrinsic semiconductor, n = p: = n|e|(e + h) = p|e|(e + h) Number of carriers (n,p) controlled by thermal excitation across band gap: n = p = C exp (- Eg /2 kT)
C : Material constant Eg : Magnitude of the bandgap
University of Tennessee, Dept. of Materials Science and Engineering

Si
free electron

Si Si

Si

Electrical conduction in intrinsic Si, (a) before excitation, (b) and (c) after excitation, see the response of the electron-hole pairs to the external field. Note: holes generally have lower mobilities than electrons in a given material (require cooperative motion of electrons into previous hole sites)
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## 3. Electrical properties of semiconductors Semiconductors

Semiconductors are the key materials in the electronics and telecommunications revolutions: transistors, integrated circuits, lasers, solar cells. Intrinsic semiconductors are pure (as few as 1 part in 1010 impurities) with no intentional impurities. Relatively high resistivities Extrinsic semiconductors have their electronic properties (electron and hole concentrations, hence conductivity) tailored by intentional addition of impurity elements

Extrinsic Semiconductors

## Engineer conductivity by controlled addition of impurity atoms: Doping

Room Temp
University of Tennessee, Dept. of Materials Science and Engineering

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

n-type semiconductors In Si which is a tetravalent lattice, substitution of pentavalent As (or P, Sb..) atoms produces extra electrons, as fifth outer As atom is weakly bound (~ 0.01 eV). Each As atom in the lattice produces one additional electron in the conduction band. So NAs As atoms per unit volume produce n additional conduction electrons per unit volume Impurities which produce extra conduction electrons are called donors, ND = NAs ~ n These additional electrons are in much greater numbers than intrinsic hole or electron concentrations, ~ n|e|e ~ ND |e|e Typical values of ND ~ 1016 - 1019 cm-3 (Many orders of magnitude greater than intrinsic carrier concentrations at RT)
University of Tennessee, Dept. of Materials Science and Engineering
Si 4+ Si 4+ Si 4+ Si 4+ Si 4+

E field
Si 4+ free electron P 5+ Si 4+ Si 4+

Si 4+

P 5+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

n-type

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

(a)
Si 4+ Si 4+ Si 4+ Si 4+ Si 4+ Si 4+

(b)
Si 4+ Si 4+

Si 4+

Si 4+ hole

B 3+

Si 4+

Si 4+ hole

Si 4+

B 3+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

Si 4+

p-type

(a)

(b)

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

p-type semiconductors Substitution of trivalent B (or Al, Ga...) atoms in Si produces extra holes as only three outer electrons exist to fill four bonds. Each B atom in the lattice produces one hole in the valence band. So NB B atoms per unit volume produce p additional holes per unit volume Impurities which produce extra holes are called acceptors, NA = NB ~ p These additional holes are in much greater numbers than intrinsic hole or electron concentrations, ~ p|e|h ~ NA |e|h Typical values of NA ~ 1016 - 1019 cm-3 (Many orders of magnitude greater than intrinsic carrier concentrations at RT)
University of Tennessee, Dept. of Materials Science and Engineering

## Semiconductors n-type more electrons

Conduction band Conduction band
Donor state

Energy

## Free electrons in the conduction band

Valence band

Band Gap

Valence band

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For an n-type material, excitation occurs from the donor state in which a free electron is generated in the conduction band.
University of Tennessee, Dept. of Materials Science and Engineering

(a)

(b)
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## Semiconductors p-type more holes

Conduction band Conduction band

Energy

Band Gap

## 4. Electrical properties of ceramics and polymers

Hole in the valence band

Acceptor state

Valence band

(a)

Valence band

(b)
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For an p-type material, excitation of an electron into the acceptor level, leaving behind a hole in the valence band.
University of Tennessee, Dept. of Materials Science and Engineering

## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Temperature Dependence of carrier Concentration and Conductivity Our basic equation: = n|e|e + p|e|h Main temperature variations are in n,p rather than e , h Intrinsic carrier concentration n = p = C exp (- Eg /2 kT) Extrinsic carrier concentration
low T (< room temp) Extrinsic regime: ionization of dopants mid T (inc. room temp) Saturated regime: most dopants ionized high T Intrinsic regime: intrinsic generation dominates
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Dielectric Materials A dielectric material is an insulator which contains electric dipoles, that is where positive and negative charge are separated on an atomic or molecular level

Intrinsic

Saturation ln p, n

Extrinsic

{ln p/ [(1/T)]} = Eg / 2 k

When an electric field is applied, these dipoles align to the field, causing a net dipole moment that affects the material properties.

1/T

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Capacitance Capacitance is the ability to store charge across a potential difference. Examples: parallel conducting plates, semiconductor p-n junction Magnitude of the capacitance, C: C = Q/V
+++++

## Polarization Magnitude of electric dipole moment from one dipole: p = qd

D

----- -

Parallel- plate capacitor, C depends on geometry of plates and material between plates C = r o A / L
A : Plate Area; L : Plate Separation

- - - + ++ - - - + ++ - - - + ++

In electric field, dipole will rotate in direction of applied field: polarization The surface charge density of a capacitor can be shown to be: D = or D : Electric Displacement (units Coulombs / m2)
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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Magnitude of dielectric constant depends upon frequency of applied alternating voltage (depends on how quickly charge within molecule can separate under applied field) Dielectric strength (breakdown strength): Magnitude of electric field necessary to produce breakdown
University of Tennessee, Dept. of Materials Science and Engineering

Increase in capacitance in dielectric medium compared to vacuum is due to polarization of electric dipoles in dielectric. In absence of applied field (b), these are oriented randomly In applied field these align according to field (c) Result of this polarization is to create opposite charge Q on material adjacent to conducting plates This induces additional charge (-)Q on plates: total plate charge Qt = |Q+Q|. So, C = Qt / V has increased
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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Surface density charge now D = = or = o + P P is the polarization of the material (units Coulombs/m2). It represents the total electric dipole moment per unit volume of dielectric, or the polarization electric field arising from alignment of electric dipoles in the dielectric From equations at top of page P = o(r-1)
University of Tennessee, Dept. of Materials Science and Engineering

Electronic

Ionic

Orientation

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Origins of Polarization

## Where do the electric dipoles come from?

Electronic Polarization: Displacement of negative electron clouds with respect to positive nucleus. Requires applied electric field. Occurs in all materials. Ionic Polarization: In ionic materials, applied electric field displaces cations and anions in opposite directions Orientation Polarization: Some materials possess permanent electric dipoles, due to distribution of charge in their unit cells. In absence of electric field, dipoles are randomly oriented. Applying electric field aligns these dipoles, causing net (large) dipole moment.

Ptptal = Pe + Pi + Po
University of Tennessee, Dept. of Materials Science and Engineering

Barium Titanate, BaTiO3 : Permanent Dipole Moment for T < 120 C (Curie Temperature, Tc). Above Tc, unit cell is cubic, no permanent electric dipole moment
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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Piezoelectricity In some ceramic materials, application of external forces produces an electric (polarization) field and vice-versa Applications of piezoelectric materials microphones, strain gauges, sonar detectors Materials include barium titanate, lead titanate, lead zirconate

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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Ionic Conduction in Ceramics Cations and anions possess electric charge (+,-) and therefore can also conduct a current if they move. Ionic conduction in a ceramic is much less easy than electron conduction in a metal (free electrons can move far more easily than atoms / ions) In ceramics, which are generally insulators and have very few free electrons, ionic conduction can be a significant component of the total conductivity total = electronic + ionic Overall conductivities, however, remain very low in ceramics.

## Electrical Properties of Polymers

Most polymeric materials are relatively poor conductors of electrical current - low number of free electrons A few polymers have very high electrical conductivity - about one quarter that of copper, or about twice that of copper per unit weight. Involves doping with electrically active impurities, similar to semiconductors: both p- and n-type Examples: polyacetylene, polyparaphenylene, polypyrrole Orienting the polymer chains (mechanically, or magnetically) during synthesis results in high conductivity along oriented direction Applications: advanced battery electrodes, antistatic coatings, electronic devices Polymeric light emitting diodes are also becoming a very important research field

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Applied Voltage
P
D

P N

## 5. Semiconductor Devices and Circuits

- - - + ++ - - - + ++ - - - + ++
Vb + Vo Vo-Vb Ec+ Ec0
Forward Bias

- - - -

- + - + - +
Vb +
Vo

++ ++ ++

Reverse Bias

Vo+|Vb|

Ev+ Ev0

## University of Tennessee, Dept. of Materials Science and Engineering

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Lower Barrier , I

Higher Barrier, I

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## The Semiconductor p-n Junction Diode

P
D

- - - + ++ - - - + ++ - - - + ++

n p

Vh Ve

A rectifier or diode allows current to flow in one direction only. p-n junction diode consists of adjacent p- and n-doped semiconductor regions Electrons, holes combine at junction and annihilate: depletion region containing ionized dopants Electric field, potential barrier resists further carrier flow
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## Introduction To Materials Science FOR ENGINEERS, Ch. 19

Transistors The basic building block of the microelectronic revolution Can be made as small as 1 square micron A single 8 diameter wafer of silicon can contain as many as 1010 - 1011 transistors in total: enough for several for every man, woman, and child on the planet Cost to consumer ~ 0.00001c each. Achieved through sub-micron engineering of semiconductors, metals, insulators and polymers. Requires ~ \$2 billion for a state-of-the-art fabrication facility

## MOSFET (Metal-Oxide-Semiconductor Field Effect Transistor)

Nowadays, the most important type of transistor. Voltage applied from source to drain encourages carriers (in the above case holes) to flow from source to drain through narrow channel. Width (and hence resistance) of channel is controlled by intermediate gate voltage Current flowing from source-drain is therefore modulated by gate voltage. Put input signal onto gate, output signal (source-drain current) is correspondingly modulated: amplification and switching State-of-the-art gate lengths: 0.18 micron. Oxide layer thickness < 10 nm
University of Tennessee, Dept. of Materials Science and Engineering

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## Take Home Messages

Language: Resistivity, conductivity, mobility, drift velocity, electric field intensity, energy bands, band gap, conduction band, valence band, Fermi energy, hole, intrinsic semiconductor extrinsic semiconductor, dopant, donor, acceptor, extrinsic regime, extrinsic regime, saturated regime, dielectric, capacitance, (relative) permittivity, dielectric strength, (electronic, ionic, orientational) polarization, electric displacement, piezoelectric, ionic conduction, p-n junction, rectification, depletion region, (forward, reverse) bias, transistors, amplification. Fundamental concepts of electronic motion: Conductivity, drift velocity, mobility, electric field Band theory of solids: Energy bands, band gaps, holes, differences between metals, semiconductors and insulators Semiconductors: Dependence of intrinsic and extrinsic carrier conc. on temperature, band gap; dopants - acceptors and donors. Capacitance: Dielectrics, polarization and its causes, piezoelectricity Semiconductor devices: basic construction and operation of p-n junctions, bipolar transistors and MOSFETs
University of Tennessee, Dept. of Materials Science and Engineering

n-p-n or p-n-p sandwich structures. Emitter-base-collector. Base is very thin (~ 1 micron or less) but greater than depletion region widths at p-n junctions. Emitter-base junction is forward biased; holes are pushed across junction. Some of these recombine with electrons in the base, but most cross the base as it so thin. They are then swept into the collector. A small change in base-emitter voltage causes a relatively large change in emitterbase-collector current, and hence a large voltage change across output (load) resistor: voltage amplification The above configuration is called the common base configuration (base is common to both input and output circuits). The common emitter configuration can produce both amplification (V,I) and very fast switching
University of Tennessee, Dept. of Materials Science and Engineering

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