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Chapter 8 – Electronic and Optical

Materials
Pivotal Questions:
- How do electrons flow through metals?
- What happens when there are no free electrons?
- How do electronic devices operate?
- What other electrical behaviors do some
materials display?
- What are optical properties and why do they
matter?
Electronic and Optical Materials
 Electrical materials have commercial importance
because of how they conduct electricity
 Optical materials have commercial importance
because of how they reflect, absorb, or transmit
light
 All electronic and optical materials are subsets of
material categories that we have already discussed
(Metals, polymers, ceramics, carbon, or
composites)
Classification of Conductivity
 Metals have free electrons that are able to move when
the material is subjected to an electric field at absolute
zero. The nature of the metallic bond facilitates this
behavior.
 Insulators are materials that do not have free
electrons at absolute zero
 Semiconductors are a subclass of insulators that
develop the ability to conduct electrons at
temperatures greater than absolute zero
Chemistry Review
 Electrons exist in distinct energy levels and can be
described by unique quantum numbers
 The principal quantum number represent the energy
level while others address differences in angular
momentum an spin
 As long as atoms are isolated from each other, the
number of quantum states is defined rigidly as n2
Formation of Energy Bands
 When atoms are close together, free electrons from
one can move to the orbitals of the other
 The Pauli Exclusion Principle prevents electrons with
the same spin existing on the same sublevel, so the
levels split to form energy bands with slightly different
energy levels
More on Energy Bands
 The energy level of the
highest occupied band is
called the Fermi Energy
(EF)
 Only like energy levels can
interact, so electrons in a
4s level form bands with
other 4s electrons only
 When s and p orbitals are
both present, the bands
overlap Copper Aluminum
(s-only) (s and p)
Current Density
 Current density (J) is the rate of electron movement
through a unit area
J = Dq/ADt
where Dq is the total charge passing through an area
(A) in time (Dt)
 Because electrons are free to move in any direction
through the shared orbitals, an electric field (E) must
be applied to induce a net flow of electrons in a
specific direction
Drift Velocity
 The stronger the applied electric field, the faster the
electrons will flow
 Drift Velocity (vd) is the average velocity of electrons
vd =mdE
where md is a proportionality constant called the drift
mobility
Electron movement in metals
 Although there is a net flow of electrons in the
direction opposite of the electronic field, the electrons
do not flow in an orderly fashion
 The metal lattice vibrates continuously and contains
dislocations and other defects
 Electrons are repeatedly deflected between its primary
atom and the rest of the lattice

Electric Field
Electrical Conductivities for Common Metals
and Metal Alloys Near Room Temperature
Example 8-1 Continued
Electrical Resistivity (r)
 If conducting electrons were free to move
unencumbered, all metallic lattices would be free of
resistance
 Instead, collisions within the lattice create a barrier to
conductivity
 The magnitude of the barrier is the electrical
resistivity (r), which is the inverse of conductivity
r = 1/s
 Anything that creates more collisions raises resistivity
and reduces conductivity
Matthiessen’s Rule
 Three main factors combine to impact the resistivity of
a metal:
 Temperature
 Impurities
 Plastic deformation
 Matthiessen’s Rule states that each of these factors
acts independently of the other and that the total
resistivity can be defined as
r = rt + ri + rd
where t, i, and d correspond to thermal, impurities, and
deformation accordingly
Impact of Temperature on
Resistivity
 When temperature increases, the number of vacancies
in the lattice and the rate of atomic vibration both
increase
 These changes lead to more scattering and increased
resistivity
 Kinetic theory provides an explicit relationship for the
thermal portion of resistivity, but a simplified form is
commonly used:
rt = r0 + T/a
where r0 is the resistivity at one temperature and a is a
proportionality constant
Impact of Impurities on
Resistivity
 Impurity atoms are either larger or smaller than those in
the rest of the lattice, causing distortions
 The irregularity in structure increases scatter and increases
resistivity
 In metal alloys that form single phase solutions, one atom
functions as an impurity in a lattice of the other
 As the amount of the impurity increases, it can dominate
the total resistivity to the virtual exclusion of the
temperature effects (e.g. an alloy of 20% chromium - 80%
Nickel called nichrome has a resistivity 16 times higher
than pure nickel)
Nordheim’s Rule
 The resistivity of a binary Nordheim Coefficents for Copper
alloy cab be calculated Lattices
with Nordheim’s Rule
ri = CX(1-X)
where X is the percentage
of the impurity and C is
the Nordheim Coefficient Nordheim Coefficients for
 Nordheim’s Rule works Gold Lattices
well only with dilute
solutions
Impact of Plastic Deformation
on Resistivity
 Plastic deformation also increases the electrical
resistivity of the system by distorting the lattice and
increasing the amount of scattering

 The contribution of plastic deformation to the overall


resistivity tends to be far less than either temperature
or impurities
The Energy Gap
 When an electron leaves an
energy band to move to a higher
energy state it leaves behind a
positively charged vacant site
called a hole
 Electrons in the high energy state
are in the conduction band
 Covalently bonded electrons
remain in the valence band
 The energy difference between
these bands is the Energy Gap
and it is much larger in insulators
than in semiconductors Semiconductor Insulator
Intrinsic Semiconduction
 Intrinsic semiconductors are
perfect crystals with a
completely filled valence band
and completely empty
conduction band separated by
an energy gap of less than 2 eV
 Silicon is the most common
intrinsic semiconductor
 When four silicon atoms are
close together, their orbitals
overlap and form hybrids, each
containing two electrons
Electron Movement in Intrinsic
Semiconductors
 When an electric field is applied
to the silicon, electrons in the
valence band gain energy and
move to the unoccupied
conduction band
 A hole is left behind
 Light and/or heat could also be
used to provide the needed
energy
 Electrons and holes migrate in
response to the field as distinct
charge carriers
Current Density Calculation
 The current in a semiconductor conducts through both the
movement of electrons and holes
 The current density (J) can be defined as
J = enVd,e + enVd,h
where e is the charge on an electron, n is the number of electrons
in the conduction band, and Vd,e and Vd,h are the drift velocities
of the electrons and the holes, respectively
 The number of electrons in the conduction band is temperature
dependent and follows an Arrhenius relationship
n = n0 exp (–EA/RT)
Extrinsic Seminconductors
 Extrinsic Semiconductors are formed by the introduction of
specific impurities called dopants into semiconductors

 The conductivity of extrinsic semiconductors depend on the type


and number of dopants and is almost independent of
temperature

 In intrinsic semiconductors, there are always exactly the same


number of holes left in the valence band as electrons promoted
to the conduction band

 In extrinsic semiconductors, these numbers may be unequal


n-type vs p-type Semiconductors
 n-type semiconductors:
 Contain dopants that function as electron donors
 Have fewer holes in the valence band than electrons in the
conduction band
 Typically contain a Group VA atoms (phosphorus, arsenic, or
antimony)
 p-type semiconductors:
 Contain dopants that function as electron acceptors
 Have more holes in the valence band than electrons in the
conduction band
 Typically contain Group IIIA atoms (boron, aluminum, gallium, or
iridium)
Energy Gap in n-type Semiconductors
 Four of the electrons from
the group VA donor
participate in covalent
bonding, but the fifth has
no role and hovers at an
energy level just below the
conduction band
 The energy required to
promote this electron (ED)
is far less than that of a
valence band electron
Behavior of n-type Semiconductors
 At temperatures too low to overcome even ED, there is
almost no conductivity
 For the entire range of temperatures that provide enough
energy to overcome ED but not Eg, the conductivity is
controlled entirely by the number of dopant atoms present
 This allows conductivity to be governed by a controllable
feature (the number of dopant atoms) rather than by an
external variable (temperature)
Energy Gap in p-type Semiconductors
 Group IIIA dopants have only
three available electrons and
must pull one from the
conduction band to participate
in bonding
 A hole is left behind
 The hole sites have an energy
level slightly higher than the rest
of the valence band, so a smaller
energy barrier (EA) must be
overcome to create a hole in the
valence band that can migrate
and carry charge
Diodes
 Diodes are electronic switches
that allow current to flow in only
one direction
 Diodes are formed by placing an
n-type semiconductor in contact
with a n-type semiconductor to
form a p-n junction like the one
shown on the right
 The material on the p-side
conducts charge through the
movement of holes, while the n-
side conducts through the
movement of electrons
Forward Bias
 Connecting a positive terminal
of a battery to the p-side and the
negative to the n-side, electrons
and holes migrate toward the
center
 A depletion zone forms in which
recombination occurs
 As the migration continues, the
depletion zone thins and
electrons become capable of
passing through the zone and
creating current

Forward Bias
Reverse Bias
 When the battery is
hooked up with the
negative terminal on the
p-side, electrons and
holes are drawn away
from the depletion zone
 Almost no
recombination occurs
and the junction
becomes a powerful
insulator
Zener Breakdown
 When the reverse bias becomes too large, any carrier
that manages to break through the depletion zone
becomes rapidly accelerated
 Other carriers in the region respond by becoming
overly excited
 A sudden large current may develop in the opposite
direction
 This phenomenon is call Zener Breakdown
Transistors
 Transistors are amplifying or switching devices consisting of three
regions:
 An Emitter that gives off electrons (in n-p-n transistors) or holes (in p-n-p
transistors)
 A Collector that completely surrounds the emitter and collects all of the
electrons (or holes) given off
 A Base that sits between the collector and emitter and is made from a
lightly-doped, high-resistivity material
 The small voltage increase between the emitter and base results in a
large increase in current in the collector
MOSFETs
 MOSFETs (metal oxide
semiconductor field effect
transistors) have essentially
replaced classic junction transistors
 In a p-type MOSFET, 2 small regions
of p-type semiconducting material
are deposited on a large region of n-
type material and connected by a
narrow p-type channel
 One p-type region serves a source
and the other a drain
 Small changes in the applied field
result in large changes in current
Integrated Circuits
 By the middle of the 20th-century, companies could
integrate many transistors into a single microchip
 By 2006, a single chip could be imprinted with 1,000,000
transistors per square millimeter
 Integrated circuits fit three general classes:
 Analog circuits that perform amplification, demodulation,
and filtering functions
 Digital circuits who can serve as flip-flops, logic gates, and
perform other more complex operations
 Mixed Signal circuits (that contain both analog and digital)
Photoresist Lithography
 Integrated circuit production
technique that uses a wafer of
high purity silicon covered by a
photoresist coating
 Softbaking removes residual
solvents
 A transparent glass plate (called
a mask) is placed over the wafer
and a metal emulsion form a
pattern
 When UV-light is shined
through the mask, the areas not
covered by metal dissolve
 A developed then removes the
exposed material Photoresist
Capacitors
 Capacitors are charged
parallel plates with an electric
field running between the
positive and negative plate
 They serve as a means of
storing electrical energy
 The capacitance (C) of the
parallel plates is defined as
C = Q/A
where Q is the charge on the
plates and A is the cross
sectional area of one plate
Dielectric Materials
 If only air separated the
plates, a strong field would
result in sparking between
the plates
 A polarized material that
opposes the electric field
(called a dielectric
material) is placed between
the plates
 The ability of the dielectric
material to oppose the field is
given by the dimensionless
dielectric constant (K)
Dielectric Constants of Common
Materials
Capacitance with Dielectric
Materials
 The dielectric constant is a function of composition,
microstructure, temperature, and electrical frequency
 The capacitance for capacitors containing dielectric
materials is given by
C = Ke0A/d
where e0 is the permittivity of a vacuum (8.85 x 10-12
F/m) and d is the distance between the plates
Ferroelectric Materials
 Ferroelectric materials have permanent dipoles that
cause them to polarize spontaneously without an
applied electric field.
 The polarization will stop above a critical limit called
the Curie Temperature
 They are used in dynamic random access memory
systems (DRAMs) and in infrared sensors
Ferromagnetic barium titanate
 Above its Curie temperature (120C), BaTiO3 is a
symmetric FCC structure
 Below the Curie temperature, BaTiO3 shifts to a simple
cubic structure with positive charges accumulating
near the top and negatives near the bottom
Piezoelectric Materials
 Piezoelectric materials convert mechanical energy
to electrical energy or vice versa
 The piezoelectric effect is the production of an
electrical field in response to an applied electric force
 The converse piezoelectric effect is the change in
thickness of a material in response to an applied
electrical field.
 Piezoelectric materials have symmetric charge
distributions, but when the structure deforms slightly
a potential difference forms
Optical Materials
 Optical materials are special
because of the way they reflect,
transmit or refract light
 Visible light is only a small part
of the electromagnetic spectrum
 Electromagnetic radiation
displays properties of both
particles and waves
 The velocity (c) of the radiation
is the product of the wavelength
(l) and the frequency (n)
c=ln
Photons
 All electromagnetic radiation travels in discrete units called
photons, which are governed by the equation
E = hn = hc/l
where E is the energy of the photon and h is Planck’s constant
(6.62x10-34 j-s)
 When a photon interacts with any material, four possible
outcomes result:
 Absorption
 Transmission
 Reflection
 Refraction
Absorption and Transmission
 Absorption occurs
when incoming photons
give up their energy to
the valance electrons of
the material
 Transmission occurs
when the incoming
photon passes through
the material without
interacting.
Reflection
 The angle of incidence is equal
to the angle of reflection
 The Fresnel equation states that
for light with a small angle of
incidence
R = ([n1-n2]/[n1+n2])2
where n is the index of
refraction for each media and
R
is the Reflection Coefficient
The Transmission
Coefficient (T) is
T=1-R
Refraction
 The index of refraction (n)
represents the change in the
relative velocity of light as it
passes through a new
medium.
 n = 1 for light passing through
a vacuum
 For most materials, n>1
 Snell’s law relates the change
in velocity to the angle of
refraction
n1/n2 = sinq2/sinq1
Total Internal Reflection
 Snell’s law can be used to
determine a critical angle
of incidence (qc) above
which total internal
reflection occurs
qc = sin-1 (n2/n1)
Types of Reflections
 Specular reflection occurs when highly polished,
smooth materials reflect with little local variation in
the angle of reflection
 Diffuse reflection occurs when rougher, uneven
surfaces result in a wider range of reflectance angles.
 Materials with high indices of refraction (n>2) tend to
have multiple internal reflections. Diamonds and
glass sparkle because of these multiple reflections
Classification of Optical Materials
 Transparent materials allow enough light to pass
through for a clear image to be seen
 Opaque materials prevent the passage of light and no
image can be seen
 Translucent materials cover the spectrum between
transparent and opaque and allow only a diffuse image
to be seen because of the scattering of light. Milk jugs
and frosted glasses are translucent
Optical Fibers
 Optical fibers transmit signals by photons rather than electrons
 A thin glass core is surrounded by a cladding made from a material
with a higher index of refraction
 Total reflection allows the photonic signal to propagate down the
length of the glass fiber
 Absorption and scattering lead to some loss of signal strength through
a process called attenuation. The signal must be enhanced
periodically to overcome the attenuation
Other Optical Fiber Applications
 TOSLINK cables (like
the one on the right) use
optical fibers to connect
audio equipplemnt
 Colored lights are used
with optical fibers for
decorative items
Lasers
 Laser is an acronym (Light Amplification by
Stimulated Emission of Radiation)
 Lasers find use in bar code readers and in CD and
DVD players
 Conceptually, the operation of a laser is similar to an
incandescent light bulb, but the light generated is
coherent (It has a single wavelength and is emitted in a
well-defined beam)
Laser Operation
 Lasers have two main parts – a
gain medium and an optical
cavity
 The Gain Medium is a
substance that can pass from a
higher to lower energy state and
pass the associated energy to the
laser beam. Neon, helium and
argon make excellent gain media 1 – Gain Medium
 The Optical Cavity is 2 – External Power Source
essentially two mirrors that 3 and 4 – Optical Cavity
repeatedly reflect the beam of 5 – Laser Beam
light through the gain media,
increasing the intensity each
time