Electronic Materials

Silicon Age: Pervasive technology

• Communications
• Computation
• Automation
• Defense
• ………..

Factors:
• Reproducibility/Reliability
• Miniaturization
• Functionality
• Cost
• …………..

3.225 © H.L. Tuller-2001 1

What Features Distinguish Different Conductors?

• Magnitude: varies by over 25 orders of magnitude!

• metal; semiconductor; insulator

• Carrier type:
• electrons vs ions;
• negative vs positive

• Mechanism:
• wave-like
• activated hopping

• Field Dependence:
• Linear vs non-linear

3.225 © H.L. Tuller-2001 2

 How Do We Arrive at Properties That We Want?

• Crystal Structure:
• diamond vs graphite

• Composition
• silicon vs germanium

• Doping
• n-Si:P vs p-Si:B

• Microstructure
• single vs polycrystalline

• Processing/Annealing Conditions
• Ga1+xAs vs Ga1-xAs

3.225 © H.L. Tuller-2001 3

What is the Application?

• Interconnect
• Resistor
• Insulator
• Non-ohmic device
– diode, transistor
• Thermistor
• Piezoresistor
• Chemoresistor
• Photoconductor
• Magnetoresistor

3.225 © H.L. Tuller-2001 4

 Origin of Conduction Range of Resistivity

Why?

3.225 © E.A. Fitzgerald-1999 5

Response of Material to Applied Potential

I
I V=f(I)
Linear,
Rectification,
Ohmic
Non-linear, Non-Ohmic
V R
V
e-

V=IR

Metals show Ohmic behavior microscopic origin?

3.225 © E.A. Fitzgerald-1999 6

Microscopic Origin: Can we Predict Conductivity of Metals?

• Drude model: Sea of electrons

– all electrons are bound to ion atom cores except valence electrons
– ignore cores
– electron gas

Schematic model of a crystal of sodium

metal.

From: C. Kittel, Introduction to Solid State Physics, 3rd

Ed., Wiley (1967) p. 198.

3.225 © E.A. Fitzgerald-1999 7

Does this Microscopic Picture of Metals Give us Ohm’s Law?

F=-eE

F=ma v,J,σ,I
m(dv/dt)=-eE
v =-(eE/m)t t
E

t
Constant E gives ever-increasing v
No, Ohm’s law can not be only from electric force on electron!

3.225 © E.A. Fitzgerald-1999 8

 Equation of Motion - Impact of Collisions

Assume:
• probability of collision in time dt = dt/τ
• time varying field F(t)

v(t+dt) = (1- dt/τ) {v(t) +dv} = (1- dt/τ) {v(t) + (F(t)dt)/m}

≈ v(t) + (F(t)dt)/m - v(t) dt/τ (for small dt)

⇒ dv(t)/dt + v(t)/τ = F(t)/m

Note: Term proportional to velocity corresponds to

frictional damping term

3.225 © H.L. Tuller-2001 9

Hydrodynamic Representation of e- Motion

p=momentum=mv
dp( t ) p( t )
=− + F1 ( t ) + F2 ( t ) +...
dt τ
Response (ma) Drag Driving Force Restoring Force...

dp(t ) p( t )
≈− − eE
dt τ
Add a drag term, i.e. the electrons have many collisions during drift
1/τ represents a ‘viscosity’ in mechanical terms

3.225 © E.A. Fitzgerald-1999 10

 Mean-free Time Between Collisions, Electron Mobility

In steady state, dp(t )

=0
dt
−t
p(t ) = p∞ (1 − e ) τ

p∞ = − eEτ
p
-eEτ

τ
t
If the environment has a lot of collisions,
mvavg=-eEτ vavg=-eEτ/m

eτ
Define v = − µE µ=
m

3.225 © E.A. Fitzgerald-1999 11

What is the Current Density ?

E n (#/vol)

j = I/A
vd A
dx
• # electrons crossing plane in time dt = n(dxA) = n(vddtA)

• # charges crossing plane per unit time and area = j

( )
j = n v d dtA (− e ) dtA = − nevd = (ne 2τ m )E
• Ohm’s Law: j = σ E ⇒ σ = (ne 2τ m ) = j E
Dimensional analysis: (A/cm2)/(V/cm)=A/(V-cm)= (ohm-cm)-1 = Siemens/cm-(S/cm)

3.225 © H.L. Tuller-2001 12

 Energy Dissipation - Joule Heating

Frictional damping term leads to energy losses:

• Power absorbed by particle from force F:

P = W/t = (F•d)/t = F•v

• Electron gas: P/vol= n(-eE)•(-eτE/m)

= ne2τE2/m = σ E2
= jE = (I/A)(V/l) = IV/vol

• Total power absorbed: P = IV = V2/R = I2R

How much current does a 100 W bulb draw?

I = 100W/115V = 0.87A

3.225 © H.L. Tuller-2001 13

Predicting Conductivity using Drude

ntheory from the periodic table (# valence e- and the crystal structure)
ntheory=AVZρm/A,
where AV is 6.023x1023 atoms/mole
ρm is the density
Z is the number of electrons per atom
A is the atomic weight

For metals, ntheory~1022 cm-3

If we assume that this is correct, we can extract τ

3.225 © E.A. Fitzgerald-1999 14

 Extracting Typical τ for Metals

• τ~10-14 sec for metals in

Drude model

3.225 © E.A. Fitzgerald-1999 15

Thermal Velocity

• So far we have discussed drift velocity vD and scattering time τ

related to the applied electric field
• Thermal velocity vth is much greater than vD x
x
x L=vDτ

1 2 3
mvth = kT
2 2
3kT
vth =
m

Thermal velocity is much greater than drift velocity

3.225 © E.A. Fitzgerald-1999 16

Resistivity/Conductivity-- Pessimist vs Optimist

V
t
I
W
L
R = ρ L/Wt = ρ L/A ⇒ ρ(οhm-cm)

σ = 1/ρ ⇒ σ (οhm-cm)-1 ⇒ σ (Siemens/cm)

(Test your dimensions: R=V/I; σ=E/j=neµ)

Ohms/square ⇒ Note, if L=W, then R= ρ /t independent

of magnitude of L and W. Useful for working with films of
thickness, t.
R R R
3.225 © H.L. Tuller-2001 17

How to Make Resistance Measurements

Rc2 Rc1
I Rs

V/I = Rc1 + Rs + Rc2

I. For Rs >> Rc1 + Rc2 ; no problem

II. For Rs ≤ Rc1 + Rc2 ; major problem ⇒ 4 probes

3.225 © H.L. Tuller-2001 18

 How to Make Resistance Measurements

Rc2
v23 Rc3
Rc1
Rc4
I Rs

V14

4 probe method: Essential feature - use of high impedance

voltmeter to measure V23 ⇒ no current flows through Rc2
& Rc3 ⇒ therefore no IR contribution to V23

Rs(2-3) = v23 /I = σ-1 (d23/A) = ρ (d23/A)

(Note: ρ-resistivity is inverse of σ−conductivity)

3.225 © H.L. Tuller-2001 19

How to Make Resistance Measurements - Wafers

V Si
I I
d d d
R x

R+dR

j = I/2πR2 ; V = IR = Iρd/A = jρd

V23 = ⌠2d (I/2πR2 ) ρ dR = (- Iρ/ 2πR) 2d = Iρ/4πd

⌡d d

ρ = (2πd/I) V23 ; ρ = (π/ln2) V/I for d >>x

3.225 © H.L. Tuller-2001 20

10

 Example: Conductivity Engineering

• Objective: increase strength of Cu but keep conductivity high

ne 2τ eτ
σ= µ=
m m
l = vτ

Scattering length
connects scattering time
to microstructure

Dislocation
(edge)

l decreases, τ decreases, σ decreases

e-

3.225 © E.A. Fitzgerald-1999 21

Example: Conductivity Engineering

• Can increase strength with second phase particles
• As long as distance between second phase< l, conductivity marginally effected

L L
L+S
α+L β+L
α β
S
α+β

Sn Cu X Cu

β dislocation
microstructure S L
α L>l

Material not strengthened, conductivity decreases Dislocation motion inhibited by second phase;
material strengthened; conductivity about the same

3.225 © E.A. Fitzgerald-1999 22

11

 Example: Conductivity Engineering

• Scaling of Si CMOS includes conductivity engineering

• One example: as devices shrink…
– vertical field increases
– τ decreases due to increased scattering at SiO2/Si interface
– increased doping in channel need for electrostatic integrity: ionized
impurity scattering
– τSiO2<τimpurity if scaling continues ‘properly’
G
SiO2
S D
Evert

Ionized impurities
(dopants)

3.225 © E.A. Fitzgerald-1999 23

Determining n and µ: The Hall Effect

Vx, Ex
+++++++++++
I, Jx
--------- Ey
r r r r Bz
F = qE + qv × B In steady state,
Fy = −evD Bz EY = vD BZ = E H , the Hall Field
Fy = −eE y Since vD=-Jx/en,

1
EH = − J x BZ = RH J X BZ
ne
1
RH = −
ne σ = neµ
3.225 © E.A. Fitzgerald-1999 24

12

 Experimental Hall Results on Metals

• Valence=1 metals look like

free-electron Drude metals
• Valence=2 and 3, magnitude
and sign suggest problems

3.225 © E.A. Fitzgerald-1999 25

13

 Response of Free e- to AC Electric Fields

• Microscopic picture
EZ = EO e − iωt
e-
B=0 in conductor,
dp(t ) p (t ) r r r r
=− − eE0 e −iωt and F ( E ) >> F ( B )
dt τ
try p (t ) = p0 e − iωt
p0
− iωp 0 = − − eE 0
τ ω>>1/τ, p out of phase with E
eE0 eE0
p0 =
1
p0 = ω → ∞, p → 0
iω − iω
τ ω<<1/τ, p in phase with E
p0 = eE0τ
3.225 © E.A. Fitzgerald-1999 1

Complex Representation of Waves

sin(kx-ωt), cos(kx-ωt), and e-i(kx-ωt) are all waves

e -i(kx-ωt) is the complex one and is the most general
imaginary

A
iAsinθ
θ
Acosθ real

e iθ=cosθ+isinθ

3.225 © E.A. Fitzgerald-1999 2

 Response of e- to AC Electric Fields

• Momentum represented in the complex plane
imaginary

p (ω>>1/τ)
real
p (ω<<1/τ)

Instead of a complex momentum, we can go back to macroscopic

and create a complex J and σ
− nep0 ne 2
J (t ) = J 0 e − iωτ J 0 = − nev = = E0
m 1
m ( − iω )
τ
σ0 ne τ
2
σ= ,σ 0 =
1 − iωτ m
3.225 © E.A. Fitzgerald-1999 3

Response of e- to AC Electric Fields

• Low frequency (ω<<1/τ)

– electron has many collisions before direction
change
– Ohm’s Law: J follows E, σ real
• High frequency (ω>>1/τ)
– electron has nearly 1 collision or less when
direction is changed
– J imaginary and 90 degrees out of phase with
E, σ is imaginary

Qualitatively:
ωτ<<1, electrons in phase, re-irradiate, Ei=Er+Et, reflection
ωτ>>1, electrons out of phase, electrons too slow, less interaction,transmission ε=εrε0 εr=1

3x1010 cm / sec
τ ≈ 10 −14 sec,νλ = c,ν = ≈ 1014 Hz
5000 x10 −8 cm

E-fields with frequencies greater than visible light frequency expected to be

beyond influence of free electrons

3.225 © E.A. Fitzgerald-1999 4

 Response of Light to Interaction with Material

• Need Maxwell’s equations

– from experiments: Gauss, Faraday, Ampere’s laws
– second term in Ampere’s is from the unification
– electromagnetic waves!
SI Units (MKS) Gaussian Units (CGS)
r r
∇•D = ρ ∇ • D = 4πρ
r r
∇•B = 0 ∇•B = 0
r r
r r 1 ∂B
∂B ∇xE = −
∇xE = − c ∂t
∂t r
r r 4π r 1 ∂D
r r ∂D ∇xH = J+
∇xH = J + c c ∂t
∂t r r r
r r r r D = E + 4πP
D = ε 0 E + P = εE r r r
r r r r B = H + 4πM
B = µ 0 H + µ 0 M = µH
µ = µ r µ0 ;ε = ε rε 0

3.225 © E.A. Fitzgerald-1999 5

Waves in Materials

• Non-magnetic material, µ=µ0

• Polarization non-existent or swamped by free electrons, P=0
r
r ∂B For a typical wave,
∇xE = −
∂t
r E = E0 e i ( k •r −ϖt ) = E0 e ik •r e −iϖt = E ( r )e − iϖt
r r ∂E
∇xB = µ 0 J + µ 0 ε 0 ∇ 2 E ( r ) = −iϖµ 0σE (r ) − µ 0ε 0ω 2 E ( r )
∂t
r ω2 Wave Equation
r ∂∇xB ∇ 2 E (r ) = − ε (ω ) E (r )
∇x(∇xE ) = − c2
∂t
iσ
ε (ω ) = 1 +
∂ ∂E ε 0ω
− ∇2E = − [ µ 0 J + µ 0ε 0 ]
∂t ∂t
E (r ) = E0 e ik •r
∂E ∂2E
∇ 2 E = µ 0σ + µ 0ε 0 2 ω2
∂t ∂t k2 = ε (ω )
c2
ω c
v= =
k ε (ω )

3.225 © E.A. Fitzgerald-1999 6

 Waves in Materials

• Waves slow down in materials (depends on ε(ω))

• Wavelength decreases (depends on ε(ω))
• Frequency dependence in ε(ω)
iσ iσ 0
ε (ω ) = 1 + = 1+
ε 0ω ε 0ω (1 − iωτ )

iω p2τ
ε (ω ) = 1 +
ω − iω 2τ
2
ne
ω 2p = Plasma Frequency
ε 0m
For ωτ>>>1, ε(ω) goes to 1
For an excellent conductor (σ0 large), ignore 1, look at case for ωτ<<1
iω 2pτ iω 2pτ
ε (ω ) ≈ ≈
ω − iω τ 2
ω

3.225 © E.A. Fitzgerald-1999 7

Waves in Materials

ω ω σ0
k= ε (ω ) = i
c c ωε 0
ω 1+ i  σ 0  σ 0ω σ 0ω 
k=   = +i 
c  2  ωε 0  2ε 0 c 2 2ε 0 c 2 


For a wave E = E0 e i ( kz −ωt ) Let k=kreal+kimaginary=kr+iki

E = E 0 e i [kr z −ωt ]e
− ki z

The skin depth can be defined by

1 2ε o c 2 2
δ = = =
ki σω o σ o µ oω

δ
3.225 © E.A. Fitzgerald-1999 8

 Waves in Materials

For a material with any σ0, look at case for ωτ>>1

ω 2p ω<ωp, ε is negative, k=ki, wave reflected

ε (ω ) = 1 −
ω 2

ω>ωp, ε is positive, k=kr, wave propagates

ωp ω

3.225 © E.A. Fitzgerald-1999 9

Success and Failure of Free e- Picture

• Success K/σ=thermal conduct./electrical conduct.~CT

– Metal conductivity 1
Κ = c v vtherm
2
τ
– Hall effect valence=1 3
– Skin Depth  ∂E  3 3k T
cv =   = nk b ; vtherm = b
2

– Wiedmann-Franz law  ∂T  v 2 m
• Examples of Failure 13  3k T  3 nk b2Tτ
Κ =  nk b  b τ =
– Insulators, Semiconductors 3 2  m  2 m
– Hall effect valence>1 ne 2τ
σ =
– Thermoelectric effect m
– Colors of metals Κ 3  kb 
2

Therefore : =   T
σ 2 e 

Luck: cvreal=cvclass/100; ~C!

vreal2=vclass2*10
0

3.225 © E.A. Fitzgerald-1999 10

 Wiedmann-Franz ‘Success’

Thermoelectric Effect

Exposed Failure when

cv and v2 are not both
in property

E = Q∇T
3
− nk b
cv 2 nk
Thermopower Q is Q = − = =− b
3ne 3ne 2e

Thermopower is about 100 times too large!

3.225 © E.A. Fitzgerald-1999 11

Waves in Vacuum

• J, ρ = 0
• µ = µ0 ; ε = ε 0
∂2E
∇ 2 E = µ 0ε 0 Wave Equation
∂t 2
For typical wave:
E = E0 e ik ⋅r −ωt k = 2π λ ; ω = 2πν
k 2 = µ 0ε 0ω 2 Example:
Violet light (ν = 7.5 x 1014 Hz)
λ = c/ν = 400 nm
⇒ ω k = νλ = (µ 0ε 0 )
−1 2 k=2π/ λ = 1.57 x 107 m -1
ω = 2 π ν = 4.71 x 1015 s-1

For constant phase: (kx-ωt)

v phase = ω k = c → c = (µ 0ε 0 )−1 2

3.225 After Livingston 12

 Waves in Materials; Skin Depth

∂2E ∂E
∇ 2 E = µε + µσ ; µ ≅ µ0
∂t 2 ∂t
k 2 = ω 2 µε + iωµσ
k ≈ (iωµσ )
12
Conductive materials
1+ i
=± (ωµσ )1 2 = ± 1 + i
2 δ
⇒ E = E0 e i ( kx −ωt ) = E0 e − i (ωt − x δ )e − x δ
The skin depth is defined by
12
 2 
δ =  
 ωµσ 

δ
3.225 After Livingston 13

Plasma Frequency

Remember: k 2 = ω 2 µε + iωµσ

σ0 −σ 0
where σ= ≈ (ωτ >> 1)
1 − iωτ iωτ

then µσ 0  ω2 
k 2 ≅ ω 2 µε − = ω 2 µε 1 − p2 
τ  ω 
12
 ne 2 
where ωp ≅   ⇒ Plasma Frequency
 mε 

⇒ For ω>ω p; k is real number no attenuation!

ω<ω p; k contains imaginary component, wave reflected
⇒ Criteria for transparent electrode?
(Example: n=5.8 x 1027/m3; ωp = 4.3 x 1015s-1)

3.225 After Livingston 14

 Wave-particle Duality: Electrons are not just particles

• Compton, Planck, Einstein

– light (xrays) can be ‘particle-like’
• DeBroglie
– matter can act like it has a ‘wave-nature’
• Schrodinger, Born
– Unification of wave-particle duality, Schrodinger
Equation

3.225 © E. Fitzgerald-1999 15

Light is always quantized: Photoelectric effect (Einstein)

• Photoelectric effect shows that E=hν even outside the box

I,E,λ
metal Maximum
block electron Emax=h(ν-νc)
energy,
Emax

e- !

νc ν
For light with ν<νc, no matter what the intensity, no e-

3.225 © E. Fitzgerald-1999 16

 DeBroglie: Matter is Wave

• His PhD thesis!

• λ=h/p also for matter
• To verify, need very light matter (p small) so λ is large enough
• Need small periodic structure on scale of λ to see if wave is there (diffraction)
• Solution:electron diffraction from a crystal

Nλ=2dsinθ

For small θ, θ~λ/d, so λ must be on order of

d in order to measure easily

3.225 © E. Fitzgerald-1999 17

Unification: Wave-particle Duality

Ψ must be able to represent everything from a particle to a wave (the two

extremes)

wave particle
Ψ = Ae i (kx −ωt ) Ψ = ∑ an e i (k n x −ω nt )
n

k and p known exactly n = ∞ to create a delta function in ψ2

generalized

Ψ = ∑ an e i (kn x −ω nt )
n

3.225 © E. Fitzgerald-1999 18

9
 Quantum Mechanics - Wave Equation

Classical Hamiltonian
p2
+ V ( x, y , z ) = E
2m
QM Operators
 h   h  ∂
p =  ∆ E = − 
 i   i  ∂t

h2 2 − h ∂ψ
− ∆ ψ + V ( x , y , z )ψ = −
2m i ∂t

1. ψ and ∆ ψ must be finite, continuous and single valued.

2. ψψ * real with ψψ *dV = probability of finding particle in volume dV.
3. Average or expectation value of variable
α = ∫ ψ *α op ψ dV
v

3.225 © H.L. Tuller-2001 19

Time and Spatial Dependence of ψ

Assume ψ (x,y,z,t) separable into ψ(x,y,z) and φ(t)

Applying separation of variables:

− h 2 ∇ 2ψ h 1 ∂φ
+V = − =ε = constant
2m ψ i φ ∂t
Time-Dependent Equation:
φ (t ) = Ae − i (ε h )t = Ae − iωt
⇒ ε = hω
Time-Independent Equation:
2m
∇ψ + 2
(ε − V )ψ = 0
h2
Solutions: ψn -eigenfunctions; εn -eigenvalues

3.225 © H.L. Tuller-2001 20

10

 Free Particle

• One dimensional V =O
d ψ2
2mε
= − ψ = − k 2ψ
dx 2 h2
ψ = Ae ikx

h 2k 2 p2
ε = =
2m 2m

p = hk Crystal Momentum

ψ ( x, t ) = Ae i ( kx −ωt )
• Momentum
h ∂ψ
p x = ∫ψ *
dx = h k
i ∂x

3.225 © H.L. Tuller-2001 21

Particle in Box
2mε ∞ ∞
ψ = Ae ikx + Be − ikx ; k 2 =
h2
V
Boundary Conditions:
x=0 x=d
• ψ (0) = ψ ( d ) = 0

• ψ (0) = A + B = 0 ⇒ A = −B

• ψ ( d ) = A ( e ikd − e − ikd ) = 0 ⇒ 2 ASinkd = 0

nπ
k = n = 1, 2 ,3 ...
d

2  nπx 
ψ = sin   n = 1, 2 , 3 ...
d  d 

3.225 © H.L. Tuller-2001 22

11

 Particle in Box

ψ n ( x , y , z ) = A sin k1 x ⋅ sin k 2 y ⋅ sin k 3 z

n iπ
k 2 = k12 + k 22 + k 32 ki = ; n i = 1, 2 , 3 ...
d
h2 h 2k 2
εn = ( n1
2
+ n 2
2
+ n 2
3
) =
8md 2 2m

n = Quantum numbers

• Ground state E ; n1 = n 2 = n 3 = 1 not zero!

• Degeneracy

First excited state 112, 211, 121

3.225 © H.L. Tuller-2001 23

Consequence of Electrons as Waves on Free Electron Model

Traveling wave picture Standing wave picture

0
0 L
L Ψ ( x) = Ψ ( x + L)
e ikx = e ik ( x + L )
e ikx = 1
2πn
k=
L

Just having a boundary condition means that k and E are quasi-continuous,

i.e. for large L, they appear continuous but are discrete

3.225 © E. Fitzgerald-1999 24

12

 Representation of E,k for 1-D Material

h 2k 2 p 2
states E= =
electrons 2m 2m

All e- in box accounted for

EF
dE h 2 k
=
m=+1/2,-1/2 dk m
En+1
En h 2k
∆E = ∆k
En-1 Quasi-continuous m
∆k=2π/L

kF kF k
Total number of electrons=N=2*2kF*L/2π

3.225 © E. Fitzgerald-1999 25

13
 Representation of E,k for 1-D Material

h2k 2 2mE
E= ;k =
2m h
2k F L dE h 2 k
N= =
π dk m
dN dk 1 2 m 2m − 12
g (E) = = = E
dk dE L π h k
2
πh

g(E)=density of states=number of electron states per energy per length

N 2k F 2 2mEF nπ
n= = = or k F =
L π hπ 2

• n, the electron density, the number of electrons per unit

length is determined by the crystal structure and valence
• n determines the energy and velocity of the highest
occupied electron state at T=0

3.225 © E. Fitzgerald-1999 1

Representation of E,k for 2-D Material

h 2 (k x2 + k y2 )
E(kx,ky)
E=
2m

ky

kx

3.225 © E. Fitzgerald-1999 2

1
 Representation of E,k for 3-D Material

kz
ky

Ε(kx,ky,kz)
h 2 (k x2 + k y2 + k z2 )
kF E=
2m

kx
2π/L
m 2mE
g (E) =
π2 h3
Fermi Surface or Fermi Sphere
k F = (3π 2 n )3
1

hk F h 2 k F2 EF
vF = EF = TF =
m 2m kB

3.225 © E. Fitzgerald-1999 3

So how have material properties changed?

• The Fermi velocity is much higher than

kT even at T=0! Pauli Exclusion raises
the energy of the electrons since only 2
e- allowed in each level
• Only electrons near Fermi surface can
interact, i.e. absorb energy and
contribute to properties

TF~104K (Troom~102K),
EF~100Eclass, vF2~100vclass2

3.225 © E. Fitzgerald-1999 4

Effect of Temperature (T>0): Coupled electronic-thermal properties in conductors

• Electrons at the Fermi surface are able to increase energy: responsible for
properties
• Fermi-Dirac distribution
• NOT Bolltzmann distribution, in which any number of particles can occupy
each energy state/level
Originates from:

EF
...N possible configurations

T=0 T>0 If E-EF/kbT is

large (i.e. far from − ( E − EF )
1
f = ( E − EF )
EF) than
f =e k bT

e k bT
+1

3.225 © E. Fitzgerald-1999 5

Fermi-Dirac Distribution: the Fermi Surface when T>0

f(E)
fBoltz kbT kbT

1
T=0 Boltzmann-like tail, for
T>0 the larger E-EF values
0.5

µ~EF E
All these e- not
perturbed by T

Heat capacity of metal (which is ~ heat capacity of free e- in a metal):

 ∂U 
U ~ ∆E ⋅ ∆N ~ kbT ⋅ [g ( E F ) ⋅ kbT ] ~ g (E F ) ⋅ (kbT )
2
cv =   U=total energy of
 ∂T  v electrons in system
 ∂U 
cv =   = 2 ⋅ g ( E F ) ⋅ kb T
2
Right dependence, very close to exact derivation
 ∂T  v

3.225 © E. Fitzgerald-1999 6

3
 Electrons in a Periodic Potential

• Rigorous path: HΨ=EΨ

• We already know effect: DeBroglie and electron diffraction

• Unit cells in crystal lattice are 10-8 cm in size

• Electron waves in solid are λ=h/p~10-8 cm in size

• Certain wavelengths of valence electrons will diffract!

3.225 © E. Fitzgerald-1999 7

Diffraction Picture of the Origin of Band Gaps

• Start with 1-D crystal again

λ~a Take lowest order, n=1, and

consider an incident valence
1-D
a electron moving to the right
π
π i x
ki = ;ψ i = e a
d=a, a
nλ = 2d sin θ sinθ=1 π
π
−i x
Reflected wave to left: k o = − ;ψ o = e a
a
nλ = 2a 2π
∆k = k i − k o =
2π a
k=
λ Total wave for electrons with diffracted wavelengths:
πn ψ = ψ i ±ψ o
k= π
a ψ s = ψ i + ψ o = 2 cos
a
x

π
ψ a = ψ i −ψ o = i 2 sin x
a

3.225 © E. Fitzgerald-1999 8

 Diffraction Picture of the Origin of Band Gaps

Probability Density=probability/volume of finding electron=|ψ|2

2 π
ψ a = 4 sin 2 x
a
2 π
ψs = 4 cos 2 x a
a

a
•Only two solutions for a diffracted wave
•Electron density on atoms
•Electron density off atoms
•No other solutions possible at this wavelength: no free traveling wave

3.225 © E. Fitzgerald-1999 9

Nearly-Free Electron Model

• Assume electrons with wave vectors (k’s) far from diffraction

condition are still free and look like traveling waves and see
ion potential, U, as a weak background potential

• Electrons near diffraction condition have only two possible

solutions

– electron densities between ions, E=Efree-U

– electron densities on ions, E= Efree+U
• Exact solution using HΨ=EΨ shows that E near diffraction
conditions is also parabolic in k, E~k2

3.225 © E. Fitzgerald-1999 10

 Nearly-Free Electron Model (still 1-D crystal)

states
Away from k=nπ/a,
h 2k 2 p 2
E= = free electron curve dE h 2 k
2m 2 m E =
dk m
h 2k
Near k=nπ/a, ∆E = ∆k
band gaps form, strong m
interaction of e- with
U on ions

Diffraction,
Eg=2U
Quasi-continuous k=nπ/a
∆k=2π/L

-π/a 0 π/a k
∆k=2π/a=G=reciprocal lattice vector
3.225 © E. Fitzgerald-1999 11

Electron Wave Functions in Periodic Lattice

• Often called ‘Bloch Electrons’ or ‘Bloch Wavefunctions’

Away from Bragg condition, ~free electron

E
− h2 2 − h2 2 h 2k 2
H= ∇ +Uo ≈ ∇ ; ψ ≈ eikx ; E =
2m 2m 2m

Near Bragg condition, ~standing wave electron

− h2 2
H= ∇ + U o ≈ U o (x ); ψ ≈ cos Gx or sin Gx = u ( x ); E = U o (x )
2m

Since both are solutions to the S.E., general wave is

Ψ = ψ freeψ lattice = e ikx u ( x )

0 π/a k termed Bloch functions

3.225 © E. Fitzgerald-1999 12

6
 Block Theorem

• If the potential on the lattice is U(r) (and therefore

U(r+R)=U(r)), then the wave solutions to the S.E. are a
plane wave with a periodic part u(r) that has the periodicity
of the lattice
Ψ (r ) = e ik ⋅r u (r )
u (r ) = u (r + R )
Note the probability density spatial info is in u(r):
Ψ *Ψ = Ψo u * (r ) ⋅ u (r )
2

An equivalent way of writing the Bloch theorem in terms of Ψ:

Ψ (r )
Ψ (r + R ) = e ik (r + R )u (r + R ) = e ik (r + R )
e ik ⋅r
Ψ (r + R ) = e ik ⋅R Ψ (r )

3.225 © E. Fitzgerald-1999 13

Reduced-Zone Scheme

• Only show k=+-π/a since all solutions represented there

−π/a π/a

3.225 © E. Fitzgerald-1999 14

7
 Real Band Structures

• GaAs: Very close to what we have derived in the nearly free electron model
• Conduction band minimum at k=0: Direct Band Gap

3.225 © E. Fitzgerald-1999 15

Review of H atom
ψ = R(r )Θ(θ )Φ (φ )
Hψ = Eψ
Do separation of variables; each variable gives a separation constant
After solving, the energy E is a function of n
φ separation yields ml
θ gives l − µZ 2 e 4 − 13.6eV
E= =
r gives n (4πε o ) 2h n
2 2 2
n2
ml and l in Φ and Θ give Ψ the shape
(i.e. orbital shape)
The relationship between the separation constants (and therefore the quantum numbers are:)

n=1,2,3,… 0
l =0,1,2,…,n-1
ml=- l, - l+1,…,0,…, l-1, U(r)
(ms=+ or - 1/2)
-13.6eV

3.225 © E. Fitzgerald-1999 16

8
 Relationship between Quantum Numbers

s s p s p d
Origin of the periodic table

3.225 © E. Fitzgerald-1999 17

Bonding and Hybridization

• Energy level spacing decreases as atoms are added
• Energy is lowered as bonding distance decreases
• All levels have E vs. R curves: as bonding distance decreases, ion core
repulsion eventually increases E

E Debye-Huckel

R
NFE picture,
semiconductors hybridization

3.225 © E. Fitzgerald-1999 18

9
 Properties of non-free electrons

• Electrons near the diffraction condition are not

approximated as free
• Their properties can still be viewed as free e- if an
‘effective mass’ m* is used
h2k 2
E=
h 2k 2 2mec*
E=
2m h2
mec* =
∂2E
∂k 2

h2k 2
E=
2mev* Note: These
h2 electrons have
m = 2
*
ev
∂ E negative mass!
∂k 2

−π/a π/a

3.225 © E. Fitzgerald-1999 1

Band Gap Energy Trends

IV / III-V / II-VI*

II B III IV V VI MP (°K) Eg (eV) ao A

B C N O 6 / 10 3.56 / 3.16
Al Si P S 1685 / 1770 1.1 / 3 5.42 / 5.46
Zn Ga Ge As Se 1231 / 1510 / ? 0.72 / 1.35/ ? 5.66 / 5.65 / ?
Cd In Sn Sb Te
508 / 798 / ? 0.08 /0.18 / 1.45 6.45 / 6.09 / ?
∗ Fill in as many of the question marks as you can.

Note Trends: 1. As descend column, MP decreases as does Eg while ao increases.

2. As move from IV to III-V to II-VI compounds become more ionic,

MP and Eg increase while ao tends to decrease

3.225 © H.L. Tuller-2001 2

1
 Trends in III-V and II-VI Compounds

Larger atoms, weaker bonds, smaller U, smaller Eg, higher µ, more costly!

Band
Gap
(eV)
eV)

SiGe
Alloys

Lattice Constant (A)

3.225 © E. Fitzgerald-1999 3

Energy Gap and Mobility Trends

Material Eg(eV)°K µn(cm2/V·s)

GaN 3.39 150

AlAs 2.3 180

GaP 2.4 2,100

GaAs 1.53 16,000

InP 1.41 44,000

InAs 0.43 120,000

InSb 0.23 1,000,000

eτ 1 1 ∂2E
Remember that: µ= and =
m* m * h 2 ∂k 2

3.225 © H.L. Tuller-2001 4

 Metals and Insulators

• EF in mid-band area: free e-, metallic

• EF near band edge

– EF in or near kT of band edge: semimetal
– EF in gap: semiconductor

• EF in very large gap, insulator

3.225 © E. Fitzgerald-1999 5

Semiconductors

• Intermediate magnitude band gap enables

free carrier generation by three mechanisms
– photon absorption
– thermal
– impurity (i.e. doping)
• Carriers that make it to the next band are
free carrier- like with mass, m*

3.225 © E. Fitzgerald-1999 6

 Semiconductors: Photon Absorption

• When Elight=hν>Eg, an electron can be promoted

from the valence band to the conduction band
E

Ec near band gap

E=hν

k
Creates a ‘hole’ in the valence band
Ev near band gap

3.225 © E. Fitzgerald-1999 7

Holes and Electrons

• Instead of tracking electrons in valence band, more convenient to track missing

electrons, or ‘holes’
• Also removes problem with negative electron mass: since hole energy increases as holes
‘sink’, the mass of the hole is positive as long as it has a positive charge

Decreasing electron energy

Decreasing hole energy

Decreasing electron energy

3.225 © E. Fitzgerald-1999 8

4
 Conductivity of Semiconductors

• Need to include both electrons and holes in the conductivity expression

ne 2τ e pe 2τ h
σ = neµ e + peµ h = +
me* mh*

p is analogous to n for holes, and so are τ and m*

Note that in both photon stimulated promotion as well as thermal

promotion, an equal number of holes and electrons are produced, i.e. n=p

3.225 © E. Fitzgerald-1999 9

Thermal Promotion of Carriers

• We have already developed how electrons are promoted in energy with T: Fermi-Dirac distribution
• Just need to fold this into picture with a band-gap
gc(E)~E1/2 in 3-D
E

Eg
EF

gv(E) Despite gap, at non-zero

temperatures, there is some
possibility of carriers getting
into the conduction band (and
creating holes in the valence
band)
1

g(E)
f(E)

3.225 © E. Fitzgerald-1999 10

5
 Density of Thermally Promoted of Carriers
∞
Number of electrons per
volume in conduction
n= ∫ f ( E ) g ( E )dE
Ec
band
Density of electron states per volume per dE

Fraction of states occupied at a particular temperature

( E − EF )
1 −
f (E) = (E − EF ) ≈e k bT
when ( E − EF ) >> kbT
e k bT
+1
3 3 1
F ∞E −E
1  2me*  2 kbT
1  2me* 
 (E − E g )2  2  e ∫ (E − E g ) e kbT dE
2 1 2
g c (E) =  n= 2 
2π 2  h 2  2π  h  Eg

3
∞ 1 E − Eg
π  m* k T  2 F
Since ∫ x e dx = 2 −x
, then n = 2 e b2  e kbT e kbT
0
2  2πh 

NC
EF − Eg

n = NCe k bT

3.225 © E. Fitzgerald-1999 11

Density of Thermally Promoted of Carriers

• A similar derivation can be done for holes, except the density of states
for holes is used
• Even though we know that n=p, we will derive a separate expression
anyway since it will be useful in deriving other expressions

3
1  2mh* 2 1 0
 2  (− E ) 2
g v (E) =
2π 2  h



p=
−∞
∫f h ( E ) g v ( E )dE , where f h = 1 − f ( E )

3
−E
 m* k T  2 F
p = 2 h b2  e kbT
 2πh 

− EF

p = N v e k bT

3.225 © E. Fitzgerald-1999 12

 Thermal Promotion

• Because electron-hole pairs are generated, the Fermi level is

approximately in the middle of the band gap
• The law of mass action describes the electron and hole
populations, since the total number of electron states is fixed in
the system
Eg3  m* 
n = p gives E F = + kbT ln h* 
2 4  me 

Since me* and mh* are close and in the ln term, the
Fermi level sits about in the center of the band gap

3 − Eg
 k T 2
( )
3
p or n = ni = 2 b 2  me*mv* 4 e 2 kbT
 2πh 

3.225 © E. Fitzgerald-1999 13

Law of Mass Action for Carrier Promotion

3 − Eg − Eg

n = np = 4 b 2  (me*mh* )2 e kbT
2  kT  3

i ; ni2 = N C NV e kbT
 2πh 
• Note that re-arranging the right equation leads to an expression similar to a chemical
reaction, where Eg is the barrier.
• NCNV is the density of the reactants, and n and p are the products.

N C NV → e′ + h •
Eg

− Eg 2
np n
=ekT = ib

N C NV N C NV

• Thus, a method of changing the electron or hole population without increasing the population
of the other carrier will lead to a dominant carrier type in the material.
• Photon absorption and thermal excitation produce only pairs of carriers: intrinsic
semiconductor.
• Increasing one carrier concentration without the other can only be achieved with impurities,
also called doping: extrinsic semiconductors.

3.225 © E. Fitzgerald-1999 14

 Intrinsic Semiconductors

• Conductivity at any temperature is determined mostly by the size of the band gap
• All intrinsic semiconductors are insulating at very low temperatures

ne 2τ e pe 2τ h
Recall: σ = neµ e + peµ h = +
me* mh*
− Eg
This can be a
σ int = ni e(µ e + µ h ) ∝ e 2 k bT
measurement
for Eg

For Si, Eg=1.1eV, and let µe and µh be approximately equal at 1000cm2/V-sec (very good Si!).

σ~1010cm-3*1.602x10-19*1000cm2/V-sec=1.6x10-6 S/m, or a resistivity ρ of about 106 ohm-m max.

• One important note: No matter how pure Si is, the material will always be a
poor insulator at room T.
• As more analog wireless applications are brought on Si, this is a major issue
for system-on-chip applications.

3.225 © E. Fitzgerald-1999 15

Extrinsic Semiconductors
• Adding ‘correct’ impurities can lead to controlled domination of one carrier type
– n-type is dominated by electrons
– p-type if dominated by holes
• Adding other impurities can degrade electrical properties
Impurities with close electronic Impurities with very different
structure to host electronic structure to host
isoelectronic hydrogenic deep level

x
x x
+ - x
x x
Ge x P Au x
x
x x x

Si Si

Ec Ec Ec
ED
EDEEP
Ev Ev Ev

3.225 © E. Fitzgerald-1999 16

 Hydrogenic Model

• For hydrogenic donors or acceptors, we can think of the electron or hole, respectively, as
an orbiting electron around a net fixed charge
• We can estimate the energy to free the carrier into the conduction band or valence band
by using a modified expression for the energy of an electron in the H atom
me 4 13.6
En = =− 2 (in eV)
8ε o2 h 2 n 2 n
e2
me 4 m *e 4 1 13.6 m* 1
2
=e
En = 2 2 2 ε
r
→ 2 2 2 2 = − 2
8ε o h n 8ε o h n ε r n m ε2
• Thus, for the ground state n=1, we can see already that since ε is on the order of 10, the
binding energy of the carrier to the center is <0.1eV
• Expect that many carriers are then thermalize at room T
• Experiment:
• B acceptor in Si: .046 eV
• P donor in Si: 0.044 eV
• As donor in Si: 0.049

3.225 © E. Fitzgerald-1999 17

The Power of Doping

• Can make the material n-type or p-type: Hydrogenic impurities are nearly fully
ionized at room temperature
– ni2 for Si: ~1020cm-3
– Add 1018cm-3 donors to Si: n~Nd
– n~1018cm-3, p~102 (ni2/Nd)
• Can change conductivity drastically
– 1 part in 107 impurity in a crystal (~1022cm-3 atom density)
– 1022*1/107=1015 dopant atoms per cm-3
– n~1015, p~1020/1015~105
σ/σi~(p+n)/2ni~n/2ni~105!

Impurities at the ppm level drastically change the conductivity

(5-6 orders of magnitude)

3.225 © E. Fitzgerald-1999 18

 Expected Temperature Behavior of Doped Material (Example:n-type)

• 3 temperature regimes

Eg/2kb
ln(n)

Eb/kb

Intrinsic Extrinsic
Freeze-out

1/T

3.225 © E. Fitzgerald-1999 19

Contrasting Semiconductor and Metal Conductivity

ne 2τ
σ=
m

• Semiconductors
– changes in n(T) can dominate over τ
– as T increases, conductivity increases
• Metals
– n fixed
– as T increases, τ decreases, and conductivity decreases

3.225 © E. Fitzgerald-1999 20

10

 General Interpretation of τ

• Metals and majority carriers in semiconductors

– τ is the scattering length
– Phonons (lattice vibrations), impurities, dislocations,
and grain boundaries can decrease τ
1 1 1 1 1
= + + + + ...
τ τ phonon τ impur τ disl τ gb
li 1
τi = = where σ is the cross-section of the scatterer, N is the
vth vthσ i N i number of scatterers per volume, and l is the average
liσ i N i = 1 distance before collisions

The mechanism that will tend to dominate the scattering will be the mechanism with the
shortest l (most numerous), unless there is a large difference in the cross-sections

Example: Si transistor, τphonon dominates even though τimpur gets worse with scaling.

3.225 © E. Fitzgerald-1999 21

Estimate of T dependence of conductivity

• τ~l for metals

• τ~l/vth for semiconductors
• First need to estimate l=1/Nσ

1
l ph =
N ionσ ion
σ ion ∝ π x 2
x=0
+∞
∫ Ψ x Ψdx
* 2
Use Ψ for harmonic oscillator, get:
x2 = −∞
+∞
∫ Ψ Ψdx hω
*
−∞ k x2 = E = hω
e kT
−1

Average energy of harmonic oscillator

3.225 © E. Fitzgerald-1999 22

11

 Estimate of T dependence of conductivity

Therefore, <x2> is proportional to T if T

hω large compared to θ:
k x 2
= E = hω
θ
e kT − 1 θ
eT ≈ 1 +
hω = kθ T
kθ
E = θ x2 ∝T
eT −1 1 1 1
l∝ ∝ 2 ∝
σ x T
l 1 1
For a metal: σ cond ∝ µ ∝ τ ≈ = =
vF vF N ionπ x 2
vF N ionπT
For a semiconductor, remember that the carriers at the band edges are classical-like:
1
3 3
l l T −
eτ −
τ= = ∝ 1 ∝T 2 µ= ∝ T 2
vth 3kT
T2 m*
m*
3.225 © E. Fitzgerald-1999 23

Example: Electron Mobility in Ge

µ~T-3/2 if phonon dominated

(T-1/2 from vth, T-1 from x-section σ

At higher doping, the

ionized donors are the
dominate scattering
mechanism

3.225 © E. Fitzgerald-1999 24

12

 Minority Carrier Lifetimes, τ

• Minority carriers (e.g. electrons (minority carrier) in p-type material with
majority holes
τ is the time to recombination: recombination time
– means for system to return to equilibrium after perturbation, e.g. by
illumination
τ, l
Ec
Generation Recombination
E Ev
x

• Deep levels in semiconductors act as carrier traps and/or enhanced

recombination sites
Ec
Edeep Recombination through deep level
Ev

3.225 © E. Fitzgerald-1999 1

Generation and Recombination

• Generation
– photon-induced or thermally induced, G=#carriers/vol.-sec
– e.g. g = P/hν
– Go is the equilibrium generation rate
• Recombination
– R=# carriers/vol.-sec
– Ro is the equilibrium recombination rate, balanced by Go

• Net change in carrier density:

– dn/dt = G - R = G - (n - n0) / τ = G - ∆ n / τ

– Under steady state illumination: dn/dt = 0 np(t)

– np(0) = np0 + G τ
np(0)
Αfter turning off illumination: gτ
– np(0) = np0 + G τ e -t/τ np0
τ
t
3.225 © H.L. Tuller, 2001 2

1
 Key Processes: Drift and Diffusion

Electric Field: Drift

I h = epvd A; J h = epµ h E
I e = envd A; J e = enµ e E
Concentration Gradient: Diffusion

J h = −eDh ∇p
J e = eDe∇n

J hTOT = epµ h E − eDh∇p

J eTOT = enµ e E + eDe∇n

3.225 © E. Fitzgerald-1999 3

Electrochemical Potential

η j = µ j + z j qϕ Electrochemical Potential ⇒EF

µ j = µ 0j + kT ln c j Chemical Potential

ϕ= Electrostatic Potential

 − σ j  ∂η j
jj =  
 z q  ∂x
 j 
∂ϕ ∂c
=σ j − z j qD j j
∂x ∂x
∂η j
Note: =0 Under equilibrium conditions
∂x

3.225 © H.L. Tuller, 2001 4

 Continuity Equations

• For a given volume, change in carrier concentration in time is related to J

∂n ∂n ∂n ∂n ∂n
= + − +
∂t ∂t drift ∂t diff ∂t R ∂t G
∂n 1 ∂n ∂n
= ∇ ⋅ J TOT − +
∂t e ∂t R ∂t G
∂p 1 ∂p ∂p
= − ∇ ⋅ J TOT − +
∂t e ∂t R ∂t G

1-D,

∂n ∂E ∂ 2n
= nµ e + De 2 − R + G
∂t ∂x ∂x
∂p ∂E ∂2 p
= − pµ h + Dh 2 − R + G
∂t ∂x ∂x

3.225 © E. Fitzgerald-1999 5

Minority Carrier Diffusion Equations

• In many devices, carrier action outside E-field controls properties--> minority

carrier devices
• Only diffusion in these regions

Assuming low-level injection,

∂n ∂ 2n
= De 2 − R + G ∂n ∂no ∂∆n ∂∆n
= + ≈
∂t ∂x ∂t ∂t ∂t ∂t
∂p ∂2 p
= Dh 2 − R + G therefore
∂t ∂x
∆p
in n - type, R = − ∂∆n ∂ 2 ∆n ∆n
τh = De − + G in p - type material
∂t ∂x 2 τe
∆n
in p - type, R = − ∂∆p ∂ 2 ∆p ∆p
τe = Dh − + G in n - type material
∂t ∂x 2 τh

3.225 © E. Fitzgerald-1999 6

 Use of Minority Carrier Diffusion Equations

• Example: Light shining on a surface of a semiconductor
x
n-type
∆p(x)? 0
hν
∂∆p ∂ 2 ∆p ∆p
= Dh − + G =0 in bulk
G at x=0 (assume infinite ∂t ∂x 2 τh
absorption coefficient to simplify
example) Steady state solution

Now use boundary conditions of the problem:

∂ 2 ∆p ∆p
= @ x = ∞, ∆p = 0
∂x 2 Dhτ h Units of length:
∴A=0 minority carrier
try ∆p = Ae + Be ax − ax
x
diffusion length, Lh
−
Dhτ h
Ae + Be
ax − ax
∆p = Be
a 2 Ae ax + a 2 Be − ax =
Dhτ h @ x = 0, ∆p = Gτ h
∆p
Gτh
1 ∴ B = Gτ h ∂∆p
a= J h = eDh
∂x
Dhτ h −
x

∆p = Gτ h e Lh
x
3.225 © E. Fitzgerald-1999 7

Semiconductor Electronics

• Single crystalline - largely Si

some III - V compounds

• Dominated by many nearly identical, highly engineered junctions

• DRAMS (today) ≈ 109 transistors

• Microprocessors (2002) ≈ 108 transistors

• Total ≈ 1018 yr ≈ 106/person/day

3.225 © H.L. Tuller, 2001 8

 Junction Fabrication Processes

3.225 © H.L. Tuller, 2001 9

CMOS Devices

3.225 © H.L. Tuller, 2001 10

 The p-n Junction (The Diode)

• Note that dopants move the fermi energy from mid-gap towards either the
valence band edge (p-type) or the conduction band edge (n-type).

p-type material in equilibrium n-type material in equilibrium

p~Na n~Nd

n~ni2/Na p~ni2/Nd

N  N 
E F = −kbT ln a  E F = E g + kbT ln d 
 NV   NC 

Ec Ec
EF

EF
Ev Ev

What happens when you join these together?

3.225 © E. Fitzgerald-1999 11

Drift and Diffusion

- - - - + +
+ + +
- - - - +
+ +
Holes diffuse
Electrons diffuse

- - - - + +
- - - - + + + +
+ +
E

An electric field forms due to the fixed nuclei in the lattice from the dopants

Therefore, a steady-state balance is achieved where diffusive

flux of the carriers is balanced by the drift flux

3.225 © E. Fitzgerald-1999 12

 Joining p and n

p n

Ec
EF

Ev
Carriers flow under driving force of diffusion until EF is flat

- - +
- - + +
+
Holes diffuse
Electrons diffuse

3.225 © E. Fitzgerald-1999 13

Space Charge, Electric Field and Potential

- - - - + +
- - - - + + + + Metallurgical junction
+ +
xp xn
W: depletion or space charge width

ρ N d xn = N a x p

ρ ( x) 2ε r ε oVbi Nd
E=∫ dx E xp =
ε e Na (Nd + Na )

2ε r ε oVbi Na
xn =
e Nd (Nd + Na )
V
V = ∫ E ( x)dx Vbi W=
2ε r ε oVbi N a + N d
e Nd Na

3.225 © E. Fitzgerald-1999 14

7
 What is the built-in voltage Vbi?

p np n
eVbi nn
Ec
EF
pp eVbi
pn Ev
eVbi=EFn-EFp
 p  N   p   n2 
E Fp = − k b T ln  = − k b T ln a  E Fn = − kbT ln n  = − kbT ln i 
 NV   NV   NV   NV N d 

k bT  N a N d 
∴Vbi = ln 2

e  ni 
We can also re-write these to show that eVbi is the barrier to minority carrier injection:
− eVbi − eVbi

pn = p p e k bT
n p = nn e k bT

© E. Fitzgerald-1999

Qualitative Effect of Bias

• Applying a potential to the ends of a diode does NOT increase current through
drift
• The applied voltage upsets the steady-state balance between drift and
diffusion, which can unleash the flow of diffusion current
• “Minority carrier device”
np

eVbi nn
Ec +eVa
EF
pp -eVa
eVbi
pn Ev

− e (Vbi −Va ) − e (Vbi −Va )

n p = nn e k bT
pn = p p e k bT

© E. Fitzgerald-1999

1
 Current Flow - Recombination, Generation

© H.L. Tuller, 2001

Qualitative Effect of Bias

• Forward bias (+ to p, - to n) decreases depletion region, increases diffusion
current exponentially
• Reverse bias (- to p, + to n) increases depletion region, and no current flows
ideally
Forward Bias Reverse Bias
np np
eVbi-e|Va| nn
Ec nn eVbi+e|Va|
EF
Ec
pp eVbi-e|Va|
pp EF
Solve minority pn eVbi+e|Va|
carrier diffusion Ev
Ev
equations on each
pn
side and determine Va
J at depletion edge + - I
V=f(I)
Linear,
Rectification,
 D n 2 D n 2  a   qVa 
qV
Ohmic
J = q e i + h i  e kbT − 1 = J o  e kbT − 1 Non-linear, Non-Ohmic
L N
 e a L N 
d 
   V
h   

Di k bT Li = Diτ i V=IR
=
i q
© E. Fitzgerald-1999

2
 Devices

Solar Cell/Detector Reverse Bias/Zero Bias

Jedrift
Ec
EF

Jhdrift Ev

LED/Laser
Jediff
Ec Laser
EF
•population inversion
Ev •reflectors for cavity
Jhdiff

© E. Fitzgerald-1999

Potential Wells - Heterojunction Lasers

Energy bands of a light-emitting diode under forward bias for a double

heterojunction AlGaAs-GaAs-AlGaAs structure.

© H.L. Tuller, 2001

 Transistors

Bipolar (npn) base

Jdiff Jdrift collector
emitter
Ec
EF

Barrier, controlled by VEB

VBC Ev
VEB
emitter

base

collector

© E. Fitzgerald-1999

Field Effect

© H.L. Tuller, 2001

4
 Transistors
gate
FET source
x drain

n p n

x=metal is a MESFET

x=metal/poly Si/oxide is a MOSFET

CMOS

© E. Fitzgerald-1999

Polycrystalline Solar Cells

• Local field enhances minority carrier capture → reduced

minority carrier lifetime
• majority carriers experience potential barrier → increased
resistivity; reduced effective mobility
• boundaries intersecting p-n junction provide shorting paths →
increase Io, decrease Voc.

© H.L. Tuller, 2001

 Effect of Traps (Defects) on Bands

• Trapping (Fermi level in defect) creates depleted regions around defect

•EF position in semiconductor away from

N 
E F = E g + kbT ln d  traps in n-type material
 NC  •EF pulled to mid-gap in defect/trap area

Edonor
Ec
EF
Etrap

Ev

EF pulled to trap level in defect

Depleted regions; internal electric field

© E. Fitzgerald-1999

Other Means to Create Internal Potentials:

Heterojunctions
• Different semiconductor materials have different band gaps and electron
affinity/work functions
• Internal fields from doping p-n must be superimposed on these effects:
Poisson Solver (dE/dx=V=ρ/ε)
Vacuum level

ϕ2 ϕ1

Eg1 EF Eg2

Potential barriers for holes

Substrate

and electrons can be created

Thin films
inside the material

© E. Fitzgerald-1999

6
 Quantum Wells

EC

n=3
hν n=2
n=1

EV
L
If we approximate well as having infinite potential boundaries:
nπ
k= for standing waves in the potential well
L
h 2k 2 h 2n 2 We can modify electronic
E= *
= transitions through quantum wells
2m 8m* L2

© E. Fitzgerald-1999

Artificially Modulated Structures

© H.L. Tuller, 2001

 Photodetectors/Solar Cells

E-h pairs generated by photons with energy

hγ ≥ E g
are separated by the built-in potential gradient at the p-n junction.

The current voltage characteristics are given by

I = I o [exp(qV kT ) −1] − I p
where Ip is the photo-induced “reverse current.”

Junctions/Functions

Junction Function Application

P/n Injection/diffusion/collection
Metal/semiconductor Blocking (reverse bias)
Acceleration/breakdown
Tunneling
Injection/confinement/recombination
Generation/separation
Separation/confinement
M/I/S Inversion/depletion/accumulation
p-n rectifier, switch
p-n-p transistor
Avalanche and tunnel diodes
LED, injection laser
Solar cell, photodiode
High electron mobiity devices
Quantum devices
MOSFET

© H.L. Tuller, 2001

 The Capacitor

+ +V
-- +
- I=0 always in ++ ∇⋅E =
ρ
- capacitor
+ εo
-- + −d
2
ρ ρt Q
t E= ∫
−d εo
dx = =
ε o Aε o
d/2 d/2
ρ 2
−t

d
2
Qd
V= ∫ Edx = Aε
−d o
E 2

Q Qd
=V =
C Aε o
εo A
V C=
d

3.225 © E. Fitzgerald-1999 1

The Capacitor

• The air-gap can store energy!

• If we can move charge temporarily without current flow, can store even more
• Bound charge around ion cores in a material can lead to dielectric properties

•Two kinds of charge can create plate

charge:
•surface charge
•dipole polarization in the volume
•Gauss’ law can not tell the difference
(only depends on charge per unit area)

3.225 © E. Fitzgerald-1999 2

 Material Polarization

+ -
+ - +
+ - + + - --
+- + -
++ - + + - -
- -
-
P ε rε o A
C =
d
E
D = ε o E + P = εE
P is the Polarization
ε = ε rε o D is the Electric flux density or the Dielectric
P displacement
εr = 1+ = 1+ χ χ is the dielectric or electric susceptibility
εoE

All detail of material response is in εr and therefore P

3.225 © E. Fitzgerald-1999 3

Origin of Polarization

• We are interested in the true dipoles creating polarization in materials (not

surface effect)
• As with the free electrons, what is the response of these various dipole
mechanisms to various E-field frequencies?
• When do we have to worry about controlling
– molecular polarization (molecule may have non-uniform electron density)
– ionic polarization (E-field may distort ion positions and temporarily create dipoles)
– electronic polarization (bound electrons around ion cores could distort and lead to
polarization)
• Except for the electronic polarization, we might expect the other mechanisms
to operate at lower frequencies, since the units are much more massive
• What are the applications that use waves in materials for frequencies below the
visible?

3.225 © E. Fitzgerald-1999 4

 Application for Different E-M Frequencies

Methods of detecting Other satellite, 10-50GHz

these frequencies λ=3cm-6mm (‘mm wave’)
Fiber optics
λ=1.3-1.55µm
Cell phones DBS (TV)
λ=14-33cm λ=2.5cm
‘MMIC’, pronounced ‘mimic’
mm wave ICs

In communications, many E-M waves travel in insulating materials:

What is the response of the material (εr) to these waves?

3.225 © E. Fitzgerald-1999 5

Wave Eqn. with Insulating Material and Polarization

r
r ∂B
∇xE = −
∂t
( )
r r r r
r r ∂D nonmag r r ∂ ε o E + P insulating r ∂E
∇xH = J + → ∇xB = J +   → ∇xB = ε
∂t ∂t ∂t
r r r r
( D = ε 0 E + P = εE )

∂2E εr ∂2E
∇ 2 E = µ 0ε 0ε r =
∂t 2 c 2 ∂t 2
E = E0 ei ( k •r −ϖt ) = E0 eik •r e −iϖt = E (r )e − iϖt
ω 2ε r E ( r )
∇ 2 E (r ) = −
c2
c2 2 So polarization slows down the
ω2 = k velocity of the wave in the
εr
material
c c
ω= k optical
→ k
εr n

3.225 © E. Fitzgerald-1999 6

 Compare Optical (index of refraction) and Electrical Measurements of ε

Material Optical, n2 Electrical, ε

diamond 5.66 5.68 Only electronic polarization

NaCl 2.25 5.9 Electronic and ionic polarisation

Electronic, ionic, and

H2O 1.77 80.4 molecular polarisation

Polarization that is active depends on material and frequency

3.225 © E. Fitzgerald-1999 7

Microscopic Frequency Response of Materials

• Bound charge can create dipole through charge displacement.

• Hydrodynamic equation (Newtonian representation) will now have a
restoring force.
• Review of dipole physics:
r
-q d +q
- +
r r
Dipole moment: p = qd
r
p
Applied E-field rotates dipole to align with field:
r r r
Torque τ = pxE
r r
Potential Energy U = − p ⋅ E = p E cosθ
r r

3.225 © E. Fitzgerald-1999 8

 Microscopic Frequency Response of Materials

• For a material with many dipoles:

r r r r r
P = Np = NαE ( p = αE )
(polarization=(#/vol)*dipole polarization)
α=polarizability
r
P Nα
χ= r , so χ =
εo E ε0

r r
p = αE Actually works well only for low density of dipoles, i.e. gases: little screening

For solids where there can be a high density: local field

For a spherical volume inside (theory of local field),
r
Eext r r P
Eloc = E ext +
3ε o
Eloc

3.225 © E. Fitzgerald-1999 9

Microscopic Frequency Response of Materials

• We now need to derive a new relationship between the dielectric constant and
the polarizability
D = ε r ε o Eext = ε o Eext + P
P = ε r ε o Eext − ε o Eext
 2 + εr 
Eloc = Eext  
 3 
Plugging into P=NαEloc:

ε r ε o E ext − ε o E ext = Nα
(ε r + 2 ) E
ext
3
Nα
(ε r − 1)ε o = (ε r + 2 )
3

ε r − 1 Nα α
Clausius-Mosotti Relation: = = Where v is the volume per dipole (1/N)
ε r + 2 3ε o 3νε o
Macro Micro

3.225 © E. Fitzgerald-1999 10

 Different Types of Polarizability

Highest natural frequency • Atomic or electronic,αe Lightest mass

• Displacement or ionic, αi

Lowest natural frequency

• Orientational or dipolar, αo Heaviest mass

α = αe + αi +αo
As with free e-, we want to look at the time dependence of the E-field: E = E o e − iω t
∂ 2 x m ∂x
m = − eE − Kx
∂t 2 τ ∂t
Restoring Force

Response Drag Driving Force

m &x& = − eE − Kx
− iω t
x = xo e
m ( −ω 2 ) x o = − eE o − Kx o
So lighter mass will
eE o eE o
xo = = have a higher critical
 K
m ω 2 − 
(
m ω 2 − ω o2 ) frequency
 m
K
ωo =
m

3.225 © E. Fitzgerald-1999 11

Classical Model for Electronic Polarizability

• Electron shell around atom is attached to nucleus via springs

+ +

r r
E E
K K r
p
Zi electrons,
mass Zim
r

Z i m&r& = − Kr − Z i eEloc , assume r = ro e − iωt

3.225 © E. Fitzgerald-1999 12

 Electronic Polarizability

eEo
ro =
 2 K 
eEo K m ω − 
ro = ; ω oe = mZ i 
(
m ω 2 − ω oe2 ) mZ i 

−ω If no Clausius-Mosotti,
p = qd = − Z i er ; p = po e i t
Nα e NZ i e 2
εr = 1+ = 1+ = n2
po =
Zie2
Eo = α e E o
εo ( )
ε o m ω 2 − ω oe2
(
m ω 2 − ω o2 ) εr
2
Zie
αe =
(
m ω 2 − ω oe2 )
NZ i e 2
1+
ω >> ω oe , α e = 0 ε o m(ω oe2 )

Zie2 1
ω << ω oe , α e =
mω oe2
ωoe ω

3.225 © E. Fitzgerald-1999 13

QM Electronic Polarizability

• At the atomic electron level, QM expected: electron waves

• QM gives same answer qualitatively
• QM exact answer very difficult: many-bodied problem

E1 e2 f10 E − E0
α e (ω ) = ; ω10 = 1
m ω102 − ω 2 h
E0

f10 is the oscillator strength of the transition (ψ1 couples to ψo by E-field)

For an atom with multiple electrons in multiple levels:

e2 f j0 E j − E0
α e (ω ) = ∑ ; ω j0 =
m j10 − ω
j ≠0 2 2
h

3.225 © E. Fitzgerald-1999 14

 Ionic Polarizability

• Problem reduces to one similar to the electronic polarizability

• Critical frequency will be less than electronic since ions are more massive
• The restoring force between ion positions is the interatomic potential
E(R)
Parabolic at bottom near Ro
k ( R − Ro ) 2
E=
2
Nuclei repulsion
∂E
F= = k ( R − Ro )
∂R

Ro +
-
R
Electron bonding in between ions
F = kx ⇒ σ ij = Cijkl ε kl

3.225 © E. Fitzgerald-1999 15

Ionic Polarizability
Eloc
•2 coupled differential eqn’s
- + •1 for + ions
•1 for - ions
w = u+ − u− , w
&& = u&&+ − u&&−
- + 1
M=
1 1
+
p M+ M−
u- u+ && = −2 Kw + eEloc
Mw
Ionic materials always have ionic and
Eloc = Eo e −iωt , w = wo e −iωt
electronic polarization, so:
eEo 2K
wo = , ω oi =
e 2 (
M ω oi2 − ω 2 ) M
α tot = α i + α e = α + + α − +
(
M ω −ω 2
oi
2
) po = ewo = α i Eo
e2
αi =
(
M ω oi2 − ω 2 )
3.225 © E. Fitzgerald-1999 16

8
 Ionic Polarizability

• Usually Clausius-Mosotti necessary due to high density of dipoles

ε r − 1 Nα tot 1  e2 
= = α + + α − +
εr + 2 3ε o 3ε o v  ( 
M ω oi2 − ω 2 )
By convention, things are abbreviated by using εs and ε∞:

ω << ω oi ,
ε s −1
=
1  e2  εr
α + + α − +
ε s + 2 3ε o v  ( ) 
M ω oi2 

ε ∞ −1 n2 −1 1
[α + + α − ]
ω >> ω oi , = =
ε ∞ + 2 n 2 + 2 3ε o v εs
n2=ε∞
ε∞ − ε s ε +2
∴ εr = ε∞ + , ωT2 = ω oi2  ∞ 
ω2  εs + 2 
−
ωT2
1
ωT ω

3.225 © E. Fitzgerald-1999 17

Orientational Polarizability

• No restoring force: analogous to conductivity

H C +q
O θ
O O
H
p=0 -q
- p +
For a group of many molecules at some temperature:
−U pE cosθ

f = e k bT = e k bT
Analogous to conductivity, the
molecules collide after a certain After averaging over the polarization of the
time t, giving: ensemble molecules (valid for low E-fields):

αDC p2
αo = α DC ~
1−iωτ 3kbT

3.225 © E. Fitzgerald-1999 18

 Dielectric Loss

• For convenience, imagine a low density of molecules in the gas phase

• C-M can be ignored for simplicity
• There will be only electronic and orientational polarizability
N α DC
ε r = 1 + χe + χo = n2 +
3ε o (1 − iωτ )
ε’,ε’’
Nα DC
ωτ << 1, , ε r = ε so = n 2 +
3ε o αe+αi
ε so − n 2
εso
∴ ε r = n2 +
1 − iωτ

We can write this in terms of a

real and imaginary dielectric
constant if we choose:
αe
n2
ε r = ε '+ iε ' '
ε so − n 2 ε − n2 -2 0 +2
ε ' = n2 +
1+ω τ 2 2
; ε ' ' = so 2 2 ωτ
1+ ω τ
logωτ
Water molecule: τ=9.5x10-11 sec, ω~1010
microwave oven, transmission of E-M waves

3.225 © E. Fitzgerald-1999 19

Dielectric Constant vs. Frequency

• Completely general ε due to the localized charge in materials

ε molecules

αo ions

αi electrons
n2
αe
1

1/τ ωT ωoe ω
Dispersion-free regions, vg=vp
3.225 © E. Fitzgerald-1999 20

10
 Dispersion

• Dispersion can be defined a couple of ways (same, just different way)

– when the group velocity ceases to be equal to the phase velocity
– when the dielectric constant has a frequency dependence (i.e. when dε/dω not 0)

ω Dispersion-free ω=
c
k
εr
Dispersion vp =
ω
=
c
=
∂ω
= vg
k εr ∂k

ω c ∂ω
vp = = ≠ = vg
k ε r (ω ) ∂k

3.225 © E. Fitzgerald-1999 21

11
 Spontaneous Polarization
p2 C
Remember form of orientational polarization: α or = =
3kT kT
With C ≡ Curie constant

Define a critical temperature Tc by Nα N  C 

=   =1
3ε 0 3ε 0  kTc 
or NC
Tc =
3ε 0 k

Tc Nα or
Noting further =
T 3ε 0
3Tc
Thus
χ=
T − Tc Fig. 1. The Curie-Weiss law illustrated for (Ba,Sr)TiO3
From L.L. Hench and J.K. West, Principles of Electronic
Ceramics, Wiley, 1990, p. 243.

3.225 © H.L. Tuller, 2001 1

Ferroelectrics

• Each unit cell a dipole!

• Large PR (remnant polarization, P(E=0)
• Coercive Field EC, electric field required to bring P back to zero.

Two equivalent-energy atom positions Can flip cell polarization by applying

E large enough reverse E-field to get over
barrier
P
PR Ps

∆E

Ec E
‘normal’ dielectric
Ro R

3.225 © E. Fitzgerald-1999 2

1
 Ferroelectrics

• ‘Confused’ atom structure creates metastable relative positions of

positive and negative ions

3.225 © E. Fitzgerald-1999 3

Ferroelectrics

Applications
• Capacitors
• Non-volatile memories
• Photorefractive materials
3.225 © H.L. Tuller, 2001 4

 Characteristics of Optical Fiber

• Snell’s Law

θ1
n1
Boundary conditions for E-M wave gives
Snell’s Law:
n2
n1 sin θ1 = n2 sin θ 2
Refraction θ2

Internal Reflection: θ1=90°

θ1 n1
n1
n2 θ 2 = θ c = sin −1
θ2 n2

Glass/air, θc=42°

3.225 © E. Fitzgerald-1999 5

Characteristics of Optical Fiber

• Attenuation
– Absorption
• OH- dominant, SiO2 tetrahedral mode
– Scattering
• Raleigh scattering (density fluctuations) αR~const./λ4 (<0.8 µm
not very useful!)
• Dispersion
– material dispersion (see slide i13)
x
– modal dispersion • Light source always has ∆λ
• parts of pulse with different l propagate
at different speeds

Black wave arrives later than red wave

y n1

n2
Solution: grade index
n

3.225 © E. Fitzgerald-1999 6

3
 Characteristics of Optical Fiber

3.225 © E. Fitzgerald-1999 7

Characteristics of Optical Fiber

3.225 © E. Fitzgerald-1999 8

 Colors Produced by Chromium

Above: alexandrite, emerald, and ruby.

Center: carbonate, chloride, oxide.
Below: potassium chromate and ammonium dichromate.

3.225 © H.L. Tuller, 2001 9

Chromium Electronic Structure

Electron distribution in the ground state of a chromium atom (A) and a trivalent chromium ion (B).

3.225 © H.L. Tuller, 2001 10

Octahedral Environment of Transition Metal Ion

Interaction of the d orbitals of a central ion with six ligands in

an octahedral arrangement.

3.225 © H.L. Tuller, 2001 11

Crystal Field Splitting

The splitting of the five 3d orbitals in a tetrahedral and an octahedral ligand field.

Note: When the element is a mid-gap dopant, transitions within this element lead to
absorption and/or emission via luminescence

3.225 © H.L. Tuller, 2001 12

 Optical Transitions in Ruby

Optical absorption spectrum tied to Cr transitions in ruby.

3.225 © H.L. Tuller, 2001 13

Optical Transitions in Emerald

Optical absorption spectrum tied to Cr transitions in emerald.

3.225 © H.L. Tuller, 2001 14

 Designer Wavelengths

Variation of band-gap energy with composition x of In1-xGaxAs.

3.225 © H.L. Tuller, 2001 15

Band-Gap Colors

Mixed crystals of yellow cadmium sulfide CdS and black

cadmium selenide CdSe.

3.225 © H.L. Tuller, 2001 16

 Light Sources

• Photoluminescence
• Cathodoluminescence
• Electroluminescence

3.225 © H.L. Tuller, 2001 17

Challenges for New Millenium

♦ Energy
• Conversion
• Storage
• Conservation

♦ Emissions
• Smoke stack
• Automotive

Needed: advances in sensors,

actuators and energy conversion
devices.

3.225 18

Harsh Environments Ceramic Sensors

Automotive
Emissions

Factory
Emissions
Process Control

Aerospace
Performance

3.225 19

Electroceramics

Ceramics:
• Traditionally admired for their stability
• Mechanical
• Chemical
• Thermal

• Exhibit other key functional properties

• Electrical, Electrochemical, Electromechanical
• Optical
• Magnetic

3.225 20

10

 Electroceramics Versatility

Atmosphere dependent conductivity (I. High Strain (Pb0.98La0.02(Zr0.7Hf0.3)1-xTixO3 AFE­

Kosacki and H.L. Tuller, Sensors & FE System (C. Heremans and H.L. Tuller, J. Euro.
Actuators B 24-25, 370 (1995).) Ceram. Soc., 19, 1139 (1999).)

Semiconducting; Electrochemical; Piezoelectric;

Electro-optic; Magnetic, …...

3.225 21

Feedback Control System

Chemical
Signal
System
Sensor
Chemical
Species
Actuator
Micro-Processor
Electrical Signal
Power
Other Input

3.225 22

11

 Sensors for Exhaust Gas Monitoring

Requirements
• clear dependence on pO2
• short response times < 100 ms
• 700<T<1000°C
• long term stability …

3.225 23

Sensor Materials

Electrical Signal compatible

Chemical
Environmental Stimulus
Gas Sensor with Microprocessor System

Requirements of Gas Sensor Materials

• High sensitivity
• High selectivity
• Reproducibility
• Fast response time
• Compatibility with Si microelectronics
• Long term stability
• Small size
• Low cost

3.225 24

12

3-Way Catalyst Conversion Efficiency

3.225 25

Potentiometric Gas Sensor

Nernst Potential

PO2(Exhaust) PO2(Ref)

E = (kT/4q) ln {PO2/ PO2(Ref)}

3.225 26

13

 Auto Exhaust Sensor

• Requirements

• Sensitivity

• Reproducibility

• Robust

• Low cost

3.225 27

Sensor Trends and Challenges

•Miniaturization (e.g. biological implants)

•Integration - logic, amplification, telemetry

•Portability - low power dissipation

•Rapid response

•Cost

Neural recording/stimulation microprobe. Probes

15µm thick 2-4mm long. (Najafi and Hetke, IEEE
Trans. Biomed. Eng. 37, 474 (1990).)

3.225 28

14

 Measurement of Gas Sensor Performance

• Gas sensing materials:

1. Sputtered ZnO film (150 nm
(Massachusetts Institute of Technology)

2. Sputtered SnO2 film (60 nm)

(Fraunhofer Institute of Physical Measurement Techniques)

• Target gases: Electrical

Measurement
H2, CO, NH3, NO2 , CH4

• Operating temperature: Pt electrode H2

H2
320 - 460 ºC SiO2 layer H2 H2

ZnO film

Si wafer

3.225 © H.L. Tuller-2001 1

Mechanisms in Semiconducting Gas Sensor

• Bulk: Change in stoichiometry

..
OO= 2e’ + VO + 1/2 O2(g)

Induce shallow donors: density related to PO2

..
n2 [VO ] PO2 1/2 = KR(T) ⇒ n = (2 KR(T))1/3 PO2-1/6

modulate

Bulk electronic conduction

3.225 © H.L. Tuller-2001 2

 Resistive Oxygen Sensors Based on SrTiO3

E 1
− A ±
σ∝e pO kT
2
m
semiconducting oxide

pOExhaust
2

U I

Electrode

3.225 © H.L. Tuller-2001 3

Influence of Dopants on Electrical Conductivity of SrTiO3

0.995 λ 1,005
1
T = 800 °C
0
log(σ / (Ωcm)-1 )

do
no
rd
-1 op
ed
ac
-2 ce
pto
rd
op
-3 ed

-4
acceptor donor
Sr2+ Ti4+ O2-3 -5
-20 -16 -12 -8 -4 0
log(pO2 / bar)
Acceptors: Al, Ni, Fe
Donors: Nb, Ta, Sb, Y, La, Ce, Pr, Nd, Pm, Sm, Gd

3.225 © H.L. Tuller-2001 4

Temperature Independence: High Acceptor Concentration in SrTiO3

electrical conductivity / (Ω cm) -1 Sr(Ti0,65Fe0,35)O3

1
m = 0,2
950°C
900°C
Response times
T / °C t90 / ms
0,1 850°C
900 6.5
800°C
800 26
750 83
750°C 700 185

10-20 10-15 10-10 10-5 100

pO2 / bar [1] Menesklou et al, MRS fall
meeting, Vol. 604, p. 305-10 (1999).

3.225 © H.L. Tuller-2001 5

Oxygen Sensor in Thick Film Technology

3.225 © H.L. Tuller-2001 6

Transient Behavior of Porous Sr1-xLaxTiO3 for x=0.005 and x=0.03

T = 850 °C
0,1

0,01 X=0.03
σ / S/cm

X=0.03
1E-3

Sr1-xLaxTiO3 porous ceramic

1E-4
T = 850°C

1E-5
0 5 10 15 20 25 30 35
t/h

3.225 © H.L. Tuller-2001 7

Mechanisms in Semiconducting Gas Sensor

• Interface - Gas adsorption

2e’ + O2(g) = 2O(s)’
Induce space charge barrier

modulate

Grain boundary barrier

1. Surface conduction

2. Grain boundary barrier

3.225 © H.L. Tuller-2001 8

4
 Sensor Configuration

A single 9 mm2 chip sensor array with:

• four sensing elements with interdigitated structure electrodes
• heater
• temperature sensor

3.225 © H.L. Tuller-2001 9

Schematic Cross Section of Mounted Sensor

3.225 © H.L. Tuller-2001 10

 Resistance Response to Gas Environment

M 9710746 20V S1219a

Schematic of Gas Sensor Structure ZnO(Ar:O2=7:3) 1 Datum: 23.02.2001 - 27.02.2001 S1219b

Steuerdatei: allgas_h2.stg S1219c
Meßprotokoll: 273 S1219d
100k

Electrical
Measurement

Pt electrode

resistance / Ohm
H2
H2 H2 H2
SiO2 layer
ZnO film
Si wafer

0 20 40 60 80

• ZnO film (150 nm)

110 110
100 100
90 90
80 80

• Electrode: Pt(200 nm)/Ta(25 nm) film

Pt-100 resistance / Ω
70 70

Gas flow / sccm

60 60
50 50
40 40

• Insulation layer: SiO2 layer (1 µm)

30 30
20 20
10 10
0 0

• Substrate: Si wafer -10

0
MFC2
20
Temp
40
NO2 NH3
60 80
time / h
-10

Feuchte CO NO2kl H2
Temp:360C, H2, CO, NH3 (10, 50 and 100 ppm), NO2 (0.2, 0.4, and 2 ppm)

[ Pfad: \ alpha missy Messungen messplatz_1 ] M. Jägle / 27.02.2001

3.225 © H.L. Tuller-2001 11

MicroElectroMechanical Systems - MEMS

Bulk Micromachining Surface Micromachining

Micromachining - Application of microfabrication tools, e.g. lithography, thin

film deposition, etching (dry, wet), bonding

3.225 © H.L. Tuller-2001 12

6
 Gas Sensors and MEMS

• Miniaturization
• Reduced power consumption
• Improved sensitivity
• Decreased response time
• Reduced cost

• Arrays
• Improved selectivity

• Integration
• Smart sensors

3.225 © H.L. Tuller-2001 13

Microhotplate

3.225 © H.L. Tuller-2001 14

 Microhotplate Sensor Platform

NIST Microhotplate Design

3.225 © H.L. Tuller-2001 15

Microhotplate Characteristics

• Milli-second thermal rise and fall times

programmed thermal cycling
low duty cycle

• Low thermal mass

low power dissipation

• Arrays
enhanced selectivity

3.225 © H.L. Tuller-2001 16

 Harsh Environment MEMS

• High temperatures

• Oxidation resistant

• Chemically inert

• Abrasion resistant

Wide band gap semiconductor/insulator

3.225 © H.L. Tuller-2001 17

Photo Electro-chemical Etching - PEC

Features:
• materials versatility e.g. Si, SiC, Ge, GaAs, GaN,
etc.
• precise dimensional control down to 0.1 mm
through the use of highly selective p-n junction
etch-stops
• fabrication of structures with negligible internal
stresses
• fabrication of structures not constrained by
specific crystallographic orientations

3.225 © H.L. Tuller-2001 18

 Photo Electro-chemical Etching - PEC

• Electro-chemical
etching
-
p-type h+ h+ h+ h+ +
semiconductor

Light source
• Photo electro­
chemical etching electrolyte

- -
n-type
h+semiconductor h+
+ +

3.225 © H.L. Tuller-2001 19

Examples ...

• Arrays of stress free

4.2 µm thick cantilever
beams.

• Photoelectrochemically
micromachined cantilevers
are not constrained to
specific crystal planes or
directions.

• Similar structures
successfully
micromachined from SiC
by Boston MicroSystems
personnel

3.225 © H.L. Tuller-2001 20

10

 Smart Gas Sensor

A Self Activated Microcantilever-based Gas Sensor

1. A device capable of sensing a change in environment and
responding without need for a microprocessor
2. A device has both gas sensing and actuating function by
integration of semiconducting oxide and piezoelectric thin films.

Sensor

Chemical Micro-
Environment Processor

Actuator Microfluidic structure

3.225 © H.L. Tuller-2001 21

Smart Gas Sensor

1. Semiconducting oxide thin films for high gas sensitivity

: Microstructure (Nano-Structure) and Composition
2. Piezoelectric thin films for providing actuating function
3. Thin film electroceramic deposition methods for integrating with
silicon microcantilever beam
: Compatibility with Si micromachining technology
4. Microcantilever structures for the self activated gas sensor
: High performance in chemical environment

3.225 © H.L. Tuller-2001 22

11

 Resonant Gas Sensor

• Resonant Frequency: fR = 1/2l (µo/ρo)1/2

where l = resonator thickness, µo = effective shear modulus and ρo =
density

• Mass change causes shift in resonant frequency : (m0 - ∆ m) / mo

≈ (f + ∆ f) / f

Gas Sensor elements :

(I) Active layer interacts with environment
- stoichiometry change translates into mass change
(II) Resonator transduces mass change into resonance frequency change

∆m Active layer
Electrode

∆f Resonator

Electrode

3.225 © H.L. Tuller-2001 23

Choice of Piezoelectric Materials

• Temperature limitations of piezoelectric materials

Material Max Operating Limitations

o
Temperature ( C)
Quartz 450 High loss

LiNbO3 300 Decomposition

Li2B4O7 500 Phase transformation

GaPO4 933 ? Phase transformation

La2Ga5SiO4 1470 ? Melting point

(Langasite)

3.225 © H.L. Tuller-2001 24

12

 Design Considerations

• Bulk conductivity dependent on temperature and PO2

→ contributes to resonator electrical losses

Modify bulk conductivity - how?

• Stability to oxidation and reduction process

→ limited oxygen non-stoichiometry
→ slow oxygen diffusion kinetics

Defect chemistry and diffusion kinetics study

• fR (T) : Temperature dependence of resonant frequency

→ need to differentiate from mass dependence

Minimize @ intrinsic and device-levels

3.225 © H.L. Tuller-2001 25

Langasite : Bulk Electrical Properties

• Single activation energy in the temperature range 500 -

900 °C
• Extrapolated room temperature conductivity: σ = 4.4×10 -18
S cm-1 T [°C]
900 800 700 600 500
-4
10
Y-cut

-5
10
σ [S cm ]
-1

-1
σ0 = 2.1 S cm
-1
-6
EA = 105 kJ mol
10

-7
10
8 9 10 11 12 13
4
10 /T [1/K]

3.225 © H.L. Tuller-2001 26

13

 Langasite : fR (T)

• Temperature dependence of the resonance frequency (fR)

of a resonator device with difference mass loads.

1,77

1,76

1,75
fA [MHz]

1,74

1,73 Contact 1 (fCo1)

Contact 2 (fCo2)
1,72
Calculation fCo1+ ∆f(∆mCo2)
1,71

0 100 200 300 400 500 600 700 800

T [°C]

3.225 © H.L. Tuller-2001 27

Ongoing Activities

• Resonator (Langasite) -- H.Seh & H. Fritze

– Defect chemistry
– Oxygen diffusion/exchange studies
– Bulk conductivity dependence on T and PO2

• Active Layer (PCO) -- T. Stefanik

– Transport-Defect chemistry correlations

• Gas Sensor --
– Add active layer (PCO) using PLD ⇒ nanocrystalline vs
microcrystalline
– Sensor testing

3.225 © H.L. Tuller-2001 28

14

 Magnetic Materials

• The inductor

Φ B = LI (Q = CV)
1 ∂B ∂Φ B ∂I
∇× E = − (CGS) =L
c ∂t ∂t ∂t
1 ∂
( ) 1 ∂Φ
∫ ∫ ∇ × EdS = − c ∂t ∫ ∫ BdS = − c ∂t B VEMF = −
∂NΦ B
∂t
= −L
∂I
∂t
Φ B ≡ magnetic flux density ∂I ∂V
V =L (recall I = C for the capacitor)
∂t ∂t
∫ ∫ ∇ × EdS =∫ E ⋅ dl (Green's Theorem) ∂I
1 ∂Φ B Power = VI = LI
V = ∫ E ⋅ dl = − (explicit Faraday's Law) ∂t
c ∂t
1 1
Energy = ∫ Power ⋅ dt = ∫ LIdI = LI 2 = NΦ B I
2 2
 1 2
 capacitor CV 
 2 
1
3.225 © E. Fitzgerald-1999 1

The Inductor

4π 1 ∂E
∇× B = J+
c c ∂t
4π 4π
∫ ∫ ∇ × BdS = ∫ B ⋅ dl = c ∫ ∫ J ⋅ dS =
c
I

4π
B= In
c
N = n ⋅ length = nl
Nφ B N ( BA) 4π 2
L= = = n lA
I I c

2
3.225 © E. Fitzgerald-1999 2

1
 Magnetic Permeability and Susceptibility

Insert magnetic material

Magnetic dipoles in material can line-up in magnetic field
B = H + 4πχH = H + 4πM
B magnetic induction
∂M χ magnetic susceptibility
M = χH = χ µ = 1 + 4πχ H magnetic field strength (applied field)
∂H M magnetization
B = 4πM + 1 B = µH

MKS:

B = µ0(H+M) = µ0nI + µ0M

µr = B/ µ0H = 1 + (M/H) = 1 + χm

3
3.225 © E. Fitzgerald-1999 3

Maxwell and Magnetic Materials

• Ampere’s law ∫ H ⋅ dl = I = 0
• For a permanent magnet, there is no real current
flow; if we use B, there is a need for a fictitious
current (magnetization current)
• Magnetic material inserted inside inductor
increases inductance
 4π  Material Type χ
Φ B = BA ~ 4πMA = 4πχHA = 4πχ  In  A
 c 
NΦ B (4π ) 2 Paramagnetic +10-5-10-4
2
L= = n lAχ
I c
Diamagnetic -10-8-10-5
L increased by ~χ due to
magnetic material
Ferromagnetic +105

4
3.225 © E. Fitzgerald-1999 4

 Microscopic Source of Magnetization

• No monopoles
• magnetic dipole comes from moving or spinning electrons
Orbital Angular Momentum
µ µ is the magnetic dipole moment
r r
Energy = E = − µ ⋅ H = − µ H cos θ
A I
e-
L
ΦB
What is µ? For θ=0, E = − µH ≈ −Φ B I since energy ~ LI 2 and for 1 loop L =
I
Φ B = ∫ ∫ H ⋅ dS ~ HA
∴ µH = Φ B I = HAI and ∴ µ = IA
e ω
I =− A = πr 2
c 2π
e
µ = − ωr 2
2c
5
3.225 © E. Fitzgerald-1999 5

Microscopic Source of Magnetization

• Classical mechanics gives orbital angular momentum as:

r r r
L = r × p = mr 2ω
e eh
µL = − LQM = − LZ = − µ B LZ Example for l=1:
2mc 2mc
+µBH
 eh 
 µB =  0
 2mc  E(H=0)
LZ = ml = −l,...,0,...l -µBH

Spin Moment µs

+(1/2)µBg0H
e Q. M . eh
µs = − S = − g0 S z = − g0µ B SZ
mc 2mc E(H=0)
1 -(1/2)µBg0H
S Z = mS = ± g 0 = 2 for electron spin
2

6
3.225 © E. Fitzgerald-1999 6

 Exchange

E~-JS1S2

J negative, E~+S1S2--> Energy if

J positive, E~-S1S2--> Energy if

Fe, Ni, Co ---> J positive!

Other elements J is negative

Rule of Thumb:
r interatomic distance
≡ > 1 .5
2ra 2(atomic radius)

J is a function of distance!
7
3.225 © E. Fitzgerald-1999 7

Ferromagnetism

M (T ) ∝ (TC − T )
β
M β ≈ 0.33 - 0.37 B=H+4πM
Br, Ms
χ (T ) ∝ (TC − T )
−γ
γ ≈ 1.3 - 1.4 Domain rotation

Irreversible boundary displacement

reversible boundary displacement

Hc H
‘normal’ paramagnet

TC T

Easy induction, “softer”

Magentic anisotropy
hardness of loop dependent on crystal direction
comes from spin interacting with bonding
8
3.225 © E. Fitzgerald-1999 8

4
 Domains in Ferromagnetic Materials

N S N S N

S N S N S
Domain wall or boundary
Magnetic domain Flux closure
Magnetic energy
No external field
1 2
8∫
= B dV

9
3.225 © E. Fitzgerald-1999 9