Solids

Eisberg & Resnick Ch 13 & 14

RNave:
http://hyperphysics.phy-astr.gsu.edu/hbase/solcon.html#solcon

Alison Baski:
http://www.courses.vcu.edu/PHYS661/pdf/01SolidState041.ppt

Carl Hepburn, “Britney Spear’s Guide to Semiconductor Physics”.

http://britneyspears.ac/lasers.htm
http://hyperphysics.phy-astr.gsu.edu/hbase/solcon.html#solcon
 OUTLINE
• Review Ionic / Covalent Molecules
• Types of Solids (ER 13.2)
• Band Theory (ER 13.3-.4)
– basic ideas
– description based upon free electrons
– descriptions based upon nearly-free electrons
• ‘Free’ Electron Models (ER 13.5-.7)
• Temperature Dependence of Resistivity (ER 14.1)
 Ionic Bonds

RNave, GSU at http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/bond.html#c4

Ionic Bonds
 Ionic Bonding

RNave, Georgia State Univ at hyperphysics.phy-astr.gsu.edu/hbase/molecule

 Covalent Bonds

RNave, GSU at http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/bond.html#c4

 Covalent Bonding
SYM ASYM ASYM SYM
spatial spin spatial spin

space-symmetric tend to be closer

Covalent Bonding
not really parallel, but spin-symmetric

Stot = 1

Stot = 0

not really anti, but spin-asym

space-symmetric tend to be closer

 TYPES OF SOLIDS (ER 13.2)

CRYSTALINE BINDING

• molecular
• ionic
• covalent
• metallic
 most organics
inert gases
Molecular Solids O2 N2 H2

• orderly collection of molecules held together by v. d. Waals

• gases solidify only at low Temps
• easy to deform & compress
• poor conductors
 NaCl
Ionic Solids NaI
KCl
• individ atoms act like closed-shell, spherical, therefore binding not so directional
• arrangement so that minimize nrg for size of atoms

• tight packed arrangement  poor thermal conductors

• no free electrons  poor electrical conductors
• strong forces  hard & high melting points
• lattice vibrations absorb in far IR
• to excite electrons requires UV, so ~transparent visible
 Ge Si
Covalent Solids diamond

• 3D collection of atoms bound by shared valence

electrons
• difficult to deform because bonds are directional
• high melting points (b/c diff to deform)
• no free electrons  poor electrical conductors
• most solids adsorb photons in visible  opaque
 Fe Ni Co
Metallic Solids config dhalf full

• (weaker version of covalent bonding)

• constructed of atoms which have very weakly
bound outer electron
• large number of vacancies in orbital (not enough
nrg available to form covalent bonds)
• electrons roam around (electron gas )
• excellent conductors of heat & electricity
• absorb IR, Vis, UV  opaque
BAND STRUCTURE
Isolated Atoms
Diatomic Molecule
Four Closely Spaced Atoms
Six Closely Spaced Atoms
as fn(R)

the level of interest

has the same nrg in
each separated atom
 Two atoms Six atoms Solid of N atoms

ref: A.Baski, VCU 01SolidState041.ppt

www.courses.vcu.edu/PHYS661/pdf/01SolidState041.ppt
Four Closely Spaced Atoms
conduction band

valence band
Solid composed of ~NA Na Atoms
as fn(R)

1s22s22p63s1
 Sodium Bands vs Separation

Rohlf Fig 14-4 and Slater Phys Rev 45, 794 (1934)
 Copper Bands vs Separation

Rohlf Fig 14-6 and Kutter Phys Rev 48, 664 (1935)
Differences down a column in the Periodic Table:
same valence IV-A Elements
config

Sandin
The 4A Elements
 Band Spacings
in
Insulators & Conductors
electrons free to roam

electrons confined to small region

RNave: http://hyperphysics.phy-astr.gsu.edu/hbase/solcon.html#solcon
 How to choose F

and

Behavior of the Fermi function at

band gaps
Fermi Distribution for a selected F

1.5

Probability of an energy occuring

(not normalized) 1

T=0
1000
5000

0.5

0
0 1 2 3 4
Energy

1
n( ) 
e (  F ) / kT  1
 How does one choose/know F

If in unfilled band, F is energy of highest energy electrons at T=0.

If in filled band with gap to next band, F is at the middle of gap.

 Fermions
T=0

RNave: http://hyperphysics.phy-astr.gsu.edu/hbase/solcon.html#solcon
Fermions T > 0
Number of Electrons at an Energy 
In QStat, we were doing

Tot KE    n   N    d
0

distrib fn Number of ways

to have a particular
energy

Number of electrons
at energy 
 # states

probability
of this nrg
occurring

# electrons
at a given nrg
Semiconductors
ER13-9, -10
 Semiconductors
~1/40 eV

• Types
– Intrinsic – by thermal excitation or high nrg photon
– Photoconductive – excitation by VIS-red or IR
– Extrinsic – by doping
• n-type
• p-type
~1 eV
•
 Intrinsic Semiconductors

Silicon

Germanium

RNave: http://hyperphysics.phy-astr.gsu.edu/hbase/solcon.html#solcon
 Doped Semiconductors
lattice
p-type dopants n-type dopants
 5A doping in a 4A
lattice

5A in 4A lattice

3A in 4A lattice
5A in 4A lattice 3A in 4A lattice
 ‘Free-Electron’ Models
• Free Electron Model (ER 13-5)
• Nearly-Free Electron Model (ER13-6,-7)
– Version 1 – SP221
– Version 2 – SP324
– Version 3 – SP425
• .
  

*********************************************************

• Free-Electron Model
– Spatial Wavefunctions
– Energy of the Electrons
– Fermi Energy
– Density of States dN/dE E&R 13.5
– Number of States as fn NRG E&R 13.5
• Nearly-Free Electron Model (Periodic Lattice Effects) – v2 E&R 13.6
• Nearly-Free Electron Model (Periodic Lattice Effects) – v3 E&R 13.6
 Free-Electron Model (ER13-5)
 

classical description
p2 2 K 2
  
2m 2m
Quantum Mechanical Viewpoint
In a 3D slab of metal, e’s are free to move
but must remain on the inside
 

2 2
    0   E
2m
Solutions are of the form:
8
    xyz   sin k x x sin k y y sin k z z
L3

nz 
With nrg’s: L

 
h2
8mL2
n 2
x n 2
y  n 2
z 
At T = 0, all states are filled
up to the Fermi nrg

 fermi 
h2
8mL2
n 
2
x  n 2
y  n 2
z  max

A useful way to keep track of the states that are filled is:

nx2  n y2  nz2  n 2 max

 h2
 fermi  n 2 max
8mL2
total number of states up to an energy fermi:

3
N  2 1  volume
of 
  21 4 nmax
8
 sphere  8 3

2/3
h 3N 
2
 fermi   
8m   V 

# states/volume ~ # free e’s / volume

Sample Numerical Values for Copper slab

N
= 8.96 gm/cm3 1/63.6 amu 6e23 = 8.5e22 #/cm3 = 8.5e28 #/m3
V
2/3
h 3N 
2
 fermi    fermi = 7 eV
8m   V 

nmax = 4.3 e 7

so we can easily pretend that there’s a smooth distrib of nxnynz-states

 
Tot KE    n    N    d
Density of States 0

How many combinations of are there

within an energy interval  to  + d ?
2/3
h 3N
2

 fermi   
8m   V 
3/ 2
 V   8mE 
N    2 
 3  h 
1/ 2
 V  3  8mE  8m
dN     2  dE
 3  2 h  h2

8 V
dN
dE

h3
2 m 3
 1/ 2
E 1/ 2
At T ≠ 0 the electrons will be spread out among the allowed states

How many electrons are contained in a particular energy range?

 number of ways to have   probability of 

   
 a particular energy   this energy occuring 

8 V
3
 2m 
3 1/ 2
E 1/ 2 1
( E  f ) / kT
h e 1
this assumes there are no other issues
 Distribution of States:
Simple Free-Electron Model vs Reality
Problems with Free Electron Model
(ER13-6, -7)
 

****************************

1) Bragg reflection
2) .
3) .
Other Problems with the Free Electron Model
• graphite is conductor, diamond is insulator
• variation in colors of x-A elements
• temperature dependance of resistivity
• resistivity can depend on orientation of crystal & current I direction
• frequency dependance of conductivity
• variations in Hall effect parameters
• resistance of wires effected by applied B-fields
• .
• .
• .
Nearly-Free Electron Model
version 1 – SP221

k  /2

2
a /2 /2
k

2
a /2 /2
k
 Nearly-Free Electron Model
version 2 – SP324

This treatment assumes that when

a reflection occurs, it is 100%.
• Bloch Theorem
• Special Phase Conditions, k = +/- m /a
• the Special Phase Condition k = +/- /a
  
~~~~~~~~~~ (x) ~ u e i(kx-t)
amplitude

In reality, lower energy waves are sensitive to the lattice:

(x) ~ u(x) e i(kx-t)

Bloch’s
Amplitude varies with location
Theorem

u(x) = u(x+a) = u(x+2a) = ….

 (x) ~ u(x) e i(kx-t)
u(x+a) = u(x)

(x+a) e -i(kx+ka-t) (x) e -i(kx-t)

(x+a) e ika (x)

Something special happens with the phase when

e ika = 1

ka = +/ m  m = 0 not a surprise

m = 1, 2, 3, …
 
k   ,  2 , ...
a a

What it is ?
 
Consider a set of waves with +/ k-pairs, e.g. k  
a

k = + /a moves  k =  /a moves 

This defines a pair of waves moving right & left

Two trivial ways to superpose these waves are:

+ ~ e ikx + e ikx  ~ e ikx  e ikx

+ ~ 2 cos kx  ~ 2i sin kx
 + ~ 2 cos kx  ~ 2i sin kx

+|2 ~ 4 cos2 kx |2 ~ 4 sin2 kx

Kittel
 Free-electron Nearly Free-electron

Kittel

Discontinuities occur because the lattice is impacting the movement of electrons.

 Effective Mass m*
A method to force the free electron
model to work in the situations where
there are complications
free electron KE functional form
2 k 2
 
2 m*

ER Ch 13 p461 starting w/ eqn (13-19b)

 Effective Mass m*
-- describing the balance between applied ext-E and lattice site reflections

1 1  2

m*  2 k 2

m* a =  Fext

q Eext
 2) greater curvature, 1/m* > 1/m > 0,  m* < m 
net effect of ext-E and lattice interaction
provides additional acceleration of electrons

m = m*

At inflection pt
greater |curvature| but negative,
net effect of ext-E and lattice interaction
de-accelerates electrons

No distinction between m & m*,

1) m = m*, “free electron”, lattice structure does
not apply additional restrictions on motion.
 Another way to look at the discontinuities

2 k 2 apply perturbation from lattice

2 k 2
  
2m 2 m*
Shift up implies effective mass has decreased, m* < m,
allowing electrons to increase their speed and join
faster electrons in the band.
The enhanced e-lattice interaction speeds up the electron.

Shift down implies effective mass has increased, m* > m,

prohibiting electrons from increasing their speed and making
them become similar to other electrons in the band.
The enhanced e-lattice interaction slows down the electron
From earlier: Even when above barrier,
reflection and transmission coefficients can
increase and decrease depending upon the energy.
 change in motion
due to applied field
enhanced by change in reflection coefficients

change in motion
due to reflections
is more significant
than change in motion
due to applied field
Nearly-Free Electron Model
version 3
à la Ashcroft & Mermin, Solid State Physics

This treatment recognizes

that the reflections of electron
waves off lattice sites can
be more complicated.
A reminder:
Waves from the left behave like:
 from  t e iKx
 from  e iKx  r e  iKx the
the left
left

2 K 2
 
2m
Waves from the right behave like:
 from  t e  iKx  from  e  iKx  r eiKx
the
right the
right

2 K 2
 
2m
 sum  A left  B right

unknown weights
Bloch’s Theorem defines periodicity of the wavefunctions:

sum  x  a   e ika
sum  x 

  x  a
sum  e ika
  x
sum
Related to
Lattice spacing
 Applying the matching conditions at x  a/2

sum  x  a   e ika sum  x    x  a

sum   x
 e ika sum

A + B A + B A + B
A + B

left right left right

left right right
left

And eliminating the unknown constants A & B leaves:

t 2  r 2 iKa 1 iKa
cos ka  e  e
2t 2t 2 K 2
 
2m
For convenience (or tradition) set:

t  t e i 2
1 t  r
2
r   i r e i

cos Ka   
 cos ka
t
 cos Ka   
 cos ka
t
Related to
Energy Related to
possible
2 K 2 Lattice spacings
 
2m

allowed solution regions

allowed solution regions
Superconductivity
ER 14-1, 13-4
Temperature Dependence of Resistivity

R Nave: http://hyperphysics.phy-astr.gsu.edu/hbase/solids/supcon.html#c1

Joe Eck: superconductors.org

Temperature Dependence of
Resistivity

L
R  
A
• Conductors
– Resistivity  increases with increasing Temp
 Temp   but same # conduction e-’s  

• Semiconductors & Insulators

– Resistivity  decreases with increasing Temp
 Temp   but more conduction e-’s  
First observed Kamerlingh Onnes 1911
Note: The best conductors & magnetic materials tend not to be superconductors (so far)

Superconductors.org Only in nanotubes

 Superconductor Classifications
• Type I
– tend to be pure elements or simple alloys
–  = 0 at T < Tcrit
– Internal B = 0 (Meissner Effect)
– At jinternal > jcrit, no superconductivity
– At Bext > Bcrit, no superconductivity
– Well explained by BCS theory

• Type II
– tend to be ceramic compounds
– Can carry higher current densities ~ 1010 A/m2
– Mechanically harder compounds
– Higher Bcrit critical fields
– Above Bext > Bcrit-1, some superconductivity
Superconductor Classifications
 Type I

Bardeen, Cooper, Schrieffer 1957, 1972

“Cooper Pairs”

e e

Symmetry energy ~ 0.01 eV

Q: Stot=0 or 1? L? J?
Popular Bad Visualizations:

correlation lengths

Sn 230 nm
Pairs are related by momentum ±p, Al 1600
NOT position. Pb 83
Nb 38

Best conductors  best ‘free-electrons’  no e – lattice interaction

 not superconducting
More realistic 1-D billiard ball picture:

Cooper Pairs are ±k sets

Furthermore:
“Pairs should not be thought of as independent particles” -- Ashcroft & Mermin Ch 34
• Experimental Support of BCS Theory
– Isotope Effects
– Measured Band Gaps corresponding to Tcrit
predictions
– Energy Gap decreases as Temp  Tcrit
– Heat Capacity Behavior
 Semiconductor
or
Normal Conductor Superconductor
Another fact about Type I:

-- Interrelationship of Bcrit and Tcrit

 Type II
Yr Composition Tc
May InSnBa4Tm4Cu6O18+ 150
2006

2004 Hg0.8Tl0.2Ba2Ca2Cu3O8.33 138

1986 (La1.85Ba.15)CuO4 30

YBa2Cu3O7 93
mixed normal/super

Q: does BCS apply ?

actual ~ 8 m

Sandin
 Type II – mixed phases
fluxon

Q: does BCS apply ?

Y Ba2 Cu3 O7 crystalline

may control the electronic config of the conducting layer

La2-x Bax Cu O2 solid solution

Another fact about Type II:

-- Interrelationship of Bcrit and Tcrit

 Applications
OR
Other Features of Superconductors

http://superconductors.org/Uses.htm
Meissner Effect
 Magnetic Levitation – Meissner Effect

Kittel states this explusion effect

is not clearly directly connected
to the  = 0 effects

Q: Why ?
 Magnetic Levitation – Meissner Effect

LX01 Test Vehicle

003 581 km/h 361 mph

005 80,000+ riders
005 tested passing trains at relative 1026 km/h

http://www.rtri.or.jp/rd/maglev/html/english/maglev_frame_E.html
 Maglev in Germany (sc? idi)
32 km track
550,000 km since 1984
Design speed 550 km/h

NOTE(061204): I’m not so sure this track is superconducting. The MagLev planned for the Munich area will be. France is also thinking about a sc maglev.
Josephson Junction
~ 2 nm
 Recall: Aharonov-Bohm Effect
-- from last semester

affects the phase of a wavefunction

i ( p  eA) r1 / 
~ e
~ eikx ~ eipx / 
A
Source
B
i ( p  eA ) r2 / 
~ e
 SQUID
superconducting quantum interference device
o

i right
 ~ o e
i left
 ~ o e
  ~ o e i
  fn (location)

Add up change in flux as go around loop

qB
   dl  n 2
Aharonov  Bohm
   

loop


2 
B  n
q

2 
 2.07  10 15 Telsa m 2
( 2e )
 Typical B fields

(Tesla) (# flux quanta)

 http://www.csiro.au/science/magsafe.html

Finding 'objects of interest' at sea with MAGSAFE

MAGSAFE is a new system for locating and identifying submarines.

Operators of MAGSAFE should be able to tell the range, depth and

bearing of a target, as well as where it’s heading, how fast it’s going MAGSAFE will be able to locate
and if it’s diving. targets without flying close to the
surface.
Image courtesy Department of
Building on our extensive experience using highly sensitive magnetic Defence.
sensors known as Superconducting QUantum Interference Devices
(SQUIDs) for minerals exploration, MAGSAFE harnesses the power
of three SQUIDs to measure slight variations in the local magnetic
field.

MAGSAFE has higher sensitivity and greater immunity to external noise than conventional
Magnetic Anomaly Detector (MAD) systems. This is especially relevant to operation over shallow
seawater where the background noise may 100 times greater than the noise floor of a MAD
instrument.
 http://www.csiro.au/science/magsafe.html

Phillip Schmidt etal. Exploration Geophysics 35, 297 (2004).

Arian Lalezari
 SQUID
2 nm

1014 T SQUID threshold

Heart signals 10 10 T
Brain signals 10 13 T
• Fundamentals of superconductors:
– http://www.physnet.uni-hamburg.de/home/vms/reimer/htc/pt3.html
• Basic Introduction to SQUIDs:
– http://www.abdn.ac.uk/physics/case/squids.html
• Detection of Submarines
– http://www.csiro.au/science/magsafe.html
• Fancy cross-referenced site for Josephson Junctions/Josephson:
– http://en.wikipedia.org/wiki/Josephson_junction
– http://en.wikipedia.org/wiki/B._D._Josephson
• SQUID sensitivity and other ramifications of Josephson’s work:
– http://hyperphysics.phy-astr.gsu.edu/hbase/solids/squid2.html
• Understanding a SQUID magnetometer:
– http://hyperphysics.phy-astr.gsu.edu/hbase/solids/squid.html#c1
• Some exciting applications of SQUIDs:
– http://www.lanl.gov/quarterly/q_spring03/squid_text.shtml
• Relative strengths of pertinent magnetic fields
– http://www.physics.union.edu/newmanj/2000/SQUIDs.htm
• The 1973 Nobel Prize in physics
– http://nobelprize.org/physics/laureates/1973/
• Critical overview of SQUIDs
– http://homepages.nildram.co.uk/~phekda/richdawe/squid/popular/
• Research Applications
– http://boojum.hut.fi/triennial/neuromagnetic.html
• Technical overview of SQUIDs:
– http://www.finoag.com/fitm/squid.html
– http://www.cmp.liv.ac.uk/frink/thesis/thesis/node47.html
 Sn 230 nm
Al 1600
Pb 83
Redraw LHS Nb 38

Best conductors  best ‘free-electrons’  no e – lattice interaction

 not superconducting