Chapter 10 & 11

Molecular Bonds & Band Structure

Semiconductors
Superconductivity
Lasers

Harris, “Modern Physics”

Eisberg & Resnick, “Quantum Physics of Atoms, Molecules,

Solids, Nuclei, and Particles”
 Outline
• 10.1 Molecular Bonding (~2 atoms together)
– pages 334-342
• 11.1 Band Theory (~1023 atoms together)
– pages 387-392

• 11.2 Semiconductor Theory

– mainly pages 395-398
• 10.5 Superconductivity
– pages 362-381

• 10.2 Stimulated Emission & Lasers

– mainly pages 342-347
 MOLECULES
(~2 atoms together)

Ionic & Covalent Bonds

Molecular Excitations
Rotation, Vibration, Electric
 Ionic Bonds

ENERGY Ionization + Electron + Attraction of + Pauli

BALANCE= Affinity Cores Repulsion of
Electrons
RNave, GSU at http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/bond.html#c4
Ionic Bond Energy Balance

Ioniz Electron Coul Pauli Energy

Affinity Attraction Repulsion Balance
NaCl 5.14 -3.62 -6.10 0.31 -4.27

NaF 5.14 -3.41 -7.46 0.35 -5.34

KCl 4.34 -3.62 -5.39 0.19 -4.49

HH 13.6 -0.76
 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 Ref: Harris

 Ionic vs Covalent Bond Properties

• Ionic Characteristics • Covalent Characteristics

– Crystalline solids – Gases, liquids, non-
crystalline solids
– High melting & boiling point – Low melting & boiling point

– Conduct electricity when – Poor conductors in all

melted phases

– Many soluble in water, but – Many soluble in non-polar

not in non-polar liquids liquids but not water
 Molecular Excitations
Rotational Spectra


1 1 2
I 2
2
rot KE ~  Lop  (  1)
2 2I 2I

moment of inertia
rotational A.M.
 Rotational Spectra

Photon Energy  hf
Ref: Harris
Molecular Excitations Molecule
“Spring Const”
( N/m )

Vibration HF 970

HCl 480

HBr 410

Hi 320

CO 1860

NO 1530
Vibration (in an Electronic state)
 Ocean Optics: Nitrogen N2

~ 0.3 eV

~ 0.4 eV

http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/atspect.html
Electronic + Vibration

Ref: Harris
 Electronic + Vibration + Rotation
2.550 eV
2.656 eV

electronic excitation gap

vibrational excitation gaps

Ref: Eisberg&Resnick
 Electronic + Vibration + Rotation
Vibrational Well Vibrational Well

2.656 eV
depth ~ 0.063 eV

electronic excitation gap

vibrational excitation gaps

Ref: Eisberg&Resnick
 Electronic, Vibration, Rotation
Electronic ~ optical & UV
~ 1 – 3 eV

Vibration ~ IR
~ 10ths of eV

Rotation ~ microwave
~ 1000ths of eV

Harris 9.24
 Some Molecular Constants
Molecule Equilibrium Dissociation Vibrational Moment of
Distance NRG freq Inertia
Ro (Å) Do (eV) v a (cm-1) Bb (cm-1)
H2+ 1.06 2.65 2297 29.8
H2 0.742 4.48 4395 60.8
O2 1.21 5.08 1580 1.45
N2 1.09 9.75 2360 2.01
CO 1.13 9.60 2170 1.93
NO 1.15 5.3 1904 1.70
HCl 1.28 4.43 2990 10.6
NaCl 2.36 4.22 365 0.190

Notes: a) vibrational frequency in table is given as f / c

b) moment of inertia in table is given as hbar2/(2I) / hc
 SOLIDS
(~10x atoms together)
Isolated Atoms
Diatomic Molecule
Four Closely Spaced Atoms

conduction band

valence band
 Two atoms Six atoms Solid of N atoms

ref: A.Baski, VCU 01SolidState041.ppt

www.courses.vcu.edu/PHYS661/pdf/01SolidState041.ppt
 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
Conductors vs insulators vs semiconductors
 Conductors & Insulators at T=0

Harris9.35a
 Conductors & Insulators at
T>0

Harris9.35b
Semiconductors
&
Superconductors

Rex Thorton
p 395-398
p 362-381
 Two atoms Six atoms Solid of N atoms

ref: A.Baski, VCU 01SolidState041.ppt

www.courses.vcu.edu/PHYS661/pdf/01SolidState041.ppt
Temperature Dependence of
Resistivity

L
R  
A

Ag m
Cu 
C amorphous 

Rubber 
Air 
 Conductors & Insulators at T=0

Harris9.35a
 Conductors & Insulators at
T>0

Harris9.35b
• 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  
 Semiconductors
~1/40 eV gap
• Types
– Intrinsic – by thermal excitation or high nrg photon
~1 eV gap

– Photoconductive – excitation by VIS-red or IR

– Extrinsic / Doped
• n-type
• p-type
•

~1-4 eV gap

~0.01 eV gap with adjustable charge carrier density

 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

Almost free, but not quite

Sandin, “Modern Physics”

5A in 4A lattice

3A in 4A lattice
 Bands in n-doped
Semiconductor

9.44
 Bands in p-doped
Semiconductor

9.45
Superconductivity

First observed Kamerlingh Onnes 1911

Note: The best conductors & magnetic materials tend not to be superconductors (so far)

Superconductors.org Only in nanotubes

Discovery of “Type II”
--- CuxOy
 Superconductor
• Type I Classifications
– 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
Normal Conductor or
Superconductor
Superconductors and Semiconductors are the same animal from a band model viewpoint
Another fact about Type I:

-- Interrelationship of Bcrit and Tcrit

 Type II
Yr Composition Tc
Mar (Tl5Pb2)Ba2MgCu10O17+ 20 C
2011 293 K

Oct 3C
2010 (Tl4Pb)Ba2MgCu8O13+ 276K

May InSnBa4Tm4Cu6O18+ 150

2006

2004 Hg0.8Tl0.2Ba2Ca2Cu3O8.33 138

1987 YBa2Cu3O7 93

1986 (La1.85Ba.15)CuO4 30

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

 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 Shanghai
 Maglev in Germany
32 km track
550,000 km since 1984
Design speed 550 km/h
Regularly operated at 420 km/h

http://en.wikipedia.org/wiki/2006_Lathen_maglev_train_accident
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.
 Maglev Frog

A live frog levitates

inside a 32 mm
diameter vertical bore
of a Bitter solenoid in
a magnetic field of
about 16 Tesla at the
Nijmegen High Field
Magnet Laboratory.

http://www.hfml.ru.nl/pics/Movies/frog.mpg
Josephson Junction
~ 2 nm
 SQUID
superconducting quantum interference device
o

i left i right
 ~ o e  ~ o e

The phase of the wfn in left and right branches is different

because of the penetrating flux.
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).

 http://nextbigfuture.com/2007_10_28_archive.html
http://en.wikipedia.org/wiki/Magnetoencephalography

http://www.neurevolution.net/2007/08/20/magnetoencephalography/

http://www2.fz-juelich.de/nic/Publikationen/Broschuere/sonstiges-e.html
 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