Germanium: From

Its Discovery to High

Speed Transistors
E.E. Haller
UC Berkeley & LBNL
EECS Solid State Seminar
March 18, 2011
3/18/2011 E. E. Haller 1
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 2
 Anno 1886
• Discovery of a new element in the IVth column: Germanium by
Clemens Winkler: C. Winkler, “Mittheilungen über das Germanium,”
J. für Prakt. Chemie 34(1), 177-229 (1886)

• The first 4-wheel motor car by Daimler & Benz

• Coca-Cola is formulated in Atlanta by a pharmacist

• Walter Schottky is born, the future father of the metal-semiconductor

theory

• Elemental Fluorine is isolated by Moisson

• Patents are filed in the US and Great Britain for the mass production of
Aluminium

3/18/2011 E. E. Haller 3
 D.I. Mendelejev and C.A. Winkler at the meeting of the 100th anniversary of
the Prussian Academy of Science, Berlin, March 19, 1900.

3/18/2011 E. E. Haller 4
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 5
 From the “Physics of Dirt” to a
Respectable Science
Karl Lark-Horovitz joined the
Physics Dept., Purdue
University in 1929. In 1942 he
made the fateful decision to
work on Germanium,
Germanium not on
Galena (PbS) or Silicon. The
first transistor was built at Bell
labs with a slab of Purdue
Germanium! Based on the
Purdue work, Germanium
became the first controlled and
understood semiconductor.

3/18/2011 E. E. Haller 6
 Purdue University Results

Karl Lark-Horovitz
3/18/2011 E. E. Haller 7
 Purdue University Results

3/18/2011 E. E. Haller 8
 Purdue University Researchers

Louise Roth Anant K. Ramdas

Ge single crystal
(50th anniversary!)
3/18/2011 E. E. Haller 9
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
hpGe detectors
• Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 10
 Point Contact Diodes and Transistors

• How to detect the weak radar pulse echoes?

• Cat’s whisker metal point contacts to polycrystalline Ge

and Si formed diodes sufficiently fast to work as mixers

for radar reception in WWII

• “Tapping” rectifiers to optimize their performance

3/18/2011 E. E. Haller 11
 The MIT Radiation Laboratory

The title page of MIT’s

Radiation
Laboratory Series
Volume 15.
This series gives a
detailed
account of the Radar
R&D activities
at MIT during WWII.
3/18/2011 E. E. Haller 12
 !

3/18/2011 E. E. Haller 13
 Discovery of the Transistor
• Controlling big power with little effort: amplification
• The Bell labs vision: Mervin J. Kelly
• Minority carrier injection and lifetime
• December 24, 1947
• The point contact transistor: shows the principle of
amplification but is very fragile (J. Bardeen and W.
Brattain)
• The junction transistor (W. Shockley)
• Are single crystals required?
• The generations of Ge and Si transistors: point contact Ge
transistor
Ge junction transistor
alloyed Ge transistor

Ge mesa transistor (fmax = 500 MHz, Charles Lee, 1954)

Si planar transistor (Jean A. Hoerni, 1960)

3/18/2011 E. E. Haller 14
 The first transistor fabricated by Bell Laboratories’ scientists
was this crude point-contact device, built with two cat’s
whiskers and a slab of polycrystalline germanium.
3/18/2011 E. E. Haller 15
 Point contact
transistor
schematic

The famous lab book entry of

Christmas eve 1947:

3/18/2011 E. E. Haller 16
 William Shockley,
John Bardeen and
Walter Brattain (left
to right) are gathered
together around an
experiment in this
historic 1948 photo-
graph. The first
point contact tran-
sistor remains on
display at AT&T
Bell Labs in
Murray Hill, New
Jersey.

3/18/2011 E. E. Haller 17
 Is Polycrystalline Material Reproducible?

Variation in melting practice and its effect on the physical

characteristics of the silicon ingot
3/18/2011 E. E. Haller 18
 Jan Czochralski

Sketch of
a modern
CZ-puller
3/18/2011 E. E. Haller 19
 Teal and Little’s Hard Fought Victory*

Uniformity of crystal geometry obtainable with the pulling

technique (i.e., the Czochralski technique).
*G.K. Teal and J.B. Little, Phys. Rev., 78 (1950) 647
3/18/2011 E. E. Haller 20
 The First Semiconductor
Energy Band Structure

Physical Review 89(2) 518-9 (1953)

3/18/2011 E. E. Haller 21
 The First Integrated Circuit

The first integrated germanium circuit built by J. Kilby at

Texas Instruments in 1958.
3/18/2011 E. E. Haller 22
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 23
 Applications of Germanium in Nuclear
Physics: GeLi and hpGe Detectors

First Li drifted p-i-n Ge

diode: D. V. Freck and J.
Wakefield, Nature 193, 669
(1962)

3/18/2011 E. E. Haller 24
 Ultra-Pure Ge: NA-ND
2x1010cm-3

The Lawrence
Berkeley Laboratory
ultra-pure germanium
growth apparatus. A
water-cooled RF-
powered coil surrounds
the silica envelope of
the puller. About half
of the 25 cm long
crystal has been grown.

3/18/2011 E. E. Haller 25
 The Berkeley High-Purity Ge Team

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 Dopant Impurity Profiles

Impurity profiles in an ultra-pure Ge crystal with some boron (B, dot-

3/18/2011 dash line) segregating towards the
E. E.seed end contaminates the crystal.
Haller 27
 Ultra-pure germanium detector with closed-end coaxial contact geometry. The borehole
reaches to within in ~ 2 cm of the backsurface of the p-i-n device and forms one contact.
The whole outside surface except the flat portion surrounding the hole forms the other
contact. Large volume detectors with small capacitance can be achieved with the coaxial
geometry. (Courtesy of P.N. Luke, Lawrence Berkeley National Laboratory)
3/18/2011 E. E. Haller 28
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 29
 Physics with Ultra-Pure Germanium:
Exciton Condensation

After C. D. Jeffries, Science 189(4207), 955 (1971)

3/18/2011 E. E. Haller 30
 Electron-Hole Drops

Photograph of a long-lived
electron-hole drop in a 4-
mm disk of ultra-pure
germanium. The sample is
mounted in a dielectric
sample holder and stressed
by a 1.8-mm-diam screw
discernible on the left.
See: J. P. Wolfe, W. L.
Hansen, E. E. Haller, R. S.
Markiewicz, C. Kittel, and C.
D. Jeffries, Phys. Rev. Lett.,
34 (1975) 1292.
3/18/2011 E. E. Haller 31
 Hydrogen Permeation Studies
with Crystalline Germanium

Ref.: R.C. Frank and J.E. Thomas Jr., J. Phys. Chem. Solids 16, 144 (1960)
3/18/2011 E. E. Haller 32
 Self-Counting Tritium Doped
Ultra-Pure Ge Detector

Tritium Labeling*:


3  3
1 T  2 He
Samples taken from tritium-
atmosphere-grown ultra-pure
Ge crystal at different
locations were fashioned into
radiation detectors, counting
the internal T decays. The H
concentration varies between
5x1014 and 2x1015 cm-3.
[*Ref.: W.L . Hansen, E.E.
Haller and P.N. Luke, IEEE
Trans. Nucl. Sci. NS-29, No.
3/18/2011 E. E. Haller 1, 738 (1982)] 33
 Hydrogen and Dislocations in Ge

(Preferentially etched (100) Ge surface)

Ref.: E. E. Haller et al., Inst. Phys. Conf. Ser. 31, 309 (1977)
3/18/2011 E. E. Haller 34
 Hydrogen and Dislocations in Ge

(Preferentially etched (100) Ge surface)

Ref.: E. E. Haller et al., Inst. Phys. Conf. Ser. 31, 309 (1977)
3/18/2011 E. E. Haller 35
 The V2H Center in Dislocation Free,
H2 Atmosphere Grown Germanium

Log (hole concentration) against

reciprocal temperature 1/T of a
dislocated (+) and an undislocated
(V2H) (o) Ge sample cut from the same
crystal slice. The net impurity
concentration of shallow
acceptors and donors is equal for
both samples. The V2H acceptor
(Ev + 80 meV) only appears in the
dislocation free piece (rich in
V2H (EV+80meV)+ H vacancies); its concentration
depends on the annealing
V2H2 (neutral) temperature, [Ref.: E. E.Haller et
al., Proc. Intl. Conf. on Radiation
Effects in Semiconductors 1976,
N.B. Urli and J.W. Corbett, eds.,
Inst. Phys. Conf. Ser. 31, 309
(1977)]
3/18/2011 E. E. Haller 36
 Photo Thermal Ionization
Spectroscopy (PTIS)

(from the thermal bath)

(from the spectrometer)

PTIS: Photo-Thermal Ionization Spectroscopy allows the study of extremely low

dopant concentration [as low as 1 acceptor (donor) in 1014 host atoms]
3/18/2011 E. E. Haller 37
 Typical PTI Spectrum of
ultra-pure germanium.
The 5
5
5 mm3 piece of
the crystal had two ion
implanted contacts on
opposite faces. The net-
acceptor concentration is
2
1010 cm-3. Because of
the high resolution, the
small lines of B and Ga
can be seen clearly.

3/18/2011 E. E. Haller 38
 Discovery of an Isotope Shift in the Ground State
of the Oxygen-Hydrogen Donor and the Silicon-
Hydrogen Acceptor in Germanium

pure H2

51
eV
isotope
shift!

pure D2

Ref.: E.E. Haller, Phys. Rev. Lett. 40, 584 (1978)

3/18/2011 E. E. Haller 39
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 40
 Extrinsic Ge Photoconductors for Far
Infrared Astronomy

Interest: the far IR spectral range (50 to 2000
m) contains

information of great interest for the chemical composition of
the Universe (vibrational and rotational molecular bands), for
galaxy, star and planet formation and evolution, for views
through cold and warm dust

Far IR

3/18/2011 E. E. Haller 41
 Extrinsic Ge Photoconductors
• Shallow dopants in Germanium have ionization energies near
10 meV (corresponding to 80 cm-1 or 125
m). The low
temperature photoconductive onset at
max  125
m lies in
the far IR.
• Three generations of photoconductors:
Far IR
photons

Blocking Layer
Far IR Far IR
photons photons Absorbing
Layer

Ge:Ga photo- Stressed Ge:Ga Ge:Ga

conductor photoconductor Blocked Impurity
(5x5x5mm3, (5x5x5mm3, Band detector

max 125
m )
max 230
m ) (
max > 250
m )
before 2000 current after 2007
3/18/2011 E. E. Haller 42
 The Spitzer Space Telescope

- Launched in August
2003 on a two stage
Delta rocket with 9 solid
fuel boosters

- The liquid He cooled

0.85 m telescope is
on an earth orbit
vis-à-vis the earth

- wavelength range 3
m

< l < 180
m

- Lifetime : up to 5 years

3/18/2011 E. E. Haller 43
 Observations with Ge Photoconductors

From visible
light to the
far infrared.

Galaxy
Messier 81
at a distance
of 12 Million
light years!
3/18/2011 E. E. Haller 44
 Neutron Transmutation
Doped (NTD) Germanium
• Irradiation of Ge with thermal neutrons
• Neutron captures and decays: 70 EC
Ge(n,  ) 3271Ge 71
 31 Ga (acceptor)
32
11.2d
74 75 
75
32 Ge(n,  ) 32 Ge  33 As (donor)
82.2m
76 77 

32 Ge(n,  ) 32 Ge  3477 Se (double donor)
11.3h
• Homogeneous impurity distribution reflects uniform neutron flux and uniform
isotopic distribution
• Reproducibility: NGa =
70 N70
Ge Ge

• Ultra-pure starting material

• Neutron doping levels >> residual impurities

3/18/2011 E. E. Haller 45
 R versus T-1/2 for several NTD Ge
Thermistors

=
o exp (To/T)1/2

3/18/2011 E. E. Haller 46
 Silicon Nitride Micromesh
‘Spider-web’ NTD Ge Bolometers

Spider-web architecture provides

low absorber heat capacity
minimal suspended mass
low-cosmic ray cross-section
low thermal conductivity = high sensitivity

Sensitivities and heat capacities achieved to date:

NEP = 1.5 x 10-17 W/
Hz, C = 1pJ/K at 300 mK
NEP = 1.5 x 10-18 W/
Hz, C = 0.4 pJ/K at 100mK

Detectors baselined for ESA/NASA Planck/HFI

Arrays baselined for ESA/NASA FIRST/SPIRE

Planned or operating in numerous sub-orbital experiments:

BOOMERANG Caltech Antarctic balloon CMB instrument

SuZIE Stanford S-Z instrument for the CSO
MAXIMA UC Berkeley North American balloon CMB instrument
BOLOCAM CIT/CU/Cardiff Bolometer camera for the CSO
ACBAR UC Berkeley Antarctic S-Z survey instrument
BICEP Caltech CMB polarimeter
Archeops CNRS, France CMB balloon experiment
BLAST U. Penn Submillimeter balloon experiment
Z-SPEC Caltech Mm-wave spectrometer
QUEST Stanford CMB polarimeter

Courtesy J. Bock, NASA-JPL

3/18/2011 E. E. Haller 47
 Metal-Insulator Transition with NTD 70Ge

=
o exp (To/T)1/2

The left side shows the experimentally determined T0 of 14 insulating

samples as a function of Ga concentration (). The right side shows the
zero temperature conductivity
(0) obtained from the extrapolations

(T) for ten metallic samples as a function of Ga concentration (•).
K. M. Itoh, et al., Phys. Rev. Lett. 77(19), 4058-61 (1996).
3/18/2011 E. E. Haller 48
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 49
 STABLE ISOTOPES
75As
70Ge, 72Ge, 73Ge, 74Ge, 76Ge
69Ga, 71Ga
Z

N
3/18/2011 E. E. Haller 50
 95% ENRICHED, ULTRA-PURE Ge SINGLE CRYSTALS
3/18/2011 E. E. Haller 51
 Excitons in 70Ge, nat.Ge and 74Ge

3/18/2011 E. E. Haller Courtesy Gordon Davis, et al. 52

 Thermal Conductivity of Solids

Valery Ozhogin and

Alexander Inyushkin,
Kurchatov Institute,
Moscow

3/18/2011 E. E. Haller 53
 Change of the direct Ge Bandgap with Isotope Mass

C. Parks, et al., Phys. Rev B. 49, 14244 (1994)

3/18/2011 E. E. Haller 54
 Self-Diffusion in Isotope Structures
74Ge (> 96%) 70Ge (> 95%) natGe
After annealing (55 hrs / 586˚C)

natG

3/18/2011 E. E. Haller H. Fuchs et al., Phys. Rev. B 51, 55

16871 (1995)
 The First Ge Isotope Superlattice

G. Abstreiter, Munich
3/18/2011 E. E. Haller 56
 Raman Lines of the Ge Isotope Superlattice

Experiment Theory

Spitzer, et al., Phys.

Rev. Lett. 72, 1565
3/18/2011 E. E. Haller (1994) 57
 Topics to be discussed
• Discovery of Germanium and Early History
• From the “Physics of Dirt” to a Respectable Science
• Point Contact Diodes and Transistors
• Applications of Germanium in Nuclear Physics: GeLi and
High-Purity Ge detectors
• New Physics with Ultra-Pure Germanium
• Infrared Photoconductors and Bolometers
• Isotopically Controlled Germanium
• Germanium Speeds Up Silicon Transistors

3/18/2011 E. E. Haller 58
3/18/2011 E. E. Haller 59
3/18/2011 E. E. Haller 60
3/18/2011 E. E. Haller 61
 Summary
• The 120 year history of the element Ge is rich in
science and technology
• Today Ge has returned to mainstream electronics
because of its excellent transport properties and
engineering of bandstructures using strain
• More interesting findings will be made…Long live
Germanium!

3/18/2011 E. E. Haller 62
3/18/2011 E. E. Haller 63
 EXTRAS

3/18/2011 E. E. Haller 64
3/18/2011 E. E. Haller 65
 Pure H2 atmosphere

Mixed atmosphere:
H/D = 1/1

Pure D2 atmosphere

The D(O,H) donor in Ge contains exactly one H atom!

Ref.: E. E. Haller, Inst. Phys. Conf. Series 46, 205 (1979)
3/18/2011
E. E. Haller 5/18/2010 E. E. Haller 66
 The Acceptor A(H,C) in
Ultra-Pure Germanium
•The groundstate of A(H,C) is split
by 1.98 meV, leading to two series
of ground-to-bound excited state line
series (blue and red). The intensity
ratio of corresponding lines is pro-
portional to a Boltzmann factor
exp [1.98 meV/kBT ].
• Only crystals grown in a H2
atmosphere from a graphite crucible
contain this acceptor.
• Upon substitution of H with D the
ground state shifts by 51
eV to lower
energies.
• Joos et al., Phys. Rev. B 22, 832
Ref.: E. E. Haller, B.Joos and L. M. Falicov,
Phys. Rev. B 21, 4729 (1980)
(1980) modeled this center with
a tunneling hydrogen complex.

3/18/2011 E. E. Haller 67
 The Acceptor A(H,Si) in Ultra-Pure
Germanium
• The groundstate of A(H,Si) is split
by 1.07 meV, leading to two series
of ground-to-bound excited state line
series (blue and red). The intensity
ratio of corresponding lines is pro-
portional to a Boltzmann factor
exp [1.1 meV/kBT ].
• Only crystals grown in a H2
atmosphere from a SiO2 crucible
contain this acceptor.
• Upon substitution of H with D the
ground state shifts by 21
eV to lower
energies.
• Kahn et al., Phys. Rev. B 36, 8001
Ref.: E. E. Haller, B.Joos and L. M. Falicov, (1987) modeled this and other centers
Phys. Rev. B 21, 4729 (1980)
[A(H,C), A(Be,H), A(Zn,H)] with
trigonal complexes.

3/18/2011 E. E. Haller 68
 The Cu triple
acceptor in Ge binds
up to three
interstitial H or Li
atoms. Each bound
H or Li reduces the
number of
electronic states by
one (i.e., CuH3 is
neutral)

Position of the acceptor levels of copper and its complexes with hydrogen and lithium in
germanium. [Ref.: E.E. Haller, G.S. Hubbard and W.L. Hansen, IEEE Trans. Nucl. Sci.
NS-24, No. 1, 48 (1977)]

3/18/2011 E. E. Haller 69
3/18/2011 E. E. Haller 70
 Hillocks or dimples?

3/18/2011 E. E. Haller 71
 Neutron Transmutation Doped Ge
Thermistors for Bolometers
Bolometers have two components: an absorber (TeO2) and
a thermometer (NTD Ge)
•Thermometer and absorber (heat
capacity C) are connected by a weak
thermal link (G) to a heat sink (To)
•Incoming energy is converted to heat
in the absorber:
T=To +(Psignal + Pbias)/C
•Temperature rise is proportional to the
incoming energy
•Temperature rise decays as energy
flows from the absorber to heat sink:
3/18/2011

= C/G 72
E. E. Haller
 CUORE/CUORICINO Double Beta
Decay:An Italian-US Experiment

• Absorber: TeO2 single crystals,

~ 1000 kg

• Temperature: 5 mK

• Thermal Sensors: NTD Ge

• Support: Copper, Teflon

3/18/2011 E. E. Haller 73
 X-Ray Performance: Single
X-Ray Counting

0.35 mm x 0.35 mm x 7
m tin absorber + NTD 17 Ge thermistor

A publication describing an earlier measurement of 3.08 eV is: E. Silver, J. Beeman, F. Goulding, E.E. Haller, D. Landis and N. Madden,
Nuclear Instruments and Methods in Physics Research, Volume 545, 3, (2005), 683-689.
Courtesy Eric Silver, Harvard
3/18/2011 E. E. Haller 74
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3/18/2011 E. E. Haller 77
 H. Mataré 2003 H. Welker 1970
Working in Paris at the Westinghouse research laboratories, Herbert Mataré and
Heinrich Welker made transistor observations using multipoint contacts. Welker
went on to discover III-V compound semiconductors in the early 1950s, opening the
world of optoelectronics.
3/18/2011 E. E. Haller 78
 After annealing (55 hrs / 586˚C)

natGe

H. Fuchs et al., Phys. Rev. B

51, 16871 (1995)

3/18/2011 E. E. Haller 79
 A High-Mobility Germanium QWFET

December 6, 2010 - At IEDM 2009, Intel announced a record breaking quantum well field effect transistor (QWFET); a 35nm
gate length device capable of 0.28mA/μm drive current and peak transconductance of 1350μS/μm. These QWFETs used
InGaAs as the quantum well channel material. At this week’s IEDM 2010 in San Francisco, Intel (Hillsboro, OR) will again
demonstrate a first: a high-mobility germanium QWFET that achieves the highest mobility (770 cm2/Vsec) with ultrathin oxide
Thickness (14.5Å) for low-power CMOS applications. This hole mobility is 4
higher than that achieved in state-of-the-art p-
channel strained silicon devices. These results involve the first demonstration of significantly superior mobility to strained
silicon in a p-channel device for low-power CMOS. The biaxially strained germanium QW structure (Figure) 1 incorporates a
phosphorus doped layer to suppress parallel conduction in the SiGe buffers.

3/18/2011 E. E. Haller 80