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SEMICONDUCTOR
HETEROJUNCTION
TOPICS:
INTRODUCTION
AND OVERVIEW
A. G. MILNES
Carnegie-Mellon
(Received

University,

Pittsburgh,

17 June 1985; in reuisedform

PA 15213, U.S.A.
31 Ju!v 1985)

Abstract-Semiconductor
heterojunctions
with ideal lattice matching, well-controlled
in fabrication,
yield
devices that cannot be achieved in any other way. These devices include modulated-doped
high-speed
field-effect transistors,
ultra-high-gain
and high-speed
bipolar transistors,
efficient injection lasers and
light-emitting
diodes and sensitive photo-detecting
structures.
Atomic reconstructions
take place at
heterojunction
interfaces
and are process-fabrication-dependent
and not adequately
understood.
The
barrier discontinuities
observed are therefore scattered in value and also somewhat dependent
on the
determination
method. Many papers in this Special Issue contain review aspects of these matters. Others,
however, are specific contributions
on very particular heterojunction
topics. Not all aspects of heterojunctions are dealt with by the papers that follow, and the present article is intended for newcomers to the
field as a brief commentary
on topics that are not adequately represented.

1. INTRODUCTION

semiconductor
heterojunction
structures up to fifteen years ago are described in the
and Metal-Semiconductor
book, Heterojunctions
Junctions,
by Milnes and Feucht[l],
and in Semiconductor
Heterojunctions,
by Sharma
and
Purohit[2]. Various aspects have also been reviewed
in other volumes [3,4].
Up to the early 1970s, the only heterojunction
successes that had been achieved were those with
injection lasers [3]. The GaAs/Al,Ga,
_-xAs doubleheterojunction
laser fabricated by liquid-phase
epitaxy was exhibiting
threshold-current
densities of a
few hundred
amperes/cm*
and ability to function
above room temperature because of the carrier inversion-confinement
and optical confinement made possible by the band discontinuities.
Other devices involving heterojunctions
were of marginal value, such
as the nCdS/pCu,S
solar cell[5], or even existed
only as concepts that had not been realized in any
meaningful way.
With the development
of epitaxy methods, particularly organometallic
CVD and molecular-beam
epitaxy in the mid 1970s, growth technology improved
in precision
and ability to handle
ternary and
quatemary
III-V semiconductors[4]
and a new era
began
for semiconductor
heterojunction
devices.
Control became possible in compositionOand
in doping over distances as small as 50 or 100 A and lattice
matching was improved to 10~3-10~4. The devices
that followed included high-quality lasers and optical
detectors,
negative-electron-affinity
structures, modulated-doped
FETs and high-gain
high-speed
bipolar transistors. Also in laboratories across the world
many structures
are being studied involving heterojunctions
that are yet to find significant applications.
The present limitations in the experimental control
of heterojunction
spike barriers and in the ability of
Developments

in

99

theoretical
treatments
to match these barriers are
briefly discussed
in the section that follows. This
issue contains papers by Margaritondo
and by Wang
dealing with these matters in detail. Section 2, also,
touches on lattice matching and factors determining
interface states. Three important uses of heterojunctions namely, FETs, bipolar transistors
and light
detectors
and emitters are then mentioned
and finally, there is a brief discussion
of quantum-well
structures
and
strained-layer
superlattices
and
speculative bandgap-engineering
concepts.
2. ENERGY-BAND
STEPS CREATED
HETJZROJUNCTIONS

BY

In a homojunction
the energy gap does not vary
across the junction
(except for possible bandgap
narrowing produced by heavy doping) and so conduction and valence-band-edge
steps are similar and
controlled by Poissons equation. However, in a heterojunction
between
two different semiconductors
the variations can be quite different since they may
include energy steps AE, and AE,. that are abrupt
to within a few tens of angstroms. These variations
allow the designer a degree of freedom in independent control of majority- and minority-carrier
flow
(1).
In metal-semiconductor
junctions,
the simple
work-function
electron-affinity
model does not usually predict successfully the observed Schottky-barrier heights[7-91.
The failure to do so has been
attributed
to interface-state
pinning and more recently
the role of interface
reactions
has been
evoked[lO, 111. Attempts to devise new simple models, such as the common-anion
model[7],
useful
though this is, have not stood the test of detailed
experimental
examination.
In heterojunctions
there
is a similar failure of simple models. The first-order
primitive
model is that of Anderson-Shockley
in

A. G. IM1I.Nt.S

100

which AE, is postulated


to be the difference of the
semiconductor
electron affinities [l, 21. This intuitive
model is useful as an introductory
concept for students, but the model is not well representative
of
experimental
results. Quantum-mechanical
modeling
has been attempted
with various degrees of success
as discussed by Margaritondo
and by Wang in this
issue. The problem of obtaining such models in a
form matching experimental
results is frustrated by
atomic reconstructions
that take place at heterojunction interfaces,
even the most abrupt and carefully
prepared [12]. Complicated
situations cannot be expected to lead to very simple models. The Anderson-Shockley
model, and the recent dipole-minimization model of Tersoff[l4] will probably remain the
main vehicles for introducing students to the subject.
Some measured
values of AE,, for a number of
binary semiconductors
with Si or Ge applied[l5]
are
presented
in Table 1 and compared with the values
expected from the electron-affinity
model (EA). The
EA predictions
are often far from these measured
values (16). Departures
of i0.15 eV, or even more,
are common.
Tersoffs model postulates that each semiconductor
has states in the bandgap at or near the interface and
at some energy level EB - E,,, often near the midgap, the states change from acceptor to donor in
nature. Tersoff proposes that when a heterojunction
is formed the EB values on the two sides of the
junction line up and this determines the band offset
A E,,. If the band-diagram
did not line up in this way
then charge transfer would occur between the states
on either side of the interface and this would create a
dipole
field: so from energy considerations
the
system favors dipole minimization
and therefore
equalization
of the EB levels. Values of EB may be
estimated from A E,, measurements
for a set of heterojunction
pairs and a transitivity
table prepared,
something like the table presented by Margaritondo
in this issue. The state-transition-energy
EB may be

Table 1. Experimental
valence-band
discontinuitiea
compared with the values expected from the
electron-affinity
model[l5]
Electron-Affinity
Predictions
(eV)

Experimental
(eW
Substrate
Gc!
Si

Si

Ge

-0.17

Si

Model

Ge

-0.31
0.31

0.17

GAS
GaP
GaSb
InAs
InP
InSb

0.05
0.95
0.05
0.15
0.57
0.00

0.35
0.80
0.20
0.33
0.64
0.00

0.27
0.33
-0.37
0.15
0.55
- 0.34

0.70
0.64
~ 0.07
0.46
0 85
~ 0.03

CdS
CdSe
CdTe
ZnSe
ZnTe

1.55
1.20
0.75
1.25
0.85

1.75
1.30
0.85
1.40
0.95

1.30
0.49
0.64
1.68
0.64

1.61
0.80
0.94
1.99
0.96

expected to play a similar role in Schottky-barrier


formation
if E, is a fairly intrinsic property of the
semiconductor.
Therefore
the model provides
a
bridge between
Schottky-barriers
and heterojunctions since it implies that if Schottky barrier heights
are known for two semiconductors
for a common
reference
material
such as Au, these results may
perhaps be used directly to construct the heterojunction barrier diagram for these two semiconductors.
Further discussion of the Tersoff model appears in
the papers by Margaritondo
and Wang in this issue.
The precise value of the model is something
that
time and further experimentation
will establish, but
at the very least it is useful as an academic tool in
developing heterojunction
concepts for students.
Literature searches of the 2000 or more papers that
have been published on heterojunction
topics in the
last decade show that experimental
values of band
discontinuities
are scattered widely by perhaps f 0.1
eV. Not all measurement
techniques yield the same
band discontinuities
for specimens of the same semiconductor
compositions[17],
and the nature of the
preparation
method may contribute to the values of
discontinuities
that are present. For instance. the
A E,, values for Ge grown on (111) Ga. (100) Ga.
(110,100) As and (111) As (111) As surfaces of GaAs
have been reported as 0.48, 0.55, 0.56, 0.60. and 0.66
eV, respectively[lS].
On the other hand, other
workers have not seen orientation
dependencies
in
AlGaAs/GaAs
heterojunctions[l9]
and the weight
of the evidence is for no orientation
dependence
in
well prepared junctions.
Methods for measuring heterojunction
barriers include: (a) photo-emission
spectroscopy
relative to
core bands (this involves taking the difference between two large numbers that have corrections that
are of order iO.l eV and are imperfectly
known);
(b) photoluminescence
of superlattices
with parabolic wells (this rather critically depends on knowledge of effective mass); (c) CV apparent
doping
profiles (this is only really useful for nh and pP
structures);
and (d) measurement of A E,, by study of
thermal emission of holes in a PIP structure [a technique developed
by S. L. Wright and J. Batey. J.
Appl. Phys. 57(2), 484(1985)].
The
conclusions
of such
studies
with
the
GaAs/AlGaAs/Ge
system are that barriers
of
GaAs/AlGaAs
are near-enough
commutative,
namely A E,?/ = A EIfjA so the order of growth has
relatively little effect. Secondly it is concluded that in
this three-component
system the barriers are fairly
closely transitive, namely A E;:/ + A E,f< + A E, 4
= 0. The values are typically, according to Katnani
and Bauer (1985 Electronic
Materials Conference,
Boulder,
CO) AlAs/Ge
A E,, = 0.78 k .07, AlAs/
GaAs A E, = 0.39 of: .07 and GaAs/Ge
A E,, = 0.44 f
.06 eV.
The variation of the barrier A E,, as a function of
Al content
(x) in the system Al,Ga, ~, As/GaAs
has been reported as a linear relationship
over the
whole range x = O-l and is given by A E,, = 0.551(Al)

Introduction and overview


eV in PIP structures. This is not a fixed fraction of
either the direct or indirect bandgap difference. In
another study (M. Heiblum, 1985 IEEE Device Research
Conference)
structures
that were metal
(molybdenum)/iGaAs/nAl,Ga,_,As
were
examined by internal photoemission
for x in the range
O-0.4, and it was concluded
that A E,/A E, was
about 0.60-0.64 in agreement with other work [20,21]
and that A E,, was about 0.47x(Al) eV. For a AER of
about 0.5 eV at x about 0.4, the 0.64 factor corresponds to a barrier for electrons of 0.32 eV.
Several of the papers in this issue discuss heterojunction-band-discontinuities.
All measured
values
however are not presented
and a transitivity
table
must be used or the general literature
must be
searched for AE,., A E,, values once a potential user
has selected the heterojunction-pair
of interest. As a
guide to heterojunction-pair
selection the following
rules may be suggested.
(a) Select the prime semiconductor
of the active
region with due regard for the bandgap
and the
mobilities required.
(b) Select the paired semiconductor(s)
on the basis
of very close lattice match (say 10e3) and probable
A E, , A E,, values from the literature.
(c) This will commonly involve a binary substrate
and a transition
to ternary or quaternary
compounds [22]. Select a fabrication process that is compatible with this and is not likely to have severe
cross-doping
problems
(such as may occur in
Ge-GaAs
structures if As enters the Ge). Furthermore, thermal-expansion
coefficient differences must
be considered
if a substrate such as Si is used. For
lattice-mismatched
heterojunctions,
with mismatch
greater
that 0.5%, the odds are strongly against
achieving useful performance
if minority-carrier
actions are involved or if trapping actions are likely to
adversely affect the performance
of the device that is
under consideration.
Similar remarks apply to heterojunctions
involving polycrystalline
layers.
Strained-layer
superlattices
are presently
under
study as discussed briefly in Section 8 of this introductory paper, as a way of tailoring effective lattice
dimensions
and bandgap modulation.
3. LATTICE

MATCHING

AND INTERFACE

STATES

Lattice matching
is a very important
factor in
determining
the quality of epilayers in heterojunction devices. A diagram of energy gaps versus lattice
constants for a wide range of ternary three-five and
two-six semiconductors
is given as Fig. 1. Available
substrates
are normally binary in nature, such as
GaAs or InP, since direct attempts
to melt-grow
ingots of ternaries usually result in phase-separation
effects. The heterojunction
pairs GaAs/Al ,.Ga, _ , As
are naturally close in lattice constants,
but can be
further refined in lattice matching by the addition of
small amounts of an element such as phosphorus.
Growth
can be by liquid phase epitaxy (LPE),
molecular-beam
epitaxy (MBE) or chemical-vapordeposition
(CVD). There is evidence that with LPE

101

the interfaces are graded over 100 A or more because


of back-etching
of the melt[23] and may not be
uniform on a scale of lo-50 pm in composition
along the plane of the junction[24].
The LPE technology is less frequently used these days, partly for
this reason but mainly because CVD technology
appears more interesting as a manufacturing
process.
In 0 S,Ga, 47A~ grown on InP is another technologically important
pair since the devices made possible by this heterojunction
are of use in optical-fiber
communications.
The conduction band discontinuity
between these materials has been reported as about
40% of the bandgap difference[2.5]. Stress and dislocations in such structures have been measured by
Chu et a1.(26).
Other alloy semiconductors
may be grown latticematched
to InP, as may be seen from Fig. 2 the
quaternary
alloy diagram for In, _.,Ga,P, _zAsz [27].
Further
data of this nature useful for planning
lattice-matched
bandgap-varying
structures are found
in Kressel and Butler[3]. Other useful references
include Nakajima et al. [28] on In, ,Ga r As, )PYon
InP; Williams et al.[29] also on III-V quatemary
alloys: Neuse 1301 on (AlGa) (AsSb) quatemaries;
Osamara
et al. [31] on Al-Ga-Sb;
and Masu
et al. [32] on (Al YGa, _ ,)In,,, As.
Films of GaSb, SAs, 5 and Al ,Ga, .~Sb,. As, ~,
have been grown by MBE, lattice-matched
to InP[33]
but with some evidence of compositional
modulation
due to spinoidal
decomposition.
CdS is also approximately
a lattice match to InP and a A E, of 0.56
eV has been reported[34].
In general if the device requires that a lattice
mismatched
film be grown, it is customary to provide
a lattice-graded
interface
layer.
For instance,
In,, zGa,, As might be grown on GaAs by providing
a sequence of thin layers stepped in composition
between 0 and 20% In. The stepped composition
of
the buffer layer is cooled between each step to allow
strain relief. By this process threading dislocations
tend to be turned into the surface plane instead of
continuing into subsequent layers.
This kind of approach has been applied to the
growth of GaAs on Si with the aid of a thin buffer
layer of Ge. The Ge nucleation layer grown on the Si
is heavily dislocated (1012 cme2) because of the 4%
lattice mismatch, and the first layer of GaAs grown
is similarly dislocated.
Growth of the GaAs by a
sequence of 10 growth interrupts, and thermal cycles,
reduces the dislocation density by one or two orders
of magnitude relative to GaAs grown without interruption, which shows a 10 cme2 surface dislocation
density[35,36].
It must be noted however that the
thermal-expansion
coefficient of Si is less than that
of GaAs and the grown layer is in tension and liable
to cracking and there also may be bending of the
wafer.
Recently, however, it has been concluded that the
provision
of a thin buffer layer of Ge is not an
advantage
and that surprisingly good quality GaAs
can be grown directly on (100) or 4 off (100) Si

102

A. G. MILNES

3.6

2.8
2
w 2.4
Y8

2.0

%
$

1.6

&
[L 1.2
:
0.8

5.40

5.46

5.56

5.64

5.72

5.00

5.88

LATTICE

CONSTANT,

Fig. 1. Energy gap versus lattice constant

GaAs

GaP

.Y

120
220ev

1 10

210
100

200
1.90
180

090

1.70
160

Fig. 2. Lattice constant and energy gap (77 K) as a function


of composition
for the quaternary
alloy In, _ ,Ga,P,
;As,.
The solid lines are constant energy gap curves; the dashed
lines are lattice constant curves obtained by application
of
Vegards law. The intersection of the energy gap curves with
the lattice constant curves makes it apparent that the energy
gap may be varied while a fixed lattice constant is maintained, indicating
a variety of heterojunction
possibilities
from the infrared
to the yellow for the quaternary
alloy.
(After Coleman er al. Reprinted with permission
from J.
Appl.
Phvs. 47, 2016 (1976j.j

wafers
subjected

by molecular-beam
to a cleaning

epitaxy.
process

5.96

The Si wafers

are

at 900 or 1000 C and

growth
is begun at a low temperature
such as
400-450C
and at a slow rate. This presumably

6.04
a0

6.12

% (300

for three-t&z

6.20

6.28

6.36

6.44

I
6.52

K)

and two-six

semiconductors.

results in small closely spaced nucleation sites that


interact with each other in such a way that by the
time 1200-1500
A of layer has been grown the
surface tends to be single crystal that is not excessively dislocated and a further thickness can be grown
at a more normal temperature 570C or higher, and
at a normal growth rate (- 1 pm/hr).
Quite good
MESFET
and MODFET
performances
have been
achieved on such material (R. Fischer et cd., 1985,
IEEE Device Research Conference,
Boulder, CO).
Furthermore
it has been shown that GaAs grown by
MOCVD on Si gives similar device performance
(T.
Nonaka
et al., 1985, IEEE Device Research Conference, Boulder, CO).
This is a promising technology since it may allow a
mixture of III-V and Si devices on large commercially convenient
Si substrates.
The III-V devices
offer optoelectronic
performance possibilities that the
Si devices cannot deliver. The GaAs layers on Si
wafers have not been widely available for enough
examination
to determine their limitations. It may be
surmised that they will be subject to having strain
effects that might influence long-term stability and
that the minority-carrier
performance
will be unimTime will tell whether
this technology
pressive.
survives as viable and worthy of transfer from the
laboratory
to production.
In another approach
GaAs of FET quality has
been grown by MBE on Ge by the provision of a 1
pm
quantum-well-structure
interface
of GaAs(AlGa)As [37].
The quality of the interface region in a high-grade
heterojunction
such as Al rGa, _ 1As/GaAs
is of spe-

Introduction
cial interest.
When grown by MBE the interface
width (lo-90% Alp-p height) has been measured as
about 15 A by Auger profiling[23].
In general the
interface
of Al.Ga,-,As
grown on GaAs (termed
the normal interface) is superior in electrical properties to the interface of GaAs grown on Al,Ga, _ .As
(termed the inverted
interface) [38]. The valenceband discontinuities
have also been found to exhibit
dependence
on the growth
sequence
by some
workers[39] and not by others. The reason for this is
not properly known and the effect is usually dismissed as a consequence
of greater interface roughness
and possibly greater contamination.
In a quantumwell structure,
photoluminescence
possibly associated with carbon has been detected in the first few
tens of A of GaAs grown (40).
Transport
of electrons and holes across an idealized (100) interface of GaA-GaAlAs
has been modeled by Osbourn
and Smith[41] who predict, for
example,
that an electron near the X minimum
normal
to the interface
in Ga, _ \ Al, As should
transmit
into the X valley of GaAs with much
greater probability
than it transmits
into the r
minimum of GaAs.
Continuing
the discussion of the perfection
of a
heterojunction,
consider now the interface states at,
for instance,
an n-GaAs/N-Al,
25Ga,,,, As interface (the large N is by convention
associated with
the material
of larger bandgap).
Measurement
is
usually made by causing a depletion region to spread
through the interface as reverse bias voltage is applied with the aid of a Schottky barrier on the
nGaAs or in a p+ nN structure (42). If there is a A E,
at the interface and no interface electron traps, there
will usually be an accumulation region and depletion
region on the two sides of the inteiface. If in addition to a A EC there is an interfacial sheet of traps
the C-V profile of apparent
concentration
versus
depletion
width (42) becomes as shown in Fig. 3.
Kroemer
et al. [43,44] have shown how to calculate
the interface trap density and the band discontinuity
A E, from such data and the method is valid even if
the junction
is graded. From Fig. 3 the apparent
sheet density of electron traps may be determined to
be 3 X 10 cmm2. Application of deep-level transient
spectroscopy
(DLTS) suggests that ~the traps are
spread over a distance of about 140 A on the GaAs
side of the interface (the GaAs having been grown
after the AlGaAs in this specimen) with a concentration of about 2 X 1016 cmm3. The trap-level average
energy was estimated as about E,, - 0.66 eV. From
the threshold-current
density (about 3 KA/cm2)
for
an injection
laser containing
this interface a nonradiative
interfacial
recombination
velocity S( =
auN,) of about lo4 cm/s was inferred. For 3 x 10
states cm-
this would represent
a capture cross
section u of 8 X lo-l5 cm2 in rough agreement with
an estimate of capture cross sections from the DLTS
measurements.
The physical nature of the states is
not known.

103

and overview
18
; lo 2

P-n JUNCTION

I
n-N INTERFACE

,+n-GoAs-----

Y0

$
F
E
Y
s
Y
7
G 10

FOR PROFILE

1$k,
0

1000
DEPLETION

Jg,,2
, 1

2000

3000

WIDTH,W(V)(i)

Fig. 3. C-V doping profile of P+- n-N DH laser structure


used to study interface
states. The position of the n-N
interface
at 0.17 pm was determined
by direct measurements in a scanning electron microscope. The tic marks on
the profile indicate the values of the reverse bias voltage in
the C-V measurement.
The Debye length of 100 A indicates the lower limit on spatial resolution[42].

Consider other measurements


of this nature. In a
study of an Al,,,,Ga,
xsAs/A10,4, Ga,,, As double
heterostructure
as a function of active-region
thickness the value of S obtained
was close to lo3
cm/s[45].
Such a low value lends to have little
adverse affect on device performance.
Since 1.55 pm is the wavelength of minimum attenuation in optical fibers, attention has focussed on
In o,sXGao,4,As which has a suitable bandgap (equivalent to 1.62 pm) and is a lattice match to InP. A
confining
material is needed for laser action and
In o 52Al, 4RAs (bandgap 1.47 eV and a match to InP)
has been used. Capacitance
profiling applied to a
Au/Ti
N-In,,,Al,,,,As/n-In,,,Ga,,,As/n
InP
structure yielded 0.50 eV for the conduction
band
discontinuity
(corresponding
to about 70% of AE,)
[46]. An interface charge density of 4 X 10 cm-*
was obtained which is high enough to suggest that
the junction was somewhat imperfect.
A study has been made of the recombination
properties of LPE grown In,Ga,_,P/GaAs
heterojunctions
as a function
of the degree
of lattice
mismatch[47].
This and other related studies have
been discussed by Aspnes[48] with the results presented in Fig. 4. The measured interface surface
recombination
velocity is seen to vary linearly with
the lattice mismatch. The density of dangling bonds
at the interface may be expected to vary as 8Aa,/a,,
and so to be about 2.5 x 1013 cm-2 for a 1% lattice
mismatch [49] and 2.3 x 10 cm- 2 for a 0.01% match.
The relationship
between the dangling-bond
density
and the number of misfit dislocations in the plane of
the interface and threading dislocations
developing
from the interface
depends on strain effects and
impurity-related
defects perhaps present at the interface. The relationship between the interface recombi-

A. G.

104

MILNES

most heterojunctions.
However, the need for lattice
matching may not be quite as severe as suggested by
Fig. 4. There are studies in progress with latticemismatched
heterojunctions
that are not thin enough
to be pseudomorphic
that suggest that other effects
enter, and that equating of recombination
centers to
the dangling-bond
density of the simple mismatch
model is open to question, perhaps by as much as
two orders of magnitude. However, there is no doubt
that the better the lattice match, the better the chance
of the device being good.
4. HETEROJUNCTION
FIELD-EFFEfl
TRANSISTORS

Fig. 4. Interface recombination velocities for lattice-mismatched heterojunctions as a function of relative mismatch
c = Au,,/u,,. Data are as follows: (a,~), In,Ga, _ ,P/GaAs.
determined from measurements of photoinduced short-circuit currents in p-n junctions; (O,O), In.Ga, ,P/GaAs.
from heterojunction solar cells; (m) Pb, , Sn ,Te/PbTe,
minority-carrier lifetime measurements on double heterostructure lasers; (+), Al,,,Ga,,As/GaAs.
Filled and open
symbols represent epitaxial layers in compression and tension, respectively (after Aspnes (481).

nation density NR and the dangling-bond


N,, and
dislocation
densities is unclear. The recombination
velocity is given by uv,NR where u is the recombination cross section and U, is the thermal velocity
- lo7 cm s-. If NR is taken equal to NDB, as
assumed by Kressel[49], then
s = olo7SAa,/a;
= 2.5 x 10220Aa,/a,i.
This leads to the theoretical lines shown in Fig. 4 for
two assumed values lo-l4 and lo-l5 cm2 of capture
cross section.
If a film of thickness d is cladded on both faces by
a heterojunction
interface of recombination
velocity
S, and if the film thickness is much less than the
minority-carrier
diffusion length as in a laser, then
the relationship
that applies for the effective lifetime
7 is

where 7R is the bulk lifetime. If 7B is lo- corresponding to a GaAs minority-carrier


diffusion length
of about 10 pm and if d is 10m4 cm, then it is seen
that a value of recombination
velocity of lo3 cm/s
or less makes 2S/d an acceptably small term in its
of Fig.
4 for
effect
on
7. If the results
are generally valid, then lattice
In ,Ga,
, P/GaAs
matching
to closer than 10m4 may be desirable in

This Special Issue on Heterojunctions


has five
papers dealing with field-effect transistors but these
involve special topics. Therefore, some of the fundamentals are discussed below and some key references
given. The May 1986 issue of IEEE Transactions on
Electron Devices is to be devoted entirely to heterojunction FETs so the present discussion is brief.
GaAs because of its high electron mobility has the
potential
of outperforming
Si FETs. GaAs FET
principles
are discussed
in a volume edited by
DiLorenzo and Khandelwal[50].
There is further discussion in the papers by Baliga et u/.[Sl] and by
Wieder [52]. A major problem with GaAs is that it is
not easy to obtain a low enough density of states
at the interface
between GaAs and an insulator
or native
oxide)
to make
(SiO,, Si,N,, Al,O,
MISFETs that are effective. Hence CMOS operation
is not easy to achieve.
For low-power-dissipation
circuits, where normally
off devices are needed, it is necessary to use MESFET
structures
that are fully depleted by the inherent
built-in Schottky barrier voltage and to bias these
with a voltage of about 0.5 V to achieve turn-on.
With these enhancement
MESFETs the GaAs logicgate-delay versus power-dissipation
parameters tend
to be in the region of the performance
graph shown
in Fig. 5. Thus the GaAs MESFET technology
is
superior in performance
to Si technologies (except at
present in yield and price). GaAs-heterojunction
bi-

Fig. 5. Power-delay
gies. The diagonal
product (from

regiona of various transistor technololines are lines of constant power-delak


IEEE Spectrrtv~. p 2X (Feb. 19X4))

Introduction

polar transistors are seen to be significantly higher in


power dissipation,
with a slight edge in speed, but
are capable of delivering larger output currents or
powers for heavier loads. The Josephson-junction
technology has reliability and ultra-low temperature
system-integration
problems and seems unlikely to
be pursued at present.
The technology labeled MODFET 77 K in Fig. 5 is
of special interest.
Modulation-doped
field-effect
transistors
have very high electron mobility in the
GaAs channel since this is maintained relatively free
of ionized-impurity
scattering because the dopants
that supply the channel electrons are confined to an
(AlGa)As region parallel to the channel that is separated from it by a heterojunction
conduction-band
barrier. This effect is useful even at 300 K but
becomes impressive at 77 K. The structures are also
termed
selectively
doped
FETs (SD FETs) or
high-electron-mobility
transistors
(HEMT) or twodimensional
electron-gas
FETs (TEGFETs).
The
concept dates from Bell Laboratories
work in 1978
and the history to 1984 has been reviewed by Morkoc
and Solomon [53] and the materials aspects discussed
by DiLorenzo
et al. [54].
A typical MODFET energy diagram is that shown
in Fig. 6. The A1,,,SGa,,,,As
layer (0.1 pm) is doped
1.5 x 101scm~3. Thus electrons pass over a 100 A
undoped region into a heterojunction
notch in a 0.2
pm GaAs layer to form an almost two-dimensional
surface-channel
layer of lo* electrons
cm * [55].
The Hall mobility in the surface layer is about 9000
cm*/Vs at 300 K and perhaps as high as 2 x 10
cm*/Vs at 77 K (56). Typical transconductances
are
100~200 mS/mm at 300 K and 300 mS/mm at 77 K
for devices of gate lengths l-3 pm[57-591. Matters
that have been of concern in the fabrication
of
MODFETs
include the following.

N 5 = 1.14 X td2cm-2

Depleted

Fig. 6. Typical

(300K)

I
I

MODFET (AlGa)As-Ga.As
(after Morkoc).

energy diagram

and overview

105

(a) Imperfections
of the interfaces, particularly the
inverted (GaAs grown on AlGaAs) interface [60-621.
(b) The proportioning
of the device, including the
role of the undoped (AlGa)As region, in improving
the channel mobility and aPfecting the available sheet
charge and so the device transconductance[63].
The
selective placing of the Si doping impurities in the
(AlGa)As effectively makes the devices insulated-gate
field-effect
transistors
with the undoped (AlGa)As
acting as the gate insulator[65,66].
(c) The discovery that Si doping of the (AlGa)As
causes deep donor vacancy complexes (termed DX
centers)
to develop
in the doped layer and the
MODFETs
then exhibit collapse of I V characteristics in the dark and threshold voltage Vr instabilities
associated
with change of channel electron concentration
with light illumination
and temperature [59,64]. The effect may be studied by examination of a persistent-photoconductivity
effect [68] at
77 K and is the subject of papers in this issue.
Si doping of GaAs does not produce deep donors
and GaAs does not normally exhibit persistent photoconductivity.
For improved threshold stability the
doped (AlGa)As layer in a MODFET may be replaced by an AlAs/n-GaAs
superlattice
(for instance an active 0.5 pm undoped GaAs layer followed by a 450 k superlattice
of alternating 20 A
layers of undoped
AlAs and Si doped GaAs with
an equivalent
superlattice
doping
level of 2 x
10IXcm [59].
(d) Understanding
the noise-level-determining
factors in MODFETs. Laviron et d. [69] find room-temperature
noise figures of 1.07 dB with associated
gains of 10.5 dB at 10 GHz for 0.5 pm gate length
structures. At 100 K and 17.5 GHz the noise figure
becomes 0.34 dB with associated gain 9.6 dB.
(e) Attention
must be given to minimizing
the
parasitic resistances
and capacitances
of the slructures if the full advantages of potential high-speed
performance
are to be obtained[70-721.
Dualgate-heterojunction
FETs of master-slave
flip-flops
formed by four cross-coupled
AND/NOR
gates where
each four-input AND/ NOR gate consists of two dual
gate SDHTs of 1 pm gate length[73] have operated
as a divider at 5.5 GHz at room temperature
and
10 GHz at 77 K. One-kilobit
RAMS based on
MODFETs
have been demonstrated
with access
times of less than 1 ns.
(f) Another
aspect of MODFETs
that has been
explored with some success is the feasibility of pchannel devices. Sheet-carrier concentrations
of 1 x
10 cm have been obtained with 77 K hole mobilities of 3650-5000
cm V-- s in Be-doped
(AlGa)As/GaAs
structures[74].
Transconductances
of about 30 mS/mm at 77 K have been obtained for
1.5-2 pm gate lengths[75]
and p-channel
devices
exhibit very little shift of threshold
voltage with
light [76].
Structures that consist of (1nGa)As grown on InP
have
been
giving
interesting
performances.
nIn o &a,, 47As doped 10 cm exhibits a 300 K

A. G. MILNES

106

electron mobility of 8000 cm*/Vs, which is almost


twice that for GaAs of comparable doping. The gap
between
the r central valley and the L satellite
valley is larger than for GaAs and therefore
an
electron overshoot velocity that is higher by a factor
of two is perhaps achievable[77].
A number
of junction
or insulated
gate FET
structures
have been made in (InGa)As[78-821
and selectively
doped
FETs
have been
made
with Ga,,,In,
53As/Alo4XIn,,,,As
[83]. Recently,
Rosenberg
et al. (1985 IEEE Device Research Conference,
Boulder,
CO) have demonstrated
a high
electron
mobility
transistor
that has a GaAs substrate and a thin (300 A) pseudomorphic-strained
active layer of In,,,Ga,
ssAs followed by a GaAs
spacer layer and a GaAs ( n = 2-8 x 10%mP ) layer
to provide the carriers for the 6 X 10 cm - electron
gas. For 1 pm gate lengths the g,, observed was 170
mS/mm
at room temperature
and the 77 K electron mobility
was 40,000 cm*/Vs.
An important
feature of the device is that it does not exhibit
collapse of the IV characteristics
in the absence of
light since AlGaAs and its D-X center is not part of
the structure.
Much remains to be studied in high speed FET
GaAs structures[84-881
including the performance
of various vertical- and permeable-gate
structures
[89-921.

n+

Substrate

b Collector
(a)

5. BIPOLAR

HETEROJUNCIION

TRANSISTORS

In conventional
(homojunction)
n+pn
bipolar
transistors
the emitter is more heavily doped than
the base to control the reverse injection from base to
emitter that otherwise would reduce the current gain.
The valence-band
barrier AE,, for heterojunction
transistors,
such as the N(AlGa)As/pGaAs/nGaAs
structure,
eliminates
this problem and the base region may be more heavily doped than the emitter[l].
This results in a base resistance that is reasonably
low even if the base is made very thin to lower the
base transit time. The low base resistance therefore
reduces
the base-emitter
and base-collector
RC
time-constant
terms that also limit the frequency
response of the device provided the associated capacitances can be held small by emitter and collector
doping control.
One of the important
applications
of heterojunction bipolar transistors
is likely to be in analog to
digital converter
circuits where very high sampling
rates are desirable and the circuits require the high
driving power (large transconductance)
of an HBT.
The achievement
of very-high-frequency
performance in a bipolar heterojunction
transistor depends
critically
on minimizing
device
parasitic
time
delays[93]. In a normal transistor configuration
the
collector
area is larger than the emitter area, as
shown in Fig. 7(a), so the collector capacitance-base
resistance
time constant
in a heterojunction
transistor may be a factor limiting the frequency
response
unless
this is addressed
in the design.
Krocmer [94] has shown how this may be reduced by

n+

1,i

Substrote

Emitter
(b)
Fig. 7. The two single heterojunction bipolar transistor
structures discussed in the text. (a) The conventional
emitter-up/collector-down
configuration. (b) The inverted,
emitter-down/collector-up
configuration. Note the relative
positions of the narrow and wide bandgap layers in the two
structures; note also the position of the heterojunction. The
devices illustrated are single heterojunction devices but the
concept is equally valid for double heterojunction tran
sistors[95].

use of an inverted (collector-up)


design in which the
current flow is restricted to the small collector region
of the structure by the barriers of the wide-gap npi
junction
near the base in Fig. 7(b) if this is of low
leakage current. With such a structure the relative
frequency performance
of bipolar heterojunction
and
homojunction-transistors[95]
has been estimated to
be about 1.7:1 although this is yet to be demonstrated.
An (AlGa)As/GaAs
heterojunction
transistor should have a much higher current gain than a
GaAs homojunction
transistor if the emitter-base
interface is well prepared[96]
but this is not always
seen for reasons that are not fully examined, nevertheless serviceable current gains of lo-100 are common. The modeling of (AlGa)As/GaAs
devices presents special problems that have not yet been fully
resolved[97]. The papers by Ankri et al. and Fischer
et al. in this issue discuss
matters
relevant
to
emitter-injection
action in the (AlGa)As system.
In a typical heterojunction
bipolar transistor the
emitter may be nAl,,,Ga,,As,
the base pGaAs (0.1
pm 10 cm 3, and the collector nGaAs on a semiinsulating substrate. The two emitter fingers may be
4.5 pm wide and 10 pm long. In such a design[98]
the current gain i,/i,,
observed was 90 and the
transconductance
per emitter
width
was 4750
mS/mm.
The common-emitter
current-gain
cut-off
frequency
fr was 25 GHz corresponding
to an
emitter-to-collector
transit time of 6.4 ps of which

Introduction and overview


5.2 ps was emitter charging time. It was considered
that this could be reduced to obtain an fr of 50
GHz. Other research groups have obtained comparable performances
[99-1021, so heterojunction
bipolar transistors
are promising
devices for ultrahigh-speed
integrated
circuits. Propagation
delay
times of about 50 ps per gate have been achieved in
ring oscillators. This issue of Solid-State Electronics
contains a study of current-mode-logic
HBT circuit
performance
by Katoh et al. that predicts switching
times between 30 and 10 ps. The d.c. characteristics
of double heterojunction
bipolar transistors are discussed in the paper by Ankri et al.
Grading of the base region of an HBT to improve
base transit time by provision of a quasi-electric-field
in the base has been examined by Hayes et al.[103].
Heterojunction
bipolar transistors tend to exhibit a
significant collector/emitter
offset voltage because of
the difference
in base-emitter
and base-collector
turn-on voltages unless a second heterojunction
is
provided
at the base-collector
junction.
Compositional grading of the emitter to base region however
smooths out the conduction band discontinuity
and
so reduces
the emitter-base
junction
turn-on
voltage[l04]
and reduces the need for a double heterojunction
structure.
Numerical
modeling
of heterojunction
bipolar
transistors
with graded bases suggest that a currentgain cut-off frequency
of 100 GHz should be obtainable [105]. Monte
Carlo simulations [106,107]
suggest that in a base region of 1000 A with a
quasi-electric
field of about 20 kV/cm there is nearballistic transport of the electrons and a current-gain
cut-off frequency
of even 150 GHz might be expected. Ballistic transport has also been considered
in 0.25 pm gate-length FETs[lOS] with prediction of
fr up to 160 GHz. Hot carriers may cross barriers in
real-space transfer and become trapped [109], as in Si
MOSFETs, so such predictions must be viewed with
caution.
The basic concept that electrons in short devices
may attain high velocities and result in fast charge
transfer
is however a matter of continued
interest [llO-1121. Ballistic transport implies collision-free
transit
over distances
shorter than a mean free
path for the particular electron energy. The presence
of a conduction
band spike (energy discontinuity)
at
a heterojunction
emitter has some influence on the
energy distribution
of the electrons injected in the
base and the mean free paths may be affected by this
and contribute
to the degree of ballistic transport in
narrow base transistors.
A GaAs planar-doped
version of this has been reported by Hollis et al. but
with limited performance[ll3].
Although
the discussion
has centered
around
(AlGa)As/GaAs
structures,
heterojunction
bipolar
transistors
have been fabricated
in the (AlIn)As/
(GaIn)As/InP
system [114,115]. More studies with
this and other materials systems are in progress. It is
noteworthy
that nA1 a 35Ga, 65P/pGaP/n
GaP bipolar transistors
have demonstrated
useful transistor

107

operation at temperatures
up to 550 C and might be
of value for geothermal and other specialized applications[ll7,118].
In recent years Si bipolar transistors
have been
studied with emitters of SIPOS or n doped hydrogenated amorphous silicon [119,120]. The low mobilities and localized energy states that exist in such
emitters are performance-limiting
factors. Recently
Sasaki et al. (1985 IEEE Device Research Conference, Boulder, CO) have reported an amorphous
SiC:H emitter for a Si base-collector
heterobipolar
transistor.
The AE,. and AE,, values observed are
0.16 and 0.54 eV, respectively, with the 1.8 eV emitter
material.
Also recently there has been progress with the
growth of strained Ge,,,Si,,
layers on Si and bipolar
transistor action may be expected from these.

6. LIGHT DETECI-ION WITH HJXEROJUNCIION


DIODES AND TRANSISTORS

Silica fibers are of low loss in the 1.3-1.6 pm


wavelength range and therefore there have been extensive studies of light-detecting
diodes and transistors in this range involving ternary or quaternary
III-V semiconductor
heterojunction
structures. The
ability to sense low light levels with fast response
time and high gains is of prime importance in optical
communication
systems.

6.1. Diode Detectors


Conventional
photodiode structures have been well
reviewed by Melchior [121] and others [122]. If a PIN
form is used the photons are absorbed in a depleted
region of high field and the gain is increased by
avalanche
multiplication
and nanosecond
electron
transit times are readily achieved. However care in
design and fabrication
is needed to obtain uniform
avalanche action [123,124] and low dark currents.
The performance
of a heterojunction
avalanche
photodiode
with nIn, s,Ga,,,,As
as the light absorbing layer and npInP as the avalanche multiplication
junction is shown in Fig. 8. Separate absorption and
multiplication
regions tend to reduce tunneling components of dark current and in this structure 1 x 10m4
A cmm2 at 0.9V, is achieved, where V, is the junction breakdown voltage[l23]. When illuminated with
1.15 pm light, the diode has a maximum multiplication gain of 880 and an external quantum efficiency
of 40%.
Structures of this kind tend not to perform well at
high bit rates because the bandwidth is restricted by
hole trapping at the valence-band
discontinuity
at
the InP/InGaAs
interface. These holes must escape
by thermal emission in the recovery phase and this is
a relatively slow process. The incorporation
of a 0.3
pm intermediate
layer of n In, ,Ga,, As,, 65POs5 between the nIn o.ssGa,47As (10 pm) absorbing layer
and the npInP multiplication
junction
solves this
problem and allows a gain of 40 or 50 at 0.9 VB and
a dark current density of 5 x 10m4 Acm (13 nA)

108

A. G. MILNES

10 -I-

In other studies with separate absorber and multiplication


regions,
Al, 48In, 52In/Ga,
47In, 53As
avalanche photodiodes
have exhibited good performance [126]. A typical structure and the corresponding energy diagram are shown in Fig. 9. The advantage claimed for this particular
version of an
SAM APD is that the A E,, value is low. This reduces
the pile-up effect of holes at the notch and so the
detector
response
time is shorter than for other
material combinations.
Hole trapping at a heterojunction
interface is the
essential feature of operation of the modulated barrier photodiode
of Fig. 10. The device although not
superfast is sensitive to low light powers and may
have a d.c. optical gain of 1000 in the nanowatt
illumination
range[127,128].
The gain is caused by
barrier lowering produced by the accumulation
of
the photogenerated
holes in the valence band notch
region at the source-gate interface. The rise time is
about 50 ps and the fall time about 600 ps for 0.83
pm pulse illumination.
This may be compared with 2
ns for a phototransistor
in the low-gain base-controlled condition or lo-100 ns in the high-gain Roating-base condition.
A typical avalanche photodiode
of 50-100 ps response time needs a bias voltage of 20 V or more

/l\zn-InGaAc

..

-11
KI

AuSn

L
40

20

30

40

50

BIAS

VOLTAGE

REVERSE

V,(V)

(a)

IO3

10-4

J
IO
si
5

IO

-E

P+ *0.48I0.52

&
5
g
5
II

As

-7
10

-E
10

-E
10

GY : : % . _.
(a)

-1c
10

10
REVERSE

20
BIAS

30
40
VOLTAGE

50
(VI

60

(b)
nEc

Fig. X. A hetcrojunction
avalanche
photodiode
with
In ,)57Cra,,47As
.
absorbing layer and nInP avalanche multiplication layer and window layer [123]. (a) Dark currents as
a function of reverse bias voltage for several diodes made
from the same wafer. Inset shows a schematic cross section
of the HAPD with buffer layer. (b) Typical photocurrent
of the waveagainst reverse bias voltage as a parameter
length of incident light.

=0.55ev

(b)

coupled
420

Mb/s

with
and

excellent

performance

1 Crb/s[125].

at bit

rates

of

Fig. 9. Avalanche
photodiode
of (GaIn)As/(AlIn)As.
(a)
Schematic of the 1.3 Frn avalanche detector with separate
absorber
and multiplication
regions. (b) Energy-band
di.
1.
agram unaer reverse-mas conaltlom

Introduction

and overview

109

Ge-Au

CONTACT

(a)
hv

(b)
Fig. 10. An (AlGa)As/GaAs
low-light photodetector
structure. (a) Schematic diagram of the majority-electron
photodetector.
Incident photons are absorbed partly in the gate
but most in the drain region. (b) Schematic representation
of the energy band diagram of the majority-electron
photodetector under normal bias condition.

although
adequate.
mission
essentially

if avalanche

gain

A low voltage
of light

energy

a miniature

is sacrificed

may

through
solar

a few volts

be generated
a fiber

cell structure

To

(b)

SAMPLING

SCOPE

2 DEG

is

by transto what

is

providing

of power [129].
In a few applications
there may be interest in
high-speed
photodetectors
that require no external
bias voltage. Such a structure is shown in Fig. 11.
The light pulse passes through the (AlGa)As window
layer and generates
electron-hole
pairs in the
p- GaAs layer where they are separated by the builtin electric field of the junction region[l30]. Electrons
drift towards
the heterojunction
interface
of the
selectively doped Al,,,Ga,,,As/GaAs
structure and
are collected by the Au-Ge electrodes. The photogenerated holes drift towards the pm GaAs and semiinsulating
GaAs substrate and induce electrons in
the conductive
epoxy and a transient signal is coupled into the stripline. Pulses with rise times of 30
ps, and 60 ps width at half maximum, have been
detected. This detector appears suitable for integration with modulation-doped
field-effect transistors.
Photoconductive
detectors can in some respects be
comparable
to photodiode
PIN detectors
in high
performance
in high-data-rate
long-wavelength
lightwave communications
systems. Photoconductive
detectors can exhibit gains of a few hundred at low
frequencies
and gains of the order of 10 at high bit
rates. The gain is less sensitive to temperature
than
for an avalanche
photodiode.
On the other hand,
the detectors with such photoconductive
gain show
long (nanosecond)
fall times. In a study of a
detector grown on
Ga,, ,,Ine 53As photoconductive
an Fe doped semiinsulating
InP, the received optical
milliwatts

(cl
Fig. 11. Bias-free Al,Ga, _xAs/GaAs
photodetector.
(a)
Cross-sectional
view of the bias-free photodetector
(not
drawn to scale). The dashed line indicates the existence of
the two-dimensional
electron gas. Note that the Ge-Au
contacts penetrate the n-Al,,,Ga,,As
layer. (b) Schematic
diagram showing the mounting scheme of the detector. (c)
Energy-band
diagram
of the
selectively
doped
Al, aGa, ,As-GaAs
structure.
The built-in electric field
separates
the photogenerated
electron-hole
pairs, as indicated by the straight arrows. The inserted circuit diagram
illustrates
the electron flows (indicated
by arrows). The
capacitance
C is associated with the semiinsulating
GaAs
substrate. Resistance
R, (or R2) represents the series resistance associated with the electrode No. 1 (or No. 2).

power necessary for a bit error rate of lo-


pm was - 34.4 dBm at 1 Gb/s[l31,132].

at 1.3

6.2. New Photodetector Device Concepts


Although avalanche multiplication
provides desirable gain it also contributes
to signal degeneration
and noise. If the ionization coefficient for holes is

110

A. G. MILNES

comparable
with that for electrons the holes created
in the first ionizing action travel backwards
and
create further hole-electron
pairs that have the effect
of deteriorating
the response to a pulse of light.
Ideally then in avalanche photodiodes
a high ionization rate for electrons (a) and low rate for holes
(p) is desirable.
In Si the ratio a/p
is about 20
and reasonably
acceptable
excess noise factors are
obtained for Si avalanche photodiodes
(APDs) operating at photon energies above the Si bandgap (corresponding
to wavelengths
shorter than 1.1 pm).
However for smaller bandgap materials the ratio of
a/b
is not so favorable. Ideas have been proposed
for overcoming this problem that involve gradedLgap
APDs, superlattice
and staircase APDs and channeling APDs[133-1371.
The concept
of the graded-staircase
avalanchemultiplier
photodiode
is illustrated
in Fig. 12. At
each A E, step the electric
field is high and the
electrons ionize hole electron pairs as suggested by
the arrows in Fig. 12(b). The holes do not ionize
in their reverse flow to the cathode because the
A E,, steps are small. In progress towards construction
of such
a photodiode
a superlattice
of
has been studied and an effecAl o 45Ga,, 55As/GaAs
tive a//3 ratio of 8 demonstrated.
However graded
structures
are needed to eliminate electron trapping
at AE< notches and there are problems still to be
overcome.
The concept

for a channeling avalanche photodiode is shown


in Fig. 13. The structure
consists of
alternate
widegap
p- and low-gap
n-layers and

(a)
.,

E,

(b)
Fig. 13. A proposed channeling structure for an avalanche
photodiode.
(a) Schematic of the channeling APD. (b) Band
diagram of the channeling APD ( ER1 > E 2). c is the parallel field causing carriers to ionize. AE,. ias been assumed
negligible with respect to A E,

voltage is applied so that all the layers are depleted.


The explanation
of device operation that follows is
taken directly
from the Capasso-Tsang-Williams
paper [134].

Fig. 12. Proposed staircase avalanche photodiode.


(a) Unbiased graded multilayer region. (b) The complete staircase
detector under bias. The arrows in the valence band indicate that holes do not impact ionize.

Suppose
that radiation
of suitable
wavelength is absorbed in the lower gap
layers thus creating electron-hole
pairs.
The two p-n heterojunctions
formed at
the interfaces between the relatively narrow bandgap and the surrounding higher
bandgap
layers serve to confine electrons to the narrow bandgap layers while
sweeping holes out into the contiguous
wider bandgap p-layers where they are
confined by the potential. The parallel
electric field c causes electrons confined
to the narrow bandgap layers to impact
ionize. Holes generated in this way are
swept out in the surrounding higher gap
layers before undergoing ionizing collisions in the narrower gap layers since
the layer thickness is made much smaller
than the average hole ionization distance
l/p.
In conclusion, electrons and holes
impact ionize in spatially separated re-

111

Introduction and overview


gions of different bandgap. Holes in the
wider gap layers impact ionize at a much
smaller rate compared
to the electron
ionization
rate in the relatively lowgap
material, due to the exponential
dependence of a,/3 on the bandgap, so that
a/@ can be made extremely large. Note
that this structure has the advantage of
providing a high a/P ratio at very high
gains (> 100) because
electrons
and
holes impact ionize in different materials. A typical design for 1.3-1.6 pm
detectors
would have p- and n-layer
thicknesses
of 0.5-1.0 pm and doping
levels p = n = 106/cms. The p layers
could be of InP or Al,,,In,
52A~ and
the n layers of In,,,Ga,,,As.
These
materials can be grown lattice matched
to a semiinsulating
Fe doped InP substrate. The estimated a//3 ratio is = 350
for a parallel field of = 2 X lo5 V/cm
at a gain of = 150 for a layer length of
= 25 pm.
There are technological
difficulties in fabricating
such structures
and it remains to be seen whether
good performance
can be achieved.

6.3. Phototransistors
Bipolar-junction
and field-effect transistors may be
used as light detectors.
In the bipolar device the
transistor
is designed so that illumination
creates
carriers in the base region. The supply voltage is
applied between the collector and the emitter, and
the base floats at a potential
VEB that suits the
current flow and photoinduced
carrier conditions as
shown in Fig. 14. There is a buildup of excess holes
in the base and so development
of the voltage I,,
that allows a small hole current related to the photon
flux to flow into the emitter. However, the voltage
&.a causes a much larger current of electrons to flow
from emitter to collector. Thus the photon-induced
carriers are multiplied
by the injection gain of the
transistor,
provided the base is free to find its own
potential. A heterojunction
transistor with wide-gap
emitter provides an optically transparent
emitter region for photons within a certain energy range, and
also the high gain associated with the A E,, barrier at
the heterojunction
interface. Interface recombination
may reduce this gain and it is not unusual to find
that the transistor gain is low at low currents or low
light levels. At nW power levels the current gain
(h,,)
or optical gain may be 30 or 40 and rise to
many hundreds
at high signal power levels. The
performance
of heterojunction
phototransistors
in
the material system InGaAs/InP
has been studied
by Chand et al. [138] who conclude that many of the
recent reports of very high optical and current gains
may involve avalanche multiplication
as in Fig. 14(c)
enhancing
the gain of the HPTs. The gain dependence (on the base-collector
voltage) reported
by

(b)

Cc)
Fig. 14. Heterojunction
phototransistor
action. (a) Operation with floating base. (b) Energy-band
diagram with hole
accumulation
in the base causing emitter-base
bias and
electron injection
and collection. (c) Optical-input
power
and voltage dependence of optical gain.

Chand et al. and attributed to avalanche multiplication is not generally observed to such a degree. If
holes are being generated by avalanche at a high rate
and must escape from the base by emission into the
emitter, then an unstable switching or looping-action
might be expected. Since this is not seen then it is
possible that heavy recombination
is taking place in
the base of Chands structure or at the emitter-base
interface. Narrowing of the base width with increase
of &.a is another factor that could contribute to the
dependence
of the gain on I&. There is more to be
examined here in respect of HPT gain and frequency
response. The response time of a graded-base phototransistor may be a few tens of picoseconds[l39].
Wavelength-selective
photodetectors
are of potential interest
in wavelength-division
multiplexing
transmission
systems and in heterojunction
tran-

112

A. Ci. bfII.NES

sisters some degree of selectivity can be achieved by


choice of a suitable absorbing layer in the optical
path as shown in Fig. 15 [140]. The power dependent
gain-bandwidth
performance
of heteroJunction
bipolar phototransistors
for communication
systema
has been considered by Milano et ul.1141].
Modulation-doped
FETs may be used as photodctectors. The structure
shown in Fig. 16(a) has a
gate-drain
spacing of > X pm and a gate length of
>
20 pm, and in spite of these large dimensions it
exhibited (for GaAs laser pulses) a rise time of 12 pb
with a full width at half maximum of 27 ps[140].
The a.c. (> 20 MHz) external quantum efficiency
was nine times more than for a PIN diode.
MODFET detectors therefore offer comiderable
pcrformance promise.
In general a PIN detector must be followed by a
transistor to provide increased gain. Fig. 16(b) shows
the integration
of a PIN InGaAs detector with an
InP MISFET transistor [143]. PIN-FET
integration
has
also been
based
on the AlGaAs/GaAs
system[144].
6.4. Photocwltuic Solur Cells
There is extensive
literature
on heterojunctions
applied to solar power generation [145~~147]. The May
1984 IEEE Trunsuctlons on Electron Dec$ices is an
issue devoted entirely to photovoltaics
and a broader
review appears in IEEE Spectrum for March 19X4.
In general polycrystalline
heterojunction
solar cells
show
degradation
effects
and do not exhibit

AU-5

hL 3

OHMIC

CONTACT

SOURCE
n+-GoAs12008,2x,d*
UNDOPED Al,

SUbSTFcATt

I
\

Au-9
OHMIC

CC,NTA:CT

(3)

I .,,

Fig.
15. A
InGaAaP/InP

wacclength

xlective

heterojuncrion

phototransistor-. (a) Structure \*ith selective

ahsorbing

layx

(h) Band diagram.

75iil

SEMI-INSULATING

Ge-AU

Al

(a)

AFeN,,Au

Ln DlFFlJSlON

IllP
InGaAs

sI

IrlP

tl+-IllP

(b)
(a) With modulated-doped
FET[142]. (b) With PIN detection and integrated InP MIS
FET[143].

Fig.

16. FET photodetection.

the efficiencies needed to be cost effective (perhaps


> lo-12% for air-mass-one
conditions is needed in
large arrays).
Single-crystal
solar cells based on the III-V system
are capable of performances
that exceed those of Si
cells. Single junction efficiencies of 20% or more are
possible with well designed and fabricated heteroface
cells of AlGaAs/GaAs
at high solar-concentration
conditions.
In multijunction
cascade
structures
(tandem-cells)
the predictions are for 35% efficiency,
but for various technological
reasons the present
performance
is below that of single crystal cells.
7.

cn?r

3 Gao7As(

HE~ER~.JUNCTIONLIGH~-EMI~IN~;OIODES
AND INJEffION
LASERS

Heterojunctions
have made significant contributions to light-emitting
diodes by allowing ternary
and quaternary
structures
to be grown effectively,
and by providing carrier confinement and low interfacial-recombination
and window action. Typical
structures are shown in Fig. 17(a),(b),(c). The GaAs
structure of Fig. 17(b) provides a CW output of 5.X
mW, or a radiance of 92 W/sr cm, at 150 mA [14X].
The InGaAsP
structure has a total hemispherical
light output of 1.2 mW at 200 mA (10 KA/cm)
and
is capable of coupling 40 PW of optical power into a
63 PW core 0.21 NA optical fiber. The proJected
lifetime at room temperature is estimated to be over
10 h[149]. This issue of Solid-State Electronics contains a paper by Komiya et ul. that is concerned with
luminescence
from InGaAsP.
Very often an LED has a hemispherical
emitting
structure
to focus the light into an approximately
parallel beam by minimizing total internal reflection.
However another approach by Thornton et (11.(1985
IEEE Device Research Conference, Boulder, CO) is

Introduction
LIGHT
GaAs

EMITTING

REGION

METAL

CONTACT

SUBST
GoAs(
1225

-2pm

GoAs

(~)
GoAs

SUBSTRATEtn

CONTACT

and overview

113

The IEEE Spectrum for December 1983 contains a


review of single-frequency
semiconductor
lasers for
fiber-optic systems. These references are sufficient to
introduce
newcomers
to the field. Contributions
on
injection
lasers were not invited for this issue of
Solid-State Electronics in view of the very specialist
nature of present developments
and the coverage
available elsewhere.

GaAs (n

8. QUANTUM-WELL
STRUCTURES
STRAINED LAYER SUPERLATTICES
BANDGAP ENGINEERING

GaAs(p
Zn DIFFUSION

(b)

n-lnGaAsP(Eg

=lOZ/~rn)
(Eg

p-lnGoAsP(Eg

(c)

=l

2711)

=l 02pm)

AuSn

Fig. 17. Typical light emitting diode structures. (a) Double


heterojunction
structure
with GaAs light emitting region
and Burrus-type
geometry for coupling to an optical fiber.

(b) Structure with Zn diffusion to reduce series resistance.


(c) Structure with InGaAsP active layer that emits at 1.27

to take a GaAs laser structure and almost entirely


eliminate
the reflection at one emitting surface by
providing
an antireflection
coating of ZrO,. This
suppresses laser action at high current densities (perhaps even to 6-8 times the current density typical
for laser action in a similar structure with a complete
FabryPerot
cavity). In this way 200-350 mW of
CW light has been obtained from an edge-emitting
device at room temperature
with no active cooling
and power conversion efficiencies obtained of about
3%. The structureless
far-field pattern so obtained,
with absence of laser speckle, is of value in certain
applications.
The general principles of light-emitting
diodes have
been discussed
by Bergh and Dean [150] and by
Pilkuhn [151]. Extensive use of visible-light-emitting
diodes already exists and may be expected to grow as
high-brightness
high-efficiency
low-cost diodes are
developed [152]. Diodes are available in red, orange,
yellow and green. Blue emitting diodes of SIC are
expected to come to market soon.
Turning now to semiconductor
injection-lasers,
the
role of heterojunctions
has been of the essence almost from their first inception. No attempt will be
made here to review or highlight this role[3,153].
The June 1983 and June 1985 issues of the IEEE
Journul of Quuntum Electronics are given to semiconductor lasers. The IEEE Journal of Quuntum Electronics also publishes many of the papers given at
the International
Semiconductor
Laser Conferences.

AND
AND

Semiconductor
superlattice
and quantum-well
structure
studies were initiated by Esaki and coworkers about 1970. One kind of superlattice
consists of periodic layers, a few hundred angstroms
thick, of a homogeneous
single-crystal
semiconductor with large doping swings to form n-i-p-i
structures. Such structures may be expected to have unusual conductive, capacitance and optical properties.
More usually quantum-well
superlattice
structures
involve periodic thin layers of two (or occasionally
more) different semiconductors
and the semiconductors are often selected to be closely lattice-matched.
Sometimes
they may be lattice-mismatched
so that
alternate layers are in elastic tension or compression
and average in lattice constant to the lattice of the
substrate on which they are grown. A journal Superluttices and Micro-structures, published by Academic
Press began in 1985.
In a recent review of superlattices[l54]
Esaki characterized them as types I-III as shown in Fig. 18.
Type I occurs for systems such as GaA-AlAs
and
GaSb-AlSb,
or the strained
layer structure
of
GaA-Gap.
The sum of A E, and A E,, is seen to be
equal to the bandgap difference Eg2 - Eg, of the
two semiconductors.
The type II staggered structure
is found in certain superlattices
of ternary and
quatemary
IIIIVs. Here it is seen that AE, - AE,,

ELECTRONS

TYPE

in

Ec2

5
Ev2

Fig. 1X. Discontinuities


of bandedge energies at four kinds
of superlattice
heterointerfaces:
band offsets (left), band
bending and carrier confinement (middle), and superlattices
(right) [154].

114

A. G. MILNES

equals the bandgap difference Egz - Eg,. The type


II misaligned
structure is an extension
of this in
which the conduction band states of semiconductor
1
overlap the valence band states of semiconductor
2.
This
has been
established
as occurring
for
InA-GaSb.
Electrons from the GaSb valence band
enter the InAs conduction
band and produce a dipole layer of electron and hole gas shown in Fig.
18(c). The zero gap HgTe/CdTe
interface also has
unusual properties
since interactions
between the
hole bands of the CdTe and the HgTe occur.
Semiconductor
superlattices
offer several performance features of interest for device physicists and
engineers.
The value of selective
doping
for
MODFETs
is one property that has already been
amply demonstrated.
A second property of value is
in injection-laser
structures where the provision of a
quantum-well
active region results in modification of
the density of states from a parabolic distribution
as
in bulk material
to a staircase distribution.
This
results in fewer electrons being needed to achieve the
same cavity gain and therefore a lower threshold
current density[l55]
as illustrated in Fig. 19.
Another feature of interest of superlattices
is that
defect and dislocation densities tend to be reduced in
layers grown above superlattices [156,157]. Impurities coming from the substrate are intercepted by the
superlattice [158,159].
Device quality
GaAs and
AlGaAs can be grown on Ge or Ge/Si substrates for

Al,Ga,_,

As BARRIERS

(a)

BARRIER HEIGHT OF THE GaAs/Al,Ga,_,As


MULTILAYERS
L m&l

AlAs

MOLE FRACTION
X IN Al,Ga,_,
BARRIER LAYERS
(b)

Fig. 19. Quantum well injection laser structure and performance[155].


(a) The schematic energy band diagram from
the modified multi-quantum
well laser. (b) Shows the variation of the averaged Jlh of several wafers as a function of
their respective AlAs composition
x (and barrier height) in
the Al ,Ga, _ , As barrier layers.

MODFETs
with the aid of an intermediate
superlattice layer. Interdiffusion
at Ge/GaAs
interfaces
without a quantum-well
superlattice has been studied
by Sarma et al.[160]. Certain alloy systems such as
Ga(As, Sb) have miscibility gaps but superlattices of
them can be grown and matched to InP[161].
The Ge-GaAs
superlattice
has excellent lattice
match but may exhibit planar defects in the GaAs
layers and these have been attributed
to the antiphase boundaries
expected from localized nucleation
of the GaAs on the Ge[162]. Antiphase disorder may
be reduced by careful control of nucleation conditions as found for GaAs and AlGaAs grown on
Si[163]. Control of nucleation has been studied by
Beam et al. [164,165] in the growth of Ge, Si, ,/Si
strained-layer
superlattices and conditions for avoidance of island nucleation
established.
Modulation
doping resulting in a two-dimensional
hole gas has
been demonstrated
for such structures at 4.2 K with
a h& of about 0.1 eV[165,166]. The combination of
(GeSi) and Si is expected to be of device interest in
the next few years.
One feature of superlattices
that is usually undesirable is that disordering is produced by impurities
such
as Zn at quite
moderate
temperatures
(5755615C) [167,168] and by Si at 850C [169]. This
tends to limit the formation of junctions
to in situ
doping during growth. The intermixing phenomenon
induced by diffusion in superlattices
has been discussed by Van Vechten [170].
Tunable below-gap radiation can be obtained from
staggered line-up heterojunctions
and quantum-well
structures[l71].
Perhaps of greater device interest is
the demonstration
that a long wavelength
multiquantum-well
laser with Ga,,,In,,
53A~ wells and
Al o.4xIn,, s2 As barriers can be made to cover the
range from 1.7 to 1.5 p,rn by adjustment to the well
width from 1000 to 80 A[172].
The thickness of the layers and the composition of
alternate layers may be graded in a superlattice,
as
shown in Fig. 20 for a transition
from InP to
Ga,, ,,In, 53As. Such structures have been used in
the fabrication of avalanche photodiodes[l73].
A 50 period multiple-quantum-well
superlattice of
GaAs/AlGaAs
in a PIN diode structure as shown in
Fig. 21 has an optical absorption edge that is abrupt
because of excitation resonances. Application
of an
electric held causes changes of carrier confinement in
the wells and shifts the absorption
edge to longer
wavelengths.
For 857 nm applied light a factor of 2
change of transmission
can be achieved with an 8 V
bias on the diode and the switching time is suitable
for high speed, ns fast modulation[l74].
Optically
bistable light transmission
has been demonstrated
in
such a structure[l75].
Waveguide action in superlattices is discussed
in the paper by Bhattacharya
et al. in this issue.
Another bandgap engineering idea that is emerging
is the concept
of selective mass tunneling
filters.
Tunneling probability
depends exponentially
on the
barrier E, and carrier mass m as exp( - nr/E~/ )

Introduction

and overview

115

I
I
Goo.470.53As

r3
Xl

GoAS

X2

x3

hAS

=1

(a)

I
0

DISTANCE

Fig. 20. Energy band gap of a graded gap psuedo-quaternary


GaInAsP.
The
thicknesses
of the InP and of the
varied between 5 and 55 A
Gap ,,Inc 5~As are gradually
while keeping constant the period of the superlattice (= 60
A). The dashed lines in (a) represent the average band gap.

(b) Schematics of the HI-LO heterojunction avalanche photodiode incorporating the superlattice. (c) Electric field pro tile[173].

Thus it is possible to consider a superlattice in which


there will be selective tunneling of electrons but not
of holes and this may have high photosensitive
gain
because the holes are essentially trapped while electrons make many transits of the device. Furthermore
the electron band state formation in the quantum
well insures that tunneling action selects electrons of
particular
energies hence giving an energy-resonant
tunneling action. So it is possible to envisage an npn
bipolar transistor that contains quantum wells in the
base and that transmits to the collector only electrons in selected energy ranges that correspond
to
certain values of emitter base voltage. So the device
when ultimately
refined and developed to have an
undulating
output as the emitter-base
voltage is
increased may have potential as a logic device with
multiple logic levels or possibly as providing a crude
analog to digital action.
Optical
communication
systems may in some
applications
be multiplexed
with light of several
wavelengths.
Fig. 22 shows a heterostructure
demultiplexer concept in which a detector has a well-structure graded from GaAs to InAs. Selected absorption
of light of different wavelengths in sequential wells
may allow signal separation [176].
For another potential application it has been suggested that strained layer superlattices in the InAsSb
system may be suitable for long wavelength detector
applications
[177]. Suitable
absorption
must be
achievable in a superlattice of reasonable length and
this may be a problem.
Finally in this examination
of bandgap-engineering a sawtooth
superlattice
structure proposed
by
Capasso et ~I.[1781 is shown in Fig. 23. The action
of the device depends on the lack of reflection symmetry and it is suggested that the structure may lead
to high-speed
displacement-current
photodetectors.
The explanation
of the action given by the authors
follows:

Fig. 21. Schematic view of an AlGaAs/GaAs superlattice


optical modulator. The semiconductor layers are grown via
MBE on a GaAs substrate, and then the diode is defined
lithographically. The lower portion of the figure shows the
calculated electric field strength, S, as a function of position
within the device for two applied voltages[l74].

(b)

Fig. 22. Concept for a heterostructure


light demultiplexing
device[l76].
(a) Structure. (b) Energy diagram.

. electron-hole
pairs are excited by
a very short pulse as shown in Fig. 23a.
Electrons experience a high quasielectric
field (typically > lo5 V/cm) due to the
grading whereas the total force acting on
holes is virtually negligible because of
the valence band-edge lineup in p-type
materials.
Therefore
electrons separate

A. G.

116

Fig. 23. Illustration


of the formation
and decay of the
macroscopic
electrical polarization
in a superlattice strutture [178].

from holes and reach the low-gap side in


a sub-picosecond
time (<
10 s).
This sets up an electrical polarization in
the sawtooth structure which results in
the appearance
of a voltage across the
device terminals [Fig 23(b)]. This macroscopic dipole moment and its associated voltage subsequently
decay in time
by a combination
of (a) dielectric relaxation
and (b) hole drift under the
action of the internal electric field produced by the separation of electrons and
holes.
The excess hole density decays by
dielectric
relaxation
to restore a flat
valence band (equipotential)
condition,
as illustrated in Fig. 23(c). Note that in
this final configuration
holes have redistributed
to neutralize
the electrons
at
the bottom of the wells. Thus also the
net negative charge density on the lowgap side of the wells has decreased with
the same time constant as the positive
charge packet (the dielectric relaxation
time).
When excited with 4 ps laser pulses (X = 6400 A)
at 86 MHz repetition rates, a structure graded from
GaAs to Al,,Ga,,As
exhibited a sharp rise-time
output pulse with a 200 ps decay tail. The structure
does not respond to a constant dc light signal. Unlike conventional
semiconductor
photodiode
and
photoconductive
detectors, the current carried in this
photodetector
is of displacement
rather than conduction nature since it is associated with a time-varying
polarization.
9. CONCLUSIONS

AND OVERVIEW

Heterojunction
devices envisaged many years ago
have reached new levels of performance
because of
improvements
in growth technologies and in physical

ibflLNtS

understanding
and examination
of interfaces.
This
has led to revitalization
of the concept of bandgap
engineering
and the free-thinking
produced by this
has suggested
a number of interesting
new device
concepts. Some will survive and others no doubt will
fall by the wayside, but progress is certainly being
made.
The preceding
review has attempted
to set the
stage for the papers that follow in this special issue.
Basic heterojunction
barrier studies are represented
by the papers of Margaritondo
and Wang. Bipolar
transistor
studies follow with the papers of Ankri
et al. and Katoh et al. Modulated-doped
FET structures are represented
by the papers of Look and
Norris, and Schubert
et al. and Nathan.
The first
deals with channel mobility and the others with
undesirable
trapping effects. Contacts to such structures are considered
by Mukhergee
et 01. and by
Christou and Papanicolaou.
Graded heterojunctions
are discussed in the contributions of Fischer et al. and Petrosyan. Then quantum-well
effects are examined
in the papers by
Masselink et al. and Bajaj et ul. and superlattices by
Bhattacharya
et al.
Photoeffects
in InGaAsP are studied in the contributions of Diadiuk and Groves, and Komiya et ul.
and photoeffects
in ZnSe-GaAs junctions by Zhuk
et al. Trap levels in heterojunctions
are often important and a comparative
study of admittance and
DLTS spectroscopy
for CdTe-ZnTe
heterojunctions
is offered
by Khan
and Saji. The growth
of
CdTe-InSb
heterostructures
is discussed by Blat et
(II.

The issue concludes with a paper by the Morkoc


group at the University of Illinois on the very promising performances
achieved for GaAs grown directly
on Si.
Ack~lo,lled~~emerzts-Contributors
are thanked
for their
papers and for allowing their manuscripts
to be held while
the complete set could be assembled for this special issue.
NSF Grant
ECS 82-14859 is acknowledged
for partial
support during the preparation
of my contribution.
REFERENCES

1. A. G. Mimes and D. L. Feucht, Hetero~u,rc~rro~zs crtrd


Mad Semrconductor Junctrons, Academic, New York
(1972).
2. B. L. Sharma and R. K. Purohit, Senrrconducror Ilereropnctions, Pergamon, Oxford (1974).
3 H. Kressel and J. K. Butler, Semiconductor I~crsrr~scurd
IIerero/uncfion LEDs, Academic, New York (1977)
4. H. Kressel.
Muterids for Heterqunclro~l Dwrm,
p.
287 (Annual
Review of Materials Science). Vol. 10,
Academic. New York (1980).
5. K W. Boer, Model of the CdS/Cu,S
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6. R. L. Bell. Negatwe Electron Aflnity Dwrcrv. Oxford
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I. J. 0. McCaldin, T. C. McGill and C. A. Mead. Corrclation for III-V and II-VI semiconductors
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Schottky barrier energy with anion electronegativity.
Ph_vs. Rev. Lxtt. 36. 56 (1976).
Metd-Semicondudor
Contucrs, Ox8. E. H. Rhoderick,

Introduction
ford Clarendon,
England (1978).
9. S. M. Sze, Physics of Semiconductor Devices, 2nd Edn..
Wiley Interscience,
New York (1981).
10. A. G. Milnes, Semiconductor Devices und Integrured
Electronics, Van Nostrand Reinhold, New York (1980).
11. L. J. Brillson, The structure and properties of metalsemiconductor
interfaces,
Surface Sci. Rep. 2, 123
(1982).
12. H. Kroemer, Heterostructure
devices: A device physicist looks at interfaces,
Surfuce Sci.. 132, 543 (1983).
13. S. L. Wright, M. Inada and H. Kroemer,
Polar on
non-polar
epitaxy: Sublattice ordering in the nucleation and growth of GaP on Si (211) surfaces, J. VW.
Ser. Technol. 534 (1982).
14. J. Tersoff, Theory of semiconductor
heteromnctions:
The role of quantum dipoles, Phvs. Rev. B30, 4874
(1984). See also: Phys. Rev. Left. 52, 465 (1984).
15. A. D. Katnani
and G. Margaritondo,
Microscopic
study of semiconductor
heterojunctions:
Photoemission measurement
of the valence-band
discontinuity
and of the potential barriers.,
Ph_ys. Rev. B28, 1944
(1983).
16. R. S. Batter, P. Zurcher and H. W. Sang, Jr., Inequality of semiconductor
heterojunction
conductionband-edge
discontinuity
and electron
affinity difference, Appl. Phys. Left. 43(7), 663 (1983). See also
R. S. Bauer and H. W. Sang, Jr., On the adjustability
of the abrupt
heterojunction
band-gap
discontinuity, Surface Sci. 132, 479 (1983).
17. H. Kroemer,
Barrier
control
and measurements:
Abrupt semiconductor
heterojunctions,
/. Vat. Sci.
Tech&. B2(3), 433 (1984).
18. J. R. Waldrop,
E. A. Kraut, S. P. Kowalczyk
and
R. W. Grant, Valence-band
discontinuities
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