CRITICAL REVIEW

GaN, AIN, and InN: A review

S. Strite and H. Morko,!
Materials Research Laboratory and Coordinated Science Laboratory, University of Illinois at
Urbana-Champaign, Urbana, Illinois 61801

(Received 7 November 1991; accepted 31 March 1992)

The status of research on both wurtzite and zinc-bien de GaN, AlN, and InN and their alloys is
reviewed including exciting recent results. Attention is paid to the crystal growth techniques,
structural, optical, and electrical properties of GaN, AIN, InN, and their alloys. The various
theoretical results for each material are summarized. We also describe the performance of
several device structures which have been demonstrated in these materials. Near-term goals and
critical areas in need of further research in the III-V nitride material system are identified.

I. INTRODUCTION
The 111-V nitrides have long been viewed as a promising
system for semiconductor device applications in the blue
and ultraviolet (UV) wavelengths in much the same manner that their highly successful As-based and P-based cousins have been exploited in the infrared (IR), red, and green
wavelengths. The wurtzite polytypes of GaN, AIN, and
InN form a continous alloy system whose direct band gaps
range from 1.9 eV for InN, to 3.4 eV for GaN, to 6.2 eV for
AIN. Thus, the III-V nitrides could potentially be fabricated into optical devices which are active at wavelengths
ranging from the red well into the UV.
The blue and UV wavelengths are a technologically important region of the electromagnetic spectrum in which
efforts to develop semiconductor device technology have
been thus far unsuccessful. At present, semiconductor optical devices routinely operate from the IR to green wavelengths. If this range could be extended into the blue wavelengths, semiconductor components could then emit and
detect the three primary colors of the visible spectrum
which would have a major impact on imaging and graphics
applications. Another technologically significant band occurs in the 240-280 nm range (-4.75 eV) where absorption by ozone makes the earth's atmosphere nearly opaque.
Space to space communications in this band would be secure from earth, although vulnerable to satellite surveillance. On the dark side of the earth, shielded by the sun's
radiation, imaging array detectors operating in this band
would provide extremely sensitive surveillence of objects
coming up out of the atmosphere. Like most wide band gap
semiconductors, the nitrides are expected to exhibit superior radiation hardness compared to GaAs and Si, which
also makes them attractive for space applications.
Accordingly, much effort was expended to grow and
characterize GaN, AIN, and InN in the 1960's and 1970's.
Those workers encountered significant difficulties in obtaining high-quality material. All GaN and InN had high
n-type background carrier concentrations resulting from
native defects commonly thought to be nitrogen vacancies.
1237

J. Vac. ScI. Techno!. B 10(4), Jul/Aug 1992

Also, no suitable substrate material with a reasonably close

lattice match was available, and, even in films having relatively small background electron concentrations, p-type
doping could not be achieved. Despite these difficulties,
and the lack of modem crystal growth and characterization techniques, much progress was made in understanding
the properties of these materials.
In the past several years, a number of notable advances
have been reported in the III-V nitrides. Workers have
reduced the room-temperature background electron concentration of GaN films to as little as n - 4 X 1016/cm3
and p-type GaN has been reported. AIGaN/GaN heterostructures have been grown in several laboratories resulting
in quantum wells (QWs), enhanced mobility structures,
and the demonstration of an UV quarter wave reflector.
The zinc-blende phases of GaN, AlN, and InN have been
experimentally observed and the properties of zinc-blende
GaN are beginning to be measured. These advances have
come largely as a result of the improved crystal growth
techniques presently available. We can be optimistic that
this rapid progress will continue.
A number of reviews concerning GaN l - 8 and AIN4 ,9-11
which concentrated on various aspects of the problem were
published in the 1970's and 1980's. Davis 7 recently published an overview which concentrated on recent developments in the III-V nitrides. In this work, we present a
comprehensive history of the development of the 111-V
nitrides, GaN, AIN, and InN, through the end of the 1991
calendar year. Crystal growth techniques and procedures
which have been, and are being used, for nitride growth are
described. A thorough account of the known physical
properties of each of the three nitrides is presented. We
then discuss the experimental investigations into the various nitride alloys and zinc-blende phases, and the theoretical work to date is reviewed. Finally, work on heterostructures and devices is reported. We conclude by discussing
near-term goals and identifying critical areas in need of
future research.

0734-211 X/92/041237 -30$01.00

@1992 American Vacuum Society

1237

1238

S. Strite and H. Morko: GaN, AIN, and InN

1238

II. NITRiDE THIN FILM GROWTH

Many techniques have been used to grow III-V nitride
thin films. As the technology of crystal growth was improved, each new crystal growth technique was applied to
the nitride problem and many different substrate materials
were tried. In recent times, researchers have taken advantage of the newer molecular-beam epitaxy (MBE) and
chemical vapor deposition (CVD) techniques. Virtually all
of the high-quality material which is reported today is
grown by one of these two approaches.
A. Growth techniques

The earliest investigations of 111-V nitrides were made

on small crystals or powder samples. Johnson et al.,12 in
what we believe to be the earliest report of GaN, first described the conversion of metallic Ga in a NH3 stream into
GaN via the reaction
2Ga

+ 2NH3-+2GaN + 3H 2.

Tiede et alY synthesized AIN from metallic AI, and Juza

and Hahn14 obtained InN from InF6(NH4h by the same
technique. Nearly all powder samples of GaN 15- 24 and
AINll.15.25.26 were synthesized by placing some suitable
source material in a zone furnace under flowing ammonia.
In fact, many of the popular epitaxial growth techniques
used for the 111-V nitrides evolved from this approach. 27.28
Several early workers were also able to grow small single crystals, some of very good quality. Single crystalline
GaN needles were grown by heating GaN in a stream of
NH3.29-32 Dingle et al. 3o reported the first stimulated emission in GaN from optically pumped GaN needles grown in
this manner. Edwards et al. 33 and Cox et ai. 34 obtained
AIN crystals by sintering compacted AIN powder in flowing nitrogen. Kawabe et al. 9 and Horiuchi et al. 35 grew
AIN single crystals from the sublimation of pressed AIN
powder.
One of the most popular thin film growth techniques for
early 111-V nitride investigations was reactive sputtering.
Sputtering is a relatively inexpensive and simple approach.
Although all sputtered material was polycrysta1line or even
amorphous, some important work was accomplished. For
instance, the highest quality InN reported to date was
grown by Tansley and Foley using radio frequency (rf)
sputtering. Most commonly, Ar ions were used to sputter
Ga,36-43 AI,43-54 or In36.43.53-59 onto a substrate material in
the presence of a nitrogen plasma. However, Siettmann
and Aita 59 reported that improved AIN was obtained when
Ne was used in place of Ar.
Several workers 60--62 have investigated high pressure
growth techniques for GaN in the hopes of obtaining better
nitrogen incorporation. In general, Ga metal or GaN powder sublimed at high temperature under a significant N2 or
NH3 overpressure (0.1-10 kbar) was transported to the
reaction zone in which deposition occurred. No material
grown in this manner was of particularly high quality.
The most successful epitaxial growth technique in the
early investigations of the III-V nitrides was a vapor transport CVD method first used for GaN by Maruska and
Tietjen (Fig. 1).27 Their approach involved flowing HCI
J. Vac. Sci. Technol. B, Vol. 10, No.4, Jul/Aug 1992

rc==::i

c=

-c:::IXXXxxXXXX><XXXXXZ>Q
'C0
HCl__

FIG. 1. Schematic of a vapor transport GaN growth reactor (from

Ref. I).

vapor over metallic Ga which reacted downstream at the

substrate with NH 3. Using mass spectroscopy, Ban 63
showed that the relevant chemical reaction controlling the
growth was
GaCI + NH 3...... GaN

+ HCI + H 2.

Using this method, the first single crystal GaN thin films
were realized. 27 The growth rate was quite high (0.5 fLm/
min), which allowed the growth of extremely thick films,
whose properties were less influenced by the thermal and
lattice mismatches with the substrate. However, GaN
grown by this technique had very high background n-type
carrier concentrations, typically - 10 19/cm 3. Maruska et
01. 64 later showed that Zn and Mg dopant incorporation
could be achieved by the simultaneous evaporation of the
dopant source in the HCI stream. Many workers have since
used the technique of Maruska and Tietjen for GaN
growth 65- 79 and at least two groups8(}"82 have extended this
technique to grow high quality AIN.
Many other variations of this approach have been
used. Researchers have used gaseous GaCl,83-86
GaeI 2,87 GaCI 3,11,87-89 Ga(C2H s }zCI,88 GaCI 2NH 3,90
AICI 3,81,83,85,91-95 AlBr3,96 InC1 3,97 and GaBr387.98,99 as reactants for NH 3. Pastrnak et a/. lOO,101 elected to react N2
with GaCI 3, AICI 3, and InCI 3 in their CVD process.
Dryburgh lO2 grew AIN from AISe and N 2. By introducing
PH 3, Igarashi et al. 103 achieved several percent P incorporation in GaN.
Reactive molecular-beam epitaxy (RMBE) was also a
popular approach to the nitride growth problem. Researchers hoped that RMBE would allow growth at lower
temperatures than those required by CVD. This might increase the incorporation of the volatile nitrogen species
reducing the n-type background as well as allowing the
growth of atomically abrupt nitride heterojunctions. In this
method, an AI I 04-107 or Ga l08 beam reacted at the substrate
with NH 3. However, RMBE was unable to produce highquality material at substrate temperatures in the 6OOC
range. This was probably due to the low reaction rate between NH3 and the group III metal. RMBE did produce
some reasonable material at higher substrate temperatures,

1239

1239

S. Strite and H. Morkoc;: GaN, AIN, and InN

HEED Screen

ECR

TABLE

I. Properties of prospective nitride substrates. a

Substrate
material

Symmetry

Wurtzite GaN

Hexagonal

Wurtzite A1N

Hexagonal
Hexagonal

Solid Source
HEED
Gun

FIG. 2. Schematic of a plasma enhanced MBE growth chamber using an

electron cyclotron resonance (ECR) nitrogen plasma source.

Si
GaAs
6H-SiC

Cubic
Cubic
Hexagonal

3C-SiC
InP
GaP
MgO
ZnO

Cubic
Cubic
Cubic
Cubic
Hexagonal
Cubic

but such high growth temperatures negate the potential

advantages of the technique compared to CVD.
The large background electron concentration in GaN
has most commonly been attributed to nitrogen vacancies.
Many investigators have sought to improve their crystal
growth methods in order to more completely incorporate
nitrogen. Some lO9 ,11O substituted the more reactive hydrazine in favor of ammonia. Andrews and Littlejohn III tried
Ga(C2HshNH3' which already has a Ga-N bond, as a
source material. However, the most popular method of
increasing the reactivity of the nitrogen has always been
plasma excitation of the nitrogen in either an MBE or
CVD growth environment. In the MBE approach, shown
in Fig. 2, growth results from the reaction between plasma
activated nitrogen and a beam of group III metal. Very
good material has recently been grown in this
manner. 112-119 Powell et al. 120 has used nitrogen ions from
a Kaufman ion source and elemental Ga to grow good
GaN. Matsubara and Takagil21 grew GaN from ionized
Ga clusters and N2. Gotoh l22 tried reacting Ga with
NH3 catalyzed by the presence of ionized N 2 In the CVD
approach, severa) variations have been attempted in the
presence of a plasma. Workers have reacted both trimethylgallium (TMG )41.123 and GaC1124.12S with a NH3 plasma.
Sheng et al. 126 reacted trimethylaluminum (TMA) and
NH3 in the presence of a hydrogen plasma. Wakahara et
al. 127 grew InN by reacting trimethylindium (TMI) with
microwave activated N 2. Eremin et al. m used nitrogen to
transport metallic Ga to the reaction zone where it was
reacted with active nitrogen.
However, in contrast to the MBE case, plasma excitation of the nitrogen species has not proven necessary in
CVD growth. Much of the best material grown today is
produced by conventional metalorganic CVD by reacting
TMG, TMA, and TMI with NH3 at substrate temperatures in the neighborhood of 1000 C.129-14O Some enhancements have been suggested. Fujieda et al. 109 replaced
NH3 with N2H4 and observed that significantly smaller
amount of N 2H4 was required to maintain the same growth
rate. However, they also noted that the CVD growth rate
J. Vec. Sci. Technol. B, Vol. 10, No.4, JullAug 1992

Lattice
parameters

Coefficient of
thermal expansion

a=3.189A
c= 5.185 A
a = 3.112 A
c=4.982 A
a=4.758A
c= 12.991 A.
a = 5.4301 A.
a = 5.6533 A.
a= 3.08 A.
c=15.12A.
a = 4.36 A.
a = 5.8693 A.
a = 5.4512 A.
a= 4.216 A.
a = 3.252 A.
c=5.213A
a = 8.083 A.

5.59xlO- 6/K
3.17X 10 - 6/K
4.2 X 10- 6/K
5.3 X 1O- 6/K
7.5 X 10-6/K
8.S XIO- 6/K
3.S9x 1O- 6/K
6 XlO- 6/K

4.5 X 1O- 6/K

4.65 X 10 - 6/K
10.5 X 10 - 6/K
2.9 X 1O- 6 /K
4.75X IO-6/K
7.45xlO- 6/K

aFrom Landolt-Bornstein. (Springer. New York. 1982). Vol. 17.

was limited by the decomposition of TMG, so that the

benefits of N2H4 are limited. Dupuie and Gulari 141 reported that the presence of a hot filament near the substrate increased the growth rate of AIN grown with TMA
and NH3 by two orders of magnitude. However, the use of
a hot filament immediately raises concerns about residual
contamination, most prominently oxygen, which the authors did not address.
B. Substrates

One of the major difficulties which has hindered

GaN research is the lack of a suitable substrate
material that is lattice matched and thermally compatible
with GaN. GaN, AIN, and InN have been grown
primarily on sapphire, most commonly the (0001)
orientation, but also the (2131), (1101\ ( 1120).
In
addition,
the
III-V nitrides
have been
Si,38.44.46.5O.51 ,82.87.94-96.99. 105,1 19.126.129.141-148
grown
on
GaAs,58,87,98,99,I06,113,118,125.126,147-151 NaCl,123 Gap,87,99
Inp,87.126 SiC,44,66.92,1I7.129,137,IS2-154 W, ISS ZnO,87,121,154
MgAI20 4,129.IS6,157 Ti0 2,154 and MgO. 120 Table I summarizes the lattice parameters and thermal characteristics of a
number of the prospective substrate materials for nitride
growth. Some of the most suitable substrate materials are
becoming commercially available. More reports in the future regarding GaN grown on SiC, MgO, and ZnO can be
expected.
For lack of an ideal substrate, nearly all III-V nitride
material has been grown on sapphire substrates despite its
poor structural and thermal match with the nitrides. The
preference towards sapphire substrates can be attributed to
its wide availability, hexagonal symmetry, and its ease of
handling and pregrowth cleaning, Sapphire is also stable at
the high temperatures (-1000 e) required for epitaxial
growth using the various CVD techniques commonly employed for GaN growth. Due to the thermal and lattice

1240

S. Strite and H. Morko9: GaH, AIN, and InN

mismatches between sapphire and the III-V nitrides, it is

necessary to grow a thick epilayer to obtain good quality
material.
It has been established that the crystal structure of epitaxial GaN is most strongly influenced by the substrate
material and orientation. The equilibrium crystal structure
for each of the III-V nitrides is the wurtzite structure
while GaN and InN have been observed to have the zincblende structure when grown on a cubic substrate. Cubic
GaN has been grown on (001) GaAs,1I0.1I8.149-151 cubic
SiC,117.154 MgO,120 and (001) Si. 119 Humphreys et al.,m
using low temperature growth, was able to grow zincblende GaN on (000 1) sapphire substrates. This is the
only report of zinc-blende nitride material grown on a substrate having hexagonal symmetry. All GaN grown to date
on either ( 111) Si38.85.98.99.129.147.148.154 or (III)
GaAs99.11O.113.125.147.149 has been wurtzite. This can be understood when one considers the nature of the wurtzite and
zinc-blende crystal structures. Each is an interpenetrating
sublattice of the group III and V materials in which every
atom is tetragonally coordinated with four atoms of the
opposite species. The crystal structures differ only in their
stacking sequence along the (111) axis. Therefore, growth
on a (111) plane does not act as a template for zinc-blende
growth, and the equilibrium wurtzite structure is obtained.
The zinc-bIen de crystal stacks in an ABCABC. .. arrangement while the wurtzite has an ABABAB ... configuration.
The nearest-neighbor positions are almost identical. Only
the relative positions of the second nearest neighbor differ
which explains the observed similarity in the physical
properties of the wurtzite and zinc-bien de GaN phases.
Cubic InN has been grown on (001) GaAs while AIN
. poIycrysta11'me wurtzlte.
. 159
grown by the same method IS
An advantage of using GaAs or Si substrates is that the
GaN can be deposited on a high-quality homoepitaxially
grown surface as opposed to a cleaned substrate surface
which has many more impurities and defects.
C. Nitride film crystallography

Since there exists no ideal substrate for the epitaxial

growth of the III-V nitrides, it has been necessary to devote much attention towards understanding and improving
the epitaxy of the nitrides on sapphire, SiC, GaAs, and Si
substrates. Researchers have established the epitaxial relationships between the various substrate orientations and
the nitride films grown on them. Madar et al. l60 grew GaN
on a hemispherical sapphire substrate and observed the
epitaxial relationships and GaN quality on numerous orientations. The best epitaxy was obtained with the (0001)
surface. Reasonable quality and better surface morphology
was observed on the (1120) planes tilted 10_20 towards
the [1100] axis. The highest growth rate and reasonable
crystal quality was observed on the (0114) planes. Sasaki
and Zembutsu 161 also reported improved surface morphology on the (1120) sapphire surface in addition to lower
background carrier concentrations and less midgap emission compared to the (0001) orientation. However, the
GaN grown on (000 1) sapphire had superior crystallinity
and higher incorporation of Zn dopant. Hiramatsu et al. 162
J. Vac. Sci. Technol. B, Vol. 10, No.4, Jul/Aug 1992

1240

grew GaN on (0001) sapphire having various misorientations towards both the [1010] and [1210] directions. The
best films were grown on nominally (0001) substrates, and
the film morphology was observed to degrade rapidly as
the misorientation was increased. Two groupsl29,160 have
detailed each of the epitaxial relationships observed between the various sapphire orientations and epitaxial GaN
noting those cases in which more than one relationship is
possible. Tempel et al. 157 reported a similar study for GaN
grown on MgAI 20 4. In their report of zinc-blende GaN
grown on (0001) sapphire, Humphreys et al. 158 reported
the epitaxial GaN to be (III) oriented. This is consistent
with the epitaxial relationship generally observed when the
wurtzite phase is grown on (0001) sapphire, with the
stacking order changed as described above.
Two groups 154.158 have published transmission electron
microscopy (TEM) studies of wurtzite GaN grown on
sapphire substrates. The major defects in the GaN were
double positioning boundaries, inversion domain boundaries and dislocations. GaN grown on 6H-SiC and ZnO
had similar types of defects, but the overall density was
reduced. 154
Sasaki and Matsuoka 137 investigated the epitaxial relationship between GaN and SiC by growing on both the
(0001 lSi and (OOOI)c faces. GaN grown on (0001 )Si had
better crystallinity and a smoother surface morphology in
contrast to GaN grown on (OOO1)c which exhibited hexagonally shaped islands. Photoelectron spectroscopy was
used to determine that the polarity of the epitaxial GaN
changes with the polarity of the SiC substrate face. Layers
grown on the (0001 )Si face are nitrogen terminated while
layers grown on the (OOOl)c face are gallium terminated
and oxidize more heavily. Paisley et al. I17 154 studied the
(001) zinc-blende GaNI{J-SiC interface by TEM and
noted an epitaxial relationship. The GaN film had many
defects, mainly microtwins and stacking faults, whose density decreased away from the interface. The mismatch between the two crystals was mainly relieved by thin amorphous regions at the interface.
Epitaxial growth of zinc-blende GaN on (001)
GaAs, 110.1 18,149-151 (001) Si,119 {J-SiC on Si,I17,154 and
(0001) sapphire l58 substrates has been reported. However,
if epitaxy is not achieved, the polycrystalline GaN film has
the equilibrium wurtzite structure. 87 ,147 Fujieda et al. 151
has recently reported that the crystal structure of epitaxial
GaN grown on (001) GaAs by CVD was critically dependent on the pretreatment of the GaAs surface before
growth. In order to obtain the zinc-blende phase, the authors found it necessary to expose the GaAs surface to
hydrazine for several minutes which allowed a zinc-blende
GaN template to form. If growth was begun after only 5 s
of hydrazine exposure, wurtzite GaN was obtained. This
observation is consistent with those of Troost et al. 89 ,163
who reported the formation of a - 1.3 nm thick GaN layer
resulting from the exposure of a cleaved (110) GaAs surface to atomic nitrogen.
Strite et al.I18,I64 have studied the zinc-blende (001)
GaN/GaAs interface by TEM (Fig. 3) and high-energy
electron diffraction (HEED). The interface was similar to

1241

S. Strite and H.

Morko~:

GaN, AIN, and InN

FIG. 3. Electron micrograph of the zinc-blende GaN on (001) GaAs

interface. Disordered regions are evident at the interface (arrow I) and
the majority of defects are stacking faults and microtwins propagating
along the {Ill} directions. The majority of defects nucleate at regions of
maximum interface roughness (arrow 2). Some defects annihilate at their
intersections leading to improved quality in thicker films (from Ref. 118).

the zinc-blende GaNIP-SiC and GaN/MgO interfaces observed by Paisley et al. 1l7 ,154 and Powell et al_,120 respectively_ A large number of planar defects whose density
decreased away from the interface were observed and disordered regions were present at the interface. The authors
observed that the interface disordering was lessened and
the onset of two-dimensional (20) epitaxy occurred
sooner when the Ga flux was periodically interrupted during the initial stages of epitaxy. 164
Because of the large thermal mismatch between the nitrides and their substrate materials, most epitaxial nitride
films are subject to some degree of strain which is introduced during the postgrowth cooling. A number of workers have observed residual effects from the thermal mismatch between epitaxial GaN and various substrate
materials. GaN is a hard material, and a sufficiently thick

FIG. 4. Electron micrograph of the zinc-blende GaN on (001) interface

which reveals defects in the GaAs substrate caused by thermal strain
during postgrowth cooling (from Ref. 118).

J. Vac. ScI. Technol. B, Vol. 10, No.4, Jul/Aug 1992

1241

film will actually crack the substrate material. Chu98 observed cracking of SiC substrates on which GaN was
grown and Grimeiss and Monemar l65 noticed the same for
sapphire substrates. TEM has been used to directly observe
defects in GaAs substrates caused by thermal strain from a
comparatively thin GaN film (Fig. 4). \18
Amano et al. 166 studied the effect of the thermal mismatch between GaN and sapphire substrates. The GaN
was strained under biaxial compression by an amount
which depended on the substrate orientation. From the
shift in the lattice constant and the photoluminescent peak
energy, the deformation potential for GaN was found to be
12 eV. Naniwae et al. 79 . 166 studied the strain as a function
of epitaxial layer thickness for GaN grown on sapphire.
The perpendicular lattice constant was observed to be c
= 5.187 A up to GaN thicknesses of 50 pm. Thicker films
showed a gradual relaxation to c = 5.185 A as the thickness increased to 300 pm. The photoluminescent peak energy was observed to have a similar downward trend in
energy as a function of thickness. The authors demonstrated reduced residual strain in a GaN film which was
grown on a thick GaN layer previously grown on a sapphire substrate. Strite et al. l64 observed a 1% distortion of
the lattice constant along the (001) growth axis in very
thin zinc-blende GaN layers sandwiched between GaAs
which was interpreted as due to thermally induced compressive in-plane strain. Because of the poor thermal match
between the nitrides and their substrate materials, and the
rather high growth temperature used in CVO growth processes, nearly all of the nitrides which have been reported
were probably under varying amounts of strain. This fact
has been largely ignored in the literature.
Attention has also been paid to the optimization of the
initial nitride overgrowth in order to minimize the defect
density resulting from the substrate lattice mismatch.
Yoshida et al. 108,167 were the first to observe an improvement in GaN grown on sapphire when an AIN buffer layer
was used. Akasaki et al. 168 ,169 extensively studied the effect
of an AIN buffer layer. The electron concentration in the
GaN decreased by two orders of magnitude while the mobility increased by a factor of 10. The near band gap photoluminescence (PL) was two orders of magnitude more
intense and the x-ray diffraction peak width was four times
smaller in layers having an AIN buffer layer. GaN grown
directly on sapphire nucleated in tiny microcrystallites
which led to hexagonal islands on the surface of the GaN
films. When a buffer layer was used, the AIN was more
highly oriented and the growth became 20 more quickly
allowing improved GaN morphology to be obtained. An
optimum AIN thickness of 500 Awas determined with the
GaN tending to become polycrystalline when grown on
thicker AIN layers. Kistenmacher and Brydenl70 have
noted a similar improvement in the morphology and electrical characteristics of InN grown on sapphire when an
AIN buffer layer is used. Recently, however, Nakamural?l
has been able to grow GaN of extremely high quality directly on sapphire substrates without any AIN buffer layer.
Instead, the growth was initiated with several hundred
angstroms of GaN deposited at a low temperature.

1242

S. Strite and H. MorkOCf: GaN, AIN, and InN

Lei et af. 119 have found that a low temperature initial

growth step greatly improved the quality of GaN grown on
(001) Si substrates. The low temperature growth allows
full coverage of the substrate to be quickly achieved, and
the remainder of the layer was then grown at the optimal
homoepitaxial conditions. The growth kinetics are probably quite similar to those of GaAs on Si, in which the low
temperature step is necessary to reduce the surface mobility of the Ga adatoms promoting 2D growth in favor of
island growth.
III.GaN
GaN is by far the most heavily studied of all of the
III-V nitrides, yet compared to the more commonly studied Si and GaAs semiconductors, relatively little is known
about GaN. Large background n-type carrier concentrations, the lack of a suitable substrate material, difficulties
with GaN p-type doping, and processing difficulties have
discouraged many workers in the past. There is disagreement in the literature regarding many of the physical properties of GaN as a result of measurements being made on
samples of widely varying quality. In some cases, a consensus has developed and the spurious measurements can
be disregarded. In many cases, too few measurements exist,
so we report the entire range of values.
Recently, there has been a resurgence of interest in
GaN, largely due to its potential as a blue light emitter.
Modern researchers have used improved crystal growth
and processing technology to overcome many of the difficulties reported by earlier workers. A number of laboratories consistently obtain high quality GaN with room temperature background concentrations as low as n - 4
X to l6/cm 3 on a variety of different substrates. One group
has developed a process for obtaining p-type GaN which
allowed them to demonstrate the first pn junction light
emitting diode (LED). Many groups are working on GaN
based device structures. However, much work remains to
be accomplished, both in the development of GaN device
technology, and in the determination of the fundamental
physical properties of GaN. In the following, we summarize the present state of knowledge regarding the physical
properties of GaN.
A. Chemical properties of GaN

GaN was first synthesized by Johnson et al. 12 in 1928

who noted that "Gallic nitride is an exceedingly stable
compound." It is this chemical stability at elevated temperatures combined with its wide band gap that has made
GaN an attractive material for device operation in high
temperature and caustic environments. GaN is also an excellent candidate for protective coatings due to its hardness. However, the majority of GaN researchers are interested in semiconductor device applications. While the
thermal stability of GaN should allow high temperature
processing steps to be performed, the chemical stability of
GaN presents a technological challenge. There have been
many reports describing the resistance of GaN films to the
conventional wet etching techniques used in semiconductor processing.
J. Vac. Sci. Technol.

e,

Vol. 10, No.4, Jul/Aug 1992

1242

Only two groups have described the wet-chemical etching characteristics of GaN known to be of high quality.
Maruska and Tietjen 27 reported that GaN was insoluble in
H 20, acids, or bases at room temperature, but GaN did
dissolve in hot alkali solutions at a very slow rate.
Pankove 172 was unable to etch GaN in NaOH due to the
formation of a GaOH layer on the surface, so an electrolytic etching technique was devised which obtained good
results. Material of lower quality has been observed to etch
at reasonably high rates in NaOH,98,143 H 2S04,173 and
H3P04.174,175 These etches, which are only effective against
low quality GaN, are useful for identifying defects and
estimating their densities in GaN films. To date, there exists no established chemical etching process, despite the
efforts of many researchers. Device technology will eventually require the development of some procedure. One
possibility, which has not yet been explored, is reactive ion
etching.
Several groups have studied the surface chemistry of
GaN using the techniques of Auger electron spectroscopy
(AES),4I,117,153,163 x-ray photoemission spectroscopy
(XPS),11I,137 and electron energy-loss spectroscopy
(EELS) .163 There were also a number of studies examining
the thermal stability and dissociation of GaN. However,
the material studied was generally not well characterized
and the results from different laboratories varied widely. A
number of groupsI73,177-IS2 studied the stability of GaN at
high temperature. Significant weight losses were reported
at temperatures as low as 750e by Furtado and Jacob isl
while no significant losses were observed at toooe by
Morimoto. 173 Two groupsl73,181 observed that GaN was
less stable in a Hel or H2 atmosphere while the best results
were obtained in N 2. Some controversy exists over the reaction which dominates the decomposition of GaN. Gordienko et al. 177 observed primarily (GaN) 2 dimers by mass
spectroscopy. Two groups, 16,179 both also using mass spectroscopy, observed only N 2+ and Ga + in the vapor over
GaN. In their work, Munir and Searcyl6 measured the
apparent vapor pressure of GaN and calculated the heat of
sublimation to be 72.40.5 kcallmol. Thurmond and
Logan 28 have calculated the equilibrium N2 pressure of
GaN as a function of temperature. This is clearly an area
which requires further study now that a number of laboratories are producing material which is known to be of
high quality. The thermal stability ofGaN will be a critical
parameter in applications which require high power or
high temperature operation.

B. Structural properties of GaN

Juza and Hahn 14 first reported the structure of GaN to

be wurtzite having lattice constants a = 3.18 A and c
= 5.16 A. Many other measurements40,43,76,120,183-187 of
the GaN lattice constant have been made, and the community has settled on the lattice constant values of a = 3.189
A and c = 5.185 A first reported by Maruska and Tietjen. 27
Their measurements were made over the temperature
range 300-900 K and a mean coefficient of thermal expansion of aala = 5.59 X to - 6/K was observed across the

1243

1243

S. Strite and H. Morkoc;: GaN, AIN, and InN

= 1.3 W/cm K was in good agreement with the predicted value of 1. 7 W /cm K.1O Chetverikova et al. 187 measured the Young's modulus and Poisson's ratio for their
GaN films. Channeling studies were reported by Linden et
al. 189 Table II lists the known properties of wurtzite GaN .
Several studies have observed a variation of the GaN
lattice constant with growth conditions, impurity concentrations, and film stoichiometry. Three groupSI90-I92 have
reported a larger GaN lattice constant at higher growth
rates, probably as a result of increased interstitial defects.
Lagerstedt and Monemar l91 also observed an expansion of
the lattice with heavy Zn doping while Maruska et al. l90
observed the same with Mg. It is likely that at high concentrations, the group II element begins to occupy the lattice sites of the much smaller nitrogen atom which causes
the lattice expansion.

GoN
901H1l1.

10

001

.,0

0.1 L_--'-_.............-I.....0...1.......u-_--"---'--'
100
10

T (K)

C. Electrical properties of GaN

FIG. 5. Thermal conductivity along the c axis of GaN as a function of
temperature (from Ref. 190).

entire range. Values of ilele = 3.17 X 1O-6/K and

7.75 X 10 - 6/K were approximated for the temperature
ranges 300-700 K and 700-900 K, respectively. Sichel and
Pankove l88 measured the thermal conductivity of GaN
from 25-360 K (Fig. 5). The room temperature value of

TABLE II. Properties of wurtzite GaN.

Band gap energy

Eg (300 K) = 3.39 eV
Eg (1.6 K) = 3.50 eV

Ref. 27
Ref. 72

Band gap temperature

coefficient (T > 180 K)

dEgI(dT} = - 6.0X 10- 4

eV!K

Refs. 31,65

Band gap pressure

coefficient (T = 300 K)

dE/(dP) =4.2XIO- J
eVlkbar

Ref. 207

Lattice constant
(T=300K)

a = 3.189 A
c=5.18SA

Ref. 27

Coefficient of thermal
expansion (T = 300 K)

Il.a

Ref. 27

= 5.59 X 1O- 6/K

Il.c

= 3.17 X 1O- 6!K

1.3 W!cm K

Thermal conductivity

K=

Index of refraction

n(l eV) = 2.33

n(3.38 eV) = 2.67

Dielectric constants

.EQ=

Electron effective mass

Phonon modes
(T= 300 K)

m: = 0.20

Ref. 216

Ref. 121
Ref. 211
Ref. 211

8.9
9.5
= 5.35

EO=
E",

Ref. 188

0.02mo

A1(TO) = 532 cm- I

E1(TO) = 560 em-I
E2 = 144,569cm - 1
A1(LO) = 7lOcm- 1
E1(TO) = 741 cm- I

J. Vac. ScI. Technol. B, Vol. 10, No.4, Jul/Aug 1992

Ref. 211
Refs. 68,210
Refs. 68,210
Refs. 68,210
Ref. 214
Ref. 214

Control of the electrical properties of GaN remains the

foremost obstacle hindering device efforts. Unintentionally
doped GaN has in all cases been observed to be n type with
the best samples still showing an electron concentration
n - 4 X 10 16/cm 3.171 No impurity has been shown to be
present in sufficient quantity to account for the carriers, so
researchers have attributed the background to native defects which are widely thought to be nitrogen vacancies.
All efforts, until recently, to obtain p-type doping have
resulted in heavily compensated, highly resistive films. The
development of a reliable p-type doping technique for GaN
remains a primary challenge for researchers.
Many groupsJ8.7S.83.88.140.17I,I84,187,193-197 have reported
the electrical characteristics of unintentionally doped
GaN. Their measurements have varied widely, reflecting
the crystal quality and purity of their material.
Nakamura 171 has reported the highest GaN mobilities to
date. Room-temperature and liquid nitrogen temperature
mobilities of f..L" = - 600 cm 2;V sand f..L" = - 1500
cm 2;V s at carrier concentrations of n = 4 X 1Q16fcm 3
and n = 8 X lOISfcm 3 were measured. Ilegems and
Montgomeryl84 performed temperature dependent Hall
measurements from 10-900 K on GaN having a roomtemperature background electron concentration n = 3
X 10 17fcm 3 and a room-temperature mobility of I1n
= - 300 cm 2IV s. Their data are shown in Fig. 6. In their
best layer, the mobility peaked at f..Ln = - 800 cm 2IV sat
150 K and decreased at lower temperatures which the authors attributed to the onset of impurity band conduction.
In the 300-900 K range, the mobility tended to vary with
r- 2, and at 900 K, a mobility of f..Ln = -25 cm 2;V s was
measured .
The highest GaN mobility reported to date was
achieved in an AIGaN/GaN heterostructure by Khan et
al.139.198.199 GaN having n =
10 17fcm 3 and 11 = 350
2
n
cm IV s at room temperature was grown on ",a\1\1hire by
low pressure CVD using an AIN buffer layer. A mobility
enhancement to I1n = 620 cm2IV s at room temperature
and 11" = 1600 cm 2IV sat 77 K was observed in similar
structures when a 500 A Aio. 09GIlo. 9I N cap was grown. The
peak mobility, f..Ln = 2626 cm 2IV s at 77 K, was realized in

1244

S. Strite and H.

Mork~:

GaN, AIN, and InN

1244
T ABLE III. Low temperature GaN luminescence peaks .

.9

Donor bound exciton

LO replica
2-LO replica
TO replica

3.44-3.47 eV
3.377-3.378 eV
3.286 eV
3.400 eV

Refs. 165,199,20 I,231 ,246,248

Refs. 201,248
Ref. 201
Ref. 248

Acceptor Bound
exciton

3.455 eV

Refs. 201,231,246

Cd-acceptor bound
exciton
LO replica
2-LO replica

3.45~3.455

3.364 eV
3.355 eV

Donor -acceptor
LO replica
2-LO replica
3-LO replica

3.26-3.27
3.17-3.18
3.08-3.09
2.99-3.00

T (K)
FIG. 6. Temperature dependence of the electron mobility in unintention
ally doped GaN having room-temperature background electron concen
trations (U43AI) n=2xlO 17 /cm J and (U5IAI) n=4xI0 17/cm J
(from Ref. 184).

a 2000 A GaN film grown on sapphire using an AIN buffer

layer and capped with a 1000 A AIo.\3Gao.87N layer (Fig.
7). The authors l99 attributed the enhanced mobility to increased interface conduction resulting from the presence of
a 2D electron gas at the heterointerface.

2800
AI Ga

"

2400
0;-

eV

Refs. 231,248
Ref. 231
Ref. 248

eV
eV
eV
eV

Refs.
Refs.
Refs.
Refs.

165,200,246,248
165,200,246,248
165,200,246,248
165,246

D. Optical properties of GaN

GaN is primarily of interest for its potential as a blue

and UV light emitter. For that reason, much of the effortdevoted to GaN has been directed towards determining its

'/
1'.000

GaN

AIN

2000

Il)

Sapphire (OOOll

>

E 1600

CJ

>- 1200

;::

.0

800
c.)

b.)

a.)

0
80

150

220

290

360

Temperature (K)
7. Mobility as a function of temperature for a (a) 2000 A GaN layer,
(b) 1000 A AIo.I3GIIoR7N layer, (c) a thick 1.5 f.lm GaN layer, and (d)
a heterostructure consisting of 2000 A of GaN capped by a 1000 A
AIoIJGao.87N layer (inset). The mobility value f.l. = 2626 cm 2/V s is the
highest ever reported for GaN (from Ref. 199).
FIG.

J. Vac. ScI. Technol. B, Vol. 10, No.4, Jul/Aug 1992

01 .0

1.1

1.4

a.'

1.0

SA

14

1.1

SA

Energy (eV)
FIG. 8. Room-temperature absorption spectrum ofGaN (from Ref. 27).

1245

1245

S. Strite and H. Mork09: GaN, AIN, and InN

3.IIU6

Energy (eV)

'~o~--~ao~~I~~~~I=~--ld~=-~zd~~~,~~r--'J~

FIG. 9. GaN PL spectra at several temperatures. Evident are the principle

emission peak at 3.47 eV and the 3.38 eV doublet. At lower energies, the
3.26 eV DA transition is seen to give way to the higher energy-free
electron to acceptor transition as the temperature is increased. Two phonon replica peaks of the DA and free electron to acceptor peaks are
resolved (from Ref. 200).

optical properties. A fairly complete account of the optical

properties of wurtzite GaN is possible. Table III summarizes the observed optical transitions of GaN.
Maruska and Tietjen27 were the first to accurately measure the GaN direct band gap energy to be 3.39 eV (Fig.
8). Soon after, Pankove et al. 65 reported a low temperature
(1.6 K) GaN PL spectrum. Strong near gap emission was
observed at 3.477 eV and a weaker peak was noted at 3.37
eV which split into a -10 meV spaced doublet when the
temperature was increased to 35 K. Shortly thereafter,
Dingle et al. 2OO-202 performed a detailed analysis on the low
temperature (2 K) optical spectra of high-quality GaN
samples (Fig. 9). Polarized reflection measurements observed three excitons at 3.4740.002 eV, 3.4800.002 eV,
and 3.490.01 eV. The polarization dependence of the
transitions was consistent with the valence band symmetry
of wurtzite semiconductors. The primary low-temperature
PL peak at 3.467 O.OOI eV exhibited a full width at halfmaximum (FWHM) of 5 meV. From the difference in the
reflectance and luminescence peak energies, the donorexciton binding energy was identified to be 6-8 meV. Weak
structure, similar to that reported by Pankove et al. 65 was
observed in the vicinity of 3.38 eV, often appearing as a
doublet with a spacing of 7.8 meV. It was determined that
the 3.38 eV doublet and a second doublet occurring at 3.29
eV, were longitudinal optical (LO) phonon replica peaks
of the free exciton and bound exciton peaks. From the
spacing between the replica peaks, a LO phonon frequency
of 726 cm - I was inferred. Another peak, appearing at 3.26
eV, was shown to be a donor-acceptor (DA) transition. As
the temperature was increased to 30 K, a weakening of the
DA transition was observed simultaneously with the onset
of a new band which persisted through a broad temperature range at an energy 30 meV above the DA peak. The
new higher energy band, which completely dominated
above 120 K, was identified as the free electron to bound
J. Vac. Sci. Technol. B, Vol. 10, No.4, JullAug 1992

T (K)
FIG. 10. Temperature dependence of the principle emission peak from

which the GaN band gap temperature coefficient of - 6.0 X 10 - 4 eV IK

was determined (from Ref. 65).

hole transition. The separation of the two bands was taken

to represent a lower bound of the donor binding energy.
Using a value of Eo = 9.8 obtained from the GaN phonon
energies, and a donor binding energy of 42 1 meV, an
electron effective mass m: = 0.25mo was calculated. An
acceptor binding energy of - 200 me V was also estimated.
At 300 K the energy of the highest energy transition had
decreased to 3.39 eV which is in excellent agreement with
the observations of Maruska and Tietjen. 27 This value may
be a slight underestimation of the room-temperature GaN
band gap due to band tailing effects expected to be present
in the heavily n-type material reported by both groups.
Many
workers
have
performed
PL 17,19,71,72,137,139,161,165,194,203,204 and cathodoluminescence
(CL) 22,54,76,87,88,90,205,206 spectroscopy on GaN. Others
have reported transmission,87 reflectance,72 and absorption
measurements. 36,39-43,121,123,138,206,207 Monemar72 measured
the excitonic spectrum with improved energy resolution at
3.4751 0.OOO5 eV, 3.481 O.OOI eV, and 3.493 0.OO5
eV, respectively. Hvam and Ejder l94 studied the near gap
behavior ofGaN at 1.8 K under high excitation intensities.
The exciton transition at 3.47 eV broadened with increasing excitation intensity and a new lower energy peak which
eventually showed structure at 3.453 and 3.448 eV appeared. The new peak, whose intensity. was proportional to
the square of the 3.47 eV peak intensity, was attributed to
an inelastic exciton-exciton scattering interaction. Dai et
al. 204 observed two new PL peaks in GaN. A peak at 3.476
0.OO2 eV was attributed to donor-bound excitons, and a
peak at 3.311 0.002 eV was attributed to donor-acceptor
pair recombination. Two groups22,165 have noted a small
peak at 3.435 0.01O eV which was ascribed to excitons
bound to a shallow donor. A number of workers 19,22,165,208
have observed broad midgap optical transitions in GaN at
-2.2 eV.

................,,:.:.................:.:.:.:.:.:.:.:.;,.;.;.::.;..................:.............................::.:.:.:.:.:.:.

1246

S. Strite and H.

Morko~:

GaH, AIN, and InN

1246

Several groups have measured the temperature dependence of the GaN band gap. Pankove et al. 65 estimated
a band gap temperature coefficient of dE/CdT)
= - 6.0 X 10 - 4 eVIK in the linear region above 180C
from the temperature dependence of the principle emission
peak' (Fig. 10). Monemar 72 determined the fundamental
band gap to be 3.503 0.OOO5 eV at 1.6 K and fit the
temperature dependence of the band gap to the empirical
relation

EMISSION

SAPPHIRE
(Al

E g =3.503+C5.08XIO- 4 T Z )/CT-996) eV.

Camphausen and Connellz09 studied the pressure and temperature dependence of the GaN absorption edge. Under
hydrostatic pressure up to to kbar, the GaN band gap
energy shifted by dE/(dP) = 4.2 0.4 meV Ikbar at
room temperature. The temperature dependence was measured to be dE~(dT) = - 6.7 X to- 4 eV/K. Matsumoto and Aoki I reported the temperature dependence of
the principle emission peak in the 4.2-300 K range. A
dependence of dE/edT) = - 3.5 X to- 4 eV/K was
observed from 30-150 K and - 6 X to - 4 eVIK from 150
K to room temperature. Osamura et al. 115 and Zykov and
Gaido l9 have reported values of the band gap temperature
coefficient which are about a factor of two smaller than
those quoted above.
The phonon modes of GaN have received considerable
attention. 43 ,68,158,165,200,201.210-215 Most of the measurements
have observed similar phonon spectra. Manchon et a/,21O
used Raman spectroscopy to identify four phonon modes
present in heavily n-type GaN needles. The AI [transverse
optical (TO)] and EI(TO) modes were observed at 533
and 559 cm - I while E2 modes were detected at 144 and
569 cm - I. The A I (LO) and E I CLO) frequencies were estimated to be 770 70 em - 1 and 800 70 cm - 1 from IR
reflectivity data. Cingolani et al. 214 later directly observed
the A1(LO) and E1(LO) modes at 710 and 741 cm- I
using Raman spectroscopy. Several groups165,200,201 have
observed phonon replica peaks in luminescence studies,
particularly a LO mode at 726 cm - I. Monemar et al. 213
reported phonon replica peaks within the Zn-related 2.8
and 2.2 eV emission spectra at 597 and 678 cm - I, respectively. Table III summarizes the GaN phonon spectrum.
There have been several measurements of the optical
constants of GaN.36.121.21O.211.216 Ejder 216 measured the refractive index of GaN using transmission and absorption
measurements and obtained values of n(3.38 eV) = 2.67
and n(1.0 eV) = 2.33. Matsubara and Takagi 121 studied
GaN using optical reflectivity and measured EO = 8.9.
Barker and Ilegems 211 used infrared reflectivity measurements of the phonon energies to calculate Eo = 9.5.
Kosicki et al.217 reported the optical absorption and vacuum UV reflectivity of polycrystalline GaN. Bloom et
al. 218 measured the UV reflectivity for higher quality material. In addition to the peak at the band gap, a broad
shoulder was observed at - 5.3 eV which was interpreted
as the r 5v - r 3c transition. Pankove and Schade219 studied
GaN by photoemission. By looking at n-type and insulating samples and observing thresholds of 4.1 and 5.5 eV,
respectively, the electron affinity of GaN was measured to
J. Vac. ScI. Techno!. 8, Vol. 10, No.4, Jul/Aug 1992

350

360

370

380

390

400

(Bl Wavelength (nm)

FIG. I I. (Al Configuration of the vertical cavity photopumping experi-

ment. (Bl Vertical cavity stimulated emission signal as a function of

pump intensity at room temperature: (a) 5 MW /cm 2, (b) 4.2
MW/cm 2, (cl 3 MW/cm2, (d) 2.1 MW/cm2, (el 1.5 MW/cm 2 (from
Ref. 224).

be 4.1 eV~x~2.1 eV. Cesiated GaN surfaces showed

greatly reduced emissive thresholds of 1.5 eV for both insulating and n-type GaN. Martinelli and Pankove 220 measured the secondary electron emission from cesiated GaN
surfaces and found a high escape probability of 0.36 for
secondary electrons. The authors concluded that cesiated
GaN was a suitable material for negative electron affinity
device applications.
Stimulated emission has been achieved in GaN by optical pumping in a number oflaboratories. 30,221-224 Dingle et
al. 3o were the first to report lasing in GaN. Their single
crystal GaN needles emitted at a photon energy of - 3.45
eV at 2 K. Catalano et al. 221 was able to observe 80 K
stimulated emission in GaN at 3.435 eV with an optical
gain of - 103 cm - I. Amano et al. 223 observed stimulated
emission at room temperature for the first time. Khan et
224
al.
have since reported room-temperature stimulated
emission in GaN from a vertical (c-oriented) cavity (Fig.
II). Two groups225,226 have investigated the electron-hole
plasma dynamics in GaN.

1247

S. Strite and H. MorkoCf: GaN, AIN, and InN

1247
TABLE

2.8&

IV. Impurity related GaN luminescence peaks.

Refs. 75, 9O,213,23~234,236,238

GaN:Zn (Zno.)

2.8 eV
2.5-2.6 eV

GaN:Zn (Zn As )

2.2 eV
1.8-1.9 eV

Refs. 213,236,238

GaN:Mg

3.2 eV
2.95 eV

Refs. 227,247
Refs. 205,246

GaN:Cd

2.7 eV
2.85 eV

Refs. 235,241,247,248
Ref. 231

'.rUei pro.lur.
01

~2.2

GaN:Be

eV

Zn (It"'.'

Refs. 246,247,249

GaN:Hg

2.43 eV
2.9 eV

Ref. 247
Ref. 235

GaN:C

2.15 eV

Ref. 32

GaN:Li

2.23 eV

Refs. 235,249

GaN:P

2.85 eV

Ref. 252

GaN:As

2.58 eV

Ref. 252

2.0

There has been much effort aimed at doping GaN p type

by introducing group II and IV elements. Many potential
dopants have been incorporated into GaN and their optical
properties are listed in Table IV and shown schematically
in Fig. 12. Some impurities have been observed to effectively compensate electrons in GaN leading to highly resistive material. Only recently have Akasaki and
co_workers227-229 developed a technique which converts
Mg-compensated GaN into p-type material as a result of
Conduction Band
Ga Site

N Site
~30 meV

\
Native Defect Level

Li

550
410
340
250

Cd
IIg

meV
meV
meV
meV

860 meV

225 meV

Si

Be

Zn

Mg

3.2 hll (eV)

FIG. 13. Room-temperature CL spectra for different Zn-doped GaN samples grown under various Zn partial pressures (from Ref. 244).

E. Properties of doped GaN

750 meV
700 meV

2.8

Valence Band
FIG. 12. Estimated binding energies of some substitutional acceptors in
GaN. Also shown is the shallow donor level, generally thought to be the
nitrogen vacancy, which is responsible for the n-type background carrier
concentration observed in GaN (from Refs. 32,235,241,250).
J. Vac. Sci. Technol. 8, Vol. 10, No.4, Jul/Aug 1992

electron beam irradiation. Nakamura et 01. 176 have succeeded in growing p-type GaN by metalorganic CVD
(MOCVD) which had a hole concentration p = 2
X IOIS/ cm3. Optical measurements have shown that the
acceptor levels in GaN are several hundred milli-electronvolts above the valence band edge. In order to grow GaN
which has significant p-type conductivity at room temperature, existing Mg-doping methods must be improved or
acceptor complexes which lie closer to the valence band
edge must be sought.
The most investigated27,73-75,77,88.90. 161. 196.208.2 I 3.230-246
potential p-type dopant for GaN has been Zn. Zn impurities effectively compensate GaN resulting in high resistivity
material. 27.74.75.196.233.234.239.244 Boulou et 01. 23f>--238 and
Monemar et 01. 213 have published the most complete optical investigations of the properties of Zn-doped GaN. Figure 13 shows typical emission spectra as a function of Zn
concentration. Four Zn-related peaks were observed at
room temperature. All samples exhibited the commonly
observed 2.8 eV emission.75.90.230-234.241 In addition, heavily
doped samples had additional room-temperature peaks at
1.8-1.9, 2.2, and 2.5-2.6 eV which disappeared as the temperature was decreased below 200 K. Samples exhibiting
the three midgap Zn-related peaks had weak luminescence
compared to the lightly doped samples dominated by the
2.8 eV transition, however their intensity did increase in
samples grown under nitrogen poor conditions. From these
data, both groups concluded that the 2.8 eV emission corresponds to a Znoa center while the three midgap peaks
represent a ZnAs triple acceptor site. This is in agreement
with the photoconductivity results of Pankove and
Berkeyheiser233.234 who observed that Zn, present in sufficient concentrations, favors the substitutional replacement

1248

S. Strite and H. Morkoc;: GsN, AIN, and InN

of N vacancies. This is also consistent with the observed

lattice expansion at high Zn 191 and Mgl90 doping levels
which would result from group II impurities occupying
nitrogen lattice sites. Desnica et al. 245 has proposed the
incorporation of the 67Ga isotope into GaN. Its subsequent
decay into 67Zn would guarantee that the Zn impurities
were in Ga sites and a higher dopant activation and possibly even p-type conduction might result. Pankove 8 has
provided an excellent perspective on the GaN doping problem with special attention to Zn doping. A tentative model
which is consistent with the observed data was also proposed.
Several groups have investigated the lifetime of the Zn
. Ie acceptor transitIOn.
..
Bergman et a 1241
SlOg
.
measure d a
decay time of 300 ns at 2 K while Marasina et al. 90 reported a sample dependent 150-200 ns relaxation time at
100 K which decreased to 70 ns at room temperature.
Pankove et al.2JO.233.234 reported a significantly larger relaxation time, of the order of microseconds, which was sufficiently long that the authors were led to speculate that the
radiative recombination involved a tunneling mechanism.
More work is needed to distinguish between these two contradictory results.
A number of workers27, 165,190,195.205,227.229.246 have investigated Mg doping which has also been observed to effectively compensate GaN. Liu et al.205 observed the Mg acceptor luminescence at various doping levels. The Mg peak
broadened and shifted to lower energy with increased doping, eventually reaching a minimum energy of2.95 eV. The
intensity of the luminescence remained roughly constant as
the Mg content was raised, until the luminescence was
abruptly quenched at the same concentration at which the
resistivity of the GaN began to increase rapidly. Ilegems
and Dingle 246 observed the same 2.95 eV emission. However, a number of groups176,227.247 have reported the location of the Mg acceptor peak to be 3.2 eV. More work is
needed to resolve this discrepancy.
There have been several reports231.235.241.248 which de24I
scribe attempts to dope GaN with Cd. Bergman et al.
were able to dope GaN with a small amount of Cd, but a
sufficient amount to compensate the electron background
concentration could not be incorporated. Three
groups241.247,248 have observed the Cd-related luminescence
peak at 2.7 eV while Ilegems et a/.231 reported the Cdrelated peak at 2.85 eV. Bergman et al. 241 measured a Il1-s
decay time at 77 K for their 2.7 eV emission.
Two groups246.247.249 reported Be-doped GaN. Be was
observed to effectively compensate the free electrons and
high resistivity GaN was obtained. Optical measurements
detected a broad Be-related emission at an energy of - 2.2
eV. Two groupsI65.235,247 have investigated Hg doping. No
electrical measurements were reported. Pankove and
Hutchby247 observed 2.43 eV emission in Hg-doped samples. Ejder and Grimmeiss 235 observed 2.9 eV emission and
estimated the Hg-acceptor level to be 410 meV above the
valence band.
Group IV elements have been investigated 27 ,32,203,247,250
as possible p-type dopants in the hopes that they would
.
. .m G a N . C unnmg
. ham et a1.203
occupy vacant mtrogen
sites
J. Vac. ScI. Technol.

e,

Vol. 10, No.4, JullAug 1992

1248

observed an order of magnitude reduction in the free carrier concentration when Ge doping was attempted.
Maruska and Tietjen 27 reported occasional p-type conduction in Ge-doped GaN, but later retracted this claim. 184 In
the same work, Si was observed to markedly reduce the
electron concentration in GaN to as little as n = 3
X 1016/cm3 but p-type conductivity was not achieved.
Khan et al. 250 studied the effect of Si on the PL of GaN.
Ogino and Aoki 32 observed a yellow band peaking at 2.15
eV which was attributed to a deep C acceptor approximately 860 me V above the valence band.
A number of workers 165,235,247,249 have investigated Li
doping. Pankove et al. 249 obtained compensated GaN using
Li doping. The Li acceptor luminescence was observed at
2.23 eV. Ejder and Grimmeiss 235 estimated the Li-acceptor
level to be 750 meV above the valence band.
Other impurities have also been introduced. Ion implantation was used by Pankove and Hutchby247 to introduce a
total of 35 elements into GaN and observed the optical
spectra. Al implantation at a very high dose was unsuccessful in producing the alloy shift of the primary 3.45 eV
emission to higher energy that was observed by Monemar
and Lagerstedt.25\ Monemar and Lagerstedt also reported
that high resistivity GaN was obtained when Fe or Cr was
incorporated during the growth. Metcalf et al. 252 implanted GaN with P and N and measured P-related emission at 2.85 eV and an As-related band at 2.58 eV. A
damage induced emission at 2.2 eV was also noted. Ogino
et al.23 also reported the PL spectrum of P-doped GaN.
Recently, Akasaki and co-workers have reported the
synthesis of p-type GaN and AIGaN.227-229 Magnesium
doping at a concentration of - 2 X 1020/cm3 was incorporated into GaN resulting in compensated highly resistive
material. The sample was then treated with low-energy
electron-beam irradiation (LEEBI) which had the remarkable effect of drastically reducing the resistivity of the sample to - 35 n cm. The CL spectrum of the LEEBI
GaN:Mg samples was greatly improved [Fig. 14(a)J. Hall
measurements revealed the GaN to have a hole concentration p = 2 X 1016/cm3, and a mobility I1-p = 8 cm 2IV s.
The p-type nature of the LEEBI treated GaN was further
demonstrated by the fabrication of a p-n junction LED
having rectifying current-voltage characteristics and
room-temperature emission in the UV and blueviolet [Figs.
14(b) and 14(c)]. A similar procedure was performed on
Zn-doped samples,242 and a marked increase in the luminescence intensity resulted, however p-type conduction was
not achieved. No explanation for this remarkable behavior
has been offered. Nakamura et al. 176 have recently confirmed the work of Akasaki et al. Mg-doped GaN was
grown by MOCVD which showed an initial p-type conductivity of p = 2 X 1015/cm3. Hole concentrations as high
as p = 3 X 1018/cm3 and mobilities as large as I1-p = 15
cm 2IV s were obtained after LEEBI treatment. The observation of p-type conductivity in GaN remains one of the
outstanding nitride research results in recent years.

1249

S. Strite and H. Morko-r: GaN, AIN, and InN

1249

TABLE

ENERGY (eV )

V. Properties ofwurtzite AIN.

~3~.5L-__~3~0~__--~2~r5----------,
~

R .T.

c
:J

.0

Band gap energy

Eg (300 K) = 6.2 eV
Eg (5 K) = 6.28 eV

Ref. 81
Ref. 274

Lattice constant

a=3.112A
c=4.982 A

Ref. 81

fl.a

If)

Coefficient of thermal
expansion

Thermal conductivity

K=2 W/cmK

Ref. 10

I ndex of refraction

n=2.1505

Refs. 9,34,45,281

I-

= 4.2 X 1O-6/K

Ref. 261

fl.c
- = 5.3 X 1O-6/K

400

350

600

500
WAVELENGTH ( nm)

(A)

Dielectric constants

EO

= 8.5

E",

= 4.68
= 4.84

E",

OSmA/dlv
(a)

Phonon modes

(b)

5v I

div

(B)

ENERGY (eV)

3.0

2.5
R.T

-'"
c:

:J

20mA

>
IIf)

Z
W
I-

lOrnA

x2
(b)

350
(C)

400

450

10mA

500

550

WAVELENGTH ( nm)

14. (A) Room-temperature PL spectrum of Mg-doped GaN (b)

before and (a) after LEEBI. (B) Current-voltage characteristics of (a) a
LEEBI Mg-doped Jrn diode and (b) a conventional m-;-n GaN diode
fabricated from the same layer without LEEBI. (C) Electroluminescence
spectrum of the LEEBI GaN Jrn diode at several different current levels.
UV light is emitted at high current (from Refs. 227 and 228).

FIG.

J. Vac. Sci. Technol.

a,

Vol. 10, No.4, Jul/Aug 1992

0.2

TO = 667 cm- I
E2 = 665cm - I
LO=91Ocm- 1

Refs. 45,91,94,95
Ref. 91
Ref. 283

Ref. 285

IV. AIN
AIN has some outstanding physical properties that have
attracted much interest. Its hardness, high thermal conductivity, resistance to high temperature and caustic chemicals, combined with a reasonable thermal match to Si and
GaAs, also makes AIN an attractive material for electronic
packaging applications. 253 Its wide band gap has led to
investigations of its potential as an insulating material for
GaAs and InP based electronic device structures. AIN also
has attractive piezoelectric properties which may be suitable for surface acoustic wave device applications. However, the majority of interest in AIN stems from the properties of its alloys with GaN which may permit the
fabrication of AIGaN based optical devices which are active from the blue wavelengths well into the UV.
AIN is not a particularly easy material to study and
most researchers in the field have concentrated on GaN.
Because of the reactivity of AI, high purity source material
and an oxygen-free environment are required to grow AIN
of good quality. Early measurements on oxygen contaminated material led to a number of the physical properties of
AIN, such as the band gap and the lattice constant, to be
misreported. Only recently have researchers begun to be
able to consistently grow high quality AIN using the MBE
and CVD techniques. Some researchers have undertaken
fundamental studies of AIN and many of the physical
properties of AIN have been reliably measured. Table V
summarizes the observed structural and optical properties
of AIN.
A. Structural and chemical properties

Ott,254 in 1924, first reported AIN to have the wurtzite

crystal structure with lattice constants a = 3.11 A and c
= 4.98 A.. Jeffrey and Parry255 noted that AIN varied
slightly from the ideal wurtzite structure. The presently
accepted values quoted in the literature are a = 4.982 A.
and c = 3.112 A.81 A number of smaller values, due to

1250

S. Strite and H. Morkocr: GaN, AIN, and InN

oxygen contamination, have been reported. 10 Gabe et al. 256

used x-ray techniques to measure the AIN valency and
obtained a value of - 1.8 0.8e which is approximately
midway between the ionic and covalent limits.
AIN is an extremely hard ceramic materia1257-259 with a
melting point in excess of 2000 0c. 11,257 Slack 10 measured
the thermal conductivity of AIN to be K = 2 W Icm K.
Slack and Bartram260 determined the thermal expansion of
AIN to be isotropic using x-ray techniques across a broad
temperature range (77-1269 K) and found a roomtemperature value of 2.56 X 10 - 6/ K. Yim and Paff261 measured the most commonly quoted values for the thermal
expansion coefficient of AIN. Their mean values are
!:..ala = 4.2 X 1O- 6/Kandt:..c/c = 5.3 X 1O- 6/K.
AIN exhibits a resistance to chemical etch similar to
GaN. There have been a number of AIN etches reported in
the literature,82.126,131,145,262 but none have been demonstrated for high-quality single crystal AIN. The surface
chemistry of AIN has been investigated by numerous techniques, including AES, 106,144,145,153,263-265 x-ray photoemission spectroscopy (XPS), 106,266,267 UV photoelectron
spectroscopy,51.266,268 and electron spectroscopy. 51,269-271
Slack and McNelly 11 reported that the AIN surface grows
an oxide 50-100 A thick when exposed for one day to
ambient. However, this oxide layer is protective, and no
further decomposition of the AIN samples was observed.
Elliot and Grant 106 also observed oxidation of the AIN
surface by XPS.

1250

(0001) A\N

SINGL CRYSTALS

3OQ"K

10'
i

.
a

..

,::,

9~

THICK

!5~

4,.

.O.3~

...=:e

-----PASTRNAK .taI

.!!
u

ea

10

...
=:

..//,

.S!

c.

1'- ,/
.'. "

.
0

.ll

<

10'~

/1

,;1_'. ,,'
,'it'

"

I
..':, .'

.... ,,,,
.. ,
I

10

!5

hv (eV)
FIG. 15. Room-temperature absorption spectra of AIN films of varying
thicknesses whose principle absorption edge occurs at 6.2 eV. The bump
near 4.5-4.8 eV in the data of Pastrnak et al. was attributed to oxygen
absorption bands (from Ref. 81 and references therein).

B. Electrical properties
Electrical characterization has usually been limited to
resistivity measurements due to the low intrinsic carrier
concentration and deep native defect and impurity energy
levels of AIN. Edwards and co-workers9,33 observed that
transparent AIN single crystals had resistivities p
=
1011 - 1013 n cm, a value consistent with other
reports. 34,81.126,142 However, they found that impure crystals, which exhibited a bluish color, possibly due to the
presence of AI 20C, had much lower resistivities p
= 10 3 105 !l em. These samples were p-type and Hall
measurements produced a very rough estimate of the AIN
hole mobility lip = 14 cm 2/V s. Chu et al.92 were able to
obtain both n- and p-type AIN by introducing Hg and Se,
respectively, however the resistivity of their material was
too high to allow the net carrier concentrations to be determined. Rutz l55 reported a growth technique which obtained low resistivity (p = 103 n cm) n-type AIN, however the source of the electrons was not determined. Rutz
et al. 272 observed an interesting transition in their AIN
films in which the resistivity abruptly decreased by two
orders of magnitude as the applied bias was increased. This
concept was applied in the form of a switchable resistive
memory element which operated at 20 MHz.

C. Optical properties
Vim et al. 81 characterized high-quality AIN by optical
absorption (Fig. 15) and determined the roomtemperature band gap to be direct with a value of 6.2 eV.
J. Vac. Sci. Technol. S, Vol. 10, No.4, Jul/Aug 1992

Several
groups
have
reported
comparable
values. 34,82,95,206,273-275 Many other measurements of the
AIN band gap produced questionable values, considerably
below
6.2
eV,
probably
due
to
oxygen
contamination. 9,25,26,276 Yim et al. 81 also observed a broad
emission spectrum ranging from 2-3 eV with a peak at 2.8
eV. Other investigators9,34 confirmed the presence of a 2.8
eV peak which Slack and McNelly I I have attributed to
oxygen impurities. Perry and Rutz 274 performed temperature dependent optical absorption, measuring a band gap
of 6.28 eV at 5 K compared to their room-temperature
value of 6.2 O.I eV. In the only optical study of AIN
impurities, Karel and co-workers reported on the luminescence of Mg277-279 and rare earth Z78 ,280 centers in AIN.
Measurements 9,34,8z,95,281,282 of the AIN index of refraction range from n = 1.99-2.25 with several groups9,34,45,281
reporting n = 2.15 0.05. Pastrnak and Roskovcova 281
measured the spectral dependence and the polarization dependence of the index of refraction. The long wavelength
dielectric constant of AIN has been measured by a number
of workers.45,8Z,91 ,94,95, 144,283 While the measurements range
from EO = 8.3 - 11.5, most of the measurements 45 ,91,94,95
fall within Eo = 8.5 0.2. Two groups have measured the
high frequency dielectric constant and reported E
283 AIN has also been examined
91
= 4.68 and Eoo = 4.84.
for its potential for second harmonic generation by
Yoshida et al. 142 ,284
The phonon structure91 ,106,2I5,279,283,285-288 of AIN has

1251

1251

S. Strite and H. Morkol!: GaN, AIN, and InN

TABLE VI. Properties of wurtzite InN.

Band gap energy

E8 (300 K) = 1.89 eV

Ref. 29
~

.....
Band gap temperature coefficient dEg
dT

Ref. II
= -1.8 X 1O-4 e V/K

A
A

Lattice constant

a = 3.548
c= 5.760

Electron effective mass

m: = O.llmo

Ref. 29

Index of refraction

n = 2.85
n = 2.9
n = 3.05

Ref. 55
Ref. 36
Ref. 29

Phonon modes

Ref. 29

S
U

<lO

TO=478 cmLO=694 cm- I

Ref. II

'--'
N

...,
>=1

Q)

'u

ij2
Q)

10

>=1

0
.....
+"

P<

been the subject of numerous investigations. The LO and

TO modes appear at 905 12 cm - I and 667 cm - I, respectively, and an E2 mode was observed at 665 cm - I.
Sanjurjo et al. 288 obtained the mode Gruneisen parameters
YTO = 1.6 and YLO = 1.0 from the pressure dependence of
.
T wo groups'
26289 reported
the phonon mode f requencles.
synchrotron radiation studies of AIN single crystals out to
40 eV. The 8 eV luminescence observed by Michailin et
al.2 6 was also seen by Yamashita et al. 275 using vacuum
ultraviolet reflection measurements.

V.lnN
InN has not received the attention given to GaN and
AIN, primarily because the 1.89 eV band gap of InN corresponds to a portion of the electromagnetic spectrum in
which alternative semiconductor technology is available.
Consequently, the practical applications of InN are restricted to its alloys with GaN and AIN. The growth of
high-quality InN and the enumeration of its fundamental
physical properties remains for the present a purely scientific enterprise.
InN suffers from the same lack of a suitable substrate
material and high native defect concentration that have
hindered progress in GaN and AIN. In addition, due to its
rather poor thermal stability, InN cannot be grown at the
high temperatures required by CVD growth processes, the
most popular nitride growth approach. Other workers
have cited the large disparity of the atomic radii of In and
N as a possible contributing factor to the difficulty in obtaining InN of good quality. Despite the problems inherent
to InN growth, some excellent work has been reported.
The seminal work of Tansley and Foley, first characterized
many of the fundamental physical properties of InN. However, InN remains the least understood of the nitrides. Table VI lists the measured physical properties of InN. No
group has yet reported the growth of high quality single
crystalline material which would enable detailed optical,
structural, and electrical measurements to be performed.
All of the data reported below, unless otherwise specified,
were obtained from highly conductive n-type polycrystalline InN.
J. Vac. Sci. Technol. B, Vol. 10, No.4, Jul/Aug 1992

1-1

rJl

,..Cl

cO

1.'

2.2

2.1

3.0

hv (eV)
FIG. 16. Room-temperature absorption spectrum of InN having
n = 1.6X 1016/cm J (from Ref. 290).

A. Structural and chemical properties

Juza and Hahn 14 first reported the crystal structure of

InN to be wurtzite having lattice parameters a = 3.53 A
and c = 5.69 A. These values are quite close to the other
reported values of a = 3.5480 A and c = 5.7600 A of Tansley and Foley,290 a = 3.544 Aand c = 5.718 A ofOsamura
et al., Il5 and c = 5.69 A of Wakahara and Yoshida. /27 An
unambiguous determination of the lattice constants awaits
the growth of thick single crystalline InN films.
There have been several studies 114,291 which report rapid
dissociation of InN at temperatures above 500 0c. Since no
high quality InN has yet been grown, the resistance of the
material to chemical etching is unknown. Wakahara et
al. 292 have reported successful etching of their single crystalline InN films in a hot H 3P04:H 2S04 solution. Foley
and Lyngdal m studied the surface oxidation of InN when
exposed to ambient.
B. Optical properties
A handfull of groups36,55,57,115,290,294--297 have described
optical measurements performed on InN. Reported
values 55 ,115,294 of the room-temperature InN direct band
gap range from 1.7-2.07 eV with the value of 1.89 eV
measured by optical absorption by Tansley and Foley290
(Fig. 16) being the most commonly referenced. Tansley
and Foley296 also measured the IR absorption of InN and
observed an unidentified donor level approximately 50-60

S. Strite and H. MorkoCf: GaN, AIN, and InN

1252

1252

C. Electrical properties

'0.'0,

,
.,
.

'b..o

0'0,

o ,

0
'\.

,,

It

10'1

lOiS

eole<:tron cone .. em- J

10

There have been few reports 43 ,292,298 describing the electrical properties of InN. All InN reported to date had
electron concentrations n > lO'8/cm3 with the exception
of Tansley and Foley.298 It is believed, but not proven, that
nitrogen vacancies are the cause of the large background
electron concentrations. In their work, Tansley and Foley
reported the temperature dependent carrier concentration
and electron mobility of polycrystalline InN films (Fig.
17). A room temperature carrier concentration of
5X lO'6/cm 3, which decreased to a minimum of
3X lO'6/cm3 at 150 K, was measured. The roomtemperature electron mobility of 2700 cm2IV s reached a
maximum value of 5000 cm 2/V s at 150 K. No experimental investigations of the doping properties of InN have yet
been reported.

VI. ALLOYS AND HETEROSTRUCTURES

Most semiconductor devices are optimized by heterojunctions which are commonly achieved through the use of
alloys. GaN based technology will depend heavily on its
alloys with AIN and possibly InN in order to realize practical light emitting devices in much the same manner that
GaAs is commonly alloyed with AlAs and InAs. Some
work on the properties of IU-V nitride alloys has been
accomplished, but much more will be needed.
A. AIGaN

10

100
t.~ratu"'.

FIG. 17. InN Hall mobility as a function of the carrier concentration and
temperature (from Ref. 298 and references therein).

meV below the conduction band edge. Tyagai et al.295 perfonned reflection and transmission measurements and
were able to estimate an effective mass of rn: = 0.11 rno and
an index of refraction n = 3.05 0.05. Hovel and Cuom036
reported an index of refraction n = 2.9 while Natarjan et
al. 55 measured n = 2.85. Osamura et af. 115 measured the
InN band gap as a function of temperature and obtained a
band gap temperature coefficient of dEgI(dT) =
- 1.8 X 10 - 4 eV/K. They also reported reflectance data
from which they deduced the existence of a TO phonon
mode at 478 cm - 1 and an LO mode at 694 cm - '.
J. Vac. Sci. Techno!. B, Vol. 10, No.4, Jul/Aug 1992

AIGaN has received the most attention of the 111-V

nitride alloys due-to its potential applications in AIGaNI
GaN heterostructure devices. Since the first report of a
GaN-AIN
solid
solution
in
1976,299
many
groups83,136,175,198,206,215,273,300-306 have synthesized AIGaN.
Baranov et al. 83 achieved AlxGal _ xN up to an Al concentration of x = 0.45 as measured by the relative intensities
of the Al and Ga x-ray radiation. Evidence for the presence
of small regions of zinc-blende AIGaN were reported. All
samples showed n-type conductivity with the carrier concentration and mobilities decreasing monotonically as a
function of the Al mole fraction. Hagen et al. 301 measured
the band gap of AIGaN throughout the entire compositional range and found it to vary smoothly with some bowing.
The most complete study to date on the properties of
AIGaN was performed by Yoshida et al. 206 In that work,
they reported the variation of the electron concentration,
mobility, resistivity, lattice constant, and band gap as a
function of the alloy concentration over the entire alloy
range (Fig. 18). The observed AlxGa'_xN lattice tended
to be smaller while the optical absorption edge was slightly
larger than the values predicted by Vegard's law. Resistivity increased ten orders of magnitude, from p = 10 - 4 to
P = 106 n cm, and the carrier concentration decreased
from n = 2 X 102!cm 3 to n = lO '7!cm3 as the Al
concentration was increased from zero to x = 0.40. Khan
et al. 303 measured the edge emission for AlxGa'_xN with
x<0.24 and reported a band bowing parameter b = 0.98 eV
which agrees with the value of b = 1.0 eV reported by Itoh

1253

S. Strite and H. Morko~: GaN, AIN, and InN

1253

>

., .
,.,,"

" "

.!

,,"

"

"
.,"
,

""
3.5

",.',, .,,
r .,

>GI

,,

3.0
t-

,,

~,

,,

,,

>-

co
GI

c:
lD

300

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

COMPOSI nON x

lal

~"

2.5

"I

a0

,.
0

"',

t!)

'tt ...

......

0 .............. ;::

2.0

t-

5.20

...

1.5

~ 5.10

tii

GaN

.. ..:.

w
u
;::

Mole

~ 5.00

0.4

0.6

0.8

InN

fraction of InN

FIG. 19. Compositional dependence of the InxGa, _ xN band gap at room

temperature (from Ref. 294).

...l

4.900.0

0.2

0.1

0.2

0.3

0.4

0.5

COMPOSI nON

(bl

0.6

0.7

0.8

.0.9

1..0

".~
10' I---=-.-"'---

10"

!
c

10'" ~

;::

'0" ~z
'"
10" ~
10" ~

iii'

10'0"'0-~-=o.':-\---;;-Q.2;----::O'...
3 -~-:-'0.4

fcl

IZ

COMPOSITION J

FIG. 18. Compositional dependence of the AlxGa, _ xN (a) band gap, (b)
lattice constant, (c) resistivity p, carrier concentration n, and electron
mobility IJ" at room temperature (from Ref. 206).

J. Vac. Sci. Technol. B, Vol. 10, No.4, Jul/Aug 1992

et al.175 Khan et al. 198 reported Alo.09Gao.9IN which had a

mobility of /Ln = 35 cm 2IV s for a carrier concentration
n = 5 X IOI8/cm3. CL spectra showed a single sharp
peak near the band gap and broad peaks in the visible
region. Some optical characterization of the Zn acceptor in
AIGaN have also been reported. 83, 175,304 Itoh et al. 175 studied the energy dependence of the Zn-related emissions as a
function of Al concentration. Khan et al. 302 examined the
effect of Be and N ion implantation in AIGaN films. Lyutaya et al. 299 determined Alo.5Gao.5N to be thermally stable
up to 900 0c. Two groups273,299 have reported the synthesis
of AIBN alloys, and at least two groups96,307 have investigated the AIN-AI203 composite material.
Raman scattering measurements have been performed
on AlxGa1 _xN for x<O.15 by Hayashi et 01.215 The increase of the phonon frequencies with Al mole fraction was
smaller than expected from a linear extrapolation for the
TO and E2 modes while it was slightly larger for the
E I (LO) mode. AlGaN appears to be a single mode alloy
since no splitting of any of the peaks was observed. Khan
et al. 306 claims to have measured the refractive index of
AlxGal _ xN in the wavelength range of 360-500 nm, but
has not yet published those data. However, from the chosen thickness of their quarter wave reflector, we can deduce
n(400-450 nm)-2.42 for Alo.2Gao.sN. This value falls
roughly onto a linear extrapolation between the GaN and

1254

S. Strite and H.

Morko~:

GaN, AIN, and InN

AIN indices of refraction and casts doubt upon the index

bowing observation of Hayashi et 01.215
Itoh et 01.175 observed cracks in the form of V-shaped
grooves forming on AIGaN grown on GaN. The cracking
was attributed to the lattice mismatch. Unlike AIGaAsl
GaAs, AIGaN/GaN has a significant lattice mismatch,
and care must be taken to stay within the pseudomorphic
limit. However, to date there have been no studies aimed at
measuring the critical thickness of AIGaN/GaN.
B.lnGaN

Osamura et 01. 294 reported the first InGaN alloys. They

used optical absorption measurements to determine the dependence of the InGaN band gap as a function of the alloy
composition as estimated from Vegard's law. The direct
band gap varied smoothly with alloy composition with
some bowing (Fig. 19). Reflectance measurements were
also performed and the energy of the optical phonon mode
was measured as a function of alloy composition. Nagatomo et 01.138 reported high resistivity InxGal _ xN films
with In concentrations as large as x = 0.42. The dependence of the lattice constant and the band gap of their films
was linear with In composition as determined by the relative Ka emission intensities of In and Ga. Osamura et 01.115
observed a phase separation in low In mole fraction InGaN
alloys after a 700 C anneal in argon. Yoshimoto et 01.308
used a high (800 C) CVD growth temperature to obtain
high-quality single crystalline alloys up to Ino.22Gao.78N.
The amount of indium incorporation was limited by reevaporation of the In from the surface as a result of the
high growth temperatures. Their films were of sufficiently
high quality that they were able to observe 77 K luminescence for the first time in an In containing nitride.

C. Other alloys
Kubota et 01.43 has published the only experimental
work on the InxAll _ xN alloy despite that material's potential as a lattice matched insulating barrier for GaN. The
alloy composition was estimated by applying Vegard's law
to the measured lattice constants, and the band gap was
measured by the optical absorption technique. A highly
nonlinear dependence of the band gap on alloy composition was observed. Films with large In mole fractions were
conductive, while those with large Al mole fractions were
resistive. From their data, Kubota et 01.43 estimated that
the alloy composition Ino.I7AIo.83N, having a band gap of
3.34 eV, is lattice matched to GaN. If this work is accurate,
the Ino.I7Alo.83N/GaN heterojunction system will have
very little band gap difference and may not prove useful as
a barrier material. However, more work needs to be done
in order to verify such a strange compositional dependence
of the InAIN band gap before any conclusion is drawn
regarding the potential of the InAIN alloy system.
The only experimental study of nitride group V alloy
properties was reported by Igarashi et 01.103 who investigated GaN 1- xP x for small (x.;;;0.06) P concentrations. It
has long been thought that P might compensate the nitrogen vacancies in GaN and lead to insulating films and
J. Vac. ScI. Technol. B, Vol. 10, No.4, Jul/Aug 1992

1254

possibly allow p-type doping. No measurements of any

physical properties were reported.

V". THE ZINC-BLENDE POL YTYPES

In 1977, Pankove 5 wrote that one of the remaining challenges in GaN research was "to synthesize the cubic
phase." The vast majority of research on the III-V nitrides
has been focused on the wurtzite crystal phase. However,
researchers have known for some time that GaN also has a
zinc-blende phase. 69 Mizuta et 01.149 first reported bulk
zinc-blende GaN grown on (001) GaAs. More recently,
the zinc-blende phase of InN I59 has also been observed.
There are a number of reasons that the zinc-blende polytypes have received so little attention. One is that the vast
majority ofIII-V nitride growth has been on sapphire substrates which generally transfer their hexagonal symmetry
to the epitaxial film. The zinc-blende phases of the I1I-V
nitrides do not appear to be the equilibrium crystal structure. All of the zinc-blende 111-V nitrides (with the exception of Humphreys et 01. 158 ) reported to date have been
grown on cubic substrates by non equilibrium growth techniques. A cubic substrate alone does not guarantee the
stabilization of the zinc-blende phase. Many more workers
have reported the growth of wurtzite nitrides on substrates
having cubic symmetry, however such material was usually
not epitaxial.
The zinc-blende nitrides as a whole represent an unexplored material system whose properties may be quite different from those of their wurtzite counterparts. For instance, Lambrecht and Segall have predicted that zincblende AIN will have an indirect band gap of 5.11 eV,309 a
full electron volt smaller than the 6.2 eV band gap of
wurtzite AIN. The zinc-blende polytypes may have superior electronic properties resulting from reduced phonon
scattering in the higher symmetry crystal. 310 It is also
hoped that the zinc-bIen de nitrides may be more amenable
to p-type doping. Now that the capability to grow the zincbIen de nitrides has been demonstrated, a thorough investigation of the physical properties of these materials is
timely. Table VII summarizes the properties of the zincblende nitrides which have been measured or calculated to
date.
There have been several recent studies of zinc-bien de
GaN which have begun to catalog its properties. Paisley et
117 154
01.

grew zinc-blende GaN on epitaxial 3C-SiC grown

on (001) Si substrates, while Powell et 01. 120 used MgO,
Humphreys et 01.158 grew on (0001) sapphire, Strite et
01." 8 grew on (001) GaAs, and Lei et 01." 9 used (001) Si.
The various reports are in agreement measuring a lattice
constant of -4.52 A. TEM were similar for GaN grown
on (3-SiC, MgO, and GaAs. High densities of planar defects, mostly {Ill} microtwins and stacking faults, resulting from the rather large lattice mismatches were observed.
The defect density decreased away from the GaNI
substrate interface. Powell et 01.120 noted the existence of
small regions of wurtzite GaN in the bulk zinc-blende GaN
crystals. Zinc-blende GaN grown on /3-SiC and GaAs had
a highly disordered region at the substrate interface, from

1255
TABLE

1255

S. Strite and H. Morkoq: GaN, AIN, and InN

ENERGY

VII. Properties of the zinc-blende nitrides.

3.6

f.....(J)

Zinc-blende OaN
Eg = 3.30 0.Q2 eV
Eg = 3.4SeV
Eg = 3.2eV

Band gap energy

(T=300K)

Ref. 120
Ref. 118
Ref. 119

34

3.5

HI eV
3.3

3.2

,---.----r-----ri--------,----r-----~_____;__

(5
>-z
~

w
u

0= 4.52-4.55 A
0=4.54 A
0=4.531 A
0=4.5 A
0= 4.520.05 A

Ref.
Ref.
Ref.
Ref.
Ref.

Donor-acceptor peak
Energy (T= 53 K)

3.196eV

Ref. 118

Free electron-acceptor
Peak energy (T = 53 K)

3.262 eV

Ref. 118

Phonon mode

740 cm- I
403 cm- I

Ref. 158
Ref. 118

Zinc-blende AIN
Theoretical band-gap energy

Eg = 5.11 eV (indirect)

Ref. 309

Theoretical lattice constant

0=4.33

Ref. 309

Zinc-blende InN
Theoretical band gap energy
(T=300K)

Eg = 2.2eV

Ref. 323

Lattice constant (T = 300 K)

0=4.98A

Ref. 159

Lattice constant
(T= 300 K)

149
117
120
118
119

(J)

zH

:J
-l

0
0

I
0-

u
w
>
H

f-

-l

cr

3400

which the majority of the defects originated in the GaAs

case. The exact nature or chemistry of the disorder has not
been determined.
Powell et al. 120 measured resistivities of p = 106 n cm
when the nitrogen ion to Ga flux ratio was maximized. The
mobilities were quite low with Jln - 10 cm2IV s. Lei et al. 119
determined from thermopower measurements that their
zinc-blende GaN was n-type. A carrier concentration of
n , 3 X 1016/cm 3 was estimated from the temperature
dependence of the resistivity.
Optical measurements were performed on the zincblende GaN grown on MgO, Si, GaAs, and sapphire. Powell et al.l2 obtained a band gap of 3.300.02 eV from
room-temperature optical absorption measurements. Lei et
al. 1I9 using the same technique measured a 3.2 eV band
gap, and the index of refraction below the absorption edge
was determined to be n = 2.5. Strite et al. 1I8 reported the
low-temperature CL spectrum of GaN (Fig. 20) and tentatively identified the free electron to acceptor and DA
transitions and a phonon mode at 403 cm - I. A temperature coefficient of - 3.5 X 10 - 4 eV /K was measured for
the free electron to acceptor peak in the linear region above
180 K from which a room-temperature band gap value of
3.45 eV was estimated. Humphreys et al. IS8 performed Raman spectroscopy on their zinc-blende GaN films and tentatively identified a phonon mode at 740 cm - I.
Recently, Strite et al. IS9 has reported the growth of the
J. Vac. ScI. Technol.

a, Vol. 10, No.4, JuliAug 1992

3500

31;00

3700

~AVELEtIGTH

3800

3900

4000

<1100

IN MIGS [ROMS

FIG. 20. CL spectrum of zinc-blende OaN at 53 K. Luminescence is

observed at energies as large as 3.52 eV (a'). Peaks band c may be
phonon replicas of peak a. From their behavior as a function of temperature, peaks a and f3 have been tentatively identified as the free electron
to acceptor and DA transitions, respectively (from Ref. 118).

zinc-blende InN polytype. X-ray characterization determined the zinc-blende InN lattice constant to be a = 4.98
0.01 A which is approximately equal to the value obtained when the volume of the wurtzite InN unit cell is
conserved in the transformation between crystal structures.
The InN films were highly conductive having an electron
concentration n = IOw/cm 3 and a mobility Jln = 220
cm 2IV s. TEM reveals the existence of both wurtzite and
zinc-bien de domains which nucleate at stacking faults
along the (111) planes.
None of the zinc-blende nitrides grown to date have
rivaled the optical quality of the best wurtzite material. In
order to better understand the properties of the zinc-blende
polytypes, the growth conditions must be optimized and
thicker films, which are less affected by defects resulting
from the lattice mismatch with the substrate material,
must be grown. One challenge that researchers in the zincblende nitrides face is the metastability of their films with
respect to the wurtzite phase which has led to domain
formation. However, the zinc-bIen de nitrides have become
a viable material system in their own right with a potential
similar to the wurtzite nitrides for device applications.
High priority should be placed on the effort to grow highquality zinc-blende AIN, or at least high Al fraction AlGaN, and to measure the properties of the zinc-blende
polytypes. These new materials should provide an active
and fruitful research topic for years to come as investigators attempt to quantify their potential.

VIII. THEORY
A number of workers have published band structure
calculations for both wurtzite and zinc-blende GaN, AIN,
and InN, and one group considered the band structure of

1256

S. Strite and H.

Morko~:

GaN, AIN, and InN

1256

>5
~ 4
IIJ

AlN

FIG. 21. Calculated band structure of wurtzite GaN (from Ref. 218).

AIGaNAs alloys. Other theoretical efforts have been directed towards understanding the origin of the large free
carrier concentration through a study of the native defects
of InN and its GaN and AIN alloys. Investigators have

12~~----r---r-~~--~~.-~
..~---r-.

.......
"I
'.

....

10

I,

'.

'"

ilU~

'" I'

o ,',......

I"

..

..

-2

""

..

-4
-6

"

'"

~.

...'. .....
., '.
'I

....

11

'"

"..

-8

-16 ..........

..................1""""--+--.......

..............

......... .

K X

FIG. 22. Uncorrected band structure of zinc-blende GaN. The corrected

band gap value is 3.40 eV (from Ref. 314).

J. Vac. Sci. Technol. B, Vol. 10, No.4, Jul/Aug 1992

calculated the energy levels of deep level defects in AIN as

well as the properties of the zinc-blende AIN/SiC interface.
Investigators have also calculated the conduction properties of GaN in an effort to predict the performance of GaN
in high frequency electronic device applications.

A.GaN

..
GaN

.. '.'........

.'
,
'.

...

2 .'

".,.'

....

.....
........ ,,'.

.....

.'

FIG. 23. Calculated band structure of wurtzite AIN (from Ref. 311).

The first GaN band structure was calculated by

Bloom311 who used a pseudopotential method to accurately
obtain a 3.5 eV direct band gap. Later, Bloom et al. 218 used
an empirical pseudopotential approach fit to experimental
reflectivity data to generate an improved band structure
(Fig. 21). Pseudopotential band structures have also been
reported by Bourne and Jacobs 312 who adjusted their calculation to fit the experimental value of the GaN band gap,
and by Jones and Lettington 313 who obtained a band gap
value of 3.50 eV. Bloom et al.218 also calculated a band
structure for zinc-blende GaN predicting a 3.5 eV band
gap. The only other zinc-blende GaN band structure calculation was performed by Lambrecht and Sega1l 314 (Fig .
22) who used a first-principles technique within the local
density functional framework to predict a direct band gap
of 3.40 eV and a lattice constant of 4.50 A.
Two groups have investigated the conductivity of GaN
with an eye towards electron device applications. Littlejohn et af.315 used Monte Carlo techniques, which considered phonon, piezoelectric, and ionized impurity scattering, to calculate the velocity field relationship for GaN.
The drift velocity was found to peak at 2 X 107 cm/s at a
field of 105 VIcm. A low field room-temperature electron
mobility of 100-1300 cm 2/V s was also calculated over an
ionized impurity density range of 102o/cm 3_1017/cm 3. Das
and Ferry 310 considered the hot electron microwave conductivity for GaN. The ac mobility and dielectric constant

1257

S. Strite and H. Morko~: GaN. AIN. and InN

1257
19

17

.:(.,
::' . ,'
15 .... -.'
13

....

'j":I.. ~,.

._ 5 ....... :,.........
'.~ 3 ... ,::::' '::".
.
I

...... f

,~.,

. r-....

'.

........ 1--'"

11

7.

......

..

.., '

.... ......
.'.
.. .' .
' :-0.

-. ....
1 .

......{

.......

>
.!.
>
iw

.. ,...-

.......
"
,'

. :: .

..'
'

'

5
.::......

.,//-

.. ~/

'. "

'3::'.................
......... 'i

-5

'2
-4

-6

'12

t1

r t.

ASH

ALUMHPK

'. .... .""

\.">~

",,:

-3

.: . . ... . ...

~3"-""

. ..........

-1

10

ffi

'6

1
1

>" 2

FIG. 25. Calculated band structure of wurtzite InN (from Ref. 322).

of wurtzite GaN were found to be unaffected up to a limit

of 10 12 Hz over a broad range of high electric field values.
The authors concluded that GaN is a suitable candidate for
microwave device applications.

is more than a full electron volt less than the band gap of
wurtzite AIN. This is quite a provocative result considering
that the GaN polytypes have similar band gaps, and the
zinc-blende InN band gap is predicted to be equal to its
wurtzite counterpart. An indirect band gap in zinc-blende
AIN presents the interesting possibility of observing an
indirect-direct band gap transition in the zinc-blende AIN
alloys with GaN and InN.
There have been two reports concerning the energy levels of substitutional impurities and native defects in AIN.
Jenkins and Dow320 calculated the energy of the nitrogen
vacancy and found that it lies deep within the band gap, in
contrast to their own earlier work 32 ! which predicted the N
vacancy to be very near the conduction band edge. The
experimentally observed high resistivity of AIN would
seem to indicate that the N vacancy, if prevalent, must lie
deep within the forbidden band.

B.AIN

C.lnN

-7

-9
1
............. ~

-11

.
-15 ........

-13

'

........ ....-

---1'-"

,,-

....

...

1 .....

.....
r

KX

FIG. 24. Uncorrected band structure of zinc-blende AIN. The corrected

band gap value is 5.11 eV (from Ref. 309).

316

Hejda reported the first calculation of the electronic

structure of AIN using the orthogonalized plane wave
method. Although a direct gap was found, the value of2.35
eV (and later 3.91 eV 317 ) was much smaller than the experimental band gap of 6.2 eV. Bloom3 !! (Fig. 23) and
Jones and Lettington 3\3 used pseudopotential methods to
obtain more accurate direct band gaps of S.25 and 5.31 eV,
respectively. Kobayashi et al.3\8 reported a band structure
with a 6.2 eV direct band gap calculated using the semiempirical tight binding method. Ching and Harmon 3!9 reported an uncorrected direct band gap of 4.4 eV calculated
by a self-consistent first principles linear combination of
atomic orbitals approach which is known to underestimate
the band gap vaiue. Their calculated values of various material properties gave good agreement with the available
experimental values.
Lambrecht and Sega1l309 have performed the only band
structure calculation to date for zinc-blende AIN using
first-principles techniques within the local density functional framework (Fig. 24). They predict an indirect 5.11
eV band gap with a conduction band minimum in the X
valley and a lattice constant of 4.33 A. The band gap value
J. Vac. Sci. Technol. B. Vol. 10, No.4, JullAug 1992

Only two groups have published band structures for

InN. Foley and Tansley 322 used an empirical pseudopotential approach to calculate a 2 eV room-temperature direct
band gap for wurtzite InN (Fig. 25). Their calculation
predicted an effective mass for the conduction electrons of
= O.12mo, a heavy-hole (hh) effective mass of
=
O.5mo, a light-hole (lh) effective mass of
h
mit = O.17mo, and a refractive index of n = 2.88O.05.
The band gap and the refractive index predictions show
good agreement with their own experimentally measured
values. Jenkins et al. 323 used a nearest-neighbor empirical
tight binding approach to predict a direct 2.2 eV lowtemperature band gap for wurtzite InN. The calculated
electron effective mass was m: = O.59mo and the hh effective mass was
= 2.7mo. Calculations of the zinc-blende
InN band structure predicted a direct band gap energy
identical to the wurtzite phase. Tsai et al. 324 used the
pseudofunction method to self-consistently solve the one
electron Schrodinger equation in a local density approximation and obtained an uncorrected direct band gap of 1.3
eV for wurtzite InN. This value reflects the tendency of
local density theory to underestimate the band gap. The

m:
m:

m:h

1258

S. Strite and H.

Morko~:

GaN, AIN, and InN

calculated effective masses were m: = O.34-0.37mo and

1.6-1.7mo The donor and acceptor binding energies
reported by Tansley and Foley are most consistent with the
calculated values of Tsai et al. 324
In an effort to understand the experimentally observed
n-type conductivity of all InN films grown to date, Jenkins
and DOW 320 considered various native defects in InN. It
was concluded that nitrogen vacancies were the most likely
candidates for the experimentally observed n-type behavior
of InN. Possible p-type dopants were examined, but the
calculated acceptor binding energy (-0.3 eV) was found
to be too large to permit thermal ionization of acceptors at
room temperature.

1258

Energy (eV)

m~h =

4.0

One of the potentially major advantages of GaN over

other candidates for blue and UV light emitting devices lies
in the possibility of AIGaN/GaN/InGaN heterostructure
devices. The lattice mismatch between AIN and GaN is
much smaller than that of ZnS and ZnSe which should
allow more flexibility in device design. Also, the III-V
nitrides can benefit directly from the vast amount of work
J. Vac. Sci. Technol.

CD

= 30K

e,

Vol. 10, No.4, JullAug 1992

3.4

confining

.5

3.2

lay.~

.~
rn

I.U
CD
.~

f tI

'0

CC

3000

IX. HETEROSTRUCTURES AND DEVICES

3.6

AIo.. lcGao.eeN GaN saw

Lz = 150A

'in

D. Alloys

Jenkins and Dow 320 considered alloys of wurtzite InN

with both GaN and AIN. All stoichiometries were found to
have direct band gaps ranging smoothly from 2.2 eV for
InN to the 6.2 eV for AIN. The energy level of the nitrogen
vacancy was found to vary smoothly with alloy composition, and thus it remains a shallow acceptor in InGaN and
becomes a deep level in InAIN as the Al mole fraction is
increased. Although no suitable p-type dopant for InN was
found, many substitutional impurities which are deep levels in InN are predicted to move out of the gap becoming
shallow donors and acceptors as the alloy concentration of
GaN and AIN are increased. Carbon and sulphur are predicted to be fairly shallow p-type dopants in InGaN and
InAIN. However, in the case of GaN, this prediction is
based on the calculated C and S shallow acceptor levels in
GaN which are smaller than the experimental values. Jenkins and Dow conclude that Ino.s5Gao,]sN and
lno.4Alo,oN are excellent candidates for blue-green wavelengths emitters which can be doped both n- and p-type.
No calculations are available for nitride alloys having the
zinc-blende structure.
Munich and Pierret 325 examined the AIGaAsN alloy
system using quantum dielectric theory. Phase transitions
were predicted from the zinc-blende to wurtzite crystal
structure for GaASo. 2s No,n and AIASo,l7No83 with the majority of the AIGaAsN phase space having the zinc-blende
structure. Band gap values over the full range of compositions were calculated with a transition to an indirect band
gap ocurring at large AI and As mole fractions (e.g.,
AIASo,7No,) and Alo,sGao,2Aso,84NO,]6)' Heterojunction
band offsets of AEc = 0.24 eV and AEv = 4.33 eV were
predicted for AIN/GaAs, but these values are contradicted
by the less lobsided experimentally estimated values of
AEc = 1.8eVandAEv = 2.8eV. 106

3.8

3400

3200

3600

4000

3600
0

Wavelength (A)

tal

Energy (eV)
4.0

3.8

3.6

3.4

3.2

A10.14GauaN GaN SQW

Lz

= 300.4

T = 30K

3000

3200

(b)

3400

3600

3800

4000

(b) 300

A GaN

Wavelength (A)

FIG. 26. PL spectra at 30 K for (a) 150

(from Ref. 326).

A and

QWs

published on the III-V arsenides. Workers have begun to

explore nitride heterostructures and layered structures for
device applications. The acoustic properties of AlN have
been explored with an eye towards applications in surface
acoustic wave devices. Many groups have reported GaN
LEDs which are active throughout the visible wavelength
range into the UV. The III-V nitrides, especially AIN,
have received considerable attention for their insulating
properties, particularly as a potential isoelectronic insulator for GaAs field effect transistors.
A. Layered structures

The earliest layered III-V nitride structure was grown

by Kubota et al. 43 in the GaN/lnN system, however, a
large amount of interface diffusion caused the formation of

100

(a)

452

80

~
~

1259

S. Strite and H. Morko~: GaN, AIN, and InN

1259

60

AGaN

18 X
Periods

.....

u
UJ

465 A AIGaN

....I

U.

452 A GaN

UJ

c::

AIN Buffer
20

Sapphire (1000)
450 nm Filter

0
350

390

430

470

510

550

WAVELENGTH (nm)
100

(b)

402

80

g
~ 60

:>
j::
uUJ

AGaN

18 X
Periods

c::

AIN Buffer
20

0
270

A AIGaN
402 AGaN

413

u. 40

....I

FIG. 28. Experimental configuration of a typical m-;-n GaN LED (from

Ref. 334).

Sapphire (1000)
400 nm Filter
310

350

390

430

470

WAVELENGTH (nm)

FIG. 27. Measured reflectivities vs wavelength for the (a) 450 nm and (b)
400 nm AIGaN/GaN quarter wave reflectors exhibiting maximum reflectivities of 80% and 95%, respectively (from Ref. 306).

an InGaN alloy. Sitar et a/. IS3 reported the growth of the

first AIN/GaN superlattice. Khan et al.326 grew the first
Alo.14Gao.86N/GaN quantum wells (QWs) (Fig. 26). The
PL energy shifts as a function of GaN QW thicknesses
were in agreement with the predictions of a simple model.
Itoh et al.327 have also reported AlGaN/GaN QW structures. Khan et 01. 198 later reported significantly enhanced
GaN mobilities in AIo.Q9GCIQ.9IN/GaN layered structures.
Recently, Khan et 01. 306 have fabricated a quarter wave
mirror from an 18 period Alo.2G30.8N/GaN superlattice
(Fig. 27). Peak reflectivities of 80% at 442 nm and 95% at
375 nm were measured. This result and their observation
. 1 caVIty
. I
' 10
. G aN, 224 repof room temperature vertlca
as10g
resent two major advances towards the successful realization of an UV surface emitting laser.

B. Surface acoustic wave devices

One of the main focuses of AIN research to date
has been on its piezoelectric properties with an eye
(SAW)
towards
surface
acoustic
wave
devices. 52,93,112, 130-132.142.146.IS6.262.328.329 Collins et al.328 first
examined the acoustic properties of AIN and concluded
J. Vac. ScI. Technol. B, Vol. 10, No.4, Jut/Aug 1992

that its very high surface wave velocity, resistivity, chemical, and thermal stabilities could potentially lead to gigahertz transducers based on that material. Kline and
Lakin262 confirmed the prediction by demonstrating a 1.0
GHz All AIN/GaAs acoustic resonator device.

C.LEDs
After the initial report by Pankove et al. 33o of a GaN
LED, numerous workers have fabricated similar structures. Due to the inability to dope GaN p type, these devices were not conventional p-n junction LEOs, but rather
metal-insulator-n-type semiconductor (MIN) structures
in which a heavily compensated insulating GaN region was
grown on uncompensated n-type GaN (Fig. 28). A side
contact to the n-type GaN was formed in order to avoid
the difficulties related to the chemical etching of GaN. It
was theorized by Pankove and Lampert 331 that light emission was obtained when hot electrons impact ionized luminescence centers in the compensated region. A hot electron
model was strongly supported by the observation of antistokes emission in which the electroluminescence was at a
higher energy than was being supplied by the applied bias
to the electrons. 332 Pankove and Levin 333 reported a detailed scanning electron microscopy study of GaN LEOs.
Depending on the compensating impurity, MIN
structures
have
emitted
violet,64.334-336
blue, 193.196.236.239.244.332.335-340
green, 193.236.239.337.338.341.342
yellow,193.236.239.338.341-343 orange,193.33b and red 336 light at
frequencies up to 50 MHz.344 By selectively depositing metallic electrodes to form MIN electroluminescent diodes,
Pankove345 demonstrated a blue-green GaN numeric display. Pankove and Norris 346 also reported electrolumines-

1260

S. Strite and H.

Morko~:

GaN, AIN, and InN

cence from AIISi3N,v'GaN structures which exhibited a

broad spectrum optical response under electrical pulse
stimulus. In these structures, a large electric field was
thought to generate holes at the n-type GaN surface which
recombined when the field was removed.
Only recently have conventional p-n junction LEOs
which emit in the UV and blue wavelengths been reported
by Akasaki et al. 227 ,229 and Nakamura et al. l76 The first
such structure 227 used the LEEBI procedure to activate
acceptors in Mg-doped GaN to obtain p-type material.
Electroluminescence was observed near the band edge at
3.35 eV and in the blue at about 2.9 eV. Akasaki et al. m
have since introduced AlGaN to increase carrier confinement in a recently described double heterojunction
AlGaN/GaN LED. Nakamura et al. 176 have demonstrated
the most impressive GaN LED to date. Their structure
was grown on sapphire substrates using a low temperature
GaN buffer layer and later was treated with LEEBI to
activate Mg acceptor sites. The resulting pn diode emitted
at 430 nm at a power level ten times greater than comparable SiC LEDs with an external quantum efficiency as
large as 0.18 %. These impressive results are the clearest
indication yet that GaN is capable of reaching its potential
as a short wavelength optical semiconductor material.

D. Nitride metal-insulator semiconductor (MIS) and

metal-semlconductor (MS) diodes

Researchers have realized for quite some time that the

wide band gap AIN and GaN materials have potential as
insulating materials for semiconductor devices. 347 The 111V nitrides are expecially attractive as insulating materials
for GaAs because they are isoelectronic and no suitable
insulating material for GaAs has emerged to date. Mirsch
and Reimer 46 and Hariu et al. 39 reported the first AIN and
GaN MIS structures, respectively. Lakshmil43 investigated
GaN/Si MIS structures and noted a breakdown field of 5
MV fcm. Chu and Kelm 82 studied the dielectric properties
of AIN in grown on Si. AIN films having a 300-400 A
thickness had an average dielectric strength of 15 MV Icm.
The rf sputtered AIN had slightly lower dielectric
strengths with breakdown observed around 6 MV fcm. Elliot and Grant 106 made a detailed study of AllAINfGaAs
MIS diodes using polycrystalline AIN, however no devices
of good quality were attained. Irene et al. 94 measured a
breakdown field of 4 MVIcm in polycrystalline AlN grown
on Si substrates. The effect of oxygen content in the AlN
insulator was also investigated. Hantzpergue et al. l44 reported reasonable C-V characteristics in AIN/Si MIS
structures although the insulator was too leaky to allow the
observation of inversion. Bauer et aJ. 95 reported that
Frenkel-Poole conduction was dominant in their AllAINf
Si MIS structures at high electric fields.
Fujieda and co_workers348-352 have reported on AINf
GaAs diodes in the most detail. The surface state distribution of both n- and p-type structures was probed by C- V
measurements (Fig. 29).348 The influence of the initial
GaAs surface stoichiometry, AsH 3 flux and sample temperature control between AlN and GaAs growth was inJ. Vac. Sci. Technol. S, Vol. 10, No.4, Jul/Aug 1992

1260
200r---~------------------~

lJ...

a.

w
u

f-

a..

FIG. 29. Capacitance-voltage characteristics of an AIN/nGaAs MIS diode (from Ref. 350).

vestigated, and the use of a H2 ambient was observed to

improve device quality by eliminating As at the
interface. 35o A similar study was performed on n-type InP
(Fig. 30).351 An enhancement of the thermal stability of
MIS diodes was observed to result from the insertion of a
thin amorphous Si interlayer at the AlN/GaAs
interface. 352
Two recent investigations of the insulating properties of
zinc-blende GaN grown on (001) GaAs have been described. Strite et al. IM have reported Au/GaN/GaAs MIS
structures of reasonable quality (Fig. 31). Capacitancevoltage characteristics showed that the diode could be
swept from accumulation nearly to inversion which allowed an interface state density of 5 X lOll/eV cm 2 to be
estimated. Martin et al. 15o reported the electrical characteristics of GaAs/GaN/GaAs semiconductor-insulatorsemiconductor (SIS) diode structures. From temperature
dependent current-voltage measurements, a conduction
band offset of -0.9 eV was estimated for the GaN/GaAs
heterojunction which is approximately half of the band gap
difference between the two materials.
Khan et al. 302 have investigated the Schottky diode
properties of GaN in which insulating GaN was obtained
by N or Be ion implantation. Ohmic contacts were formed
in the unimplanted regions and Crl Au Schottky barriers
were formed in the insulating region. The barriers were
rectifying with low reverse leakage. A spatial distribution
of the carrier concentration in the implanted GaN was

200

(I)

;;:
~
w
u

<t

100

t::

u
<t
Q.

<t
u

0
-10

-5

10

VOLTAGE (vol1)
FIG. 30. Capacitance-voltage characteristics of an AINln-InP MIS diode
(from Ref. 351).

1261

S. Strite and H. Morkoc;: GaN, AIN, and InN

1261

120

"'~
;; l~ -.~

100

&;' 80

2:

8,0-

, ,

00- 1)

Appuerl Volt&&t (\'1

<lJ
U

I'i

2 60r

'0
C1l

40
I

)~

20

-4

-2

2
0
Applied Voltage (V)

FIG. 31. Capacitance-voltage and current-voltage characteristics of a

zinc-blende GaNln-GaAs MIS diode (from Ref. \64).

obtained using C- V measurements. Morimoto and

Ushi0 353 have reported the electrical properties of Zn/GaN
Schottky diodes.

X. SUMMARY AND FUTURE AREAS FOR

RESEARCH
The III-V nitrides are an interesting, challenging, and
technologically important material system which has the
potential for optical devices active throughout the entire
visible spectrum and extending far into the UV wavelengths. For that reason, considerable effort has been directed towards growing high quality material and understanding the properties of GaN, AIN, and InN. Although
the crystal growth technology was not yet available to allow early investigators to successfully grow device quality
material, many of the fundamental physical properties of
these materials were accurately measured in the 1970's.
The problem of the high background electron concentration, the necessity of heteroepitaxial growth on a poorly
matched substrate, and the lack of a suitable p-type acceptor material, which could not be overcome by early investigators, all remain as challenges for today's researchers.
However, with the passage of time, many of the problems which were insurmountable two decades ago, may
now be within reach. Much has been learned over the past
two decades about heteroepitaxy. Improved crystal growth
techniques, such as CVD and MBE have enabled researchers in many laboratories to begin growing high quality
nitride materials which have excellent crystallinity and significantly reduced background electron concentrations.
Recently, researchers have reported a process which successfully achieves p-type doping and the first p-n junction
GaN LED was fabricated. Room-temperature lasing has
been achieved in GaN and layered heterostructures such as
QWs and reflecting mirrors, which will be necessary for
J. Vac. Sci. Technol. B, Vol. 10, No.4, JullAug 1992

GaN-based lasers, have been demonstrated for the first

time. These advances have stimulated renewed interest in
the 111-V nitrides.
Although the recent spate of success is impressive,
much work remains to be accomplished for the nitrides to
even distinguish themselves as the leading candidate for
blue light emitting devices. These tasks naturally divide
themselves into two categories. The first involves continued
study of the fundamental physical properties of these materials so that researchers are in a better position to evaluate the true potential of the nitride material system. The
second is a continued effort towards the growth and processing of device quality material and the demonstration of
device concepts. Each of these two approaches will serve to
identify potential problems and highlight areas of common
interest between the two efforts.
With the wealth of high quality GaN and AIN available
today, it should be relatively easy for several independent
laboratories to perform measurements on material known
to be of high quality. Many of the fundamental physical
properties of the nitrides which will have a major bearing
on the performance of nitride-based devices are not known.
Some of the quantities which should be relatively easy to
measure are the wavelength dependent index of refraction
and dielectric constants, the coefficients of thermal expansion, the thermal conductivity, the elastic properties, and
the temperature dependence of the band gap. Some other
properties such as the effective masses and the location of
the indirect conduction band minima may prove more difficult to determine experimentally, but are worthy of some
investigation.
The nitride alloys AIGaN, InGaN, and InAIN are in
need of significantly more attention than they have received thus far. Nearly all the desirable nitride-based optical devices will require at least one of these alloys, yet
reliable measurements are scarce for all of these materials.
UV detectors and light emitters will require a knowledge of
the alloy dependence of the AIGaN band gap. In order to
grow thicker heteroepitaxiallayers, it may be necessary to
utilize the lattice matched AIGaN/lnAIN heterojunction
system. The most efficient blue laser designs will call for
strained InGaN QWs in the active region and AIGaN cladding. It is therefore important to determine the fundamental physical quantities across the entire AIGaN alloy range
as well as for low In mole fraction InGaN and InAIN. In
addition, the quantities unique to heterostructures, such as
the band offsets and the strain dependence of the band gap,
need to be measured.
The zinc-blende polytypes are essentially an entirely
new, alternative material system which should be considered as a candidate for device applications. Nearly nothing
is known about these materials. However, with the advent
of non equilibrium growth techniques, zinc-blende GaN
has passed from a curiosity to a material under serious
investigation in several laboratories and the zinc-blende
polytypes of InN and AIN have very recently been observed for the first time. At this point, it can only be said
that the properties of the zinc-blende nitrides and alloys
need to be further studied. It is entirely possible that many

1262

S. Strite and H. Morkol?: GaN, AIN, and InN

of the difficulties confronting researchers in the wurtzite

material system, such as the p-type doping problem, can be
more easily overcome in the zinc-blende polytypes.
One of the attractive properties of SiC, the ability to
grow heterojunctions between the different polytypes, may
also be possible for GaN. In SiC, this is achieved by varying the growth temperature. At least one group has been
able to grow zinc-blende GaN on sapphire by lowering the
growth temperature. Perhaps this technique can be extended to grow zinc-blende GaN on the wurtzite GaN.
There is also a need for further theoretical study of the
III-V nitrides. The improved computational facilities and
theoretical understandings which have been developed
since the time in which much of the extant theory work
was accomplished should allow improved data to be generated. Quantities such as the effective mass values, higher
energy band positions, densities of states, and heterojunction band offsets, which present significant experimental
challenges, perhaps may only be readily studied in the near
term by theoretical techniques. Thermodynamic and total
energy calculations can predict the energy difference between the zinc-blende and wurtzite polytypes. Theorists
are in a position to study the native defects of the nitrides
in order to determine the origin of the free carriers in
undoped material. Similar techniques can be applied to
predict materials which have the potential to be shallow
acceptors in GaN. In general, the theoretical development
of the 111- V nitrides has lagged behind the experimental
work. Many techniques which have been refined on the
more commonly studied Si and GaAs semiconductors,
should be applied to the nitrides. Such work would guide
experimentalists and device designers as well as help them
interpret their experimental data.
In the second category, researchers need to continue
their aggressive approach aimed at realizing as many device structures as the material quality will permit. Much of
the groundwork for future devices can be laid now, while
the outstanding problems of p-type doping and material
processing are addressed concurrently. In addition, the effort to extend our present capabilities should identify potential obstacles to successful device structures as soon as
possible.
The search for a p-type dopant must continue with the
highest priority. The reports of p-type conduction in Mgdoped GaN offer the most promising avenue of endeavor.
The LEEBI process should be attempted on GaN compensated with other group II and IV impurities in order to
determine whether Mg is the optimum dopant material. It
remains the experimentalist's challenge, under the guidance of the theorists, to identify the mechanism by which
LEEBI converts Mg compensated GaN to p-type material.
Much more study of the potential p-type dopants is needed.
Only Zn and Mg have been studied in any detail, and much
of that activity occurred in the 1970's. It is time for a
reexamination of the properties of potential acceptor impurities using today's sophisticated growth techniques.
With the reduced background concentrations in the best
layers grown today, it will also soon be necessary to begin
investigating n-type dopants as well. Until the doping
J. Vac. Sci. Technol.

e,

Vol. 10, No.4, Jul/Aug 1992

1262

problems are fully surmounted, the 111-V nitrides can

never be considered a viable material for device applications.
Another historical problem, the lack of a suitable substrate, has been mitigated in recent years. Although most
nitride growth continues to occur on sapphire substrates,
alternative substrate materials have recently become commercially available. SiC, MgO, or ZnO should eventually
lead to superior material as a result of their improved thermal and lattice matches to the nitrides. As the quality of
those substrate materials continues to improve, nitride researchers need to begin investigating these alternatives
more vigorously.
The problems in processing GaN have been generally
acknowledged to exist, but have received little attention as
a research problem. To date, no reliable etching procedure
exists, nor is there any standard procedure for forming
ohmic contacts to GaN. These problems should be addressed now, so that the device processing technology is in
place when the material quality issues are resolved. Unlike
the past, when only a few laboratories had access to the
best material and focused on more pressing scientific issues, GaN samples should be widely available to researchers. Some recent developments in fabrication technology,
such as reactive ion etching and rapid thermal annealing,
may be useful for GaN processing.
In conclusion, we have attempted to present the present
body of knowledge regarding the 111-V nitride materials
GaN, AlN, and InN as completely as possible. The structural, electrical, and optical properties of each material
were reviewed. We have also covered the various alloy
systems between these materials and their zinc-blende
polytypes. A review was made of the theoretical work
which has been published on the III-V nitrides and their
alloys. The various device structures which have been demonstrated were described. Finally, we identified the major
outstanding problems facing nitride researchers and suggested problems of importance which should be addressed
in the near future.
Note added in proof Professor R. F. Davis of North
Carolina State University has grown the first zinc-blende
AIN on 3C-SiC surfaces in 1989.

ACKNOWLEDGMENTS

This work was supported by the Office for Naval Research Contract No. NOOOI4-89-J-1780 and the Department of Defense Contract No. DOE-AC-02-76ER-01198.
The authors wish to thank M. Yoder of the Office for
Naval Research for his enthusiasm for and encouragement
of the III-V nitride effort. S. S. wishes to acknowledge the
support of an AFOSR Graduate Fellowship.

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