Wet Thermal

Journal of ElectronicOxidation
Materials, Vol. of
28, GaN
No. 3, 1999 257
Special Issue Paper

Wet Thermal Oxidation of GaN

E.D. READINGER,1 S.D. WOLTER,1 D.L. WALTEMYER,1 J.M. DELUCCA,1
S.E. MOHNEY,1 B.I. PRENITZER,2 L.A. GIANNUZZI,2 and R.J. MOLNAR3
1.—Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, PA 16802. 2.—Department of Mechanical, Materials and Aerospace
Engineering, University of Central Florida, Orlando, FL 32816. 3.—Massachusetts Institue of
Technology, Lincoln Laboratory, Lexington, MA 02173-9108

Thermal oxidation of GaN was conducted at 700–900°C with O2, N2, and Ar as
carrier gases for 525–630 Torr of H2O vapor. Upon oxidation of both GaN
powders and n-GaN epilayers, the monoclinic β-Ga2O3 phase was identified
using glancing angle x-ray diffraction. The chemical composition of the oxide
was verified using x-ray photoelectron spectroscopy. In experiments conducted
using GaN powder, the oxide grew most rapidly when O2 was the carrier gas for
H2O. The same result was obtained on n-type GaN epilayers. Furthermore, the
thickness of the oxide grown in H2O with O2 as the carrier gas was found to be
proportional to the oxidation time at all temperatures studied, and an activation
energy of 210±10 kJ/mol was obtained. Scanning electron microscopy revealed
a smoother surface after wet oxidation than was reported previously for dry
oxidation. However, cross-sectional transmission electron microscopy revealed
that the wet oxide/GaN interface was irregular and non-ideal for device fabrication,
even more so than the dry oxide/GaN interface. This observation was consistent
with poor electrical properties.
Key words: GaN, thermal oxidation

process. The electrical properties of the thermal oxides

INTRODUCTION
Group III nitrides and their alloys are under rapid
development for optoelectronic devices in the blue,
green, and ultraviolet (UV) portion of the spectrum,
with applications including data storage, displays,
and detectors. They are also receiving attention for
high power and high temperature electronics. While
much work has been done to study the native thermal
oxides on semiconductors such as Si and more recently
SiC and the Al-bearing III-V semiconductors, very
few studies have been conducted on the thermal
oxidation of GaN. Wolter et al. studied the oxidation
of GaN in dry air1 which resulted in the formation of
a polycrystalline oxide with a rough surface.2 It was
speculated that wet oxidation of GaN might result in
the formation of an oxide with improved polycrystalline
morphology or even an amorphous oxide. Therefore,
in this study, we have investigated the thermal
oxidation of GaN in H2O vapor and examined the
effect of different carrier gases upon the oxidation
(Received July 27, 1998; accepted December 4, 1998)
are also evaluated.
PROCEDURE
GaN powder (–325 mesh) with a purity of at least
99.99% (metals basis) was oxidized in H2O vapor for
5 h at 700–900°C using ultra-high purity (UHP) O2,
N2, and Ar as carrier gases. Oxidation of samples in
dry O2 at the same temperatures was also performed
for comparison. The powder samples were
characterized using a Phillips multipurpose
diffractometer, and θ–2θ scans were performed using
CuKα radiation. The relative peak intensities were
compared for similar oxidation conditions to give
qualitative information about oxide growth rates.
GaN epitaxial layers were grown on (0001) sapphire
using a vertical hydride vapor phase epitaxy process3
with a sputtered ZnO pretreatment. The n-type films
were grown at 1050°C for one hour at a rate of
15 µm/h and had a carrier concentration of 2.2 × 1017
cm–3. The samples were rinsed in acetone, methanol,
and deionized (DI) water, after which they were
placed in a 1:1 solution of HCl:DI water for 60 s and

257

258
Fig. 1. Bragg-Brentano XRD scan of GaN powders oxidized at 900°C
for 5 h. The symbol (*) marks prominent β-Ga2O 3 oxide peaks. Peaks
not identified as Ga2O3 are from GaN.
a
b
Fig. 2. (a) SEM image of the surface of the oxide grown on a GaN
epilayer at 800°C for 30 h in wet oxygen, and (b) SEM image of the
surface of the oxide grown on a GaN epilayer at 900°C for 25 h in dry
oxygen.
rinsed in DI water.
The samples were placed in a quartz boat within a
quartz tube, and then the tube was purged with the
carrier gas for at least 20 min before it was placed in
a horizontal furnace. Once the tube was placed into
the furnace, gases were diverted into the previously
by-passed bubbler. Using a thermocouple inserted in
the quartz tube, we determined that the time for the
Readinger, Wolter, Waltemyer, DeLucca, Mohney,
Prenitzer, Giannuzzi, and Molnar
sample to reach the intended temperature did not
exceed 6 min. The carrier gases were maintained at a
flow rate of 25 sccm through a bubbler containing DI
water heated to 93 ±1°C. Oxidation was performed at
700–900°C for 1–50 h, and results were compared to
a previous study of the oxidation of GaN in dry air.1,2,4
Following oxidation, the quartz tube was removed
from the furnace and allowed to cool in air to room
temperature before the sample was removed.
A consistent volume of DI water was used in the
bubbler before each experiment, which has been
reported to increase the reproducibility of the partial
pressure of water vapor transferred to the furnace.5 In
addition, heating tape maintained at approximately
110°C was used on the gas feed line from the bubbler
to the tube furnace to minimize condensation between
the bubbler and furnace. The atomic percent of H2O
vapor present in the carrier gas was estimated to be
77±8% for any given furnace temperature and carrier
gas combination. These calculations were based on
the flow rate of the gas and the volume of H2O lost
from the bubbler.
The initial identification of the thermal oxide was
performed using glancing angle x-ray diffraction (XRD)
using CuKα radiation. A Kratos analytical XSAM 800
pci system with a MgKα x-ray source was used for x-
ray photoelectron spectroscopy (XPS) with a chamber
base pressure of 1 × 10–9 Torr. The Ga 3d, N 1s, and O
1s core level peaks were chosen for study to further
corroborate the oxide identification.1,6 Further analysis
was performed using a Phillips XL-20 scanning
electron microscope (SEM) to examine the oxide
surface using a secondary electron detector, and the
oxidized GaN epilayers were examined in cross section
after cleaving the sapphire wafer. These cross-sectional
samples were used to measure layer thicknesses in
order to extract data on growth kinetics. The thermal
oxide was also imaged at greater magnifications using
cross-sectional transmission electron microscopy
(TEM) on samples prepared by a focused ion beam
technique.7 Both wet and dry oxidation conditions
were compared using a Philips 420T TEM.
Finally, electrical measurements of the wet and dry
thermal oxides formed on n-GaN epilayers were
conducted. Knowing the growth kinetics for the
oxidation of GaN, 100 nm thick oxides were grown at
900°C in both wet and dry O2. Upon oxidation, contact
windows to the GaN were sputtered through the oxide
using an Ar+ sputter source. A large area Al ohmic
contact was then sputter deposited on the contact
window. To complete the metal-oxide-semiconductor
structure, Pt dots 150 µm in diameter were sputter
deposited on the oxide surface. The current-voltage
characteristics were measured using a Keithly 236.
RESULTS AND DISCUSSION
XRD scans of the GaN powder samples oxidized at
900°C for 5 h in H2O vapor showed diffraction peaks
that were indexed as β-Ga2O3 (Fig. 1). The greatest
oxide peak intensities resulted while using O2 as the
carrier gas for H2O vapor (wet oxidation), followed by
Wet Thermal Oxidation of GaN 259

dry oxidation in O2, and then by wet oxidation using characteristics were not found to be symmetric about
UHP N2 and Ar as carrier gases. Of the powder the current axis (see Fig. 4), and there was significant
samples oxidized in H2O vapor at 750°C for 5 h, only scatter in the I-V data. In forward bias, breakdown
the sample oxidized in wet O2 revealed any oxide occured in conjunction with a sudden drop in oxide
peaks, albeit weak ones. These findings were consistent resistivity, which was irreversible. Under reverse-
with the thicknesses of the thermal oxides grown on bias, part of the applied bias dropped across the
n-GaN epilayers on sapphire, as determined by cross- depletion region in the GaN, and breakdown was
sectional SEM. reversible. Thus, the oxide resistivities and breakdown
When oxidation temperatures on thin film samples strengths were estimated from the forward bias portion
exceeded 700°C, an oxide was observed by cross- of the curve. It should be noted that dry oxides
sectional SEM. Thin film samples oxidized in wet O2 consistently gave better results with resistivites of
at 700°C showed some surface pitting for times less 109–1011 Ω-cm and apparent breakdown field strengths
than 50 h, with slight oxide growth also seen at times of 2 × 105 V/cm, again measured under forward bias.
greater than 50 h. Like the powder, the oxide was These values for the thermal oxides are 2–4 orders of
indexed as β-Ga 2O3, this time using glancing angle magnitude lower compared to PVD Ga2O3 on GaAs.9
XRD. All peaks can be indexed as β-Ga2O3 and the TEM samples were prepared from both wet and dry
pattern cannot be indexed as any other known polytype thermal oxidation conditions using a focused ion beam
of Ga2O3. The orientational relationship between Ga2O3 (FIB) technique.7 Examination of the thermal oxide
and GaN was not determined. XPS analysis also formed at 900°C for 70 min in wet O2 and for 5 h in dry
confirmed the formation of gallium oxide with strong
signals from both the Ga 3d and O 1s peaks. The Ga
3d peak position observed at 20.7 eV is indicative of
Ga-O bonding and was observed in a past study of
Ga2O3 grown on GaN in dry air.1,8 The peak positions
were referenced to that of Au, which was deposited on
the specimens by sputtering.
SEM analysis was used to quantitatively examine
the oxide thickness as well as qualitatively
characterize the oxide surface. Figure 2a shows an
SEM micrograph of an oxide approximately 500 nm
thick grown on GaN at 800°C for 30 h. The starting
thickness of the GaN was approximately 14 µm, and
it was observed that after thermal oxidation there
was little change in overall film thickness (Ga2O3 +
GaN). It is also apparent when comparing the oxide
surface in Fig. 2a to that of the dry oxide of Fig. 2b that
wet oxidation results in a much smoother surface. A
general observation made during the wet oxidation Fig. 3. Thickness of the oxide grown in wet O2 at different temperatures.
experiments is that the lower oxidation temperatures The vertical error bars provide an estimate of the error in the
measurement of the oxide due to the irregular thickness. Horizontal
resulted in smoother oxide surfaces. error bars due to the time needed to attain thermal equilibrium in the
When directly comparing the growth rates of the quartz tube (<6 min) cannot be seen because they are too small.
oxide in dry air (or dry O2) to the rates in wet O2 (H2O
+ O2), it was found that wet oxidation is approximately
15 times faster. As plotted in Fig. 3, the wet oxide
grows linearly with time, indicative of reaction rate
limited kinetics. Although the kinetics are linear, the
mechanism for the enhanced oxidation of GaN in wet
Log|Current (A)|

O2 is still unclear. An activation energy (Q) for oxidation

in wet O2 was calculated to be 210±10 kJ/mol. This
value is much less than the value of 300 kJ/mol found
for oxidation of GaN in dry air,2 which also grows
linearly with time.
Some initial steps were taken to electrically
characterize the thermally grown oxides. Oxides 100
nm thick were grown in wet and dry UHP O2 at 900°C.
Metal-oxide-semiconductor capacitor structures were
then fabricated. Resistivities and breakdown field
strengths were extracted from the current-voltage (I-
V) measurements for the wet oxide, giving resistivities
on the order of 108–1010 Ω-cm and apparent breakdown Fig. 4. The I-V characteristics for MOS structures created by growing
field strengths from 5 × 104–1 × 105 V/cm. The I-V 100 nm thick Ga2 O3 on GaN in wet O2.

260
a
b ization. The support of Cirent Semiconductor for the
Fig. 5. (a) Cross-sectional TEM micrograph of Ga2O 3 on GaN oxidized
at 900°C for 70 min in wet O2 . The dark overlayer is a sputtered Cr layer
required for the TEM sample preparation procedure, and (b) cross-
sectional TEM micrograph of Ga2 O3 on GaN oxidized at 900°C for 5 h
in dry O2. The dark overlayer is sputtered Cr.
O2 are shown in Figs. 5a and 5b, respectively. These
micrographs clearly show the polycrystalline nature
of the oxide. It is obvious that the wet oxide yields a
much smoother surface morphology than that of the
dry oxide; however, the oxide/GaN interface is more
irregular in the wet oxide. Intrusions of oxide can be
seen in both samples with more severe disruption of
the GaN occurring under the wet conditions. Certainly
these finger-like structures of oxide into the
semiconductor are undesirable for potential device
applications and may be responsible for the even
poorer electrical characteristics of the wet oxide
compared to the dry oxide.
CONCLUSIONS
The wet thermal oxidation of GaN was conducted
with O2, N2, and Ar as carrier gases for H2O vapor
pressures from 525–630 Torr at 700–900°C. GaN was
Readinger, Wolter, Waltemyer, DeLucca, Mohney,
Prenitzer, Giannuzzi, and Molnar
found to have good stability in oxidizing environments
up to 700°C. Above this temperature, the oxide was
found to grow most rapidly in water vapor with O2 as
a carrier gas at a temperature of 900°C, and wet
oxidation in Ar and N2 at 900°C resulted in very thin
oxides compared with those formed in wet or dry O2.
Glancing angle XRD confirmed the presence of
monoclinic β-Ga2O3 on n-GaN epilayers, and XPS
analysis verified the chemical composition of the
oxide. Analysis of the thermal oxide on GaN epilayers
was also performed using SEM. Surface analysis
verified the formation of a smooth oxide under wet
thermal oxidation compared with that of dry oxidation.
Thickness measurements by cross-sectional SEM
revealed linear growth kinetics and an activation
energy of 210±10 kJ/mol for wet oxidation in O2.
Electrical characterization of 100 nm oxides grown on
GaN revealed resistivities on the order of 108–10 10 Ω-
cm and apparent breakdown field strength of 7.5 × 104
V/cm for wet oxidation, compared with 109–1011 Ω-cm
and 2 × 105 V/cm for dry oxidation. Wet oxidation
consistently gave even poorer electrical results than
dry oxidation, probably due to the very irregular
morphology at the wet oxide/GaN interface.
ACKNOWLEDGMENTS
The authors would like to thank Dr. Brian Luther
for his assistance in creating the electrical test
structures and Dr. Theresa Mayer and Dr. Fan Ren
for discussions regarding the electrical character-
use of their FEI 611 FIB workstation is greatly
appreciated. Funding for this research was provided
by the National Science Foundation, grant DMR-
9624995.
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