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Journal of ElectronicOxidation
Materials, Vol. of
28, GaN
No. 3, 1999 257
Special Issue Paper
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
257
Readinger, Wolter, Waltemyer, DeLucca, Mohney,
258 Prenitzer, Giannuzzi, and Molnar
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)|
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-
b ization. The support of Cirent Semiconductor for the
Fig. 5. (a) Cross-sectional TEM micrograph of Ga2O 3 on GaN oxidized use of their FEI 611 FIB workstation is greatly
at 900°C for 70 min in wet O2 . The dark overlayer is a sputtered Cr layer appreciated. Funding for this research was provided
required for the TEM sample preparation procedure, and (b) cross- by the National Science Foundation, grant DMR-
sectional TEM micrograph of Ga2 O3 on GaN oxidized at 900°C for 5 h
in dry O2. The dark overlayer is sputtered Cr.
9624995.
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