Deuterium incorporation and diffusivity in plasma-exposed bulk Ga2O3

Shihyun Ahn, F. Ren, Erin Patrick, Mark E. Law, S. J. Pearton, and Akito Kuramata

Citation: Appl. Phys. Lett. 109, 242108 (2016); doi: 10.1063/1.4972265

View online: https://doi.org/10.1063/1.4972265
View Table of Contents: http://aip.scitation.org/toc/apl/109/24
Published by the American Institute of Physics

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 APPLIED PHYSICS LETTERS 109, 242108 (2016)

Deuterium incorporation and diffusivity in plasma-exposed bulk Ga2O3

Shihyun Ahn,1 F. Ren,1 Erin Patrick,2 Mark E. Law,2 S. J. Pearton,3,a) and Akito Kuramata4
1
Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, USA
2
Department of Electrical Engineering, University of Florida, Gainesville, Florida 32611, USA
3
Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611, USA
4
Tamura Corporation and Novel Crystal Technology, Inc., Sayama, Saitama 350-1328, Japan
(Received 7 October 2016; accepted 2 December 2016; published online 16 December 2016)
Deuterium incorporation depths of 0.13–0.65 lm were obtained in bulk, single-crystal Ga2O3
during exposure to 2H plasmas for 0.5 h at 100–270  C. The data were fit using the Florida Object
Oriented Process Simulator simulation code. The estimated diffusivities were in the range of 2.3
 1014–6  1013 cm2/Vs over this temperature range. The activation energy for diffusion was
0.30 6 0.08 eV, suggesting that the diffusing deuterium migrates as an interstitial. The solubility of
the deuterium exhibited an activation energy of 0.35 eV. Subsequent annealing at 500  C removed
85% of the deuterium out of the Ga2O3, with an activation energy of 1.35 eV. This indicates that
the outdiffusion is mediated through defects or molecule formation. The thermal stability of deute-
rium retention is lower (150  C shift to lower temperatures) than when the deuterium is incorpo-
rated in the Ga2O3 by direct ion implantation, due to trapping at residual damage in the latter case.
The incorporation depths of deuterium in the Ga2O3 are significantly less than in bulk ZnO under
the same conditions, where we observed incorporation to 25 lm. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4972265]

There is a significant interest in the use of Ga2O3
for applications in high power electronics1–9 and truly solar-
blind ultraviolet (UV) photodetectors.10–14 Monoclinic
b-Ga2O3 has a bandgap of 4.9 eV, good chemical and ther-
mal stability, high optical transparency in both UV and visi-
ble regions, and good thermal conductivity. The latter will
still be an issue for many power devices operating at high
current levels, but it might be addressed using advanced
heatsinks like diamond or microfluidic approaches or transfer
to a metal substrate, all of which are currently being devel-
oped for GaN electronics. Ga2O3 has a very high theoretical
breakdown electric field (8 MV/cm),5,6 leading to a Baliga
figure-of-merit almost four times higher for Ga2O3 compared
to GaN.3–7 Experimental breakdown field values have
reached 3.8 MV/cm in Ga2O3, and these are already higher
than the bulk critical field strengths of GaN and SiC.6 Ga2O3
remains transparent well into the ultraviolet (UV) part of the
spectrum, allowing its use as a transparent conducting oxide
in this region.10–13 These deep-UV photodetectors need to
have a cut-off wavelength of 280 nm for solar blindness.
Conductivity control is of particular interest in transpar-
ent conducting oxides like Ga2O3. Oxygen vacancies and
cation interstitials traditionally have been invoked as the
causes of conductivity. In recent studies, hydrogen impurities
have been found to be the dominant shallow donors in sev-
eral important cases like ZnO and In2O3.15–20 There is evi-
dence from theory17 and from experimental measurements of
the properties of muonium (a light ion analog of hydrogen
that is often used to provide a guide to how hydrogen will
behave in semiconductors)18 that hydrogen is also a shallow
donor in Ga2O3, but little is known of its properties such as
diffusivity, thermal stability, and migration energies in this
material.
a)
Electronic mail: spear@mse.ufl.edu
In this letter, we report an investigation of the diffusion
of deuterium in Ga2O3 during exposure to 2H plasmas and its
thermal stability. The deuterium is found to be incorporated
into the Ga2O3 at temperatures as low as 100  C and can be
evolved from the material by subsequent annealing under O2
at 500  C.
The starting sample was a bulk b-phase Ga2O3 single
crystal with (201) surface orientation (Tamura Corporation,
Japan) grown by the edge-defined film-fed growth method.
Hall effect measurements showed that the sample was unin-
tentionally n-type with an electron concentration of 3
 1017 cm3. The plasma exposed samples were treated for 30
min at 100, 200, and 270  C in a 0.5 Torr, 13.56 MHz dis-
charge.21 Sections of the 200  C treated sample were then
annealed for 5 min at either 500 or 600  C under flowing O2 in
a face-to-face configuration to measure the thermal stability
of the deuterium. All of the samples were examined by
Secondary Ion Mass Spectrometry (SIMS). The latter was per-
formed in a magnetic sector Cameca system using a Csþ ion
beam with 14.5 keV energy and 24 incident angle.22
Figure 1 shows SIMS profiles of 2H in plasma exposed
Ga2O3, for different sample temperatures during the plasma
treatment, as well as the simulated curves. The experimental
profiles follow those expected for diffusion from a constant
or semi-infinite source.23 The incorporation depths of 2H are
fairly similar to those observed for the same type of plasma
exposure of GaN or GaAs under similar conditions, where
depths of 1 lm are observed.24,25 The incorporation depths
are, however, much less than in ZnO, where depths of 25 lm
were reported.21 It is likely that the hydrogen isotope must
diffuse as an interstitial under these conditions, with little
trapping by the lattice elements or by defects or impurities.
The position of 2H in the lattice after immobilization has not
yet been determined experimentally, but theoretically, the
lowest energy state for Hþ is forming an O-H bond with

0003-6951/2016/109(24)/242108/3/$30.00 109, 242108-1 Published by AIP Publishing.

242108-2 Ahn et al. Appl. Phys. Lett. 109, 242108 (2016)

FIG. 1. SIMS profiles of 2H in Ga2O3 exposed to deuterium plasmas for 0.5

FIG. 2. SIMS profiles of 2H in Ga2O3 exposed to deuterium plasma for 0.5 h
h at different temperatures and fits to experimental deuterium profile data
at 200  C and then annealed at 400 or 500  C for 5 min under flowing N2.
using the FLOOPS simulator.

(a shift of 150  C), most likely due to trapping at residual

three-fold coordinated oxygen, but there were many configu-
damage in the Ga2O3 created by the nuclear stopping pro-
rations close in energy.17
cess. The activation energy for the rate constant of loss of
We were able to accurately simulate the deuterium diffu-
deuterium from the Ga2O3 was 1.35 eV from the FLOOPS
sion using the Florida Object Oriented Process Simulator
code, much larger than that for the in-diffusion, and it had
(FLOOPS).26–28 FLOOPS has been used extensively to model
diffusion and impurity migration in silicon technologies, so it similar values for both plasma-introduced and direct-
is well suited for this task.28 Figure 1 also shows fits to the implanted deuterium. This means the loss of deuterium is
experimental data using this simulator, with excellent agree- mediated through an additional process in both cases, which
ment for the higher temperatures where the deuterium is well is likely to be trapping at implant-induced damage such as
above the background detection sensitivity of the SIMS and vacancies in the case of the implanted deuterium.30 The deu-
beyond the near-surface region caused by non-equilibrium terium that is incorporated from plasma exposure is likely to
effects during the sputtering of the sample. The extracted acti- diffuse as an interstitial but then comes to rest on a vacancy
vation energy for diffusion was 0.30 6 0.08 eV, with an acti- or forms deuterium molecules that lead to different kinetics
vation energy value for the solubility of 0.35 eV. The for the loss of deuterium from the Ga2O3. We assume that
activation energy for diffusion was also obtained using a sim- the rate limiting step is the annealing of the interstitial-
ple estimate of the diffusivity D, from D ¼ X2/4t, and where X vacancy Frenkel pair and find that the dissolution of this
is taken to be the distance at which 2H concentration has fallen cluster occurs with an activation energy of 1.35 eV. The
to the background concentration of 1015 cm3 and t is the lower concentration of defects in the plasma–treated Ga2O3
plasma exposure time at each temperature. In this case, the means that deuterium can escape the crystal at lower
value was 0.33 eV, consistent with the value from FLOOPS. temperatures.
The range of diffusivities of 2.3  1014–6  1013 cm2/V s In summary, deuterium is found to exhibit significant
from 100–270  C is about three orders of magnitude lower diffusion in Ga2O3 when incorporated by plasma exposure,
than in ZnO over a comparable temperature range.21 Note that with an estimated activation energy for diffusion of 0.30 eV.
the absolute diffusivities of 1H would be 40% larger than The activation energy for diffusion is indicative of interstitial
the values for 2H because of the inverse mass relationship for
diffusivities of isotopes.23 The small activation energy is con-
sistent with the notion that the atomic hydrogen diffuses in
interstitial form.
Figure 2 shows SIMS profiles of a Ga2O3 sample
exposed to a 2H plasma of 0.5 h at 200  C, and then annealed
for 5 min under O2 at different temperatures. There is a sig-
nificant loss of 2H even after a short anneal at 400  C, with
virtually all of it evolved out of the crystal by 500  C. This is
in sharp contrast to 2H in GaN, where much higher tempera-
tures (800  C) are needed to evolve the deuterium out of
the sample.29
Figure 3 shows the percentage of 2H remaining (measured
by SIMS) as a function of post-plasma annealing temperature.
The 2H was initially incorporated by plasma exposure at
FIG. 3. Fraction of 2H remaining as a function of post-plasma annealing
200  C, followed by annealing at different temperatures. When
temperature. The sample was initially exposed to a deuterium plasma at
compared to the thermal stability of 2H incorporated by direct 200  C and then annealed under O2 to measure the thermal stability of the
implantation,30 the 2H is more thermally stable in the latter case incorporated deuterium.
242108-3 Ahn et al. Appl. Phys. Lett. 109, 242108 (2016)

10
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