Correlation of growth temperature, photoluminescence, and resistivity in GaN

nanowires
A. Alec Talin, George T. Wang, Elaine Lai, and Richard J. Anderson
Citation: Applied Physics Letters 92, 093105 (2008); doi: 10.1063/1.2889941
View online: http://dx.doi.org/10.1063/1.2889941
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APPLIED PHYSICS LETTERS 92, 093105 2008

Correlation of growth temperature, photoluminescence, and resistivity

in GaN nanowires
A. Alec Talin,1,2,a George T. Wang,3 Elaine Lai,1 and Richard J. Anderson1
1

Sandia National Laboratories, Livermore, California 94550, USA

Center for Integrated Nanotechnologies, Albuquerque, New Mexico 87185, USA
3
Sandia National Laboratories, Albuquerque, New Mexico 87185, USA
2

Received 27 December 2007; accepted 8 February 2008; published online 3 March 2008
The photoluminescence and electrical transport of GaN nanowires grown by metal catalyzed
metal-organic chemical vapor deposition were investigated as a function of substrate temperature
during growth. As the growth temperature increased from 800 to 900 C, the electrical conduction
mechanism changed from space-charge limited to ohmic transport, the nanowire resistivity dropped
from 107 to 103 cm, and the band edge luminescence increased by more than two orders of
magnitude. A strong correlation between the resistivity and the fraction of band edge luminescence
for individual nanowires was observed. 2008 American Institute of Physics.
DOI: 10.1063/1.2889941
Group III-N nanowires grown by metal nanoparticle
catalyzed chemical vapor deposition CVD have recently
attracted considerable interest, motivated by the desirable
optoelectronic properties of this material system, the high
crystalline quality of the nanowires, and the potential of integrating these quasi-one-dimensional nanostructures with
Si.1 Particularly attractive device applications include vertically oriented nanoscale laser diodes and high electron mobility transistors.2,3 The growth mechanism which results in
the GaN nanowires is vapor-liquid-solid VLS or vaporsolid-solid epitaxy VSS, whereby gas phase Ga and N precursors dissolve in transition metal catalyst such as Ni, and
precipitate as single-crystalline nanowires. Numerous transmission electron microscopy TEM studies have shown that
VLS derived GaN nanowires, grown under a variety of conditions i.e., precursors, substrate temperature, etc., have
high crystalline quality with low dislocation density, though
stacking faults are frequently observed.4,5 Unlike extended
defects, characterization of point defects such as impurities,
vacancies, and substitutions is far more challenging. However, in nanowires, the impact of point defects may, in fact,
be more pronounced, since dislocations in bulk or thin film
GaN act as sinks or getters for point defects.6 Furthermore,
conditions that favor nanowire growth, including substrate
temperature Tsub and III-V precursor ratio, depart significantly from the conditions typically employed for device
quality thin film GaN growth, and may further increase the
concentration of point defects.4
In this letter, we describe the results of electrical and
optical characterization of GaN nanowires grown by metal
catalyzed metal-organic CVD MOCVD where only one
growth condition, the substrate temperature, is varied from
800 to 900 C. We use a simple platform that was specifically designed for combined electrical and optical characterization of individual nanowires as compared to ensembles.
Our results show that for a 100 increase in substrate temperature Tsub during growth, the average nanowire resistivity decreases by nine orders of magnitude, while band edge
luminescence BEL intensity increases by more than three
a

Electronic mail: aatalin@sandia.gov.

orders of magnitude. Furthermore, we show that for the entire set of nanowires investigated here, the resistivity and
photoluminescence PL are strongly correlated. Comparison
of our results with previous work on GaN nanowires grown
under similar conditions but without the use of carbonbearing precursors strongly suggests that residual carbon incorporated during growth is responsible for the effects observed here.
The growth of GaN nanowires used in this study was
described in detail previously.4 Nickel catalyst in the form of
nickel nitrate hexahydrate was diluted in ethanol and depos 02 oriented sapphire substrate.
ited dropwise onto a 2 in. 11
Nanowire growth was carried out in a home-built MOCVD
rotating-disk cold-wall reactor with trimethyl gallium and
ammonia precursor with the substrate held at 800, 850, or
900 C. Extensive TEM analysis indicated that these nano 0 orientation, are single crystalwires have primarily a 112
line, and are generally free from dislocations.4
Electrical contacts to individual nanowires were
fabricated by first spin casting a nanowire suspension
in ethanol onto degenerately doped Si wafers with 100 nm
thick thermal oxide. Next, arrays of interdigitated, individually electrodes were defined on the substrate using optical
lithography, followed by an O2 plasma etch to remove residual photoresist, electron beam evaporation of Ti/ Au
10 nm/ 100 nm metallization, lift-off, and finally an anneal
at 600 C for 5 min in a vacuum furnace. This approach
does not require direct-write electron beam lithography and
generally results in tens of individual nanowire devices per
wafer.
PL spectra for individual nanowires were collected using
a home-built system, with a HeCd laser focused though a
32 reflective objective, and a charge coupled device CCD
camera/spectrometer OceanOptics combination coupled
to the electrical probe station microscope. The resulting laser
spot incident on the sample had a diameter of 10 m and a
total cw power of 2 mW. Note that this power density
cannot be directly compared with bulk GaN experiments,
since in our case the nanowire diameter is much smaller than
the spot size. A Semrock band pass filter was used to
eliminate the reflected laser light from reaching the CCD

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92, 093105-1
2008 American Institute of Physics
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FIG. 3. Color online Nanowire resistivity plotted vs the normalized BEL

intensity. The last three data points were not included in the data fit.

with nonsymmetrical I-V curves i.e., the negative portion

for I-V in Fig. 1e. The log-log plot reveals a power law
behavior where I Vn, with n 1 i.e., Ohmic behavior for
nanowires grown at 900 C and n 2 for nanowires grown
at 800 and 850 C.
The lower BEL intensity observed with lower Tsub sugcamera or the spectrometer. Current-voltage I-V measuregests that these nanowires have a low free electron concenments were performed using a computer controlled Keithley
tration, and that the extra carriers created upon photon ab237 source-measure unit.
sorption recombine nonradiatively at defect sites. However,
PL spectra collected from three different GaN nanowires
the concentration of the defects responsible for YL remains
grown at 800, 850, and 900 C are shown on a log scale in
essentially unchanged, as evident by the relative invariance
Figs. 1a1c, respectively. Also included are insets of the
in the YL band with Tsub. According to Reshchikov and
luminescence images of the three nanowires. The PL specMorkoc,7 the broad YL band with peaks at 2.2 and
trum for the nanowire grown at 800 C contains a broad
2.5 eV originates from two charge states of the same deyellow luminescence YL band centered at 2.3 eV, and
fect, a complex involving a gallium vacancy VGa and a shalonly a shoulder at 3.4 eV, where BEL is usually observed
low oxygen donor on a N site ON.
at for GaN at room temperature. The sharp lines in Fig. 1a
The I V2 power law dependence observed for nanoabove 3 eV are part of the background and originate from the
wires grown at 800 and 850 C indicates that electrical
HeCd laser. However, as Tsub is increased to 850 C, the
transport is dominated by space-charge limited conduction
BEL peak grows by approximately ten times, and increases a
SCLC.8 SCLC in Si and compound semiconductor nanofactor of approximately thirty for Tsub of 900 C. In comwires has recently been reported by several groups.9,10 SCLC
parison, the broad YL band remains approximately unarises when the carriers injected from the contacts exceed the
changed. The undulations in the YL band are due to optical
thermal free carrier concentration in the specimen, and is
interference of the Semrock filter, used to remove the retypical of insulating materials where transport is not limited
flected laser light, for wavelength above 360 nm.
by contact resistance.8 In order to estimate the nanowire reI-V characteristics for the same three nanowire specisistivity, we fit the I-V characteristics to I = Vn, where is a
mens are shown in Figs. 1d1f, together with the scanconstant, and then evaluate the resistivity at V = 1 V using the
ning electron microscope images of the nanowire specimens.
1
, where A is the nanoexpression nanowire = A / LdI / dVV=1
Additional I-V characteristics for nanowires grown at all
wire cross sectional area measured in the middle and L is the
three temperatures are displayed on a log-log plot in Fig. 2,
nanowire length spanning between the two metal electrodes.
where we show the less resistive portion for those specimens
In Fig. 3, the nanowire resistivity is plotted versus the integrated BEL intensity normalized by the total integrated luminescence intensity, i.e., BEL/ BEL+ YL. The data were
fitted to a power law function which yielded the best fit of
= 4.7 104BEL/ BEL+ YL6.4, and where the three data
points corresponding to the highest BEL/ BEL+ YL values
were not included in the mathematical fit. This apparent
change in the resistivity-PL relationship at the higher BEL
intensity is possibly due to other factors, such as impurity
and phonon scattering, playing a stronger role in determining
the electrical transport once the free carriers are no longer
compensated by the traps present in those nanowires with the
lower BEL intensity.
The strong decrease in resistivity and increase in BEL as
a
function
of Tsub in our study is unlikely due to extended
FIG. 2. Color online A sample of I-V curves collected for nanowires
defects, as TEM analysis revealed no appreciable difference
grown
at
different
substrate
temperatures.
The
green
dotted
lines
indicate
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in dislocation density for nanowires grown at different Tsub.
I V and I V2 relationships.
FIG. 1. Color online Photoluminescence spectra collected at room temperature using HeCd laser with a spot size of 10 m in diameter and a
power of 2 mW for GaN nanowires grown at a 800 C, b 850 C, and
c 900 C. df I-V characteristics for the same three nanowires.

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FIG. 4. Nanowire resistance divided by the length vs the nanowire width

measured midway between the two metal electrodes.

A similar conclusion with respect to lack of PL dependence

on dislocation density was also reached by Sun et al. who
studied bulk GaN films with widely different dislocation
densities.11
Besides bulk point defects, surface states can also deplete the free carriers within a nanowire owing to the high
surface to volume ratio.12,13 To address this possibility, we
have measured the resistance of a set of nanowires grown at
900 C with diameters ranging from 100 to 750 nm.
These results are shown in Fig. 4, where the two electrode
resistances are divided by the nanowire length, and are plotted versus the nanowire diameter. A sharp increase in resistance is indeed observed for diameter below 150 nm, suggesting that band bending due to surface states completely
depletes those nanowires. This result is in agreement with the
previous experiments of Calarco et al., as well as with a
rough estimation of the depletion width assuming planar
contacts and assuming surface energy level at 0.5 eV below
the conduction band minimum, and an unintentional n-type
doping of 1017 / cm3.12 The BEL intensity of these thinner,
900 C grown nanowires is lower compared to those with
larger diameters, but this effect was not investigated systematically in this study and will be addressed in the future. To
diminish the effects of surface depletion on the correlation of
Tsub with PL and resistivity, only nanowires with diameters
of 200 nm were used to compile the data shown in Figs. 2
and 3.
Previously, Stern et al. investigated electrical transport in
GaN nanowires grown under similar conditions, but without
the use of metal-organic precursors for the Ga source.14 Unlike in the present case, Stern et al. observed that the carrier
concentration was 1019 / cm3 with little dependence on the
substrate temperature in the range of 800 1100 C. Comparison of our results with those of Stern et al. suggests that
possible carbon incorporation during growth from the trimethylgallium precursor is responsible for the low BEL in-

tensity and the high resistivity observed at the lower growth

temperatures. Bulk GaN films doped with carbon at
1017 / cm3 are indeed insulating, with the C substituting nitrogen acting as either shallow or moderately deep acceptor.7
Furthermore, while bulk GaN specimens with high carbon
content have been reported to have strong YL, a clear correlation between carbon concentration and YL intensity was
not observed.7
In conclusion, we have shown that substrate temperature
can substantially affect the luminescence and resistivity of
metal catalyzed MOCVD grown GaN nanowires, and that an
increase from 850 to 900 C can results in a factor of 30
increase in BEL intensity, and a factor of 104 decrease in
resistivity. We have also shown that these changes are not
related to YL intensity, nor do they originate from surface
related effects. Finally, by comparison with previous work on
GaN nanowires grown without carbon-bearing precursors,
we suggest that carbon incorporation at the lower Tsub is
responsible for the observations reported in this study.
This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. Department of Energy,
Office of Basic Energy Sciences user facility. Sandia National Laboratories is a multiprogram laboratory operated by
Sandia Corporation, a Lockheed-Martin Company, for the
U.S. Department of Energy under Contract No. DE-AC0494AL85000.
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