APPLIED PHYSICS LETTERS

VOLUME 79, NUMBER 25

17 DECEMBER 2001

Interactions between gallium and nitrogen dopants in ZnO films grown

by radical-source molecular-beam epitaxy
K. Nakaharaa) and H. Takasu
Optical Device Research and Development Division, ROHM Corporation Limited, 21 Mizosaki-cho Saiin,
Kyoto 615-8585, Japan

P. Fons, A. Yamada, K. Iwata, K. Matsubara, R. Hunger, and S. Niki

Optoelectronics Division, Electrotechnical Laboratory, 1-1-4 Umezono, Tsukuba, Ibaraki 305-8568, Japan

Received 22 January 2001; accepted for publication 26 September 2001

It has been recently predicted that the co-doping of an acceptor nitrogen and a donor aluminum,
gallium, indium in a 2:1 ratio will dope ZnO p-type due to a reduction in the Madelung energy
making the nitrogen acceptor energy level more shallow. We have been growing gallium and
nitrogen co-doped ZnO films by radical-source molecular-beam epitaxy by use of oxygen and
nitrogen radicals supplied via rf radical source cells. Diode-like currentvoltage characteristics and
donor acceptor pair-like photoluminescence emission were observed for a Ga and N doped ZnO film
grown on an undoped ZnO buffer layer. However, Hall measurements revealed that the conductivity
was n-type. Formation of a non-ZnO phase in the sample was confirmed by secondary ion mass
spectroscopy and x-ray diffraction measurements. Zn and ZnO secondary ion intensities fell
sharply by two orders of magnitude in going from the undoped ZnO layer to the highly co-doped
ZnO. X-ray diffraction measurements indicated the formation of ZnGa2O4. 2001 American
Institute of Physics. DOI: 10.1063/1.1424066

ZnO has a 3.37 eV room-temperature direct band gap

and has also attracted attention as a useful material for UV
optoelectronic applications. The large excitonic binding energy 60 meV of ZnO also raises the interesting possibility
of utilizing excitonic effects in room-temperature devices. In
fact, room-temperature optically pumped UV emission from
ZnO films has been reported.13
In order to realize ZnO-based semiconductor devices, it
is indispensable to fabricate ZnO films with p- as well as
n-type conductivity by controllable extrinsic doping. Unfortunately, however, ZnO is naturally only n-type due to the
presence of native defects making acceptor doping of ZnO
difficult.
Yamamoto et al. proposed, however, a acceptor doping
method, donoracceptor co-doping based upon firstprinciple calculations.4 They reported two main conclusions.
First, nitrogen N incorporation on oxygen O sites in ZnO
increases the Madelung energy, causing localization of the N
levels. Second, codoping with aluminum Al, gallium Ga,
or indium In enhances the incorporation of N and the formation of 2NGa complex in ZnO decreases the Madelung
energy, making p-type doping of ZnO possible.
Based on these predictions, Joseph et al. recently reported that p-type ZnO films with low resistivities can be
fabricated by pulsed laser deposition using Ga and N
codoping.5 However, they used glass substrates, and consequently their ZnO films were polycrystalline with low carrier
mobilities. To make ZnO-based semiconductor optoelectronic devices, epitaxial p-type ZnO with good crystallinity
is needed.
We have previously reported on the growth of high quala

Electronic mail: Ken.Nakahara@dsn.rohm.co.jp

ity undoped ZnO films with high carrier mobilities and low
residual electron concentrations grown on sapphire substrates by radical-source molecular-beam epitaxy
RS-MBE.6 9 There has been no detailed reports on the behavior and mechanisms of N or GaN doping into single
crystalline ZnO films, and thus, we report here on the behavior and the complications associated with Ga and N co-doped
ZnO films grown by RS-MBE. Although the initial motivation for the current work was to grow epitaxial p-type ZnO
using RS-MBE, the results reported here indicated that the
Ga and N co-doping is fraught with serious problems.
Samples were grown by RS-MBE. The machine configuration is described in Ref. 9. Source materials were elemental Zn 7N, elemental Ga 7N, oxygen gas (6N, O2),
and nitrogen gas (6N, N2). Metal sources were supplied via
conventional Knudsen cells, and gas sources were separately
supplied via rf RS cells. Both the O2 and N2 gas flow rates
were 0.3 sccm with a rf power 300 W. The operating conditions of the RSs were fixed in all experiments.
0) plane sapphire as
We used both sides polished (112
substrates. Both of the substrate treatment methods before
growth and the growth conditions used in this letter have
been reported in Ref. 9. As discussed in the same reference,
a high T sub 600 C is effective in reducing the residual carrier concentration of undoped ZnO films, and therefore doping. Experiments were performed using T sub600 C.
A two-layer structure was fabricated for all films in order
to facilitate currentvoltage (I V) measurements. An undoped n-type layer 0.50.6 m thick was first grown, and
then the sample was removed from the vacuum chamber and
a Inconel shadow mask was affixed. Subsequently, the
sample was moved back to the growth chamber and the
doped layer was grown. I V measurements were then made
using In contacts between the undoped layer and the doped

0003-6951/2001/79(25)/4139/3/$18.00
4139
2001 American Institute of Physics
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4140

Appl. Phys. Lett., Vol. 79, No. 25, 17 December 2001

Nakahara et al.

FIG. 2. SIMS depth profile of Ga and N concentration for Ga and N codoped ZnO films. The Ga cell temperatures were a 700 C flux: 1.5
109 Torr, and b 800 C flux: 2108 Torr, respectively.

FIG. 1. SIMS measurements of a nitrogen single doped ZnO film grown at

T sub 600 C.

layer. Beam fluxes were measured by a nude ion gauge rotated into the sample position. The Zn flux was fixed in the
range of 1 2106 Torr, and the Ga flux was varied in the
range of 2109 2107 Torr.
Absolute N and Ga concentrations were determined by
secondary ion mass spectroscopy SIMS measurements. All
SIMS data were calibrated by simultaneous measurements of
Ga or N ion implanted undoped ZnO layers.
Experiments in which films were doped with only N
were carried out before Ga and N co-doping. Figure 1 shows
a SIMS measurement of a N doped ZnO film grown at T sub
600 C. The peak at the interface between the N doped and
undoped ZnO films is due to a SIMS matrix effect caused by
air exposure after growth of the undoped buffer layer as
mentioned, and thus irrelevant to the discussion here. The N
concentration in the ostensibly N doped and undoped layers
is unchanged, and the signal levels indicate that the N concentrations are below the SIMS sensitivity limits
(1017 cm3). It is clear from this result that N doping into
ZnO films does not occur for T sub600 C. This is interpreted as being a consequence of the preferential reaction of
O over N with Zn. This preference can also be seen in the
results of other experiments, where only ZnO, not some kind
of zinc nitride, was grown even when N2O gas was used as a
source gas despite the generation of N radicals as confirmed
by in situ optical emission spectroscopy.
In spite of a lack of N incorporation into ZnO at T sub
600 C, however, co-doping with Ga was found to enhance N incorporation into ZnO. The ZnO 0002 full width
at half maximum values in a 2/ scan of the coped films
and a undoped film is nearly unchanged 0.023. SIMS results for co-doped ZnO using Ga and N are shown in Figs.
2a and 2b. As can be seen in Fig. 2, the presence of Ga
clearly enhances the incorporation of N into ZnO. The Ga
cell temperatures were 700 C flux: 1.5109 Torr for Fig.
2a, and 800 C flux: 2108 Torr for Fig. 2b. These

results are consistent with the prediction of Ref. 4, namely

that the presence of the donor Ga enhances N incorporation. The results also indicated that N incorporated in the
presence of Ga formed NGa bonds, because N does not
incorporate into ZnO without the presence of Ga as shown in
Fig. 1. The presence of NGa bonds in co-doped ZnO is one
of the prerequisites for p-type doping according to the codoping proposal.
The co-doping proposal, however, also concluded that
the formation of 2NGa complexes in ZnO is needed. To
satisfy this requirement, Ga and N atoms must be positioned
in the lattice near enough to bond to each other, leading to
the necessity of high doping levels. Toward this end, highly
Ga and N co-doped films with a Ga cell temperature 900 C
Ga flux 2.5107 Torr were carried out.
As shown in Fig. 3, diode-like I V characteristics were
observed between the highly co-doped ZnO layer and the
n-type undoped ZnO layer while both I V characteristics
between p electrodes and n electrodes were ohmic. In contrast, the N-only doped samples showed ohmic behavior, implying that the growth interruption was not responsible for
the I V behavior of the co-doped film. Photoluminescence
PL measurements of the same sample indicated that a
donoracceptor pair DAP-like emission exists, as the PL

FIG. 3. Typical I V characteristic between the highly co-doped layer and

the undoped layer. The inset shows the device configuration.
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Nakahara et al.

Appl. Phys. Lett., Vol. 79, No. 25, 17 December 2001

FIG. 4. PL measurements for a highly co-doped sample. a Excitation

power density (8.8102 W cm2) and b excitation power density
88 W cm2.

peak position blueshifted with increasing excitation power

Fig. 4. The I V and PL results suggests the presence of
acceptor levels. However, these results alone are insufficient
to unambiguously determine the conductivity type of the
sample.
In order to determine the conductivity type of the codoped sample, Hall measurements were carried out. These
measurements showed that the sample was n type with a
carrier concentration of 1.981019 cm3 and a mobility of
17.8 cm2 V1 s1. However, SIMS measurements and x-ray
diffraction XRD measurements indicated the complicating
factors, specifically the presence of an additional phase.
SIMS measurements Fig. 5 showed that Zn and ZnO
ion intensities sharply decreased by two orders of magnitudat
the interface between the co-doped layer and the undoped e

FIG. 5. SIMS depth profile of a Ga concentration and Zn secondary ion

intensity and b nitrogen concentration and ZnO secondary ion intensity.

4141

layer. As the Zn and ZnO ion intensities would not be

expected to fluctuate if the matrix remained ZnO, this implies the presence of a non-ZnO phase in the highly codoped ZnO film.
The presence of the additional non-ZnO phase was also
confirmed by XRD measurements. An -2 scan of the codoped ZnO film exhibited peaks from other than ZnO and
sapphire. The peak positions from the phase could be indexed as the spinel ZnGa2O4 phase,10 suggesting that the
non-ZnO phase is ZnGa2O4. As ZnGa2O4 is a semiconductor
with a 5 eV band gap,10 it is doubtful that the presence of
this phase could explain either the PL or diode-like I V
behavior observed. Hence, the presence of the additional
phase casts some doubt on the validity of the Hall effect
results and makes it impossible to unambiguously determine
the conductivity type of the co-doped ZnO film.
In conclusion, N doped and GaN co-doped ZnO films
were grown by RS-MBE. While N did not incorporate in
ZnO films grown at 600 C, the presence of Ga enhanced N
incorporation, consistent with the co-doping theoretical predictions. The as-grown films display some aspects reminiscent of p-type conductivity, namely diode-like I V behavior
and DAP-like PL emissions, however, from SIMS and XRD
measurements, the formation of a non-ZnO phase was confirmed, which is identified as ZnGa2O4. The presence of the
additional phase makes unambiguous determination of carrier type difficult and will undoubtably place severe restrictions on the practical utilization of the co-doping technique.

D. C. Reynolds, D. C. Look, and B. Jogai, Solid State Commun. 99, 873

1996.
2
D. M. Bagnall, Y. F. Chen, M. Y. Shen, Z. Zhu, T. Goto, and T. Yao, Appl.
Phys. Lett. 70, 2230 1997.
3
P. Yu, Z. K. Tang, G. K. L. Wong, M. Kawasaki, A. Ohtomo, H. Koinuma,
and Y. Segawa, Solid State Commun. 103, 459 1997.
4
T. Yamamoto and H. Yoshida, Jpn. J. Appl. Phys., Part 2 38, L166 1999.
5
M. Joseph, H. Tabata, and T. Kawai, Jpn. J. Appl. Phys., Part 2 38, L2505
1999.
6
P. Fons, K. Iwata, S. Niki, A. Yamada, and K. Matsubara, J. Cryst. Growth
201, 627 1999.
7
P. Fons, K. Iwata, S. Niki, A. Yamada, K. Matsubara, and M. Watanabe, J.
Cryst. Growth 209, 532 2000.
8
P. Fons, K. Iwata, A. Yamada, K. Matsubara, S. Niki, K. Nakahara, T.
Tanabe, and H. Takasu, Appl. Phys. Lett. 77, 1801 2000.
9
K. Nakahara, T. Tanabe, H. Takasu, P. Fons, K. Iwata, A. Yamada, K.
Matsubara, R. Hunger, and S. Niki, Jpn. J. Appl. Phys., Part 1 40, 250
2001.
10
T. Omata, N. Ueda, K. Ueda, and H. Kawazoe, Appl. Phys. Lett. 64,
1077 1994.

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