Journal of Luminescence 145 (2014) 884–887

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Luminescence behavior and compensation effect of N-doped

ZnO films deposited by rf magnetron sputtering under various
gas-flow ratios of O2/N2
Wei-Min Cho a, Yow-Jon Lin a,n, Chia-Jyi Liu b, Liang-Ru Chen b, Yu-Tai Shih b, Perry Chen a
a
Institute of Photonics, National Changhua University of Education, Changhua 500, Taiwan
b
Department of Physics, National Changhua University of Education, Changhua 500, Taiwan

art ic l e i nf o a b s t r a c t

Article history: The photoluminescent and electrical properties of N-doped ZnO films fabricated by rf magnetron
Received 24 March 2013 sputtering under various gas-flow ratios of O2/N2 were examined in this study. The dependence of
Received in revised form conduction type on the gas-flow rate of O2/N2 was found. The authors identified a direct correlation
13 August 2013
between the defect spectral feature and conduction type of N-doped ZnO samples and provided a
Accepted 12 September 2013
physical model for producing p-type ZnO. According to these observed results, the authors suggested
Available online 19 September 2013
that p-type conversion of N-doped ZnO may be due to a combined effect of the increased acceptor
Keywords: (substitutional nitrogen in oxygen site, zinc vacancy and interstitial oxygen) density and the decreased
ZnO donor (oxygen vacancy) density. In addition, synthesis of p-type N-doped ZnO was repeated, suggesting
Photoluminescence
that p-type ZnO can be fabricated with excellent reproducibility by rf magnetron sputtering a ZnO target
Raman scattering
doped with nitrogen.
Defect
Conductivity & 2013 Elsevier B.V. All rights reserved.

1. Introduction
ZnO with a direct band gap of
3.4 eV could be a potential
candidate for optoelectronic and spintronic applications [1–9].
Clearly understanding the luminescence behavior of ZnO is quite
essential for designing optoelectronic and spintronic devices and
improving their performance because a large amount of defects in
ZnO contribute to the visible emissions and even degrade the near
band-edge emission. In addition, the development of ZnO-based
optoelectronic devices exploring the exceptional electrical and opti-
cal properties of this material has been hindered by the difficulty in
realizing high-conductivity p-type ZnO. Therefore, it is import to
synthesize p-type ZnO thin films. Many theoretical studies have been
undertaken to understand the defects and conductivity of ZnO [10–
15]. Janotti and Van de Walle presented the theory of doping and
native defects in ZnO based on density-functional calculations,
discussing the stability and electronic structure of native point
defects and impurities and their influence on the electrical conduc-
tivity and optical properties of ZnO [10]. Yamamoto et al. have
investigated the electronic structure of n- and p-type ZnO based on
ab initio electronic band structure calculations [11]. P mono-doped
and (P, N) codoped ZnO were also investigated by the first-principles
n
Corresponding author. Tel.: 886 4 7232105x3379; fax: 886 4 7211153.
E-mail address: rzr2390@yahoo.com.tw (Y.-J. Lin).
calculations [12]. Tian and Zhao found that this significantly reduces
the acceptor level of PZn-4NO complexes and helps improving the
p-type conductivity in ZnO, suggesting that a better (P, N) codoped
p-type ZnO could be obtained under oxygen-poor condition [12].
Deng et al. used first principles density functional theory to inves-
tigate the crystal structure, impurity formation energies, density of
states and electronic structure of B–N codoped ZnO [13]. Usually, ZnO
films show the n-type electrical property due to native oxygen
vacancies (VO). Thus, the control of native defects as well as extrinsic
dopants in the ZnO film is very import. Park et al. suggested that the
fabrication and improvement of p-type ZnO films by doping is
difficult due to the compensation effect of native n-type carrier with
dopants and the low solubility of the acceptor dopants [16]. Nitrogen
is one of the dopants for producing p-type ZnO [17–21]. However, the
N-doping behavior and conduction mechanisms are still unclear.
Based on tight-binding calculations [14], that N would act as shallow
acceptor in ZnO, calculations based on density functional theory
within the local density approximation or generalized gradient
approximation have resulted in an acceptor level (0.4 eV) above the
valence-band maximum [15,16]. However, Lyons et al. suggested N is
actually a deep acceptor based on first-principles calculations and
hence cannot lead to hole conductivity in ZnO [22]. The mechanism
of the defect-related conduction type in ZnO has been studied and
remains a controversial subject. Experimental work is needed to
clarify what defects contribute to the widely observed p-type
conductivity in N-doped ZnO. Knowledge of the defect type in

0022-2313/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jlumin.2013.09.029
 W.-M. Cho et al. / Journal of Luminescence 145 (2014) 884–887
N-doped ZnO is crucial for the physical understanding of p-type
conductivity. In addition, Lee et al. found that N acceptors are mainly
compensated by VO at low N doping levels [23]. A well-known
difficult is trying to incorporate N into ZnO when O is available [24].
This is because of the higher chemical activity of oxygen than
nitrogen. Knowledge of the luminescence behavior and compensa-
tion effect inside the N-doped ZnO film is crucial for the physical
understanding of conversion mechanisms. In this study, N-doped
ZnO thin films have been synthesized by rf magnetron sputtering in
the ambient of Ar, N2 and O2. N2 was used as the nitrogen source. We
examined the effect of the gas-flow ratio of O2/N2 on the photo-
luminescent and electrical properties of the rf sputtered N-doped
ZnO films. Dependences of luminescence behavior and conduction
type on the gas-flow rate of O2/N2 were found. Compensation of
residual donors and conduction type conversion were observed. It is
shown that the creation of p-type N-doped ZnO may be due to a
combined effect of the increased acceptor [substitutional nitrogen in
oxygen site (NO), zinc vacancy (VZn) and interstitial oxygen (Oi)]
density and the decreased donor VO density.
2. Experimental details
N-doped ZnO films were grown onto glass substrates using a rf
magnetron sputtering system. A ZnO target was used in mixed Ar,
O2 and N2 ambient. The flow rate of Ar gas was fixed at 60 SCCM
(SCCM denotes standard cubic centimeter per minute). The gas-
flow ratio of O2/N2 was 0/0 (hereinafter referred to as Sample A),
7.5 SCCM/0 (hereinafter referred to as Sample B), 7.5 SCCM/7.5
SCCM (hereinafter referred to as Sample C) and 7.5 SCCM/30 SCCM
(hereinafter referred to as Sample D), respectively. The target size
is 2 in. and the target-substrate distance is 6.5 cm. The rf power
was fixed at 60 W. The substrate temperature was fixed at 450 1C.
The vacuum chamber was evacuated to a base pressure of
2  10  6 Torr and the working pressure was 5  10  3 Torr. The
ZnO film thickness was about 230 nm. The carrier concentration,
mobility and resistivity are obtained from the Hall measurements
(Ecopia HMS-3000) in the van der Pauw configuration at room
temperature. The electrodes were fabricated by depositing Au (In)
metal on the ZnO layer through a shadow mask. The HMS-3000
includes software with current-voltage curve capability for check-
ing the ohmic integrity of the user made sample contacts. Using a
He–Cd laser as an excitation source, the photoluminescence (PL)
band was observed at room temperature for the all samples. The
structures of the films were studied using X-ray diffraction (XRD)
in 2θ range of 20–601 with Cu Kα radiation. A beam voltage of
40 kV and a 30 mA beam current were used. The data were
recorded at a continuous scan rate of 31/min and the phase was
identified with JCPDS database. Raman spectra were also recorded.
With a sampling depth of nearly one micron, Raman spectroscopy
offers useful insight into the nature of defects and lattice disorder.
3. Results and discussions
The carrier concentration, mobility, conduction type and resis-
tivity of ZnO samples are shown in Table 1. Samples A and B
Table 1
Carrier concentration, mobility, conduction type and resistivity of ZnO films fabricated by rf magnetron sputtering under various O2/N2 ratios.
O2/N2(SCCM/SCCM) Conduction type
Sample A 0/0 n 2.5  1018
Sample B 7.5/0 n 8.9  1014
Sample C 7.5/7.5 p 6.8  1014
Sample D 7.5/30 p 1.9  1018
885
exhibit n-type behavior, whereas Samples C and D show p-type
behavior. The dependence of conduction type on the gas-flow rate
of O2/N2 was found. As the nitrogen flow rate increases, the
concentration of active acceptors exceeds the donor concentration,
so the conduction type changes from n to p type. A proof for this
will be given later. In addition, synthesis of p-type N-doped ZnO
(Sample D) was repeated, suggesting that p-type ZnO can be
fabricated with excellent reproducibility by rf magnetron sputter-
ing a ZnO target doped with nitrogen.
Fig. 1 shows the Raman spectra of Samples A–D under 532 nm
semiconductor laser excitation, respectively. An E2high mode at
439 cm  1 is found for all samples [25,26]. Raman scattering is an
effective technique to investigate the structure and defects.
Appearance of a mode at 570 cm  1 in the Raman spectra of
Samples C and D clearly corresponds to the formation of lattice
disorder after incorporation of nitrogen in the ZnO lattice [27,28].
The Raman spectra of Samples C and D also show the appearance
of the peak at 510 cm  1, which is characteristic of N-doped ZnO
[26–28]. It is found the increased nitrogen flow ratio may lead to
transformation from n to p type. Gai et al. suggested that the
formation energy of NO will decrease if the chemical potential of N
increases or if the chemical potential of O decreases [29]. The
chemical potential of N may be controlled by varying N concen-
tration during sputtering [30]. High N concentration implies
higher chemical potential of N [30], which can explain why an
increase in the nitrogen flow rate may lead to transformation from
n to p type. On the other hand, the formation enthalpy of the
donor VO decreases with decreasing the chemical potential of O
[31], causing the increased probability of having formed VO. The VO
concentration increases at high nitrogen flow ratio in the sputter-
ing gas mixture during film deposition, the probability of having
formed NO increases (that is, N þVO-NO). Minegishi et al.
reported p-type conduction in ZnO films deposited in an excess
of Zn in N ambient due to the possibility of formation of N–Zn–N
complexes [32]. These lead us to believe that p-type conversion
Fig. 1. Raman spectrum of N-doped ZnO films fabricated by rf magnetron
sputtering under various O2/N2 ratios.
Carrier concentration(cm  3) Mobility(cm2 V  1 s  1) Resistivity(Ω cm)
3.6 0.7
4.0 1755.6
3.1 2964.9
2.8 1.2
886 W.-M. Cho et al. / Journal of Luminescence 145 (2014) 884–887

Fig. 2. (a) XRD patterns of N-doped ZnO films fabricated by rf magnetron sputtering under various O2/N2 ratios. (b) XRD pattern of the (0 0 2) peak, showing shifting of the
center of diffraction.

of ZnO may be due to a combined effect of the incorporation of

N into ZnO and the formation of NO. The incorporation of N into
ZnO may be controlled by varying the gas-flow ratio of O2/N2
during sputtering. This should provide an alternative method for
controlling conduction type of ZnO films grown by sputtering.
Fig. 2 shows the XRD data of Samples A–D, respectively. Only
one peak corresponding to (0 0 2) plane was observed for all the
samples and no diffraction from other phases, suggesting the good
crystallinity with a high preferential c-axis orientation. The XRD
peaks can be assigned to the zinc oxide hexagonal wurzite phase.
In comparison with Sample A, the (0 0 2) peak for Sample B is not
found to shift towards lower 2θ values. However, in comparison
with Sample A, the (0 0 2) peak for Sample C (or Sample D) is
found to shift towards lower 2θ values, implying an increased
lattice parameter due to nitrogen doping. This is in accordance
with a previous report [33]. The peak shift toward lower 2θ may be
attributed to the change in stress in the films. The NO formation
may lead to a change in lattice constant, resulting in the formation
the compressive stress in the films. It is understandable that the
ionic radius of N3  is larger than that of O2  [34]. On the other Fig. 3. PL spectra of N-doped ZnO films fabricated by rf magnetron sputtering
hand, Samples C and D show p-type behavior and Samples A and B under various O2/N2 ratios.
show n-type behavior. This could be explained by the number of
holes produced by ionized NO.
Because undoped ZnO is n-type, compensation between p-type acceptor-related (VO-related) emissions. A general conclusion is
dopant centers and n-type defects is also an important concern in that a number of point defects can act as compensating donors on
producing p-type doped ZnO. To confirm the presence of defects in the p-type side. Thus in the increased nitrogen flow ratio, VO
the rf sputtered N-doped ZnO film, PL spectra were gained from defect is suppressed (more NO are formed) and the background
Samples A–D. The PL spectra of the broadband emission were electron concentration caused by this defect is insufficient to
recorded in the energy range of 1.8–3.5 eV. Fig. 3 shows the PL compensate for positive holes from acceptors (NO, Oi and VZn),
spectra of Samples A–D, respectively. PL spectroscopy is a sensitive producing p-type ZnO. The total density of states of undoped and
and powerful tool for characterizing electrically active impurities N-doped ZnO crystals is shown in Fig. 1 of Ref. [11], respectively.
and defects. As can be seen in Fig. 3, the PL spectra show four In addition, Chen et al. presented the theory of N doping in
broad peaks centered at
3.3 eV (referred to as band E),
3.0 eV ZnO based on the first-principles calculations, discussing the total
(referred to as band F),
2.5 eV (referred to as band G) and at density of state and electronic structure of defects and impurities

2.2 eV (referred to as band H), respectively. We tentatively and their influence on the electrical conductivity of ZnO [39]. It is
assign band E to the band-edge luminescence, band G to a VO- shown that a hole band is generated at the top of the valence
related emission and band H to the Oi-related emission [5,35–37]. band for N-doped ZnO samples [11,39]. As a result, the increased
Du et al. suggested that band F might originate from VZn for p-type acceptor density in the N-doped ZnO film may lead to an increase
N-doped ZnO samples [38]. In addition, Gai et al. suggested that in the hole concentration, thus resulting in transformation from n
the NO is located at 0.42 eV above the valence band edge [29]. to p type. In summary we have presented systematic trends
Thus, band F is also attributed to the NO-related emission. Transi- showing that N is incorporated into ZnO and hence leads to hole
tion of the 3-eV PL may be from the conduction band edge to conductivity in ZnO. Compensation of residual donors and p-type
the deep acceptor level (NO). It is found the increased nitrogen conversion have been observed when nitrogen was introduced
flow ratio may lead to the enhanced (reduced) intensity of the during sputtering growth at low gas-flow ratio of O2/N2.
 W.-M. Cho et al. / Journal of Luminescence 145 (2014) 884–887 887

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