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Chin. Sci. Bull. (2014) 59(12):1235–1250
DOI 10.1007/s11434-014-0154-4
Review
Research progress in ZnO single-crystal: growth, scientific
understanding, and device applications
Feng Huang • Zhang Lin • Wenwen Lin • Jiye Zhang • Kai Ding •
Yonghao Wang • Qinghong Zheng • Zhibing Zhan • Fengbo Yan •
Dagui Chen • Peiwen Lv • Xian Wang
Received: 21 December 2012 / Accepted: 26 February 2013 / Published online: 22 February 2014
Ó Science China Press and Springer-Verlag Berlin Heidelberg 2014
Abstract Zinc oxide, a wide band-gap semiconductor, has
shown extensive potential applications in high-efficiency
semiconductor photoelectronic devices, semiconductor
photocatalysis, and diluted magnetic semiconductors. Due to
the undisputed lattice integrity, ZnO single crystals are
essential for the fabrication of high-quality ZnO-based
photoelectronic devices, and also believed to be ideal
research subjects for understanding the underlying mecha-
nisms of semiconductor photocatalysis and diluted magnetic
semiconductors. This review, which is organized in two
main parts, introduces the recent progress in growth, basic
characterization, and device development of ZnO single
crystals, and some related works in our group. The first part
begins from the growth of ZnO single crystal, and summa-
rizes the fundamental and applied investigations based on
ZnO single crystals. These works are composed of the fab-
rication of homoepitaxial ZnO-based photoelectronic devi-
ces, the research on the photocatalysis mechanism, and dilute
magnetic mechanism. The second part describes the fabri-
cation of highly thermostable n-type ZnO with high mobility
and high electron concentration through intentional doping.
SPECIAL TOPIC: Wide Bandgap Semiconductor Materials and
Devices
F. Huang (&)
W. Lin
J. Zhang
K. Ding
Y. Wang

Q. Zheng
Z. Zhan
F. Yan
D. Chen
P. Lv
X. Wang
Key Laboratory of Optoelectronic Materials Chemistry and
Physics, Fujian Institute of Research on the Structure of Matter
(FJIRSM), Chinese Academy of Sciences, Fuzhou 350002,
China
e-mail: fhuang@fjirsm.ac.cn
Z. Lin
State Key Laboratory of Structural Chemistry, Fujian Institute of
Research on the Structure of Matter (FJIRSM), Chinese
Academy of Sciences, Fuzhou 350002, China
csb.scichina.com
www.springer.com/scp
Semiconductor Technology
More importantly, in this part, a conceptual approach for
fabricating highly thermostable p-type ZnO materials with
high mobility through an integrated three-step treatment is
proposed on the basis of the preliminary research.
Keywords ZnO
ZnO single crystal
ZnO-based
photoelectronic devices
Photocatalysis
Diluted
magnetic semiconductor
1 Introduction
Zinc oxide (ZnO) is believed to be an excellent candidate
for UV optoelectronics including light emitting diodes
(LEDs), laser diodes, and UV photodetectors due to its
direct wide-bandgap (3.4 eV) and large free exciton bind-
ing energy (60 meV) [1–5]. In the past decades, enormous
efforts have been dedicated to fabrication of high-perfor-
mance optoelectronic devices. An exciting progress is that
the room temperature ZnO-based LED has been fabricated
by Tsukazaki et al. [6]. However, due to the lack of high-
quality ZnO substrates, most of the existing devices are
usually based on heteroepitaxial ZnO films which are
deposited on foreign substrates, such as Al2O3 or Si. The
lattice mismatch and the out-diffusion of ions from foreign
substrates [7, 8] always results in poor crystallinity and
thus poor luminous performance. It is believed that high-
quality ZnO films can be homoepitaxially grown on ZnO
single-crystal substrates with high lattice integrity. More-
over, the heat mismatching between the films and sub-
strates can also be avoided. Thus, the performance of
photoelectronic devices will be largely enhanced.
It deserved to be mentioned that the applications of ZnO
single crystal are not just limited to semiconductor photo-
electronic devices. Due to its high lattice integrity and the
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1236
feasibility to obtain desired crystal facets, ZnO single
crystal is regarded as an ideal research subject for clari-
fying some scientific concerns still unsettled and under
dispute, particularly for some key mechanisms in semi-
conductor photocatalysis and magnetic interactions in
dilute magnetic semiconductors. In summary, ZnO single
crystal has important application and research value in the
fields of ZnO-based photoelectronic devices, photocataly-
sis, and diluted magnetic semiconductors.
The growth, structure analysis, property measurements,
and applications of ZnO materials have already been covered
by several review articles [1]. In this review, we mainly
introduce the systematic work on ZnO single crystal in our
group and the recently related progress, including growth,
application in homoepitaxially fabricated photoelectronic
devices and the underlying mechanism in photocatalysis and
diluted magnetic semiconductor based on ZnO single crystal.
2 Growth and applications of ZnO single crystals
2.1 Growth of ZnO single crystals
The melting point of ZnO is very high (1,975 °C), and it
will decompose and sublimate at temperature higher than
1,300 °C. Thus, it is difficult to obtain large-sized ZnO
single crystals using traditional melt growth processes at
atmospheric pressure. Upto now four methods have been
used to grow bulk ZnO single crystals, including pressure-
melt, chemical vapor transport (CVT), molten salt method,
and the hydrothermal technique.
2.1.1 Pressure-melt method
In 2005, researchers at Cermet Inc. (Atlanta, GA) have grown
2-inch ZnO single crystals (Fig. 1) using a patented method
involving a high-pressure O2 induction melting device [9–11].
Fig. 1 (Color online) Large-sized ZnO single crystals grown by
pressure-melt method. The growth rate of the pressure-melt method is
very high (about 1–5 mm h-1). Reprinted from [11]. Copyright 2005,
IOP Publishing Ltd
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Chin. Sci. Bull. (2014) 59(12):1235–1250
The etch pit density on the (002) plane is about *104 cm-2,
and the FWHM of the X-ray rocking curves for (002) reflec-
tions is 49 arcsec. The electron concentration of these crystals
is about 5 9 1017 cm3 with the Hall mobility of
131 cm2 V-1 s-1 at room temperature. However, this method
involves a high-pressure O2 atmosphere and a high-growth
temperature, which leads to a complex and costly growth
device (the crucible must be made by noble metals with high
melting point, such as Iridium, etc.).
2.1.2 Chemical vapor transport (CVT) method
Chemical vapor transport (CVT) method is also adopted to
grow ZnO crystals with the transport media of Zn, ZnCl2,
HCl, Cl2, NH3, NH4Cl, etc. The reaction temperature of the
source region is ranging from 800 to 1,150 °C [12–16].
Eagle Picher company [17] has obtained 2-inch ZnO bulk
single crystals using the CVT method. The etch pit density
is 104 cm-2, and the FWHM of the X-ray rocking curve for
(002) face is 40 arcsec. The carrier concentration and
mobility at room temperature are 8 9 1016 cm-3 and
150–250 cm2 V-1 s-1, respectively.
In China, Zhao’s group [18] improved the technique of
CVT growth of ZnO single crystal. By using the carbon
assisted growth technology, 4 9 10 mm ZnO single crystal
could be obtained through spontaneous nucleation. When
the GaN film deposited on sapphire single crystal was used
as the substrate, yellow ZnO crystal (30 mm in diameter,
2 mm in thickness) could be obtained (see Fig. 2). The
electron concentration and mobility at room temperature are
1017–1018 cm-3 and 97–130 cm2 V-1 s-1, respectively.
2.1.3 Molten salt method
It has been reported that PbF2, Zn3P2O8
4H2O, V2O5,
MoO3, B2O3, and the mixture of these compounds [19–23]
Fig. 2 (Color online) ZnO wafers grown by Zhao’s group [18] from
the Institute of Semiconductors, Chinese Academy of Sciences
Chin. Sci. Bull. (2014) 59(12):1235–1250
Table 1 ZnO crystals grown from non-aqueous solutions
Results
-1
Solvent T (°C) Cooling rate (K h ) Crucible
PbF2 1,000 5.4 Pt
Zn3P2O8 ? V2O5 980–1,330 1 Pt
V2O5 ? B2O3 1,150 2–5 Pt
PbF2 800–1,150 1–10 Pt
V2O5 900–1,300 1.2 Pt
could be used to grow ZnO crystal. The growth details are
shown in Table 1.
At present, high-quality ZnO single crystals can hardly
to be obtained by molten salt method. The as-grown
crystals always show a heavy green color caused by the
large amount of impurities. It is difficult to find suitable
fluxes that could effectively inhibit the introduction of the
impurities and thus improve the crystallinity. On the other
hand, whether by molten salt method or pressured melt
method, high-concentration thermal defects are inevitable
due to the high-growth temperature. Thus, these two
methods are not suitable for the large-scale growth of the
ZnO crystal with low impurity concentration and high
crystallinity.
2.1.4 Hydrothermal growth method
The hydrothermal growth is a method in which a high-
pressure water-mineralizer environment is created in order
to increase the solubility of the raw material and thus lower
the growth temperature. Compared with the pressure-melt
method and molten salt method, hydrothermal growth has
two unique advantages: (1) a low growth temperature
(300–450 °C), which can lower the intrinsic thermal defect
concentration; (2) a near-thermodynamic-equilibrium
growth condition, which results in a high lattice integrity.
Based on these two advantages, hydrothermal method is
considered as the most promising method for growing
high-quality ZnO single crystals. It is worth noting that the
industrial facilities for hydrothermal growth of ZnO are
readily accessible considering the mature massive pro-
duction of quartz crystals.1
In order to increase the solubility of ZnO, mineralizers
must be employed. The conventional mineralizers are
LiOH, NaOH, KOH, and LiCO3 [24, 25]. Generally, the
1
Up to now, industrialized hydrothermal growth of quartz crystal has
been achieved. The output of the quartz by hydrothermal method has
surpassed 1,850 tons in 2004. The technique and craft of the
hydrothermal growth have been maturely developed, which means
that industrial production of ZnO? single crystal might be realized via
this method.
1237
References
Crystal size
5 mm 9 5 mm 9 3 mm [20]
Platelets, 20 mm cross [22]
10 mm 9 5 mm 9 2 mm [23]
1–5 cm Long in \11–20[ direction [19]
Pale green, clear crystals about 8 mm across [21]
mixture of KOH and LiOH are thought as good hydro-
thermal mineralizer. If pure KOH is used, the growth will
be too fast, and thus it is not easy to control the growth
speed. When LiOH is added, the growth slows down and
the crystal quality is improved. It was first reported in
1960s by Kolb and Laudise groups [26–28] that large ZnO
single crystal could be obtained using the mixture of KOH
and LiOH as the mineralizer. In 2005, Ehrentraut et al.
have obtained ZnO single crystal of 3 inches in diameter by
improving this method, using a 200 mm diameter and
3,000 mm long autoclave. It is by far the largest crystal
produced by hydrothermal method, as shown in Fig. 3. The
FWHM of the double-crystal rocking curve for (002) face
is 8 arcsec. In Russia, it was reported that 76 mm crystal
was produced [29]. The Zhang’s group [30] has obtained 1
inch ZnO crystal using Russian method. The FWHM of the
double-crystal rocking curve for (002) face of their crystal
is 45 arcsec.
However, the conventional hydrothermal method has a
fatal flaw that due to the strong basicity of the mineralizer,
noble metals have to be used for liner materials, resulting
in significant increase in equipment cost. Therefore,
developing new mild mineralizers has become an urgent
demand before realizing the industrial hydrothermal
growth.
In order to solve the above-mentioned bottleneck
problem of the conventional hydrothermal growth method,
our group has developed a series of mild mineralizers and a
non-noble metal liner. The mineralizers can also allow a
lower growth temperature and pressure in which the low-
cost liners can be employed. Autoclaves with the largest
diameter of 90 mm have been developed to achieve 3-inch
ZnO single crystal with high-output efficiency (Fig. 4a). In
2010, a nearly 2-inch ZnO single crystal has been obtained
(see Fig. 4b, c).
The crystallinity and electrical properties of our ZnO
single crystals (FJIRSM crystals) was further investigated
[31]. As shown in Fig. 5a, the FWHM of the X-ray rocking
curves for (002) reflection is 18 arcsec. The carrier concen-
tration of the as-grown crystal is about 4.2 9 1016 cm-3.
The carrier mobility is upto 236 cm2 V-1 s-1 at room tem-
perature, which is very close to the intrinsic value (about
123
1238
Fig. 3 (Color online) Three-inch-sized ZnO single crystal grown by
Japanese researchers. Reprinted from [24]. Copyright 2006, Elsevier
Ltd
Fig. 4 (Color online) a The largest autoclave with 90 mm in
diameter; b ZnO single crystals grown in the autoclave with 90 mm
in diameter per growth circle; c 2-inch ZnO single crystal
300 cm2 V-1 s-1), and reaches a maximum value of
1,360 cm2 V-1 s-1 at 79 K. The yellow–green emission
band in the low-temperature PL spectra of FJIRSM crystals
is absent, compared to the TEW (Tokyo Denpa Co., Japan)
crystals (Fig. 5b). The above results indicate that FJIRSM
crystals possess a high crystallinity and a low native defect
concentration. Thus, the improved hydrothermal growth
method has the potential of industrial application.
2.2 Homoepitaxial ZnO-based photoelectronic devices
2.2.1 Homoepitaxial ZnO-based photodetectors
Compared with traditional semiconductor photodetector,
the GaN and ZnO-based ultraviolet (UV) photodetectors
have much shorter cutoff wavelength and can work at
higher temperature condition [32, 33]. UV photodetectors
have been used in many applications such as solar UV
123
Chin. Sci. Bull. (2014) 59(12):1235–1250
Fig. 5 a X-ray rocking curve for (002) reflection of FJIRSM single
crystals; b PL spectra of FJIRSM and TEW ZnO single crystal at
10 K temperature
radiation monitoring, ultra-high temperature flame detec-
tion, and air-borne missile warning systems [34, 35]. Solar-
blind UV photodetectors (SBPD) operating in the spectrum
region of 220–280 nm are perfectly suitable for detecting
of UV signal due to the low background radiation [36–38].
ZnO-based and GaN-based materials were used to be
adopted for applications in solar-blind photodetector.
However, further development of GaN-based photodetec-
tors is hindered by the large lattice mismatch between the
thin film and sapphire substrate. ZnO-based films are
promising material for fabricating UV photodetector, as
large-sized ZnO single-crystal substrate is available for
ZnO-based film growth. For fabricating MgxZn1-xO solar-
blind photodetector, Mg content should be at least 45 at.%.
However, many studies revealed that phase separation
occurs in the MgZnO film when Mg content is over
36 at.% [39, 40]. Recently, by adopting lattice matched
ZnO substrate, Endo et al. [41] obtained high-quality sin-
gle-crystalline Mg0.59Zn0.41O films through magnetron
sputtering method. A Schottky diode-type SBPD was fab-
ricated based on the Mg0.59Zn0.41O/ZnO heterostructure
with a semitransparent 3-nm-thick Pt film. The photodiode
Chin. Sci. Bull. (2014) 59(12):1235–1250 1239

exhibits a maximum responsivity of 0.015 A/W at the

wavelength of 220 nm, as shown in Fig. 6.
Recently, we obtained a wurtzite single-crystalline
Mg0.49Zn0.51O film on ZnO substrates by low speed reac-
tive magnetron cosputtering method [42]. Each substrate
was fabricated from ZnO single crystal grown by the
hydrothermal growth method and annealed at 900 °C in O2
ambient to achieve a low background electron concentra-
tion. Due to the lattice match between MgZnO film and
ZnO substrate, the MgZnO/ZnO heterostructure with high
degree of crystallinity was grown by cost-effective mag-
netron sputtering system, as shown in Fig. 7a. XRD mea-
surement shown in Fig. 7b confirmed that the MgZnO film
grown on ZnO substrate is a single-crystalline wurtzite
structure.
The heterostructures of MgZnO/ZnO were fabricated
into metal–semiconductor–metal SBPD. The photodetector
exhibited good break down property and relative small
dark current which can be attributed to the high quality of
the MgZnO film grown on ZnO substrate. The SBPD with
a 2-lm thick MgZnO epilayer shows a peak responsivity of
304 mA/W at 260 nm under 10 V bias, which is compa-
rable to the highest value ever reported in MgZnO-based
SBPDs, as shown in the Fig. 8. In addition, the responsivity
increases linearly with the increasing applied voltage,
indicating a photoconductive gain mechanism in the MSM
structure MgZnO photodetector.

2.2.2 Homoepitaxial ZnO-based light-emitting devices

Although it is generally thought that excellent film quality
and device performance would be obtained based on
Fig. 7 (Color online) a Cross-sectional SEM image of MgZnO/ZnO
heterostructure, and the inset shows that of the MgZnO grown on
quartz substrate, b XRD h-2h angular scan of MgZnO/ZnO
heterostructure. Reprinted from [42]. Copyright 2006, American
Institute of Physics

Fig. 6 (Color online) The spectral responsivity of the Pt/ Fig. 8 a Spectral response of the photodetectors with 2 and 0.5 lm
Mg0.59Zn0.41O Schottky photodiodes on the ZnO substrate. The inset thick MgZnO under 10 V bias, b maximum responsivity versus bias
shows the responsivity in logarithmic scale. Reprinted from [41]. voltage of the SBPD with 2 lm thick MgZnO. Reprinted from [42].
Copyright 2008, the Japan Society of Applied Physics Copyright 2006, American Institute of Physics

123
1240
homoepitaxy, reports on light-emitting devices based on
ZnO substrates are very rare yet. This can be attributed to
various factors, including crystalline quality of the sub-
strates, surface polishing technique, high cost of device-
grade substrates, etc. Nevertheless, promising future of
ZnO substrates in applications of optoelectronics can still
be expected from recent progress.
By using a laser-doping technique, a p-type ZnO layer
was prepared on an n-type ZnO substrate, and then a ho-
mojunction ZnO LED was fabricated by Aoki et al. [43]. A
zinc-phosphide compound, used as a phosphorous source,
was deposited on the ZnO wafer and subjected to excimer-
laser pulses. The current–voltage (I–V) characteristics
showed a diode characteristic between the phosphorous-
doped p-type ZnO and the n-type ZnO substrate. The
electroluminescence (EL) spectrum showed a band-edge
emission at 370–380 nm and a defect-band emission in the
region of 400–600 nm under forward current injection at
110 K.
Guo et al. [44] fabricated a transparent ZnO homo-
structural LED by depositing a relatively high resistivity
p(i)-ZnO layer on an n-ZnO single-crystal substrate using
the technique of N2O plasma-enhanced pulsed laser reac-
tive deposition. The contact between the p(i)-ZnO layer
and n-ZnO wafer was found to exhibit nonlinear and rec-
tifying I–V characteristics. A bluish white EL emission was
achieved under forward bias, and its intensity increased
with increases in the injection current.
Wang et al. [45] fabricated metal–insulator–semicon-
ductor structural diodes by N? ion implantation at mod-
erate doses into nominally undoped n-type single-crystal
ZnO substrates and post-annealing technique. The diodes
show visible luminescence at 300 K and band-edge EL at
120 K under forward bias conditions.
Typical rectifying I–V characteristics and room tem-
perature EL were demonstrated in ZnO homojunction
LEDs by Zeng et al. [46], in which a plasma-free metal-
organic chemical vapor deposition method was adopted to
grow N-doped p-type ZnO films.
Asahara et al. [47] fabricated a homostructural LED
comprising N-doped p-type ZnO film and n-type ZnO
substrate. The p-type layer was grown by plasma-enhanced
metal–organic chemical vapor deposition employing
microwave excited high-density plasma on single-crystal
ZnO substrates. It was reported that only when using
plasma and NO2, the nitrogen (N)-doped ZnO film with the
steps and terraces surface structure of two-dimensional
growth could be formed. EL in forward bias at room-
temperature and the I–V rectifying characteristics are
achieved in such homostructural LED.
Nakahara et al. [48] fabricated a MgZnO:N/ZnO het-
erostructural LED grown by MBE on ZnO substrate. NO-
plasma or NH3 gas was employed as N-source for p-type
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Chin. Sci. Bull. (2014) 59(12):1235–1250
doping. Ultraviolet near-band-edge emission (382 nm)
with an output power of 0.1 lW for a NO-plasma-doped
LED and 70 lW for a NH3-doped one at a bias current of
30 mA were presented.
Kato et al. [49] realized ZnO-based double-hetero-
structure ultraviolet LEDs on n-type Zn-polar ZnO sub-
strates by plasma-assisted MBE employing mixture gas
plasma of N2 and O2 as the N source. By using mixture gas
plasma of N2 with a little added O2, the number of N atoms
increased and N2 molecules decreased in the p-type
MgZnO layer. The fabricated LEDs had an ultraviolet near-
band-emission of around 380 nm. The integrated EL
intensity of the LED fabricated using (N2 ? O2) plasma
was more than 10 times higher than that of an LED fab-
ricated using N2 plasma. The output power of typical LED
using (N2 ? O2) plasma was estimated to be approxi-
mately 30 lW at the operation current of 20 mA.
2.3 Photocatalytic mechanism based on ZnO single
crystal
Among nanosized photocatalysis materials, ZnO with a
direct band gap of 3.37 eV has been widely used because
of its high quantum efficiency, thermal, and chemical sta-
bility as well as its nontoxicity [50–54]. Recently, the
dependence of photocatalytic activity on the crystal plane
has been concerned [55, 56]. However, these research
objects still focus on the material synthesis of micron level,
i.e., the different predominant plane was appeared by sta-
tistical distribution. Therefore, the final photoactivity is the
collective effect of different crystal plane in actual photo-
catalysis process. Then, the photoactivity of a single-
crystal plane cannot be investigated effectively.
The bulk single crystal, because of its well-defined
structure, is an excellent object to carry out the above
research despite its small surface area and thus low
photoactivity. At present, it is facile to obtain ZnO single
crystal compared to TiO2 single crystal. The band-gap
energy of ZnO is similar to TiO2, so it is possible to further
study the photocatalytic mechanism of semiconductor-
based photocatalytic materials using ZnO single crystals as
the objects. Recently, our group has carried out in-depth
research on the photocatalytic mechanism. Wang et al. [57]
adopted the bulk single crystal excluding the nanotoxicity
to study the single photocatalytic bactericidal action for the
first time. It was shown that Zn plane presented higher
photocatalytic activity than O plane during the photoca-
talysis process (Fig. 9). We consider that photo-induced
electrons and holes are apt to migrate to Zn plane and O
plane, respectively, due to the self-polarization field,
because ZnO is a kind of polar crystal. Therefore, it was
proposed that the photo-induced electrons may dominate
during the photocatalytic process of ZnO material.
Chin. Sci. Bull. (2014) 59(12):1235–1250 1241

Fig. 9 (Color online) Left: Images of bacterial colonies showing re-growth situations of surviving E. coli on agar plates after different irradiation
treatments. (UV wavelength: 365 nm; irradiation time: 1 h; incubation conditions: 33 °C for 24 h.) ‘‘No irradiation’’ means ‘‘no irradiation with
ZnO’’. Right: AFM images of E. coli under different treatments (scan size: 4.0 lm; UV wavelength: 365 nm; irradiation time: 1.0 h). Reprinted
from [57]. Copyright 2009, the Royal Society of Chemistry

Fig. 10 (Color online) The relationship between the IEF and the effective UV-light absorption layer (about 100 nm, from the surface to the
dotted line), when the thickness of the AZO TF is a 30, b 80, and c 120 nm. d SEM image of the cross section of AZO TF and ZnO SC wafer

In order to deeply investigate the influence of electric
field during the photocatalytic process, nonpolar plane
(m plane) was adopted to exclude the effect of self-polar-
ized electric field [58]. Then, the ZnO films doped with Al
were sputtered on the surface of ZnO single crystal by
magnetron sputtering. Thus, the artificial built-in electron
field was constructed owing to the different carrier con-
centrations for the ZnO single crystal and Al-doped ZnO
(AZO) films. Consequently, we can investigate the effect
of location and intensity of interface electric field on the
photocatalytic activity. As shown in Fig. 10, only when the
interface electric field lies completely in the light absorp-
tion layer, the photo-induced electrons and holes can be
separated effectively, i.e., the sputtered film must be con-
trolled in a certain thickness. Therefore, to manipulate the
interface electric field is an effective way to control the
charge separation process. Another feature of this system is
that the existence of the interface electron field can be
verified by the I–V curves, which is impossible for the
nanosized heterojunction.
2.4 Study on magnetic coupling mechanisms of DMSs
based on ZnO single crystals
The so-called diluted magnetic semiconductor is a kind of
semiconducting materials exhibiting ferromagnetism in
which the nonmagnetic cations were partially substituted
by 3d transition-metal cations [59]. Once the diluted
magnetic semiconductors come into practical use, the
obstacle of spin injection from metal to semiconductor
could be eventually overcome and the spintronic devices
would become possible [60]. Therefore, the investigation
of DMSs has become an important branch of material
science. However, behind the tremendous amount of
research works, the origin of ferromagnetism and magnetic
coupling mechanism in DMSs is still one of the most

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1242
attractive and controversial issues in the field of condensed
matter physics and material science [61]. The existing
theoretical and experimental research generally tend to
support two kinds of coupling mechanisms: the carrier-
mediated mechanism [62–65] and the defect-mediated
mechanism [66, 67]. Initially, the proposed theoretical
models (including the celebrated mean-field Zener model)
mostly related to the former one, i.e., the long-range
alignment of local spins was established by their exchange
interaction with conduction carriers in the semiconductor
matrices. Yet at the same time, this mechanism encoun-
tered lots of contradictory experimental results. With the
progress of research, there is growing evidence that mag-
netic coupling mechanism in semiconductors should be
concerned with defects. Coey et al. [66] proposed a rep-
resentative model that the ferromagnetism in DMS was
mediated by defects via the formation of bound magnetic
polaron.
Up to now, ZnO has become the most studied matrix
material of DMSs, which is predicted to be the most likely
candidate to achieve room-temperature ferromagnetism.
Thousands of works devoted to the transition-metal-doped
ZnO DMSs were published. However, most of these works
were based on thin films. Due to the intrinsic drawbacks of
thin films, these results lacked reproducibility and stability
to a large extent. Compared with thin films, bulk single
crystals grown by hydrothermal method possess defined
structures and uniform compositions should be ideal study
objects for physical mechanism of DMSs. At the same
time, single crystals are also beneficial to investigations on
the anisotropic properties of the DMSs. Recently some
research groups have carried out the study of DMSs based
on single crystals. In 2005, Shi’s group [68] obtained 1-mm
Mn-doped ZnO single crystals using high-pressure
Fig. 11 SEM image of Zn0.95Co0.05O single crystal and the AES elemental homogeneity mapping for Co, Zn, and O elements on the selected
area. Reprinted from [69]. Copyright 2006, American Institute of Physics
123
Chin. Sci. Bull. (2014) 59(12):1235–1250
hydrothermal technique. Magnetic measurements and
UV–Vis absorption spectra reveal that there exist short-
ranged interactions between the d electrons of Mn and the s
and p electrons of the host material. In ZnO matrix, the
exchange interactions between Mn2? ions are mainly
antiferromagnetic.
Our group [69] successfully grew Co-doped ZnO single
crystals with Co concentration upto 5 % using a low-
temperature hydrothermal method in 2006. The SEM
image of a Co-doped ZnO single crystal and the auger
electron spectroscopy mapping of a selected area are
shown in Fig. 11. It can be seen in Fig. 11 that the size of
the single crystal is approximately 0.4 mm 9 0.8 mm, and
Co element is uniformly distributed in the ZnO matrix.
UV–Vis absorption spectra and X-ray absorption fine
structure further confirmed that Co substitute Zn in the host
lattice.
According to magnetic measurements, we found that
Zn0.95Co0.05O single crystals only exhibit paramagnetism
at a temperature as low as 2 K. As shown in Fig. 12a,
according to the inverse susceptibility versus temperature
curve, the Crie-Weiss temperatures of the sample are close
to 0 K for both \c and ||c directions. Surprisingly, the
paramagnetism of the Co-doped ZnO single crystal
exhibits an apparent anisotropic behavior. This phenome-
non suggests that when Co2? ions occupy the tetrahedral
site of ZnO, its 4A2 ground state possesses a huge single
ion anisotropy of DS2z type. Under the tetrahedral crystal
field, the magnetic moment of Co2? prefers to lie in the ab
plane.
Our result provides a reliable evidence for Coey’s the-
ory. The electrical measurements showed that the defect
concentration of Zn0.95Co0.05O single crystal is lower than
10-4 cm-3. According to Coey’s theory, despite the high
Chin. Sci. Bull. (2014) 59(12):1235–1250
Fig. 12 a Inverse magnetization versus temperature curve of
Zn0.95Co0.05O single crystal with the magnetic field applied parallel
and perpendicular to the c axis of the crystal. b and c Magnetization
versus field plots measured at 2 and 300 K with the magnetic field
applied parallel and perpendicular to the c axis. Reprinted from [69].
Copyright 2006, American Institute of Physics
carrier concentration of the Zn0.95Co0.05O single crystal,
even if there exist ferromagnetic coupling between Co2?
ions, its Curie temperature is lower than 1.65 K. Therefore,
for a certain magnetic cation concentration, improving the
point defect concentration in the single crystal is essential
for achieving room temperature ferromagnetism. In future
studies, through manipulating the type and concentration of
point defects intentionally via doping, high-pressure
atmosphere annealing, or irradiation methods, and intrinsic
ferromagnetism could possibly be achieved in transition-
metal-doped ZnO single crystals.
3 Fabrication of thermostable n and p-type ZnO
material
In order to develop ZnO-based optoelectronic devices, both
thermostable n-type and p-type ZnO with high mobility
1243
and high carrier concentration are indispensable. The
n-type doping of ZnO material is easy to achieve, while the
p-type doping is rather difficult. Such a phenomenon is not
a surprising issue in GaN material and some II–VI com-
pound semiconductors such as ZnS and ZnSe [70–75]. The
following content comprises the fabrication of thermosta-
ble n-type and p-type ZnO with high mobility and high
carrier concentration.
3.1 Fabrication of thermostable n-type ZnO material
with high mobility and high carrier concentration
ZnO material is a naturally n-type semiconductor due to the
presence of intrinsic defects. It is believed that the intrinsic
n-type conductivity can be attributed to oxygen vacancies
and interstitial Zn. However, such a statement is still lack of
experimental confirmation. The first-principle study sug-
gested that none of these two kinds of native defect exhibited
the characteristic of high-concentration shallow donor [76].
On the contrary, DC Look suggested that Zni rather than Vo is
the dominate shallow native defects with shallow ionization
energy of 30–50 meV. Some researchers also suggested that
the naturally n-type conductivity of ZnO films can be only
attributed to hydrogen (H), which is believed to be a shallow
donor with an ionization energy of 30 meV [76–79]. This
suggestion is reasonable since H is always present in large
amounts due to its large mobility and small ion radius.
Theoretical calculations also suggested that the uninten-
tional doped H acts as a source of n-type conductivity and
behaves as a shallow donor in ZnO lattice [80].
The n-type doping of ZnO is much easier than p-type
doping of ZnO. It is generally believed that when a group
IIIA element occupies Zn sites, it can act as a shallow energy
level donor in ZnO, and thus high-density free electrons can
be generated in the transparent conducting oxides [81, 82].
Among these elements, Ga and Al are regarded as the best
dopants for obtaining high-quality ZnO materials owing to
their similar atomic radius to Zn. Myong et al. obtained
ZnO:Al films with a resistivity of 6.2 9 10-4 X cm [83]
using MOCVD method. American photovoltaic national
center found that ZnO:Ga transparent conducting electrode
(TCE) for organic LED exhibited the advantages of low
volume resistivity and more transparency in visible region,
compared with conventional In-doped SnO2. Therefore,
ZnO:Al and ZnO:Ga materials are regarded as excellent
candidates for developing high-performance TCE material
and n-type LED layer with high injection efficiency.
Currently, although the fabrication of ZnO:Al and
ZnO:Ga materials made great strides, current reports reveal
that the films prepared so far are normally with poor
thermostability, low carrier mobility, and a high concen-
tration of Ga/Al related unstable occupied states [84–88].
This is quite reasonable since the films are commonly
123
1244
fabricated via non-thermodynamic-equilibrium methods,
which could lead to the incorporation of doped atoms into
the interstitial sites of ZnO or existing as a second phase.
In summary, the main bottleneck restricting the fabri-
cation of highly n-type ZnO material is how to achieve the
goal of high thermostability and high mobility. To resolve
this problem, the strategies for fabricating highly thermo-
stable ZnO:Ga and ZnO:Al with high mobility are pro-
posed by our research group [89, 90], on the basis of the
overall understanding on thermodynamic and kinetic con-
ditions of growth and subsequent heat treatment.
3.1.1 Fabrication of highly thermostable ZnO:Al film
with high mobility
As mentioned above, ideal AZO thin films should process
high carrier mobility and carrier concentration, as well as
high thermostability. To achieve these properties, ZnO
should be heavily doped with Al and perfectly crystallized.
Currently, researchers are trying to fulfill such require-
ments by controlling a single-thermodynamic parameter,
such as the oxygen partial pressure [91]. However,
regardless of the preparation methods, low resistivity, and
high thermostability can not be simultaneously achieved
only through adjusting the oxygen partial pressure. Such a
phenomenon could be demonstrated on the basis of two
extreme thermodynamic conditions: (1) Under an O-defi-
cient atmosphere, the doped Al may be introduced as Al0.
The typical structures of such films are illustrated in
Scheme 1 (Color online) Local lattice structure, valence states, and
energy band diagram of the AZO thin films prepared under extremely
low oxygen partial pressure. a–d Al0 enters in the interstitial site of
the ZnO with a complete lattice, which forms an unstable shallow
energy level. Each interstitial Al could excite a valence electron into
the conduction band easily at room temperature
123
Chin. Sci. Bull. (2014) 59(12):1235–1250
Scheme 2 (Color online) Possible valence states of Al under
different oxidizing atmospheres during the MS process
Scheme 1. When Zn and O atoms formed a perfect lattice,
Al can only enter an interstitial position (Scheme 2) [92]. It
is generally acknowledged that interstitial Al is a shallow
donor, which can easily generate free electron into the
conduction band and results in high carrier concentration
[93, 94]. However, the interstitial Al is thermally unstable,
which may escape out of the lattice, resulting in poor
thermostability [94, 95]. (2) When the oxygen partial
pressure is high enough, the doped Al can only exist as
Al3? in the flame of spitting [92, 96] (Scheme 2).
Scheme 3 shows the typical lattice structure, the valence
states of the elements, and the energy band diagram of the
AZO film under these conditions. To satisfy the charge-
neutrality principle, two Al3? will substitute for three
Zn2?. Thus, Zn vacancy is inevitable and AZO films grown
Scheme 3 (Color online) Local lattice structure, valence states, and
energy band diagram of the typical AZO thin film prepared under an
oxidizing atmosphere. Two of three valence electrons of every Al are
involved in the chemical bond with its near oxygen atoms, and the
rest are captured by the near zinc vacancy at rather low temperature.
Thus, in the structure (ZnO)1-y[(AlZn)2(VZn)O3]y/3, all the electrons
excited from donors (substituted Al) will be captured by acceptors
(Zn vacancies), which results in the so-called compensated semicon-
ductors. So, no electron can be excited into the conduction band at
room temperature
Chin. Sci. Bull. (2014) 59(12):1235–1250 1245

under these conditions are of semi-insulating conductivity,

due to the strong self-compensation effect of Zn vacancies.
Therefore, in either case, it is rather difficult to simulta-
neously achieve high thermostability and low resistivity.
To sum up, the achievement of high thermostable AZO
with high mobility is rather difficult to be fabricated by
adjusting a single-thermodynamic growth condition during
the gas-phase deposition process.
Here in, based on the above understanding, we propose a
Scheme 5 (Color online) The possible carrier-forming mechanism in
strategy to obtain an AZO film with ideal characteristics under ZnO:Ga single crystal (On the basis of the above speculation on
two different thermodynamic conditions (see Scheme 4). carrier-forming mechanism, the carrier concentration should be half
First, a heavily doped AZO film with high-concentration zinc of Ga concentration)
vacancy is prepared under an oxidizing atmosphere. Then, a
zinc-vapor annealing treatment is employed to improve the
crystallinity and conductivity of the film by filling the zinc
vacancies with zinc atoms, based on the fact that Zn has a low
vapor pressure and low ion radius. The prepared AZO films
possess the highest mobility (36.8 cm2 V-1 s-1) ever repor-
ted. Moreover, the films also show remarkable stability in
carrier concentration, mobility, and resistivity under damp
heat treatment (85 °C) over months.

3.1.2 Growth of highly thermostable ZnO:Ga (GZO) single

crystal with high mobility

An alternative approach for obtaining thermostable highly
n-type ZnO can be expected in hydrothermal growth con-
dition. As we know, Ga dopant will exist as Ga3? ion in the
mineralizer solution. In order to satisfy charge-neutrality
principle, each two Ga ions will introduce one Zn vacancy
which is believed to be compensating centers for electron
(Scheme 5). However, in the hydrothermal solution, H is
so highly excessive that a small part of H will exist in
atomic state, then diffuses into the lattice, and finally take
place of Zn vacancies which is of poor thermostability.
Therefore, high-concentration electron will be generated by
the shallow donor HZn. Moreover, HZn is suggested to be
thermostable by DC Look. Thus, a high electron concen-
tration and thermostability can be simultaneously achieved
through this approach. As expected, the as-grown GZO
Fig. 13 (Color online) The ZnO:Ga wafer grown by hydrothermal
method
crystal (Fig. 13) exhibits a highly n-type conductivity (the
carrier concentration is 1.07 9 1019 cm-3) with high
mobility. Simultaneously, high thermal-stability is indi-
cated by the little variation of these two parameters after
being annealed at 1,100 °C for 24 h.
In order to further confirm the carrier-forming mecha-
nism proposed above, the activity efficiency of Ga dopant
is determined. Hall data and impurity analysis reveal that
the activity efficiency is nearly 50 %, which is in good
agreement with the theoretical value of the proposed
mechanism.
This work suggests that the H impurity should be paid
more attention to when trying to fabricate p-type ZnO,
since H could stably substitute for Zn vacancies, and then
generate background electron.

3.2 Fabrication of highly thermostable p-type ZnO

material with high mobility via three-step
treatments under different thermodynamic
and kinetic conditions

3.2.1 Beneficial efforts devoted to achieving p-type ZnO

Scheme 4 (Color online) The strategy for fabricating highly ther-

Currently, the main bottleneck restricting the development
mostable ZnO:Al film with high carrier concentration and high
mobility of ZnO-based photoelectronic devices is to achieve p-type

123
1246
ZnO material with all the characteristics of high thermo-
stability, high mobility, and high hole concentration. In
order to achieve high hole concentration, not only the
generation of shallow acceptors but also the self-compen-
sation effect originating from high-concentration back-
ground electrons should be taken into account. Many
researchers have contributed lots of helpful investigations
on the means of how to achieve high-concentration and
high activation efficiency of doped acceptors. To sum up,
their research ideas can be divided into four types: (1) Try
to substitute Zn ions with IA group elements such as Li and
Na; (2) try to substitute O ions with VA group elements
such as N and P; (3) co-doping, in order to stable the
formation of acceptor dopant via co-doping a second
dopant; (4) try to introduce highly active groups with
strong electronegativity during growing process, such as
interstitial F and SbZn-2VZn complex.
In the early work, most of the efforts are paid to single
doping with Li impurity belonging to IA group or N
impurity belonging to VA group. However, researchers
soon realized that single doping could hardly achieve
p-type with high thermostability. Most of works reveal that
Li doping usually lead to the coexistence state of substi-
tutional LiZn and interstitial Lii under the common ther-
modynamic conditions. Although substitutional LiZn is
regarded as an ideal shallow acceptor [97], the introduction
of equivalent amounts of interstitial Lii will eventually
compensate such a hole-generation mechanism. As for N
doping, it is found that the Zn–N bonding energy is rather
weak. Thereby, the high-concentration doping is hard to be
achieved in the present thermodynamic and kinetic con-
ditions, and meanwhile thermostability is also hard to be
achieved [98]. Afterward, researchers promptly change the
main ideas from single doping to co-doping, e.g., try to
stabilize as-generated acceptors via the introduction of a
second dopant, which can strongly bond with the targeted
dopants belonging to the IA group or VA group. For
example, the research group from Changchun Institute of
Optics, Fine Mechanics and Physics [99] reported ther-
mostable p-type ZnO:Li–N films with Li up to 6.01 % in
concentration. Such a result has been repeated in the work
of India’s Institutes of Technology (hole concentration
reaches as high as 8.2 9 1017 cm-3) [100]. Ye’s group
from Zhejiang University [101] also reported that co-dop-
ing with Mg could increase the solid solubility of Na in
ZnO, and thus p-type ZnO with a hole concentration of
8.95 9 1018 cm-3 can be achieved. Recently, intensive
attentions have been paid to the stabilization of N doping
via co-doping with the second dopant. Researchers from
Nanjing University [102] found that the existence of Te
could facilitate the doping of N. Researchers from Shi-
zuoka University [103] found that N co-doping with Be can
reduce the ionization energy of NO acceptors. In 2010,
123
Chin. Sci. Bull. (2014) 59(12):1235–1250
another group from Shizuoka University [104] found that
p-type transformation occurs when Mg content in
ZnO:Mg–N film reaches a certain level. Research ideas
related to the introduction of highly active group with
strong electronegativity included F doping and the forma-
tion of SbZn-2VZn complex. Janotti et al. [105] suggested
that interstitial Fi is a shallow acceptor. However, the
practical p-type ZnO:Fi has not reported until now, possi-
bly because interstitial Fi in ZnO lattice is thermodynam-
ically unstable; the p-type transformation via the formation
of SbZn-2VZn acceptors has also made some progress. In
2010, researchers from University of California-Riverside
[106] reported that ZnO-based light-emitting device com-
posed of Sb-doped p-type ZnO, MgZnO/ZnO/MgZnO
double heterostructure, and undoped n-type ZnO layers
was grown on c-plane sapphire substrate by plasma-assis-
ted molecular-beam epitaxy. Hall effect measurement
showed that the top p-type Sb-doped ZnO layer has a hole
concentration of 1 9 1017 cm-3. Ultraviolet emission was
achieved, which yielded an output power of 457 nW at
140 mA.
From the above research, it can be seen that the p-type
transformation is not an extremely difficult issue. However,
the fabrication of p-type ZnO with high thermostability and
mobility, which are indispensable for the development of
semiconductor devices, is unsettled till now. On one hand,
the existing works show that the research idea of achieving
p-type via introducing groups with strong electronegativity
is not advisable in the view of thermostability. For exam-
ple, phase separation always occurs when introducing the
SbZn-2VZn complex mentioned above [107]. Similarly,
there still exist some problems about the thermostability
and fabrication repeatability of p-type ZnO:N material. In
this respect, the research group from Changchun Institute
of Optics, Fine Mechanics and Physics, Chinese Academy
of Sciences has made some useful exploration. Their
research works reveal that the thermostability of p-type can
be influenced by many factors, such as light radiation, the
stress between films and substrates, and the formation of
N–N pairs [108, 109]. On the other hand, in the aspect of
the achieving high mobility, the recent research is rather
few. The most accepted research ideas can be summarized
as that high mobility can only be achieved when the film
quality are greatly improved. Such a common view can be
well confirmed by the fact that current devices with the
highest luminous efficiency are all fabricated via homo-
epitaxy method with excellent crystallinity. All of the
researches show that: (1) The thermostability of p-type
conductivity strongly depends on the films crystallinity; (2)
ZnO single-crystal substrate has obvious advantage on
growing p-type ZnO, as compared to other substrates.
It can be derived from the above-summarized researches
that the present works is only at the stage of achieving
Chin. Sci. Bull. (2014) 59(12):1235–1250
primary p-type conductivity. There is no report on such an
appropriate approach, by which the whole situation for an
ideal p-type ZnO can be taken into accounts and the three
key parameters of high thermostability, high mobility, and
high hole concentration can be achieved simultaneously.
We believed that only when the thermodynamic, kinetic
formation mechanisms and energy levels of various
impurity centers, and their influences on the film quality,
lattice integrity, and carrier mobility were fully understood
and considered, the feasible approach for fabricating highly
thermostable p-type ZnO film with high mobility and hole
concentration can eventually be proposed.
3.2.2 Analysis of thermodynamic states and kinetic
processes for achieving p-type ZnO
Here, based on the above consideration and our previous
works, we noticed some thermodynamic states and kinetic
processes in ZnO growth, which may be useful for
achieving ideal p-type ZnO. In the previous work of
growing ideal AZO thin films, we pointed out that high-
concentration Zn vacancies could be created under strong
oxidizing atmosphere [90]. The subsequent work on the
growth of Ga-H co-doping ZnO single crystal revealed
that H atom could easily enter into the Zn vacancies and
exhibit excellent thermostability. Considering that Li also
has a small atom radius, just like the case of H, it can be
expected that Li atoms can easily overcome the lattice
hindrance and then stably take the place of Zn vacancies
[89]. Thereby, p-type ZnO with high mobility and ther-
mostability can be obtained when all of doped Li atoms
stably occupy the Zn sites.
3.2.3 A conceptual multi-step approach to ideal p-type
ZnO
Herein, based on our preliminary research and above dis-
cussion, we propose a novel multi-step route to prepare
photoelectric conversion materials (see Scheme 6)
achieving high-quality p-type ZnO through three-step
treatments under difficult thermodynamic and kinetic
conditions: First, preparing high-quality single crystals or
films with high-concentration zinc vacancies under strong
oxidizing atmosphere. Second, filling the Zn vacancies
with Li atoms through a diffusion process via reducing
atmosphere annealing, which could simultaneously create
and stabilize shallow acceptors, and optimize the crystal
lattice to increase the hole mobility. Finally, treating the
single crystals or films again via an oxidizing atmosphere/
vacuum annealing to remove the excessive interstitial Li
atoms and eliminate the unstable shallow donors. Eventu-
ally, an optimized technical process for preparing p-type
ZnO with high quality and stability will be established,
1247
Scheme 6 (Color online) The flowchart of the novel multi-step route
to prepare high-quality p-type ZnO. a Stable VZn with high
concentration is formed under strong oxidation atmosphere; b After
being annealed in reducing atmosphere, Li ions fill into zinc
vacancies to form stable LiZn acceptors, while the excessive Li ions
fill into interstitial sites to form unstable Lii donors; c After being
annealed in weak oxidation or vacuum atmosphere, Lii donors will be
eliminated. Eventually, a truly p-type ZnO would be fabricated
which will provide a foothold for large-scale application of
ZnO photoelectronic materials.
4 Summary
This article mainly reviews our group’s venturing in
growing ZnO single crystal, fabricating homoepitaxial
ZnO-based photoelectronic devices, and understanding on
photocatalysis mechanism and diluted magnetic coupling
mechanism based on ZnO single crystal. Moreover, based
on our previous works, a novel multi-step route to prepare
high-quality p-type ZnO is proposed. The aim of the review
is to share our experiences in developing and understand-
ing ZnO materials.
Acknowledgments I thank my current and prior group members
(not in order): Shunle Huang, Zhongchao Lin, Jiakui Huang, Bingxi
Lin, Yishan Hou, Saiying Chen, Shicheng Lin, Guiyang Fang, Yon-
gcang Ke, Qingqing Kang, Wei Li, Ruilong Wang, Shuhui Wu, and
Guohong Wang. This work was supported by the National Natural
Science Foundation of China (60736032, 20971123, 51002153,
21007070, 51102232, 61106004 and 21103191), the National Basic
Research Program of China (2007CB936703), the Knowledge Inno-
vation Program of the Chinese Academy of Sciences (KJC2.YW.317,
KJC2.YW.W01), the Fujian Natural Science Foundation of China
(2005HZ1023, 2006F3140, 2007F3113, 2007HZ0005-3, 2010J01054,
2010J06006, 2010J05038 and 2012J05033), and the China National
Funds for Distinguished Young Scientists (50625205). I would like to
thank FJIRSM test center for years of support in facility and
infrastructure.
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