Ceramics International 45 (2019) 8388–8394

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Post-annealing induced oxygen vacancy mediated non-polar ZnO films with T

excellent opto-electronic performance
Lin Qi, Yujie Qi, Zhaoyuan Chai, Yang Qi∗
Institute of Materials Physics and Chemistry, School of Materials Science and Engineering, Northeastern University, Shenyang 110819, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The considerably enhanced opto-electronic properties of ZnO films with non-polar orientations have been rea-
Non-polar ZnO film lized by introducing oxygen vacancies. Excitation of oxygen vacancies has been achieved by oxygen-deficient
Post-annealing treatment post-annealing treatment. The existence of oxygen vacancies is directly confirmed by cross-sectional XPS and
Oxygen-deficient atmosphere positron annihilation Doppler broadening measurements. An enhanced UV-emission, more simplex green-light
Oxygen vacancy mediation
emission and sharply decreased electrical resistivity of post-annealed non-polar oriented ZnO films have been
acquired in oxygen-deficient atmosphere. I-V measurement indicates that non-polar oriented ZnO/p-Si hetero-
junction with optimized post-annealing treatment owns an excellent forward electrical transportation and ex-
tremely low threshold voltage, have great competitiveness for the commonly used one-dimensional ZnO na-
nomaterials in photo-electronic field.

1. Introduction excellent performances, which have huge potential to be comparable or

Nowadays, researchers hold soaring passion and pay more attention
to the wide band gap semiconductor-based devices with excellent
physical performance, ZnO is absolutely no exception. Some out-
standing advantages such as a wide band gap of 3.37 eV, large exciton
bonding energy of 60 meV, high thermal and chemical stability
(melting point is 2248 K), non-toxicity and bio-compatibility etc., have
made it widely applied in many areas, such as light-emitting diodes
(LEDs) and high speed heat-resisting electronic devices, especially thin
film transistor backplanes for flexible displays or the transparent active
matrix light-emitting diode displays owing to its merits of low re-
sistivity and high transparency in visible region [1–3]. All of these make
ZnO become the most potential and competitive functional material in
masses of the 3rd generation semiconductors. However, in practical
applications, the quantum confined Stark effect (QCSE) originated from
the polarization of spontaneous and piezoelectric effects in one-di-
mensional ZnO nanostructures leads to the red-shift transition, resulting
in a deteriorated IQE (internal quantum efficiency) of ZnO-based na-
nodevices.
Aimed at solving the drawbacks in the aforementioned practical
applications, tremendous attempts have been made in recent years.
People not only dissatisfy with the achievement of high-quality ZnO
nanostructures with non-polar orientations, but also demonstrate
strong interest in exploring the non-polar ZnO-based devices with
even replaceable of those commonly used one-dimensional ZnO na-
norods/nanowires in the near future, especially in the application of
opto-electronic field. Till now, multitudinous non-polar ZnO nanos-
tructures have been successfully fabricated and applied in certain fields,
such as the intensively reported opto-electronic [4,5], sensor [6,7] and
photocatalysis or catalysis fields [8], in addition, reports concerning the
non-polar surface acoustic wave devices (SAW) [9] and quantum wells
have been gained attentions gradually [10]. Some of these non-polar
ZnO-based applications exhibit even better performance than one-di-
mensional ZnO nanostructures [11]. Wang et al. fabricated a non-polar
m-plane ZnO/Al2O3/GaN heterojunction LED, which can emit blue
light with different brightness under opposite direction of electrical
field [12]. Besides, Baik et al. and Nguyen et al. report a non-polar a-
plane n-ZnO/p-GaN heterojunction LED, which possesses excellent
visible light emissions ranged from 350 to 500 nm [13,14]. For sensors
applications, the non-polar ZnO (101̄0) and (112̄0) crystal planes exhibit
some novel peculiarities as well. For example, Kaneti et al. reported a
new type of golden decorated ZnO with exposed non-polar (101̄0)
crystal planes which exhibited the highest sensitivity toward n-butyla-
mine gas, it was quite a novel finding [6]. Hence, research on the ap-
plications of non-polar ZnO nanostructures in various domains is at-
tracting increasing interest, providing great scope for further
exploration.
In previous work, non-polar oriented ZnO/Si heterojunction with

∗
Corresponding author.
E-mail address: qiyang@imp.neu.edu.cn (Y. Qi).

https://doi.org/10.1016/j.ceramint.2019.01.147
Received 22 December 2018; Accepted 21 January 2019
Available online 26 January 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
L. Qi et al.
high opto-electrical performance was successfully fabricated and used
in opto-electronic field preliminarily, which exhibited better perfor-
mance than the most reported literature concerned of this issue [4].
However, performances of ZnO films with non-polar orientations still
hardly surpass the commonly fabricated ZnO nanostructures even
though this topic has been systematically investigated for decades.
Hence, in this work, appropriate thermal activation was introduced to
enhance the performance of the synthesized non-polar oriented ZnO
films, and the effect of oxygen vacancy on the enhancement of opto-
electronic performances of thermally annealed non-polar oriented ZnO
films has been confirmed. Although there are numerous reports present
better performance of ZnO nanostructures by means of various thermal
activation treatments [15,16], however till now, discussion concerning
the optimized performance of ZnO films with non-polar orientations
evoked by thermal-annealing has been seldom reported. And these post-
annealed non-polar ZnO heterojunction with optimized physical per-
formance could be good competitor among numerous semiconductor
materials.
2. Experimental
Details for the synthesis of ZnO films with non-polar orientations
could be found elsewhere [4]. The pristine non-polar oriented ZnO
films were experienced with various post-annealing treatments: va-
cuum-annealing in 5 × 10−4 Pa, air-annealing at atmospheric pressure
and argon-annealing (99.99% purity) in tube furnace. The annealing
conditions all keep identical (550 °C for 2 h). The morphologies and
microstructures of all the films were characterized by using X-ray dif-
fraction pattern (Rigaku) with Cu-Kα radiation (λ = 1.5405 Å), field
emission scanning electron-microscope (ZEISS) and atomic-resolution
scanning transmission electron microscopy imaging (JEOL JEM-ARM
200F) at 200 kV with a high-angle annular dark-field detector and a
probe Cs-corrector. Photoluminescent spectroscopy was measured by
Raman spectrometer (Horiba-JY LabRam HR Evolution) equipped with
He-Cd laser (λ = 325 nm). Positron annihilation Doppler broadening
measurement were performed by slow positron beam facility in In-
stitute High Energy Physics [17]. Slow positrons were generated by a
1.85 GBq 22Na radiation source. The Hall Effect measured by Van der
Pauw method was performed by physical property measurement system
(Quantum Design). Cross-sectional X-ray photoelectron spectroscopy
was performed on a photoelectron spectrometer (AXIS SUPRA, SHIM-
ADZU, Japan) using monochromatic Al Kα radiation X-ray as excitation
source (1486.6 eV). Binding energies were calibrated by setting C1s at
284.6 eV. The squared-cut film samples (5 × 5 mm2) were measured
under 0.3 T permanent magnet with 1 mA at room temperature. I-V
measurements of these post-annealed non-polar oriented ZnO/p-Si
heterostructures were carried out (Keithley 238 current source&
Keithley 2182 voltmeter) by two-point method.
3. Results and discussion
The electrical properties of 1#–4#, corresponding to the as-derived,
air-annealing, vacuum-annealing and Ar-annealing conditions, are ex-
hibited in Table 1. Measured in weak magnetic field intensity (3000 GS)
is favorable to detect the intrinsic electrical properties. The conduction
type of 1#–4# are all n-type. Taking 1# as reference, the resistivities of
Table 1
Hall Effect measurement of 1#–4#.
Sample Electrical properties
ρ(Ω·cm) CN(cm−3) μN (cm2/Vs)
1# 1.43 × 104 1.42 × 1013 18.36
2# 2.71 × 103 1.30 × 1014 17.79
3# 0.186 4.91 × 1018 10.11
4# 5.68 × 10−2 1.09 × 1019 6.85
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Ceramics International 45 (2019) 8388–8394
2#–4# in various annealing atmospheres exhibit diverse decrease. It is
reasonable deduced that some defects sensitive to oxygen might play an
important role in affecting the electrical properties of non-polar ZnO
films and this deduction needs to be further confirmed, especially the
origin of the dramatically increased conductivity of vacuum/Ar-an-
nealed non-polar ZnO.
XRD spectra of 1#–4# are shown in Fig. 1(a). Observed that the non-
polar preferred orientations of 2#–4# still maintain unchanged as 1#.
The FESEM images of 1#–4# provided in Fig. 1(b)-(e) present quite
unusual morphologies, which are much different form the one-dimen-
sional ZnO nanorods/nanowires. Fig. 1(f)-(g) provide the HAADF-STEM
images of 1# and 4# along [112̄0] direction. In Fig. 1(f), a linear re-
lationship of the projection centers in each column is observed. As a
comparison in Fig. 1(g), the projection centers are not strictly linear in
each column, deviation and stretch of Zn cations are detected, which is
marked in Fig. 1(g). Enlarged intensity distribution of these projective
centers is presented in Fig. 1(h), a relatively large displacement of Zn
cations is found in 4#. This directly observed displacement of Zn cations
can reflect the excitation of oxygen vacancies induced by oxygen-defi-
cient annealing.
As is known that positrons exhibit the most sensitive recognition on
vacancy defects [18–22]. These thermally active oxygen vacancies
served as positron trap centers can further influence the positron an-
nihilation process. The S parameter-as function of incident positron
energy (S-E curves) of non-polar oriented ZnO films with various post-
annealing treatments is shown in Fig. 2(a). The larger S parameters of
3# and 4# indicate a larger number of oxygen vacancies in 3# and 4#.
Fig. 2(b) shows the W-E curves of all the films. In Fig. 2(b), the effect of
positron annihilation on core electrons becomes weak when the amount
of oxygen vacancies is increased. The W parameters of all these four
samples exhibit inversely proportional relationship to the values of S
parameter at low incident positron energy. However, the W parameter
tend to be consistent with the increment of incident positron energy,
which means the S and W parameters of 3# and 4# are not strictly
linear. This non-linear relationship indicates that there exists different
vacancy type with the increment of film depth. Here we consider that as
the smaller ZnO grains at the initial growth stage, the effect of grain-
boundary becomes significant, which provides more diffusion paths for
oxygen vacancies to aggregate to vacancy clusters near the grain-
boundaries, leading to the non-linear relationship of S and W para-
meters. Fig. 2(c) proposes three positron annihilation forms at oxygen
vacancies. According to charge conservation, the loss of oxygen atoms
leaves one or two negative charges in the lattice, the left negative
charges could annihilate with positions. However, the residual negative
charges can also break the electrostatic binding energy to become free
electrons during post-annealing, in this case, positrons could not be
annihilate at these completely ionized oxygen vacancies.
The chemical state of O1s of 1#–4# were measured by XPS in cross-
sectional view, as provided in Fig. 3. All the spectra used the commonly
standard background deduction model- Shirley background. The typical
O1s peak of 1# and 2# can be fitted well by two Gaussian-Lorentzian
convolutional peaks centered at 530.9 eV and 532.3 eV, respectively.
Meanwhile, it can be fitted well by three Gaussian-Lorentzian con-
volutional peaks centered at 530.9, 531.5 and 532.3 eV of 3# and 4#.
The low bonding energy component located at 530.9 eV is corre-
sponded to the O2− ions in Zn2+ ions in wurtzite ZnO. The highest
binding energy centered at 532.3 eV is owning to the existence of
loosely bound oxygen of ZnO film surface [23,24]. The O 1s spectra of
1# and 2# are composed of the O2− ions in lattice and chemisorbed
oxygen-containing functional groups such as -CO3, adsorbed H2O and
O2− [25]. The binding energy located at 531.5 eV is related with O2−
ions in the oxygen deficient regions, here referred as oxygen vacancy
[26,27]. It could be seen that oxygen vacancies were excited in va-
cuum/Ar (3#/4#) thermal activation atmosphere, leading to the peak
shifted toward higher binding energy. To some extent, the increment of
donor-type defects are beneficial to the enhancement of conductivity,
L. Qi et al. Ceramics International 45 (2019) 8388–8394

Fig. 1. (a) XRD spectra of 1#–4#, (b)–(e) FESEM images of 1#–4#, HAADF-STEM images for (f) 1# and (g) 4# along [112̄0] direction and (h) Signal intensity of Zn
atoms along [112̄0] direction.

and this XPS result is consistent with the Hall measurement.
In order to investigate the effect of thermal activation on the pho-
toluminescent performance of these four samples, room-temperature PL
spectra are exhibited in Fig. 4(a). UV emission located in 376 nm ori-
ginated from the NBE (near-band-edge) emissions or exciton combi-
nations, as well as a series of visible-light emissions with various in-
tensities are observed. It could be seen that UV emission centers keep
unchanged (376 nm), however, they present multifarious intensities
with variable thermal activation atmosphere. The vacuum/Ar-annealed
films (3#/4#) have stronger intensities than 1#. Oppositely, spectrum of
2# owns the weakest intensity of UV emission. Dissimilar with UV
emissions, it shows an interesting phenomenon in visible regions that
the defect-related emissions of non-polar oriented ZnO films are
aroused by thermal activation in various atmosphere, and it also pre-
sents diverse intensity in variable thermal ambient. Spectrum of 2# in
visible-light region exhibits the strongest intensities and widest range of
the composite visible-light emission, which is corresponded to the
weakest UV emission. 3# and 4# show relatively lower intensities of

Fig. 2. The spectra of (a) S parameter versus incident positron energy and (b) corresponding W parameter versus incident positron energy of as-deposited (1#) and
thermal-activated non-polar oriented ZnO films in annealing atmosphere of air, vacuum and Ar gas, and (c) positron annihilation patterns at oxygen vacancies.

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L. Qi et al.
#
Fig. 3. Cross-sectional XPS spectra of O1s of 1 and thermal activated non-
polar oriented ZnO films in atmosphere of air (2#), vacuum (3#) and Ar gas
(4#), respectively.
visible-light emissions compared with 2#. These composite visible
emission peaks are divided into several components of blue-green
emissions, as provided in Fig. 4(b–d), corresponding to 2#–4#. Aimed at
identifying the defect-related energy level distribution in ZnO bandgap.
Three separated peaks with peak values of 461 nm, 500 nm and 563 nm
Fig. 4. PL spectra of (a) 1#–4# at room-temperature in various annealing ambient, PL spectra of (b) 2#, (c) 3# and (d) 4# in visible ranges.
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are fitted well with the measured spectrum based on Gaussian fitting, as
shown in Fig. 4(b). And the intensities of these three fitted emission
peaks are enhanced with the increased visible-light wavelength. Com-
pared with the spectrum in Fig. 4(b), the visible-light emissions in
Fig. 4(c) and (d) exhibit close peak values. These two spectra in visible-
light range can be divided into dark-green emission (508/499 nm) and
light-green emission (547/560 nm).
Photoluminescent mechanism of thermal annealing non-polar or-
iented ZnO films: PL spectrum of ZnO usually composes of two sections,
one is the typical UV-light emission induced by the near-band-edge
emission or exciton combination, the other is visible-light emission
which is defect-related. Generally, besides UV-light excitation origi-
nated from the radiative transitions of photo-generated electrons, there
exists numbers of defect states within the band gap of ZnO, as depicted
in Fig. 5(a). Donor defects exactly as Zni0, Zni∗, Vo and Vo∗ are normally
located below the bottom of conduction band, these defects donate
their electrons and become ionized, and the generation of these donor-
type defects plays an essential role to the enhancement of film con-
ductivity, as presented in the following reactions [28,29]:
ZnZn ↔ Zni0 + VZn (1)
0 ∗ −
Zni ↔ Zni + e (2)
∗ ∗∗ −
Zni ↔ Zni +e (3)
0 ↔ VZn + Vo (4)
Vo ↔ Vo∗ + e− (5)
Vo∗ ↔ Vo∗∗ + e− (6)
These defects act as luminescent centers to emit visible lights, and
the process of electrons are transited from neutral or singly ionized
donor defects to valence band edge is widely accepted as the pre-
dominated mechanism to the blue/green-light emission. Acceptor
L. Qi et al.
Fig. 5. Diagrams of (a) general UV and visible-light photoluminescent mechanism of ZnO film under UV irradiation and proposed defect distribution of (b) 2#, (c) 3#/
4# within ZnO bandgap.
defects including VZn and Oi which are usually located above the top of
valence band, these defects trap electrons from conduction band, which
are served as electron trap centers. In addition, some deep level defects
are situated in the central position of ZnO band gap. These deep-level
defects usually have a relatively high ionization energy, which act as
electron-scattering centers and lead to the degradation of conductivity.
Hence, we consider that excellent conductivity must be acquired by
increasing the amount of donor-type defects which could release elec-
trons, or reducing the amount of deep level defects which served as
electron trap/scattering centers. Fig. 5(b) and (c) present the visible-
light emission mechanism of 2#–4#, respectively. The luminescent
centers could be ensured based on the separated emission peak posi-
tions in visible-light region. Observed from Fig. 5(b) that the deep-level
defects take a high proportion in these generated defects. Various kinds
of defects are emerged in the air annealing atmosphere. Here we con-
sider that air-annealing pattern attributes the formation of deep level
oxygen-related defects, and visible-light emission exhibits a pre-
dominantly yellow-green light excitation. The photoluminescent dia-
gram of the vacuum/Ar-annealed films in visible-light region is pre-
sented in Fig. 5(c). Distinguished from the defect states of air-annealed
film, it shows a more centralized and simplex distribution of defect
states centered at 2.44/2.48 eV with dark green and 2.27/2.21 eV with
light green emissions of vacuum/Ar-annealed ZnO films. Owning to the
low formation energy of oxygen vacancies at a relatively low oxygen
partial pressure [30,31], we consider that the photoluminescent me-
chanism of this simplex green light emission of vacuum&Ar-annealed
non-polar oriented ZnO films is mainly ascribed to the electron tran-
sition from neutral or single ionized oxygen vacancies center to the
valence band edge [32,33]. These oxygen vacancies originated from
vacuum/Ar-annealing atmosphere donate their electrons as carriers,
which result in an effective enhancement of electrical conductivity
(evidenced by the value of resistivity in Hall Effect measurement). A
conclusion could be drawn from the above analysis that ZnO films with
non-polar orientations in oxygen-deficient thermal activation atmo-
sphere could not only increase the conductivity to a large extent, but
also make the luminescent center more concentrated which results in
the emissive color more simplex.
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Generally, annealing temperature can induce variation of thermally-
related defects to a large extent. Aimed at identifying the optimal
temperature, investigation of annealing temperature on the con-
ductivity of non-polar oriented ZnO film in Ar-annealing atmosphere is
performed. Fig. 6(a) exhibits the XRD spectra of non-polar oriented ZnO
films annealing at 300 °C, 400 °C, 500 °C and 550 °C for 2 h in Ar at-
mosphere, respectively. These four samples are tailored into uniform
size (5 × 5 mm2) from one piece of the as the-synthesized non-polar
ZnO film (10 × 10 mm2). The predominant non-polar (112̄0) and (101̄0)
diffraction peaks, accompanied with much weaker (101̄1) and (0002)
diffraction peaks indicate the polycrystalline property and preferential
orientations along non-polar a-plane (112̄0) and m-plane (101̄0) of these
Ar-annealed ZnO films. In addition, (111) diffraction peak of Ag elec-
trode is observed at 38.12° which is induced by the measurement of
electrical resistivity. Similar with altering the annealing ambient, the
non-polar preferred orientation still remains unchanged with increased
annealing temperature, which indicates an excellent thermal stability of
ZnO films with non-polar orientations. Corresponding electrical re-
sistivities of non-polar oriented ZnO films at various post-annealing
temperature in Ar atmosphere are presented in Fig. 6(b). Increasing the
temperature from 300 °C to 400 °C lead to a dramatic reduction of
electrical resistivity from 0.62 Ω cm to 0.061 Ω cm. Continuously in-
creasing the post-annealing temperature to 500 °C, the value of elec-
trical resistivity reaches the minimum value of 0.048 Ω cm. When an-
nealing temperature continually increased to 550 °C, the value of
resistivity becomes slightly larger (0.057 Ω cm), as shown in the inset of
Fig. 6(b). This conversion of electrical resistivity with increased an-
nealing temperature is reasonable. On one hand, a relatively high an-
nealing temperature could accelerate the diffusion of atoms, which
results in the zinc and oxygen atoms deviated from the lowest energy
sites. Beyond that, some thermally-related defects could be engendered,
and act as electron trap centers or current scattering centers. These two
aspects have negative effect on the conductivity of Ar-annealed ZnO
films. Hence, it can be seen from Fig. 6(b) that the lowest electrical
resistivity of non-polar oriented ZnO film in Ar annealing atmosphere
could be acquired at annealing temperature of 500 °C.
To achieve ohmic contact, point electrode made by silver was
L. Qi et al.
Fig. 6. (a) XRD patterns of non-polar oriented ZnO films annealing in Ar gas at annealing temperature of A1 (300 °C), A2 (400 °C), A3 (500 °C) and A4 (550 °C), (b)
corresponding electrical resistivities at various annealing temperatures, (c) I-V characteristics at annealing temperature of 500 °C, the inset gives the schematic
diagram of ZnO/Si (100) heterostructure and (d) logarithmic current intensity with the voltage.
deposited at the surface of ZnO film and the back of Si (100) substrate
(the schematic diagram was provided in the inset of Fig. 6(c)). The
silver electrode was deposited in the central location on film surface
aimed at avoiding the contact between Ag electrode and Si substrate.
Rectifying property is observed from Fig. 6(c) when the bias voltage
reaches ± 2 V. Fig. 6(d) shows the I-V characteristic ten months later by
taking logarithmic value of the current with the voltage range from −2
to +2 V. The threshold voltage of this sample almost reaches 0.13 V. In
comparison with the I-V result of the pristine non-polar oriented ZnO/Si
(100) heterostructure in our previous work, a considerably enlarged
current density is acquired in this non-polar oriented ZnO/Si (100)
heterostructure annealing at Ar atmosphere. The excellent electrical
transport property is attributed to the tremendously enlarged carrier
density generated from the ionized oxygen vacancies. However, it still
remains rectifying character ten months later, indicating an excellent
VO stability of the thermal-activated non-polar ZnO-based heterojunc-
tion.
4. Conclusion
Non-polar oriented ZnO films with excellent performance have been
achieved by oxygen vacancy mediated post-annealing process.
Photoluminescence and conductivity are largely enhanced by control-
ling annealing atmosphere. The XPS and PAS results provide direct
evidences to verify a large numbers of oxygen vacancies existed in
oxygen-deficient post-annealing atmosphere, which served as donor-
type defects. The non-polar oriented ZnO/Si film device post-annealed
in oxygen-deficient atmosphere shows a considerably enlarged current
density at low forward bias. This newly type of ZnO-based hetero-
structures has great competitiveness for the commonly used one-di-
mensional ZnO nanostructures especially in application of photo-elec-
tronic field.
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