Near-infrared photoluminescence from ZnO

Mingsong Wang, Yajun Zhou, Yiping Zhang, Eui Jung Kim, Sung Hong Hahn et al.

Citation: Appl. Phys. Lett. 100, 101906 (2012); doi: 10.1063/1.3692584
View online: http://dx.doi.org/10.1063/1.3692584
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Published by the American Institute of Physics.

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Near-infrared photoluminescence from ZnO
Mingsong Wang,
1,a)
Yajun Zhou,
1
Yiping Zhang,
1
Eui Jung Kim,
2,b)
Sung Hong Hahn,
3,c)
and Seung Gie Seong
4
1
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
2
Department of Chemical Engineering, University of Ulsan, Ulsan 680-749, South Korea
3
Department of Physics and Energy Harvest-Storage Research Center, University of Ulsan, Ulsan 680-749,
South Korea
4
Division of General Studies, Ulsan National Institute of Science and Technology, Ulsan 689-805, South Korea
(Received 1 January 2012; accepted 20 February 2012; published online 8 March 2012)
Understanding the defect physics of ZnO is crucial in controlling its properties for various
applications. We report the observation of an interesting 1.64 eV near-infrared (NIR)
photoluminescence from ZnO and its evolution with annealing temperature. Based on a recent
calculation on the transition levels of native point defects of ZnO [A. Janotti and C. G. Van de
Walle, Phys. Rev. B 76, 165202 (2007)], the NIR emission can be successfully explained by the
donor-acceptor transition between V
O
and V
Zn
and/or the radiative recombination of shallowly
trapped electrons with deeply trapped holes at O
i
. VC
2012 American Institute of Physics.
[http://dx.doi.org/10.1063/1.3692584]
Zinc oxide (ZnO) is a IIVI semiconductor with a direct
wide band gap of 3.3 eV at room temperature.
1
Great inter-
est in ZnO is triggered by its prospects for use in optoelec-
tronic devices owing to its versatile combination of
interesting optical, electrical, and magnetic properties.
2
Understanding the defect physics of ZnO is necessary to
pave the way for control over its electrical conductivity and
luminescence.
3
For example, the presence of a variety of
native point defects, even in high-quality ZnO single crys-
tals, gives rise to broad visible emission bands such as green,
yellow, orange, and red ones observed at room temperature.
4
However, the assignments of point defects to specic emis-
sion bands remain speculative and highly disputable. Particu-
larly, the ubiquitous green luminescence was suggested to be
associated with oxygen vacancies,
57
zinc vacancies,
811
zinc interstitials,
12,13
or donor-acceptor transition between
defect complex.
14,15
Furthermore, the localized emission at
the surface makes the interpretation of this green band even
more complicated.
1619
In comparison to the near-band-edge (NBE) UV emis-
sion and the broad defect-related visible emissions that are
commonly observed, the near-infrared (NIR) luminescence
from ZnO has received far less attention. Lauer
20
recorded a
1.70 eV NIR emission for high temperature (9001000

C)
oxygen-annealed ZnO, which appeared only as a weak side
band accompanying the broad visible emission. In addition,
a broad emission band covering the NIR and visible spec-
trum was found to center at 1.55, 1.66, and 1.9 eV for NH
3
-
annealed,
21
electron-irradiated,
22
and N-implanted ZnO,
23
respectively. The above studies indicated that the NIR emis-
sion was normally a concomitant of the broad visible emis-
sion. However, none has monitored an independent NIR
band. Extreme care should be taken to avoid misinterpreting
the second order of the UV emission at 750 nm as a NIR
emission.
2426
In this work, we report the observation of a
1.64 eV NIR emission and its evolution with annealing tem-
perature. By combining our experimental observations with
recent theoretical calculations, possible mechanisms for the
NIR luminescence from ZnO have been proposed. The ob-
servation of this unambiguous NIR band helps one better
understand the defect physics of ZnO.
Hydrothermally grown ZnO microspheres were
employed in the present study. A precursor solution was pre-
pared by sequentially dissolving zinc nitrate, ammonium uo-
ride, and sodium hydroxide with a mole ratio of 1:6:8 to
deionized water. The precursor solution was hydrothermally
treated at 75

C for 10 h. The as-prepared ZnO was further

annealed in air for 1 h at temperatures ranging from 700 to
1000

C. Structural characterization was carried out using

x-ray diffractometer (XRD, Bruker Axs D8 Advance) with Cu
Ka radiation. Sample morphology was examined by a JEOL
JSM-7001F eld emission scanning electron microscope
(FESEM) operating at 15kV and a JEOL JEM-2100F high-re-
solution transmission electron microscope (HRTEM) operated
at 200 kV. Photoluminescence (PL) spectra were recorded at
room temperature by exciting the samples with a 325 nm
HeCd laser at an output power of 30mW. Raman spectra
were taken on a Laser Raman Spectrometer SPEX 1403 with
a HeNe laser at an excitation wavelength of 632.8 nm.
Figure 1 shows the SEM image and XRD pattern of the
as-prepared ZnO microspheres. As seen in Fig. 1(a), the
microspheres are constructed of uniform thin sheets of
20 nm in thickness. A ne arrangement of the nanosheets
in the microsphere indicates the self-assembly of nanosheets
by epitaxy.
27
The HRTEM image of a single sheet and its
corresponding fast Fourier transform (FFT) pattern shown in
the insets of Fig. 1(b) reveal the single crystalline nature of
the nanosheet. Energy-dispersive x-ray spectroscopy analysis
(coupled with SEM) reveals that there is no impurity element
(not shown). All diffraction peaks in Fig. 1(b) are identied
as the hexagonal wurtzite ZnO; no crystalline impurity is
detected.
a)
Electronic mail: wangms@ujs.edu.cn.
b)
Electronic mail: ejkim@ulsan.ac.kr.
c)
Electronic mail: shhahn@ulsan.ac.kr.
0003-6951/2012/100(10)/101906/4/$30.00 VC
2012 American Institute of Physics 100, 101906-1
APPLIED PHYSICS LETTERS 100, 101906 (2012)
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Raman spectroscopy is employed to investigate the
phase purity and crystallinity of ZnO. Figure 2 shows the
Raman spectra of the as-prepared and annealed ZnO micro-
spheres. All bands in the Raman spectra can be assigned to
wurtzite ZnO,
28
i.e., E
2
modes at 98 and 437 cm
1
, transver-
sal optical TO modes with E
1
symmetry at 409 cm
1
and
with A
1
symmetry at 380 cm
1
, longitudinal optical LO
modes with E
1
symmetry at 583 cm
1
and with A
1
symmetry
at 573 cm
1
, and the second order vibrations at 202, 331,
538, and 10501200 cm
1
. An enhanced Raman intensity for
the annealed ZnO indicates its improved crystallinity. No
Raman peaks related to impurity phases are observed con-
rming the pure wurtzite phase of the investigated ZnO.
Figure 3 illustrates the room temperature PL spectra of
the as-prepared and annealed ZnO microspheres. In addition
to a weak NBE UV emission at 385 nm, the as-prepared ZnO
exhibits a broad intense deep-level (DL) emission that
appears in the range of 440860 nm, which can be readily
Gaussian-resolved into three bands located at 566, 637, and
759 nm, respectively (Fig. 3(a)). Upon annealing at 700

C,
the DL emission maintains its broad prole while the band
intensity is weakened (Fig. 3(b)). This broad DL emission,
however, changes to separate green and NIR emissions peak-
ing at 537 (2.31) and 758 nm (1.64 eV), respectively, for
800

C-annealed ZnO. A further increase in annealing tem-

perature leads to a monotonic increase (decrease) of the NIR
(visible) emission, as seen in Figs. 3(b) and 4. The NIR band
does not shift with annealing temperature and nally domi-
nates the PL spectrum at 1000

C. Note that the 1.64 eV NIR

luminescence is not a second order of the UV emission: rst,
the absence of a UV emission can not create a second order
NIR band; second, the NIR band due to the second order of
the UV emission is much weaker and narrower than the NIR
emission shown in Fig. 3(b).
29
Therefore, we have demon-
strated unambiguously a 1.64 eV NIR luminescence from
ZnO and its evolution with annealing temperature.
FIG. 1. Typical SEM image (a) and XRD pattern (b) of the as-prepared
sheet-constructed ZnO microspheres. The insets in (b) show the HRTEM
image of a single sheet and the corresponding FFT pattern.
FIG. 2. (Color online) Raman spectra of the as-prepared and annealed ZnO
microspheres.
FIG. 3. (Color online) PL spectra of the as-prepared (a) and annealed (b)
ZnO microspheres. The broad visible-NIR emission in (a) is Gaussian-
resolved into three bands located at 566, 637, and 759 nm, respectively.
FIG. 4. (Color online) PL intensity for the visible and NIR emission bands
as a function of annealing temperature.
101906-2 Wang et al. Appl. Phys. Lett. 100, 101906 (2012)
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Although the as-prepared sample has a large surface
area, the DL emissions observed herein for the annealed
ZnO are believed to be a bulk effect rather than a surface
effect as the nanosheets become much thicker (of over
200 nm after 900

C annealing, not shown). Before interpret-

ing the NIR luminescence, it is necessary to review recent
calculations on the defect energetics and electronic structure
in ZnO. The calculations consistently indicate that oxygen
vacancies (V
O
), zinc vacancies (V
Zn
), and oxygen interstitials
(O
i
) create deep energy levels in the band gap, and among
them V
O
has the lowest formation energy.
30
Furthermore,
reliable results concerning the charge transition levels can be
obtained by aligning the electronic band structure through an
external potential, which yields the (2/0) charge transition
level of the V
O
in ZnO to be 2.22.4 eV from the valence
band maximum (VBM).
31
Therefore, one can justify the DL
emissions of ZnO provided the accurate defect levels are pre-
dicted. Recently, Janotti and Van de Walle
10
performed a
detailed study on the native point defects in ZnO. Accord-
ingly, the observed DL emissions herein are explained based
on their calculated transition levels of V
O
, V
Zn
, and O
i
. We
exclude zinc and oxygen antisites as they show a large off-
site displacement and induce a large local lattice
relaxation.
10
As illustrated in Fig. 5, exciting ZnO with photons of
energy higher than the band gap leads to the band-to-band
excitation (1) and the formation of excitons (2). Excited free
charge carriers are then trapped by V
O
, V
Zn
, and O
i
occupy-
ing the deep energy levels in the band gap (corresponding to
processes 4, 7, and 9, respectively). De-excitation and radia-
tive recombination processes 3, 5, and 6 give rise to the
emission bands at 3.23, 2.51, and 2.36 eV, respectively. The
energy level of the shallowly trapped electrons to be com-
bined with deep acceptors (V
Zn
and O
i
) is thought to be the
same as that of the excitons since the DL emissions compete
with the exciton-related UV emission.
16
It is found that both
V
O
and V
Zn
contribute to the green emission, but with
slightly different peak energy, which may explain the
observed high- and low-energy green luminescence from
annealed ZnO in different atmospheres.
7
Although the green
emission ascribed to V
O
was in question,
10
we have the fol-
lowing positive evidences for it. (i) V
O
has the lowest forma-
tion energy and, thus, is most abundant in a Zn-rich
condition,
10
e.g., reduced ZnO, and a high-energy green
emission do appear in reduced ZnO.
7
(ii) Thermodynami-
cally unstable V

O
is experimentally detected in the optically
excited ZnO by electron paramagnetic resonance, revealing
the participation of V
O
in the green emission process.
32
(iii)
Subband excitation of ZnO generates DL emissions,
32
sug-
gesting that V
O
as a deep donor is a source of green emission
(see Fig. 5, process 11); in contrast, one can never expect
any DL emission if V
Zn
is involved.
Finally, it is seen from Fig. 5 that a 1.64 eV NIR emis-
sion is generated as a result of the radiative recombination of
shallowly trapped electrons with deeply trapped holes at O
i
,
which is amazingly consistent with the observed NIR band
in Fig. 3. Alternatively, the same NIR emission is obtained
in case a donor-acceptor transition takes place between V
O
and V
Zn
. A dominant process for the NIR emission may
depend on the concentration of these native defects that are
present. The proposed recombination processes in Fig. 5 can
successfully explain the green and NIR luminescence from
ZnO. However, further investigation is required to interpret
other emission bands such as yellow and red ones.
In conclusion, ZnO microspheres constructed of nano-
sheets were prepared by a facile hydrothermal method. We
demonstrate clearly a 1.64 eV NIR luminescence from ZnO
and its evolution with annealing temperature. Combined
with the calculated defect energy levels of native point
defects in ZnO by Janotti and Van de Walle,
10
we success-
fully explain the green and NIR luminescence from ZnO.
Both V
O
and V
Zn
are responsible for the ubiquitous green
emission, while donor-acceptor transition between them and/
or the radiative recombination of shallowly trapped electrons
with deeply trapped holes at O
i
give rise to the 1.64 eV NIR
luminescence.
This work was supported by the Natural Science Foun-
dation of China (Grant No. 51002066), the Research Founda-
tion of Jiangsu University (Grant No. 09JDG004), and the
Research Fund of the University of Ulsan.
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