Electrochemical and Solid-State Letters, 7 7 J20-J22 2004

J20

0013-4651/2004/77/J20/3/$7.00 The Electrochemical Society, Inc.

PL Dependence of ZnO Films Grown on Si with Various Buffer

Layers by RF Magnetron Sputtering
Chin-Ching Lin,a San-Yuan Chen,a,z and Syh-Yuh Chengb
a

Department of Materials Science and Engineering, National Chiao-Tung University, Hsinchu, Taiwan
Industrial Technology Research Institution, Materials Research Laboratories, Chutung, Taiwan

Peculiar photoluminescence PL emission properties of ZnO films on Si buffered with SiO2 and Si3 N4 were found. The ZnO films
deposited on SiO2 /Si substrate show two double peaks in the room-temperature PL spectra, one double 374 and 394 nm in the
ultraviolet region and the other double 495 and 605 nm located in the visible region. If the ZnO film was grown on Si3 N4 /Si,
a very strong UV along with invisible deep-level emission was detected because the Si3 N4 can effectively reduce the defect
formation of oxygen vacancies and Zn interstitials compared to ZnO on SiO2 /Si and Si.
2004 The Electrochemical Society. DOI: 10.1149/1.1736594 All rights reserved.
Manuscript submitted October 23, 2003; revised manuscript received November 21, 2003. Available electronically April 29, 2004.

Zinc oxide has received an enormous amount of attention because ZnO not only has a wide direct bandgap 3.37 eV at room
temperature but also shows a large exciton binding energy 60 meV
that is much larger than that of ZnSe 20 meV and GaN 25 meV.1
The ultraviolet UV emission of ZnO is attributed to exciton-related
activities, but for visible emissions, various mechanisms have been
proposed including the involvement of zinc interstitials,2,3 oxygen
interstitials,4,5 zinc vacancies,6,7 and oxygen vacancies.8,9 Recently,
a violet emission peaked at 401 nm 3.09 eV was observed in
low-temperature photoluminescence PL spectra of ZnO films
grown on p-type Si by radio-frequency rf magnetron sputtering
under oxygen-rich conditions. Jeong et al. considered that the emission was assigned to the electron transition from the bottom of the
conduction band to the zinc vacancies level.10 In addition, Jin et al.
also found another violet emission around 420 nm (2.95 eV) for
ZnO film grown on Si substrate and reported that the violet emission
is due to a defect level in the grain boundaries of the ZnOx
crystals.11 However, the exact origin of the special emission behavior of ZnO films is not yet well understood and is still debatable.
Recently, many studies have been focused on ZnO films deposited on silicon substrate because of the development for large-scale
electronic integration devices. However, a large lattice mismatch
between Si and ZnO affects the physical characteristics and emission properties of ZnO films. Therefore, it is important to understand
the substrate, especially interface microstructure, effect on defect
transition and PL properties of ZnO films.
In this article, we try to clarify the exact origin of the unique
emission behavior of ZnO films grown on Si substrate buffered with
SiO2 and Si3 N4 layers by rf magnetron sputtering. To the authors
knowledge, it was first reported that two double emissions, one in
the UV emission region and the other in deep-level emissions, were
observed in room-temperature PL spectra of ZnO films grown on
SiO2 /Si. Furthermore, the ZnO films deposited on Si3 N4 /Si presented excellent optical and electrical properties compared to those
on SiO2 /Si and Si substrates.
Experimental
ZnO thin films (125 nm) were deposited on 4 in. diameter Si
substrates buffered with SiO2 and Si3 N4 layers by rf magnetron
sputtering using 99.99% ZnO as a target. Sputtering conditions were
optimized at a substrate temperature of 50C, rf power of 50 W,
sputtering pressure of 10 mTorr, and sputtering time of 30 min at a
gas mole ratio of oxygen to argon of 5% condition. The buffer layers
were grown by electron evaporation and the thickness of the buffer
layers for Si3 N4 and SiO2 was about 10 and 20 nm, respectively.
After sputtering, the as-grown ZnO films were annealed at 850C
for 20 min under pure oxygen and nitrogen atmospheres. The sur-

E-mail: sychen@cc.nctu.edu.tw

face morphology was examined by field-emission scanning electron

microscopy FESEM, S-4100. The crystal structure was determined
using Siemens D5000 X-ray diffraction XRD with Cu K radiation and a Ni filter. Transmission electron microscopy TEM Philips
TECNAI 20 attached with energy-dispersive X-ray spectroscopy
EDS operated at 200 keV was also used for microstructure analysis of cross-sectional interface. PL measurement was performed by
the excitation from 325 nm He-Cd laser at various temperatures.
Results and Discussion
Figure 1 shows the XRD patterns of ZnO films sputtered at Si,
SiO2 /Si, and Si3 N4 /Si, and then annealed at 850C in O2 atmosphere. Only a sharp diffraction peak of 002 at 2 34.5 can be
detected for all the films, indicating that well-defined and oriented
ZnO films have been obtained. However, the peak intensity of ZnO
film grown on SiO2 /Si substrate is much weaker compared with that
on Si3 N4 /Si substrate. This reveals that the amorphous SiO2 buffer
layer has a strong negative affect on the crystalline characteristics of
the ZnO films. The values of full width at half-maximum fwhm are
0.18, 0.16, and 0.33 for the ZnO films grown on Si, Si3 N4 /Si, and
SiO2 /Si substrates, respectively. In addition, it was observed that
the ZnO films annealed at 850C in nitrogen (N2 ) exhibit a similar
trend to that annealed in O2 atmosphere but the corresponding values 0.20, 0.19, and 0.45 of fwhm are larger in N2 atmosphere. It
implies that O2 annealing presents a more positive effect on crystalline characteristics of ZnO films than N2 annealing.
Figure 2 shows the bright-field TEM images of the ZnO films
deposited on various substrates and then annealed at 850C in O2
atmosphere. The cross-sectional microstructure of all the ZnO films
can be clearly divided into two regions: crystalline columnar shape
and interlayer flat belt. The columnar structure was grown along c
axis orientation but the interlayer forms a disorder structure that may
play a crucial important role in reducing stress due to lattice mismatch between ZnO and Si substrate. Both ZnO films deposited on
Si and Si3 N4 /Si substrates present similar cross-sectional microstructure as can be seen in Fig. 2a. However, as the ZnO film was
deposited on SiO2 /Si substrate, a large variation appears on the
microstructure as shown in Fig. 2b. A thicker disordered ZnO interlayer with rougher interface was identified for ZnO film grown on
SiO2 /Si compared to that on Si3 N4 /Si and Si. The formation of the
thicker disordered ZnO interlayer in ZnO/SiO2 /Si structure was believed to be strongly dependent on the crystal characteristics of the
SiO2 buffered layer. Some researchers reported that as the SiO2 film
was annealed at a high temperature exceeding 700C, many defects such as oxygen vacancies were easily produced and it became
the nonstoichiometric composition.12,13 As illustrated in Fig. 2c,
more oxygen vacancies are induced in the ZnO film deposited on the
SiO2 buffered layer. Furthermore, the diffusivity of the oxygen vacancies is faster than other defects in ceramic oxides. Therefore, in

Electrochemical and Solid-State Letters, 7 7 J20-J22 2004

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Figure 1. XRD patterns and fwhm inset of ZnO films sputtered at Si,
SiO2 /Si, and Si3 N4 /Si after annealing at 850C in oxygen atmospheres.

this condition, a thicker ZnO interlayer was formed on SiO2 buffered layer compared to Si3 N4 buffered layer. X-ray photoelectron
spectroscopy XPS was further used to investigate the depth profile
of element composition from columnar ZnO shape through disordered ZnO interlayer. As shown in Fig. 2c, the relative Zn/O ratio
obviously increases around the interlayer ZnO region in all cases,
implying that the ZnO interlayer disordered layer is nonstoichio
metric and contains more oxygen vacancies (VO
). Moreover, the
defect concentration of oxygen vacancy in ZnO/SiO2 /Si films was
apparently more than that in ZnO/Si3 N4 /Si films as confirmed by
XPS analysis, O 1s peak at 531.25 0.2 eV. In addition, a higher

VO
concentration was also detected in ZnO/SiO2 /Si films than that
in ZnO/Si that could be due to the diffusion of more extra defects
oxygen vacancies from the SiO2 buffered layer into ZnO films
during later thermal annealing. In contrast to SiO2 /Si and Si substrates, the diffusion of oxygen vacancies from Si3 N4 /Si into ZnO
was almost undetected.
Figure 3 illustrates the room-temperature PL spectra of ZnO
films deposited on various substrates and then annealed at 850C in
O2 atmosphere. From the spectra, note that the peak intensity of the
UV emission depends markedly on the substrates used. The ZnO
films deposited on Si substrate show a sharp free exciton peak
around 379 nm and a broad peak in the visible region between 550
and 650 nm. The PL emission peak corresponding to the UV emission appears around 377-379 nm 3.29-3.27 eV that should be a
near bandedge emission of ZnO films due to an exciton-related
activity.14 Concerning the visible emission, it should result from
deep-level emission which is generally associated with zinc interstitialsand oxygen vacancies in ZnO lattice. However, the PL spectra
of ZnO deposited on SiO2 /Si substrate are apparently different from
others. The PL spectra present two UV emissions peaked at 377 nm
3.29 eV and 394 nm 3.15 eV. The former one is the normally
observed UV peak and the latter one is similar to the one 401 nm
reported by Jeong et al. in low-temperature PL spectra of ZnO films
grown on p-type Si under oxygen-rich conditions. According to the
observation of Jeong et al., the emission band was assigned to the
electron transition from the bottom of the conduction band to the
zinc vacancies level.10 However, in our case, it may suggest that the
UV emission peak at 394 nm 3.15 eV results from the variation in
microstructure and is assigned to the transition form oxygen va
cancy (VO
) level to valence band, positioned approximately 0.20 eV
below the conduction bandedge.15 In addition to the UV emission,
the visible emission is also changed. The spectra corresponding to
the visible emission region also exhibit two broad peaks around 495
(2.50 eV) and 605 nm (2.05 eV). It implies that there may be

Figure 2. XTEM images of the ZnO grown on a Si3 N4 /Si and b SiO2 /Si
substrates after annealing at 850C in oxygen atmospheres. c Atomic ratio
(0.10) of zinc and oxygen at different depths form the surface of the ZnO
film on Si with various buffer layers.

two different defect transitions occurring at the same time. According to the defect model proposed by Lima,16 the green luminescence
(2.5 eV) corresponds to a transition from Zn to Zn and the red

).
luminescence (2.0 eV) is attributed to the oxygen vacancies (VO
It was believed that the variation of PL spectra in ZnO/SiO2 /Si was
influenced by the change of crystal characteristics thicker ZnO interlayer and rough interface between columnar ZnO and ZnO interlayer and defect concentration nonstoichiometric. According to
the investigation of Zhao et al. for asymmetric double GaAs/
AlGaAs quantum well, it was reported that the peak splitting in the
PL spectra may result from two transitions probably due to the geometric fluctuations layer-thickness fluctuation.17 Therefore, a
thicker ZnO interlayer could effectively relieve the stress to assist
the crystal growth but the disordered ZnO interlayer may induce
many defects to change the PL spectra. In contrast, ZnO/Si3 N4 /Si
structure does not exhibit those double emission peaks. Only a
strongly sharp UV peak centered at 377 nm 3.29 eV was detected.
It was believed that the ZnO film grown on Si3 N4 /Si substrate has
improved stoichiometry with few oxygen vacancies and Zn intersti-

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Electrochemical and Solid-State Letters, 7 7 J20-J22 2004

slightly compressed in low-temperature environment and the local
defect transition may be thermally quenched as evidenced from the
variation in the emission peak at 394 nm. The double peaks in the
UV region coexist in the whole temperature between 10 and 300 K
but show different intensities. This indicates that there are thermal
transfer effects. It seems that the local defect transition may be thermally quenched at low temperature and a large amount of oxygen
vacancies to induce defects transfer from oxygen vacancies (VO )
level to valence band was confined due to microstructure fluctuations. Further investigations for the temperature dependence on PL
are in progress and the results will be reported in the near future.
Moreover, although all the specimens were n-type ZnO films, the
carrier concentration of ZnO/Si3 N4 /Si sample is very close to intrinsic ZnO (1.40 1014 cm3 ) and can be increased by posttreatment. Thus, it may offer an alternative route to develop p-type
ZnO films on Si3 N4 /Si.
Conclusion

Figure 3. Room temperature PL spectra of the ZnO films deposited on various substrates after annealing at 850C in oxygen and nitrogen inset atmospheres.

tials concentration as shown in Fig. 2c because the PL emission

characteristics of ZnO films are strongly dependent on both the film
stoichiometry and the crystal quality of the film. Especially, as the
buffer layer (SiO2 ) becomes thicker in ZnO/SiO2 /Si structure, the
physical and optical properties of ZnO films become poor because a
thicker SiO2 layer induces more extra defects during annealing. In
contrast, in ZnO/Si3 N4 /Si structure, a thicker buffer layer (Si3 N4 )
prevents the formation and diffusion of extra defects and, thus, the
film stoichiometry of ZnO is improved. Therefore, ZnO films grown
on Si3 N4 /Si substrate present better physical and optical properties
than those on other substrates.
Low-temperature PL measurement was performed for a more
detailed investigation of the emission characteristics. As shown in
Fig. 4, the PL spectra obtained were measured at 10 K from the
same samples as shown in Fig. 3. The ZnO films grown on Si3 N4 /Si
substrate still show the strongest exciton-related emission peak at
374 nm (3.32 eV) along with blue shift. For the ZnO film grown
on SiO2 /Si, the PL peak centered at 394 nm becomes weak and
more broadening as compared with Fig. 3 butthe deep-level emission remains unchanged. Generally, the lattice distance would be

We have shown that the emission characteristics of ZnO films

grown on Si by rf magnetron sputtering are strongly influenced by
the buffer layer. Although all the ZnO films have strong c axis
orientation and present similar columnar-like crystal structure, the
PL results in this study apparently reveal that the buffer layer plays
a crucial role in crystal quality and film stoichiometry of the disordered ZnO interlayer. In the room-temperature PL spectra, the ZnO
films deposited on SiO2 /Si substrate show two double peaks, one
double 374 nm and 394 nm near the UV peak and the other one
495 nm and 605 nm located in the visible region. In addition to the
UV emission peak at 374 nm, the peak at 394 nm 3.15 eV in the
UV region was assigned to the transition from oxygen vacancies
(Vo ) level to valence band, positioned approximately 0.20 eV below the conduction bandedge, due to the variation of the type and
concentration of intrinsic defects in the local microstructure of
ZnO/SiO2 /Si. If the ZnO film was grown on Si3 N4 /Si, a very
strong UV along with invisible deep-level emission was detected
because the Si3 N4 can effectively improve film stoichiometry and
reduce the defect formation of oxygen vacancies and Zn interstitials
compared to SiO2 on Si. Moreover, the carrier concentration of the
ZnO/Si3 N4 /Si sample is very close to that of intrinsic ZnO
(1.40 1014 cm3 ) and can be increased by post-treatment.
Therefore, the ZnO deposited on Si3 N4 /Si substrate can be used as
a potential method to develop p-type ZnO film for optoelectronic
devices.
Acknowledgment
The authors gratefully acknowledge the National Science Council of the Republic of China for its financial support through contract
NSC-92-2216-E-009-014.
References

Figure 4. Low-temperature PL spectra measured at 10 K for the ZnO films

grown at various substrates after annealing at 850C in oxygen atmospheres.

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