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Structural and Optical Characterizations of ZnO Films Grown by Reactive Electron Beam

Evaporation

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2000 Chinese Phys. Lett. 17 694

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CHIN.PHYS.LETT. Vol. 17,No.9 (2000) 694

Structural and Optical Characterizations of ZnO Films Grown by Reactive

Electron Beam Evaporation *

WU H u i - Z h e n ( 2 B ~ ) ' t 2 ,XU Xiao-Ling (@@&), QIU Dong-Jiang(@z>E)',

HE Ke-Ming(.lqRg)l, SHOU Xiang (@%)
'Department of Physics, 'State Key Laboratory of Silicon Materials Science, Zhejiang University, Hangzhou 310028

(Received 16 March 2000)

Low temperature epitaxial growth of ZnO films is achieved on Si(OO1) substrates by reactive electron beam evap-
oration, Growth temperature is varied from 125°C to 420°C and the optimum temperature is found between
200" C and 300" C. X-ray diffraction shows that the ZnO films are highly c-axis oriented and the line width of (002)
diffraction peak is significantly smaller than that measured from the ZnO films deposited by magnetron sput-
tering. The combined photoluminescence and photoluminescence excitation (PLE) spectroscopic measurements
demonstrate the sharp band-absorption edge and exciton absorption in the ZnO films. PLE has also revealed that
the absorption characteristic near the band edge is remarkably improved with the increase of oxygen content in
the ZnO films, although x-ray diffraction analysis shows that the crystalline structure of ZnO films grown under
different oxygen pressures remains unchanged.

PACS: 81.15. Jj, 78.55.Et, 61. 10. -i, 78.55.-m

Zinc oxide (ZnO) is a wide band-gap (E, =
3.37eV) material.' Epitaxial ZnO film has many
potential applications, such as in nonlinear optical
devices,2 light emission device^,^>^ and transparent
electrodes for solar cells.5 High quality ZnO films are
usually grown at relatively high substrate tempera-
ture varying from 450°C to 750°C by molecular beam
epitaxy (MBE)l and metallorganic chemical vapor de-
position (MOCVD)' on sapphire substrates. Poly-
crystalline ZnO films have been grown by rf and dc
magnetron sputtering on sapphire and X-ray
diffraction shows that the line width of the dominant
diffraction peak (002) of these films is rather broad.
Furthermore, there are few reports on the systematic
study of the optical properties of ZnO films grown by
magnetron ~ p u t t e r i n g .In
~ this work, a reactive elec-
tron beam (e-beam) evaporation system is used to the
low temperature epitaxy of monocrystalline ZnO films
on Si(OO1) substrates. Combined measurements of
photoluminescence (PL) and photoluminescence exci-
tation (PLE) are used to study the optical transitions
in the ZnO films.
The ZnO films are deposited on Si(OO1) substrates
by using a reactive e-beam evaporation system. The
base pressure in the chamber is N 5 x Pa. The
cleaning processes of Si substrates use the conven-
tional Shiraki method. The substrate is resistance-
heated and its temperature varies from 125°C to
420°C. Polycrystalline ZnO (99.9% of purity) is used
as the evaporation source. To enhance the stoi-
chiometry of the deposits, oxygen is introduced into
the chamber during evaporation at the pressure of
3x Pa. It is believable that the collision of 0 2
molecules with high-energy electrons from e-beam gun
could partly ionize 0 2 molecules, because in our ex-
periment the energy of e-beam reaches 10 keV.
Film thicknesses is determined by a stylus method.
The growth rate of ZnO films on Si is about 8 nm/min.
Crystallographic morphology of ZnO film surface is
observed by Hitachi S-570 scanning electron micro-
scope (SEM) and crystalline structure of ZnO films is
analyzed by Rigaku Dmax-IIIB X-ray diffractometer
with Cu K , radiation. Photoluminescence and pho-
toluminescence excitation measurements are employed
to characterize the optical properties of ZnO films.
The energy of primary electron beam for the SEM
analysis is 20keV. SEM micrograph shows that the
surface morphology of ZnO thin films correlates well
to the growth temperature. Along with the varia-
tion of growth temperature the surface morphology
of the ZnO films is remarkably different. At very
low growth temperature (below 15OoC ) the film sur-
face is rough. The films appear brown reddish and
opaque. As growth temperature is increased, the sur-
face of ZnO films becomes uniform and smooth. High-
resolution SEM observation of ZnO films shows that
the sample grown at about 250°C has the best mor-
phology as shown in Fig. 1. The film is transparent.
The uniformly distributed bright patterns in the fig-
ure are due to the 3-D character of ZnO growth on
Si(OO1). Its peak-peak roughness is only -~200h,in
the same order as the surface roughness of films grown
by MBE.1° However, when the substrate temperature
is increased over 300°C the growth rate decreases and
the surface becomes non-uniform. The dependence of
surface morphology on substrate temperature could be
interpreted as follows. ZnO particles sputtered from
the evaporation source have energy of about 10 eV and
these energetic particles could be very "hot". When
ZnO adatoms reach sample surface, they are firstly ad-

*Supported by the National Natural Science Foundation of China under Grant No. 69606006, and Natural Science Fund of
Zhejiang Province.
@by the Chinese Physical Society
No. 9 WU Hui-Zhen et al. 695

sorbed on the surface. On the one hand, the adsorbed

atoms would move on the surface by diffusion or hop-
ping and stop at a position with lower surface poten-
tial. On the other hand, the excess energy of particles
would be transferred to substrate to reach the equi-
librium. The diffusion or hopping distance depends
on the substrate temperature. When the substrate
temperature is low, the adatoms are rapidly cooled
and diffusion or hopping distance is small. Thus the
surface is rough and its structure is polycrystalline as
shown in x-ray diffraction, which will be discussed in
the following section. As the substrate temperature
further increases, desorption of Zn and 0 on surface
would be enhanced. Thus the stoichiometry of the film
could be changed and the growth surface will become
rougher.

Fig. 1. SEM image of the surface of the ZnO film grown

on Si(OO1) at 25OOC by a reactive e-beam evaporation sys-
tem.

ZnO has a wurtzite crystallographic structure con-

sisting of interpenetrating zinc and oxygen hexagonal-
close-packed (hcp) lattice. Its lattice constants are
a = 0.32498nm and c = 0.52066nm. Figure 2 shows
the x-ray diffraction rocking curves (28) from ZnO
films deposited at different temperatures. To identify
the grain crystallites in the ZnO films and to verify
whether any grain orientation is present, the curves
are plotted in logarithm intensity. The curve ( a ) dis-
plays the result for the sample grown at 125'C. The
main peaks at 34.36' and 72.60' are identified as the
(002) and (004) diffractions, respectively. Thus one
concludes that even at very low growth temperature
the ZnO film grown by reactive e-beam is still highly
c-axis oriented. However, grain crystallites oriented in
(101), (102) and (103) are also observed in this sam-
ple. As growth temperature reaches 250'C, the film
shows monocrystalline structure and only the c-axis
orientation is observed (curve b). However, at higher
growth temperature, similar grain crystallite orienta- Fig. 3. FWHM of the ZnO (002) diffraction peak on the
tions would be observed again (curve c). Si(OO1) substrates versus growth temperature.
696 WU Hui-Zhen et al.
300 350 Eo 400 450 500
Wavelength (nm)
Fig. 4. Room temperature measured P L (dotted line) and
P L E spectrum at 475 nm (solid line) of ZnO film deposited
on Si(OO1).
Figure 3 shows the full width at half maximum
(FWHM) of ZnO (002) peaks versus growth tem-
peratures. It is seen that the FWHM of the (002)
peak is sensitive to the variation of substrate temper-
ature. The sample grown at 25OOC has the small-
est FWHM, and the FWHM of the ZnO (002) peak
from this sample is 0.28', which is significantly smaller
than that obtained from ZnO films deposited by mag-
netron sputtering(~O.7'). Compared with MBE and
MOCVD techniques, the growth temperature of ZnO
films by e-beam evaporation is significantly lowered.
Figure 4 shows the typical room-temperature PL and
PLE results from a ZnO sample deposited at 250OC.
The dotted curve shows a PL spectrum. It can be seen
that emissions from impurity energy levels at about
400, 430 and 475 nm dominate the PL spectrum. The
deep impurity levels are of 200, 416 and 690meV be-
low the bottom of conduction band. Emissions from
the deep-level impurities can usually be observed in
both MOCVD' and MBE' grown samples. It is ex-
pected that the density of impurities involved in this
sample could be higher than those grown by MBE and
MOCVD because of low vacuum in the growth cham-
ber and not high enough purity of ZnO source used
in this experiment. As for the broad shoulder around
380nm in the PL spectrum, it can be explained by
the donor levels' extending into the impurity bands
and merging with the bottom of the conduction band
because of the n-type conductance of ZnO.
The PLE experiment was described in Refs. 11 and
12. In the PLE measurements, the detection energy
is set at the low energy peak of 475 nm and excitation
line scanned from 300nm to 410nm. The PLE spec-
trum is given by solid line in Fig.4. The absorption
edge Eo is at about 386nm. The corresponding pho-
ton energy is 3.21 eV. This value is lower than the band
edge of the conduction band (3.37eV at room temper-
ature). The main contribution of the band edge shift
comes from the band tail effect due to the presence
of impurity, which can be clearly seen in the PLE.
The peak at about 370 nm (3.35 eV) is tentatively at-
tributed to the absorption of both free exciton and
free carriers. It is known that excitons in ZnO mate-
rials have large binding energy (60 meV) compared to
the average thermal energy kBT at room temperature
Vol. 17
(26meV). Thus even at room temperature the exci-
ton absorption still plays an important rule in optical
transitions though the phonon and impurity scatter-
ings in the sample will disturb the formation of ex-
citons. It is noted that the band edge in the PLE
spectrum is sharp. This indicates that the density
of states of impurities is much smaller than that at
the bottom of conduction band. It is interesting to
note that when the oxygen pressure is lowered dur-
ing ZnO growth the slope of absorption edge becomes
smaller though crystalline structure of the ZnO film is
still highly c-axis oriented. The physical mechanism is
that when oxygen pressure is lowered, the film may be
Zn-rich and large amount of 0 vacancies are possibly
created. The presence of 0 vacancies in ZnO will dis-
turb the lattice periodicity. This additional potential
scatters electrons moving in the crystal. The broad
peak a t about 345nm in the PLE is presumably re-
lated to the absorption of ZnO quantum dots, which
will be further investigated.
In summery, by using reactive e-beam evapora-
tion the high quality ZnO films are achieved on
Si(OO1) substrates. The optimum temperature for the
growth of monocrystalline ZnO film is between 200
and 30OOC. X-ray diffraction shows that the ZnO films
are highly c-axis oriented and the FWHM of ZnO(002)
peak is significantly smaller than that measured from
ZnO films deposited by magnetron sputtering. The
combined photoluminescence and photoluminescence
excitation spectroscopic measurements demonstrate
the sharp band absorption edge and exciton transi-
tions in the ZnO films by e-beam evaporation. Com-
pared to the growth of ZnO by MOCVD and MBE,
the growth temperature of high-quality ZnO films is
significantly lowered.
REFERENCES
1 D. M. Bagnall, Y. F. Chen, Z. Zhu, T. Yao, S. Koyama, M.
Y. Shen, and T . Goto, Appl. Phys. Lett. 70 (1997) 2230.
2 M. H. Koch, P. Y. Timbrel1 and R. N. Lamb, Semicond.
Sci. & Technol. 10 (1995) 1523.
3 K. Vanheusden, C. H. Seager, W. L. Wareen, D. R. Tal-
lant, J . Caruso, M. J . Hampden-Smith and T . T. Kodas, J.
Lumin. 75 (1997) 11.
4
Z. K. Yang, P. Yu, G. L. Wong, M. Kawasaki, A. Ohtomo,
H. Koinuma and Y. Segawa, Solid State Commun. 103
(1997) 459.
5 R. Scheer, T. Walter, H. W. Schock, M. L. Fearheiley and
H. J. Lewerenz, Appl. Phys. Lett. 63 (1993) 3294.
6 C. R. Gorla, N. W. Emanetoglu, S. Liang, W. E. Mayo, Y.
Lu, M. Wraback and H. Shen, J. Appl. Phys. 85 (1999)
2595.
7 A. Rose, J . Exarhos, Thin Solid Films, 308-309 (1997) 42.
8 K. Ellmer, R. Cebulla, R. Wendt, Thin Solid Films,
317(1998) 413.
9 FU Zhu-xi, GUO Chang-xin, LIN Bi-xia and LIAO Gui-
hong, Chin. Phys. Lett. 15 (1998) 45.
10 H. Z. Wu, X. M. Fang, R. Salas Jr, D. McAlister and P. J.
McCann, J. Vac. Sci. Technol. B 17 (1999) 1263.
11 W U Hui-zhen, YANG Ai-ling, WU Jian-zhong and LI
Zheng-zhi, Chin. Phys. Lett. 15 (1998) 734.
12 H. Z. Wu, J . H. Liu, G. Q. Dong, J . Z. Wu, 2. Z. Ye and
X. B. Jiang, J. Vac. Sci. Technol. B 15 (1997) 849.