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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 Hui-Zhen(2B~)'t2,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 ~puttering.~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 3 x Pa. It is believable that the collision of 02 molecules with high-energy electrons from e-beam gun could partly ionize 02 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

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sorbed on the surface. On the one hand, the adsorbed atoms would move on the
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.
be changed and the growth surface will become rougher. Fig. 1. SEM image of the surface
Fig. 1. SEM image of the surface of the ZnO film grown on Si(OO1) at
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
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-
tions would be observed again (curve c).
orienta- tions would be observed again (curve c). Fig. 3. FWHM of the ZnO (002) diffraction
Fig. 3. FWHM of the ZnO (002) diffraction peak on the Si(OO1) substrates versus growth
Fig. 3. FWHM of the ZnO (002) diffraction peak on the
Si(OO1) substrates versus growth temperature.

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WU Hui-Zhen et al.

Vol. 17

300

350

Eo 400

450

Wavelength (nm)

500

Fig. 4. Room temperature measured PL (dotted line) and PLE 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-

compared to

the average thermal energy kBT at room temperature

rials have large binding energy (60 meV)

(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 at 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.

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