o

ELSEVIER

TNn Solid Films295 (1997) 87-91

Characterization and optimization of zinc oxide films by r.f. magnetron sputtering

K.B. Sundaram, A. Khan
Department of Electrical and ComputerEngmeering, Universityof Central Florida, Orlando, FL 32816-2450, USA

Received 29 March 1996; accepted 15 August 1996

Abstract
Zinc oxide films were deposited by a r.f. magnetron sputtering using a zinc oxide target. The deposited films were characterized as a function of deposition temperature, pressure, argon-oxygen gas flow ratio, target-substrate distance. The deposition conditions were optimized to give good quality films suitable for the fabrication of surface acoustic wave device. The films deposited at temperatures as low as 250 C yielded surface acoustic wave device quality. 1997 Elsevier Science S.A. All rights reserved.
Keywords: Depositionprocesses; Sputtenng; Zinc oxide

1. Introduction
Zinc oxide (ZnO) is an n-type wide-bandgap semiconductor and has a variety of potential applications. Being a piezoelectric material, ZnO films find applications in surface acoustic wave devices (SAW) [ 1-3]. Low loss optical waveguides have been fabricated using ZnO films [4]. An electrooptic modulator is also reported using ZnO films [5]. The high optical transparency and electrical conductivity of ZnO has been used as a top contact window layer for solar cell applications [ 6,7]. ZnO thin films are used for heat-reflecting windows to enhance energy utilization in buildings [ 8 ]. ZnO films also find applications for hydrogen sensors [9,10]. ZnO films can be deposited by a variety of deposition techniques based on the specific applications one need from these films. Epitaxial ZnO films were grown on sapphire substrates by chemical vapor deposition (CVD) [11]. Recently pulse laser deposition has been tried to deposit ZnO films [ 12]. The most common technique to deposit ZnO films is by sputtering technique. Both d.c. and r.f. sputtering techniques have been used to deposit ZnO films [2,13,14]. The resistivity of the deposited ZnO films depends on the sputtering conditions. Usually, the films deposited without oxygen in the sputtering ambient are non-stoichiometric with conducting nature. This is due to the rich Zn in the deposited films [ 15]. For SAW device applications, ZnO should have a high electromechanical coupling coefficient, temperature stability, high electrical resistivity and c-axis oriented crystalline structure. Reactive d.c. sputtering using ZnO target 0040-6090/97/$17.00 1997 ElsevierScience S.A. All rights reserved PIIS0040-6090 (96) 09274--7

yielded fairly high resistive films [ 16,17]. One may need reactive sputtering using ZnO target to provide still higher resistive piezoelectric quality films suitable for SAW devices. Hence in the present work, ZnO films were deposited by an r.f. magnetron sputtering technique using ZnO target. The deposition conditions were optimized to yield SAW device quality films.

2. Experimental
2.1. Deposition o f ZnO films

The ZnO films were deposited in an r.f. magnetron (US Gun II) using a 5 cm diameter by 0.625 cm thick ZnO target (99.999% purity, Angstrom Sciences). Glass and n- type silicon wafers with a layer thermally grown 1 ~m SiO,_ were used as substrates. The n-Si wafers were of 11 f~ cm resistivity and of (100) orientation. The substrate were thoroughly cleaned with organic solvents and dried before loading in the sputtering system. The substrates were placed in the stainless steel substrate holder and a disc heater was placed on the top of the substrate. The heater was mechanically attached to the substrate holder with a piece of aluminum foil between the heater and the substrate holder to ensure good thermal contact. The temperature of the substrate was monitored with thermocouple attached near the substrate. The system was evacuated to a vacuum of the order of 5 10 -6 Torr using a cryo-pump and the substrate heating was initiated to attain

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K.B. Sundaram, A. Khan/Thm Solid Films 295 (1997) 87-91

the desired deposition temperature. The argon/oxygen gas injection was achieved through a shower head-like stainless steel tubing with a number of small opening. The ratio of argon (99.99% purity) and oxygen (99.99% purity) were dialed in the electronic mass flow meters. The gases were mixed before entering the chamber and were allowed to flow through an inlet valve to the chamber. Once the desired temperature and vacuum were achieved, a throttle valve was used to adjust the chamber pressure during sputtering. Once the plasma was struck, the pressure and the power were adjusted to the desired conditions. The reflected power was tuned to a minimum value and some times it was necessary to increase the forward power to achieve minimum condition. The ZnO target was sputter cleaned for 20 min before allowing any deposition to take place on the substrates. This allowed the system to stabilize and reach optimum condition. The substrate was then rotated to place above the target and the deposition was initiated. The thickness of the deposited films were measured using the standard optical interferometer (Bausch Lomb, Interferometer Model 31-1871 ) as well as a profilometer (Tencor Alpha Step Profllometer). X-ray diffraction studies of the films were performed using Philips Xray Diffractometer (Model XRG-3000), Cu Ka, h = 0.1542 nm. Scanning electron microscope (AMRAY, Model-1700) was used to look the vertical cross-section of the films.
2.2. Fabrication o f surface acoustic wave device

3. Results
3.1. Crystalline structure

The piezoelectric quality of the deposited ZnO films was evaluated by fabricating simple SAW delay lines. First, 1 ixm SiO2 was grown on (100) Si substrates by the wet oxidation technique at 1100 C. The ZnO film was sputter deposited using the optimum conditions listed in Table 1. The film area showing the highest reslstivity was identified for fabricating the SAW device. The lift-off photolithographic technique was used to pattern the transducers using the photoresist NR81500 (Futurrex Inc.). After developing the pattern, an aluminum film was deposited and lift-off was completed using acetone. The aluminum fingers served as transducer fingers for the SAW devices. The SAW transducer mask contained dies with different finger widths (2.5, 4.0, 6.0 and 8.0 ~m as well as finger pairs of (10, 50 and 100). The devices were tested using r.f. probes connected to a network analyzer (HP Model 8753C) to measure the SAW response. Table 1 Deposmonconditions of ZnO filmsfor SAW devices

The films deposited on glass and S i Q / S i substrate had a clear circular area about 2 cm in diameter surrounded by a cloudy annular region. The cloudy film appeared rough with voids and pits compared to clear region which appeared smooth. The two regions represent different growth conditions. The clear area is indicative of uniform growth of polycrystalline structure while the cloudy area showing more irregular growth conditions. It has been reported that a film with smooth surface features and dense packing is evident of the highest coupling factor and good piezoelectric properties [ 1]. Even though the variation of the film thickness of the two regions were marginal, the clear region was slightly thicker than the hazy region. Similar thickness variation due to spatial variation of deposition rates was observed in the d.c. diode sputtering of ZnO thin films by Minakata et al. [ 18]. The growth of clear and cloudy films may be due to the combined effects of the folio wing reasons, namely plasma confinement seen in a magnetron sputtering system, temperature variations on the substrate and oxygen/argon flow pattern in the sputtering system. The crystalline structure and orientation of the deposited films were investigated by X-ray diffraction (XRD). Figs. 1 and 2 show the diffraction patterns of the films deposited on glass substrates for clear and cloudy films. Major peaks identified compared with JCPDS file 36-1451 (International Center for Diffraction Data, 1990) for ZnO are seen at 31.8 , 34.4 , 36.3 , 47.5 , 56.6 , 62.9 , and 72.6 and equivalent to d-spacings of 0.2814, 0.2603, 0.2476, 0.19 t 1, 0.1625, 0.1477 and 0.1302 nm corresponding to (100), (002), (101), (102), (110), (103), and (004) plane reflections from hexagonal type ZnO with a = 0.32498 and c = 0.52066 nm. These are typical polycrystalline films with preferred orientations. The clear film showed the characteristic c-axis oriented peak at 20=34.4 (Fig. 1) where as the cloudy film showed a
t

'

Substrate temperataure(C) Target-substratedistance (cm) Oxygen/argon flowratio Pressure dunng sputtenng Forward power (W) Reflected power (W) Depositiontame (h) Thickness (~m)

250 2.5 2:3 1 10-z 60 0 3 1

10

2~0

30
28(deg}

60

70

80

90

Fig. 1 X-ray diffraction pattem of ZnO film (clear reglon) deposited on glass.

K.B Sundaram, A Khan ~Thin Solid Fihns 295 (1997) 87-91

89

_Z

20

3'o

/o

5'o
28(deg)

;o
Fig. 4. SEM pmture of the vemcal cross-sectionalview of the ZnO films deposited on S10=/Si.
16

Fig. 2. X-ray diffraction pattern of ZnO film (cloudy region) deposited on glass

E ~12

re

g 8
N a m 4 0 ,

i
s
T

50

100

150 200 Temperature

250 300 (~C)

350

400

Fig 5 Depositionrate versus substratetemperature. g

10

20

3~0

5'0
2 (degl

6'0

zo

T 90

3.2. Effect of temperature and resistivity

Fig. 5 shows the variation of the deposition rate with temperature for the ZnO films deposited on glass substrates. All other conditions were kept constant (O2/Ar ratio, 2:5; targetsubstrate distance, 3.8 cm; pressure, 10 -2 Torr). The deposition rate decreased as the temperature was increased. The temperature at the surface controls the mobility of the adsorbed atoms and the resulting structural development of the film. A cool surface with low adatom mobility tends to form crystallite structures that are low in density, highly porous, and have rough surfaces. High substrate temperatures enhance atom mobility and cause the re-evaporation of poorly combined structures. This causes the decrease in the rate of deposition of the film but increases the quality of the film. This also seen in Fig. 6, which shows the relationship between the resistivity of the film and substrate temperature. As the temperature increased the resistivity increased showing the nature of high quality films. The film deposited at 300 C showed resistivity as high as 107 ~2 cm.

Fig. 3. X-ray dlffractlon pattern of ZnO film (clear regmn) deposited on SiO=/&

strong peak at 20=31.8 corresponding to (100) peak (Fig. 2). Fig. 3 shows the XRD pattern of the ZnO film deposited on SiO2/Si indicating strong c-axis orientation seen for piezoelectric quality ZnO films [ 19,20]. The (002) peak seen on Si is much stronger than seen on the glass substrates. The cloudy films on SiO2/Si showed XRD pattern similar to clear films deposited on glass (Fig. 1) indicating some kind of c-axis orientation. Tominaga et al. observed that high-energy neutral atoms bombarding the substrate have a direct influence the c-axis film growth [ 19]. The energetic oxygen atoms bombard substrates mounted at positions facing the area of erosion of the target particularly seen in a magnetron system [21]. The cloudy film growth region is the area where the flux of energetic atoms bombarding the film surface is the highest. Fig. 4 shows the vertical crosssectional view of the ZnO film of nearly 2 txm deposited on SiO2/Si. The columnar growth of the film is clearly seen which is indicative of highly c-axis oriented piezoelectric quality film [ 1].

3.3. Effect of oxygen~argon ration

In order to obtain stoichiometric ZnO film, one needs a sufficient amount of oxygen with argon in the sputtering

90
1E7

K.B. Sundaram, A. Khan /

ThinSolid Films 295 (1997) 87-91

1,00E+08 g l,00E+07

g
E -= o

1E6E I,OOE+06
1E5

1,00E+05
te

1E4

~: 1 0 0 E + 0 4

lea
0

1 00E+03 300 10

50

100
Temperature

150

200 (C)

250

20
Oxygen

30 (%)

40

50

Fig 6. Reslslavityversus substratetemperature.

14.

Fig. 8. Resistivtty versus oxygen content in the sputtering ambient.

75

~"_I2
10

.._..,.o o
6 -~55 = 5

8
8 gr~ 6

~4s c~ 4
I I I I

35
50
I I I

10

20
Oxygen

30 (%)

40

10
Pressure

12

14 16 (mTorr)

18

20

Fig 7 Deposmon rate versus oxygen/argon flow ratm.

Fig. 9. Deposition rate versus sputteringpressure. with an O2/Ar ration of 2:3. Below 2 X 1 0 - 3 Torr the plasma could not be sustained. The maximum deposition rate occurred around 1.5 10 - 2 T o r r , t h e n a decreasing trend was observed. This type of behavior is mostly seen during sputter depositions.

ambient. Fig. 7 shows the deposition rate as function of oxygen/argon ratio. Again all other sputtering conditions were
maintained constant as indtcated above. Initially, the deposited rate decreased as the oxygen ratio was increased up to

15% then a small increase followed by decreasing trend was observed beyond 30%. Similar observation was seen by others [ 17]. For oxygen content in the range of 20-30%, rapid oxidation of the target takes place. Oxide targets have higher secondary electron yield than metal targets [22]. This increase m secondary electron yield causes more ionization of the sputtering gas and increase in the ion current, thus increasing the sputtering rate. A further increase in the oxygen content causes a decrease in the sputtering rate. This is attributed to the fact that oxygen chemisorbs on the target and forms a surface layer of adsorbed oxygen. This layer inhibits
the sputtering of the atoms thus reducing the rate of deposition. Also, with high oxygen content, the amount of Ar ions

3.5. Effect of target-substrate distance on the deposition rate and resistivity

The target to substrate distance is very critical on the electrical properties of the ZnO films. Figs. 10 and 11 show the dependence of the deposition rate and the resistivity with target-substrate distance. It can be seen that the deposition rate increased with the increase in distance. This effect is not
fully understood but it is possible that when the substrate is very close to the target, the negative and neutral ion b o m 18

is decreased in the sputtering ambient. Since oxygen has a

lower @uttering yield than Ar, the net sputtering rate decreases. Fig. 8 shows the effect of oxygen on the resistivity

of the film. The addition of oxygen significantly increased the resistivity to a value as high as 107 [2 cm for 50% oxygen.
It has been shown that excess oxygen is usually chemisorbed

E =,~,14 12

on the surface and bonded at the defects causing an increase

in resistivity [23]. Further, the film becomes more stoichio-

g:10
8

metric with more oxygen incorporation into ZnO. 3.4. Effect of pressure on deposition rate
The effect of the sputtering gas pressure on the depositton

8 g O '6
4 2

3
Target

4
- Substrate

5
Distance

6 (cm)

rate is shown in Fig. 9. The deposition was done at 200 C

Fig. 10 Deposmon rate versus target-substratedistance.

K B. Sundaram, A. Khan / Thm Sohd Films 295 (1997) 87-91

91

3 00E+07 g2 50E+07

~ 2 00E+07
150E+07 ~1 00E+07 s 500E+O6
000E+00

good piezoelecmc films. The depositions gave clear looking films at the center and cloudy films at the edges. It was found that the clear films correspond to highly c-axis oriented structure with high resistivity for surface acoustic wave devices.

Acknowledgements
The authors wish to thank Mr. K. Casey for the help received during the fabrication of the SAW devices and Dr. D.C. Malocha for useful discussion during the entire work. The authors also thank Sawtek Inc. (Orlando, FL) for providing the masks required for the fabrication of SAW filters.
4el ~S

~ . . ~ . _ ~ ; 2 3 4 5 6 Target-SubsirateD~stanee (cm)
NAG 5 dB/ REF -55 ~B ~.-~

Fxg. 11. Resistivity versus target-substrate distance

CHI S21 l~g

.....

t ....

t-T .... ;--

References
F.S. Hmkemell, IEEE Trans Somcs Ultrasonics, SU-32 (1985) 621 S. Manxv and A Zangvd, J Appl. Phys , 49 (1978) 2787 B.T Khun-Yakub and J.G. Struts, o Appl. Phys., 52 (1981) 4772. r. M Wu, A Azuma, T Sluosaka and A Kawabata, J. Appl. Phys, 62 (1987) 2482. [5] D Persegol, E P i c and J. Planuer, J. AppL Phys., 62 (1987) 2563. [6] J. Aranovich, A. Ortiz and R.H. Bube, J. Vac. Sci Technol., 16 (1979) 994. [7] J. Hu and R.G. Gordon, J. Electrochem Soc., 139 (1992) 2014. [8] R E I Schropp and A Madan, J. AppL Phys., 66 (1989) 2027. [9] D L. Leafy, J.O. Barnes and A.G. Jordan, J. EIectrochem. Soc., 129 (1982) 1382. [t0] A Plzzmx, N Butta, D Narduccl and M Palladino, J Electrochem Soc., 136 (1989) 1945. [ 111 M. Kasuga and M. Moctuzukl, J. Cryst Growth, 54 ( 1981 ) 185. [12] V. Cracmn, J. Elders, J.G.E. Gardemers and I W Boyd, Appl. Phys. Lett, 65 (1994) 2963 [13] T Hada, K Wasa and S. Hayakawa, Thin Sohd Films, 7 ( 1971 ) 135 [141 R J Lad, P D Funkenbusch and C R Aita, or. Vac. Sct. Technol, 17 (1980) 808. [15] G A. Rozgonyx and W J. Pohto, Appl Phys Lett., 8 (1966) 220 [16] D.K. Raimondl and E. Kay, J. Vac Sct Technol, 7 (1970) 96 [17] K B Sundaramand B K. Garside, J Phys D'AppI Phys, 17(1984) 147. [18] M. Minakata, N. Chubachi and Y. Kikuchi, Jpn J Appl Phys., 11 (1972) 1852. [19] K. Tormnaga, S. Iwamura, I Fujlta, Y. Stuntani and O. Tada, Jpn J Appl Phys, 21 (1982) 999 [2o] K Ohp, T Tohda, K. Wasa and S. Hayakawa, J Appl Phys, 47 (1976) 1726 [21] K Tommaga, T. Yuasa, M Kume and O. Tada, Jpn. J. Appl. Phys, 23 (1984) 936. [22] F S. Hlckernelt, J. Sohd State Chem., 12 (1975) 225 [23] N Croxtoru, A Sedman and K Yassxn, Thin SohdFilms, 150 (1987) 291 [24] M G. Holland and L.T. Claiborne, Proc. IEEE, 62 (1974) 582 [ 1] [2] [3] [4]

Fig. 12

Insertion loss versus frequency of a SAW delay hne filter using ZnO piezoelectric film.

bardment on the growing film is the highest which causes resputtering of the growing film. When the distance increases this bombardment decreases causing increase in growth rate. A large increase in the distance will finally decrease the deposition rate as in any sputtering technique. The resistivity of the film decreased with increase in distance. The resistivity of the ZnO film depends on the amount of oxygen incorporation in the film.
3.6. Acoustic measurement

The piezoelectric quality of the deposited ZnO films was investigated by making surface acoustic wave delay line filters. Fig. 12 shows the typical insertion loss versus frequency of a filter. The inter-digital transducer had 50 finger pairs with finger width of 4 Ixm. The insertion loss was 44 dB at a fundamental frequency of 266.9 MHZ. The velocity of the wave was calculated to be 2225.5 m s-~ which is closer to that of intrinsic ZnO [24].

4. Conclusion
ZnO films were deposited by r.f. sputtering using a ZnO target. Deposition conditions are very critical for obtaining