Materials Letters 61 (2007) 2050 2053 www.elsevier.

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Effect of oxygen partial pressure on the structural and optical properties of sputter deposited ZnO nanocrystalline thin films
Preetam Singh a , Amit Kumar Chawla b , Davinder Kaur a , Ramesh Chandra b,
b

Functional Nanomaterials Lab, Department of Physics, Indian Institute of Technology Roorkee, Roorkee, 247 667, India Nano Science Laboratory, Institute Instrumentation Centre, Indian Institute of Technology Roorkee, Roorkee, 247 667, India Received 19 August 2005; accepted 8 August 2006 Available online 28 August 2006

Abstract We report the influence of deposition parameters such as oxygen partial pressure and overall sputtering pressure on the structural and optical properties of the as-grown ZnO nanocrystalline thin films. The films were prepared by dc magnetron sputtering using Zn metal target under two different argon and oxygen ratios at various sputtering pressures. Microstructure of the films was investigated using X-ray diffraction and scanning electron microscopy. Optical properties of the films were examined using UVVisible spectrophotometer. The results show that the films deposited at low oxygen partial pressure (10%) contain mixed phase (Zn and ZnO) and are randomly oriented while the films deposited at higher oxygen partial pressure (30%) are single phase (ZnO) and highly oriented along the c-axis. We found that the oxygen partial pressure and the sputtering pressure are complementary to each other. The optical band gap calculated from Tauc's relation and the particle size calculation were in agreement with each other. 2006 Elsevier B.V. All rights reserved.
Keywords: Nanocrystalline thin films; Sputtering; X-ray diffraction

1. Introduction The fabrication and operation of modern semiconductor electronics systems, such as computers and wireless communication systems rest upon nanotechnology. The application of nanotechnology and the control and uniformity of nanostructures will become even more important for these and other yet to be invented semiconductor electronic-based systems. ZnO nanomaterials are promising candidates for nanoelectronics and photonic devices. Compared with other semiconductor materials, ZnO has higher exciton binding energy (60 meV), is more resistant to radiation and is multifunctional with uses in areas such as a piezoelectric, ferroelectric and ferromagnetic. ZnO-based semiconductor and nanowire devices are also promising for integration on a single chip [18]. The ZnO probably has the richest family of nanostructures among all materials, both in structures and in

Corresponding author. Tel.: +91 1332 285 743; fax: +91 1332 273 560. E-mail address: ramesfic@iitr.ernet.in (R. Chandra). 0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2006.08.013

properties. The nanostructures could have novel applications in optoelectronics, sensors, transducers and biomedical sciences. The nanobelts and relevant nanostructures are a unique group that is likely to have important applications in nanosize electronic, optical, sensor and optoelectronic devices. The electrical, optoelectronic and photochemical properties of undoped ZnO have resulted in use for solar cells, transparent electrodes and blue/UV light emitting devices [915]. To produce these devices, many techniques have been used to deposit nanocrystalline zinc oxide thin films. These are molecular beam epitaxy [16], metal organic chemical vapor deposition [17,18], magnetron sputtering [1921], pulsed laser deposition [22], atomic layer deposition [23], spray pyrolysis [24], filtered cathode vacuum arc [25] and ion-assisted deposition [26]. In the present study we have tried to see the effect of the oxygen partial pressure as well as the overall sputtering pressure on the structural and the optical properties of the nanocrystalline ZnO thin films prepared by dc magnetron sputtering. It has been observed that the structural and the optical properties are strongly dependent on the processing conditions, such as gas

P. Singh et al. / Materials Letters 61 (2007) 20502053 Table 1 Measured properties of the ZnO nanocrystalline thin films Sample a b c d e f Particle size (XRD) (nm) 10.8 15.7 20.8 16.2 21.6 25.3 Eg (opt.) (eV) 3.252 3.225 3.205 Eg (XRD) (eV) 3.253 3.225 3.214 3.223 3.213 3.209

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phase composition, plasma conditions and geometry of the deposition system. In this paper we report a detailed study of the properties of ZnO nanocrystalline films grown under different oxygen partial pressures during deposition. 2. Experimental ZnO nanocrystalline thin films were deposited by dc magnetron sputtering using Zn (99.99%) metal (pressed powder) target. Premixed Ar and O2 gases were used during sputtering. The samples were prepared by sputtering in an atmosphere of Ar + O2 in the ratio 9:1 and 7:3 respectively. The gas pressure was carefully monitored and kept at three different values of 20, 50 and 100 mTorr. All the other parameters were kept constant, except oxygen partial pressure and the overall sputtering pressure. Sputtering was done for a set period of time at fixed power of 50 W and at room temperature. The ZnO films were characterized by XRD for the structural properties by using Siemens-D-5000 Diffractometer. The surface morphology and the microstructure of the films were studied using scanning electron microscope (JEOL). Optical reflectance and absorption were measured in the 200800 nm wavelength range using a Shimadzu UV-2100 spectrophotometer.
3. Results and discussion Fig. 1 shows the XRD pattern of the nanocrystalline thin films of ZnO. Samples a, b and c were deposited in ArO2 mixture (9:1) at pressures of 20, 50 and 100 mTorr respectively. Similarly samples d, e and f were deposited in the ArO2 ratio of 7:3 at pressures of 20, 50 and 100 mTorr respectively. It is evident from Fig. 1 that at low oxygen partial pressure and overall low sputtering pressure the film (sample a) is a randomly oriented mixed phase (Zn and ZnO) while with an

Refractive index (n) 3.59 3.84 3.78 3.89 3.92 3.86

increase in oxygen partial pressure the film (sample d) becomes single phase (ZnO) that is highly oriented along the c-axis. But when the oxygen partial pressure is kept constant (i.e. 10%) and the sputtering pressure is increased to 50 mTorr and 100 mTorr (samples b and c) the traces of Zn metal disappear. These results show that the oxygen partial pressure and the sputtering pressure may be complementary to each other as in both cases either increasing the oxygen partial pressure from 10% to 30% keeping chamber pressure constant (samples a and d respectively) or increasing the chamber pressure from 20 mTorr to 50 mTorr keeping oxygen pressure constant (samples a and b respectively) the traces of Zn metal from the sample disappeared. All the samples show a highly intense (002) reflection (except sample a) similar to the dominant reflection of bulk ZnO. In order to calculate the particle size, d of the samples we have used the Scherrer formula [27] d 0:9k BcoshB

where , B and B are the X-ray wavelength (1.54056 ), Bragg diffraction angle and line width at half maximum. The calculated particle sizes are shown in Table 1. Fig. 2 shows scanning electron micrographs of the nanocrystalline thin films deposited in 10% and 30% of oxygen partial pressure. It is evident from Fig. 2 that the ZnO sample deposited in 10% of oxygen partial pressure [Fig. 2(a)] looks highly dense and uniform compared to the sample deposited in 30% of oxygen partial pressure [Fig. 2(b)]. But the XRD data for 10% of oxygen (sample a) shows clearly mixed phase of Zn metal and ZnO whereas films deposited in 30% of oxygen (sample d) partial pressure consist of single phase ZnO. The optical reflectance and the absorption spectra of the nanocrystalline films were recorded as a function of photon energy (h) in the wavelength range 200800 nm. In order to determine the direct optical band gap, we used the Tauc relationship [28] as follows: ahm Ahm Eg n where is the absorption coefficient, A is a constant, h is Planck's constant, is the photon frequency, Eg is the optical band gap and n is 1/2 for direct band gap semiconductor [29]. An extrapolation of the linear region of a plot of (h)2 on the y-axis versus photon energy, (h) on the x-axis gives the value of the optical band gap Eg since Eg = h when (h)2 = 0. The absorption spectra of the samples that were deposited in constant oxygen partial pressure (30%) but at a different overall sputtering pressure are shown in Fig. 3. The samples a, b and c were deposited only on silicon hence their absorption data cannot be taken. We know that the mean free path of the sputtering gas molecules is given by

Fig. 1. XRD patterns of the ZnO films at overall pressure of 20, 50 and 100 mTorr.

k 2:330 1020

T Pd2 m

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P. Singh et al. / Materials Letters 61 (2007) 20502053

Fig. 2. SEM micrograph of the ZnO films on Si substrates prepared in (a) Ar:O2 = 90:10 and (b) Ar:O2 = 70:30.

where T is the temperature, P is the pressure and m is the molecule diameter. Thus as the sputtering pressure increases there will be a decrease in the mean free path and hence an increase in the collision frequency. Due to a large number of collisions the sputtered atoms have a higher probability to agglomerate (i.e. increase in particle size) before arriving at the substrate surface. So with an increase in the sputtering pressure the particle size increases which in turn decreases the band gap. The same reason also holds for the disappearance of the Zn metal traces from the nanocrystalline films on increasing the sputtering pressure keeping the oxygen partial pressure constant at 10%. An increase in sputtering pressure decreases the mean free path, which in turn increases the probability of collision of Zn metal atoms with oxygen to form ZnO. The reflection curves for the two ZnO samples are shown in Fig. 4. Sample c was deposited in an atmosphere of Ar + O2 in the ratio 9:1 while f was deposited in 7:3 respectively at sputtering pressures of 100 mTorr. The intensity oscillations were due to the interference from the front and back surfaces of the transparent film. Assuming normal incidence, the phase difference between two light rays of wavelength , reflected respectively from the front and the back surfaces of the film is (4nt) /, since the path difference = 2tn/, where n is the refractive index and t, thickness of the film. Adjacent maxima and minima occur in the reflection data when 4nt (1 /max 1 /min) = , where max and min denote the wavelength corresponding to successive maxima and minima [30].

The increase of the fundamental band gap of the nanostructured materials due to quantum size effects (QSE) is well established. For the sake of comparison we estimated the band gaps of these nanocrystalline films from [31]
0 Eg Eg

h2 e2 1:8 2 8lR eR

for the strong confinement limit (i.e. R aB) of QSE in nanomaterial. For weak confinement limit (i.e. R aB)
0 Eg Eg

h2 8lR2

where E0 is the energy band gap for the bulk material, R is the radius of g the nanoparticle calculated from XRD data and 1 / = 1 / me + 1 / mh (me and mh being the electron and hole effective masses respectively). Here the reduced mass of the exciton is 0.242 m0 [32]. Thus we obtain Eg = E0 + 1.545R 2 (nm). The values calculated from the above given g formula nearly match to the band gap values calculated from the absorption data. It is evident from Table 1 that the samples deposited in 10% of oxygen partial pressure and sputtering pressure of 20 mTorr (sample a) have a low refractive index as compared to that of all the other samples. The reason for this might be attributed to the presence of zinc metal

Fig. 3. Band gap determination of ZnO nanocrystalline thin films from (h)2 versus h plot.

Fig. 4. Reflectance of ZnO nanocrystalline thin films at different oxygen partial pressure at 100 mTorr.

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support by DRDO (Grant No. 47612/TC) and CSIR (No. 03 (1072)/06/EMR-II) New Delhi is gratefully acknowledged. References
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Fig. 5. Particle size and the corresponding band gap for ZnO nanocrystalline films deposited in 30% of oxygen partial pressure.

atoms in the sample (a) that makes it somewhat translucent as compared to other samples and hence decreases its refractive index. Since the refractive index of the zinc metal is 1.002050 [33] hence their presence in the ZnO film decreases the overall refractive index of the film. The particle size calculated from the XRD data is plotted against the band gap calculated by using the method given in Ref. [31]. The corresponding graph [Fig. 5] contains only those samples that were deposited at 30% of oxygen partial pressure. The graph indicates that there is an inverse relationship between the particle size and the band gap in the case of nanocrystalline films. As the particle size increases with an increase in the sputtering pressure the band gap decreases.

4. Conclusion In this work we studied the effect of the oxygen partial pressure on the sputter deposited ZnO thin films. The structural properties studied using XRD and SEM were in agreement with the results obtained by optical properties. The band gap calculated from the optical data was found to be comparable to that calculated from the XRD data (particle size). The refractive indices were also calculated from the reflection data. The results show that the oxygen partial pressure and the sputtering pressure may be complementary to each other as in both cases either increasing the oxygen partial pressure from 10% to 30% keeping chamber pressure constant or increasing the chamber pressure from 20 mTorr to 50 mTorr keeping oxygen pressure constant and the same changes in the samples were observed. Acknowledgments One of the authors, Preetam Singh thanks CSIR, New Delhi for the award of a junior research fellowship. The financial