Materials Science and Engineering A 452453 (2007) 715720

Nanoindentation characterization of ZnO thin lms

Te-Hua Fang a , Win-Jin Chang b, , Chao-Ming Lin c
a

Institute of Mechanical and Electromechanical Engineering, National Formosa University, Yunlin 632, Taiwan b Department of Mechanical Engineering, Kun-Shan University, Tainan 710, Taiwan c Department of Mechanical Engineering, WuFeng Institute of Technology, Chiayi 621, Taiwan Received 14 August 2006; received in revised form 24 October 2006; accepted 3 November 2006

Abstract The effects of the indentation load, indentation-loading time and the creep behavior of 23 m thick ZnO lms deposited on a Si(1 0 0) substrate were investigated by nanoindentation. The ZnO thin lms were deposited under different sputtering powers by a radio frequency magnetron sputtering system. The crystallographic and surface properties of the lms were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). Results showed that Youngs modulus and the hardness of the lms increased as the sputtering power was increased. The hardness and Youngs modulus slightly decreased as the indentation rate and creep time were increased. The best ZnO lm mechanical properties were found at a sputtering power of 225 W. 2006 Elsevier B.V. All rights reserved.
Keywords: Thin lms; X-ray diffraction; Mechanical properties

1. Introduction Recently, ZnO thin lms have increasingly been used for various technological applications in sensor, surface acoustic wave (SAW) and piezoelectric devices [14], due to their high transparency, piezoelectric properties, wide band-gap and electro-optical characteristics [58]. Many different deposition techniques, such as spray pyrolysis [9], pulsed laser deposition [10], sputtering method [11], metal organic chemical vapor deposition (MOCVD) [12] and molecular beam epitaxy (MBE) [13] have been developed to prepare ZnO thin lms. Each method has its relative advantages for certain applications. Among them, the sputtering method is one of the most commonly used techniques due to several advantages, such as low substrate temperature, high deposition rate, uniform surface and excellent crystalline orientation. However, the build-up of internal stresses has given rise to serious concerns about the mechanical properties of sputtered ZnO lms. It has been a challenge to understand what effects the load, the loading rate and the creep behavior have on the mechanical properties of these lms. The condition that will subject the ZnO thin lms to tri-

bological interaction is caused by rubbing damage during the piezoelectric component manufacture. Nanoindentation techniques have been developed for probing mechanical properties, such as the hardness and Youngs modulus of thin lms [14]. Mayo et al. studied the effect of grain size on the hardness strain-rate sensitivity of nanocrystalline bulk ZnO and showed that lower sintering temperatures, which provide ner grain sizes, tended to promote strain rate sensitivity [15]. Recently, a number of researchers have used the nanoindentation technique to study the indentation-produced deformation and dislocation mechanisms of bulk single-crystal ZnO [1619], but the inuence of the indentation load, the indentation-loading time and the creep behavior during nanoindentation still warrant further research and discussion. In this article, the nanoindentation-induced behavior of polycrystalline ZnO thin lms deposited at various sputtering powers was investigated. The microstructural properties of ZnO lms were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The inuence on a nanometer-scale that the indentation loads, the indentation-loading time, the creep behavior and the sputtering power had on the deposited lms were also investigated. 2. Experimental details

Corresponding author. Fax: +886 2050883. E-mail address: changwj@mail.ksu.edu.tw (W.-J. Chang).

In this study, ZnO thin lms were produced on a Si(1 0 0) substrate by a radio frequency magnetron sputtering system,

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.11.008

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using a 99.99% pure, 2 -diameter Zn target, and was deposited at sputtering powers of 150, 175, 200 and 225 W. The lms thickness was measured using a stylus proler (Tencor Alpha Step 200, USA). The thicknesses of the lms were between 2 and 3 m. The detailed growth conditions of the ZnO lms have been reported in a previous study [20]. X-ray diffraction (Rigaku D/MAX-RA, Japan) was used to analyze the crystallographic structure of the ZnO lms. Crystallographic orientation was determined by XRD rotation over 2 degrees. The morphological properties of the ZnO lms surface were measured by atomic force microscopy (Shimadzu SPM-9500J2, Japan). Typical scans were taken over an area of 1 m 1 m at a constant scan speed of 2 m/s. The mechanical properties of ZnO thin lms were characterized by nanoindentation (Hysitron Triboscope, USA) using a Berkovich diamond indenter with a radius of 50 nm [21]. All indentation tests were performed at room temperature. Loadunloading experiments were performed to understand the effects of different loads. A loading time of 10 s, a hold time of 1 s and an unloading time of 10 s were used. The loads ranged from 1000 to 3000 N. For the loading rate tests, the indentationloading and unloading times ranged from 10 to 50 s at a constant load of 1000 N, the hold time was constant at 1 s. Hold time creep behavior experiments were performed using hold times of 30, 60 and 120 s at the peak load and kept at a constant load of 1000 N using loading and unloading times of 10 s. 3. Analysis The hardness and Youngs modulus as a function of the displacement of the indenter were measured from the loadingunloading of the indenter. A loadingunloading curve is shown in Fig. 1. In the AFM micrograph of Fig. 1a, trian-

gular indent can be clearly seen, with plastic behavior pile-up around the indentation. The hardness of a material is dened as its resistance to plastic deformation. Thus, hardness H is determined from maximum indentation load Pmax divided by the actual projected contact area Ac and written as: H= Pmax Ac (1)

In depth-sensing nanoindentation, the composite modulus E* is calculated by [22]: E = S 2 Ac (2)

where S is the measured stiffness and is a shape constant of 1.034 for the Berkovich tip. Youngs modulus Em is dened by: Em =
2 (1 m )

1 i2 1 E Ei

(3)

where is Poissons ratio, E the Youngs modulus, and the subscripts i and m refer to indenter and test material, respectively. Indenter properties used in this studys calculations were Ei = 1141 GPa and i = 0.07 [22] and m is assumed to be 0.3. In Fig. 1, the area under the unloading curve represents the elastic energy deformation and is represented by the area designated as We . The area between the loading and unloading curve represents the energy dissipated into the lm due to plastic deformation and is represented by the area designated as Wp . 4. Results and discussion 4.1. Structural and surface characterizations The XRD patterns for the ZnO lms deposited on Si(1 0 0) substrates at different sputtering powers are shown in Fig. 2 [20]. In Fig. 2, the intensities of the (0 0 2)-orientation can be seen to have been enhanced as the sputtering power was increased, indicating that the crystalline lm is more uniformly oriented at higher sputtering powers. In Fig. 2(a), the lm deposited at 150 W had the poorest crystallinity. As the sputtering powers increased, the (0 0 2)-peaks of ZnO lms became sharper. Base on the XRD data, the ZnO lms started to gain better crystallization when the sputtering power was above 200 W. In addition, the best crystalline structure appeared at 225 W and did not have different crystallite orientations of the same phase. The use of sputtering powers larger than 225 W led to a higher deposition rate causing the sputtered atoms to pile-up on the surface of the lm and to not have enough time to diffuse. The lm also exhibited poor substrate adhesive properties at sputtering powers greater than 225 W. The average grain size (D) of the ZnO lms was calculated from the full width at half maximum (FWHM) of the XRD (0 0 2)-peak at around a diffraction angle of 34.4 , using the Scherrer formula [23]. The average grain size (D) on the ZnO lms ranged from 34 to 42 nm as shown in Table 1. It was found that the size of the grains increased slightly as the sputtering power was increased and the surface roughness appeared to

Fig. 1. The indentation loadingunloading curve and the associated ZnO thin lm AFM indentation image.

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Fig. 3. Three-dimensional AFM image of a ZnO lm for a sputtering power of 225 W. The surface region: 1 m 1 m, Zmax = 97 nm. Fig. 2. XRD spectra of ZnO thin lms for various sputtering powers of: (a) 150, (b) 175, (c) 200 and (d) 225 W.

decrease as the grain size got larger. Since the grains are generally cone-like in shape, the structure can be characterized by the surface area of the grains. An AFM image of a 1 m 1 m surface region of a ZnO lm deposited at 225 W is shown in Fig. 3. Cone-like grains covering the ZnO surface can be seen. The average surface roughness (Ra ) and root-mean-square surface roughness (RMS) are listed in Table 1. The average surface roughness of the ZnO lms at the sputtering powers of 150, 175, 200 and 225 W were 12.7, 12.0, 12.4 and 12.3 nm, respectively. There are no special statistical differences between these surface roughness for lms formed at different sputtering powers. The smoothest surface was created at the highest sputtering power of 225 W. High frequency surface acoustic wave devices function much better when the surface of the lm is smoother [24]. This could be very useful in further SAW application development. 4.2. Investigation of loadingunloading behaviors Fig. 4(ac) shows the (Ph) curves and creep behavior (penetration depth versus indentation load) of ZnO lms deposited at 225 W and indented at various loads, loading times and hold times. In this current study, pop-ins were not observed. However, pop-ins have been observed in previous studies [1518].
Table 1 Grain size (D) and surface roughness (Ra , RMS) of ZnO lms for different sputtering powers Sputtering powers (W) 150 D Ra RMS Unit: nm. 34 5 12.7 1.3 16.4 1.6 175 37 6 12.0 1.0 15.7 1.1 200 40 6 12.4 1.0 15.9 1.1 225 42 7 12.3 0.8 14.3 0.5

This most likely can be attributed to the preparation methods of the different lms used. In Fig. 4(a), it was found that as the indentation loads increased, the penetration depths, the plastic deformation and the area Wp all increased. The deepest plastic depth was produced under the larger indentation loads. It was also discovered from the overlapping loading curves of all three indentation loads that all the ZnO lms surface properties were similar. The effect of the indentation-loading time on a nanoscale level is shown in Fig. 4(b). The indentation-loading time was dened as the time from the beginning of the indentation loading to when the maximum indentation load was reached. It can be seen that the slope of the loading curve decreased, the penetration depths and the area Wp both increased as the indentation-loading time was increased, i.e. as the loading rate was decreased. These results could be explained by the dislocation and slip behaviors causing larger plastic deformation depths to take place at the longer indentation-loading times. The creep behavior at three different hold times can be seen in Fig. 4(c). It was found that the loading curves were quite similar, but the unloading curves started from slightly greater values of hmax as the hold times were increased. In this study, the maximum indentation depth was less than 200 nm, i.e. approximately 1/10th of the lms thickness and the mechanical properties were not inuenced by the presence of the silicon substrate. At shorter hold times, a slightly steeper unloading curve occurred, which would reduce the calculated elastic surface deformation and the area Wp increased as the hold time was increased. This implies that the longer hold times allowed for more energy to be dissipated and therefore caused the creep behavior to extend further out, which in turn created the larger indentation deformations [25]. 4.3. Youngs modulus and hardness Fig. 5(a) shows the Youngs modulus and the hardness of ZnO thin lms measured under different indentation loads. The ZnO

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Fig. 4. Loaddisplacement curves of ZnO lms sputtered at 225 W under various indentation: (a) loads, (b) loading times and (c) hold times.

lms Youngs modulus ranged from 68 to 125 GPa and the hardness ranged from 4 to 6 GPa. The hardness and Youngs modulus slightly decreased as the indentation loads were increased. Similar nanoindentation tests for ZnO materials have been performed by previous studies, such as Lucca et al. [18] and Klopfstein et al. [19] studied mechanical responses for the chemomechanically polished single-crystal ZnO and obtained that the values of elastic modulus and hardness ranged from 104 to 134 GPa and 2 to 7 GPa, respectively. The greater values for Youngs modulus and hardness were achieved at the higher sputtering powers due to the ZnO lms having had better crystalline structures. The ZnO lm deposited at the sputtering power of 225 W appeared to have had the best mechanical properties in this study. The previous study showed that the wear volume decreased as the sputtering power was increased [20]. Thus, the combined data

from this study and that found in ref. [20] show that the lms with higher E and H have greater wear resistance. The ZnO lms Youngs modulus ranged from 61 to 123 GPa and the hardness ranged from 4 to 5 GPa at different indentationloading times as shown in Fig. 5(b). As the indentation-loading time was decreased both the Youngs modulus and the hardness of the lms increased. This was due to the longer indentationloading times, and leading to dislocation slip to the materials surface causing a larger degree of plastic deformation. Youngs modulus and hardness of the thin lms under the different hold times of 30, 60 and 120 s are shown in Fig. 5(c). Youngs modulus and hardness ranged from 70 to 90 GPa, and from 4 to 6 GPa, respectively. As seen in Fig. 5(c), the indentation creep tests showed that the hardness and Youngs modulus slightly decreased as the hold time was increased. These results

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Fig. 5. Youngs modulus and hardness for ZnO lms subjected to various indentation: (a) loads, (b) loading times and (c) hold times.

might be due to the surface diffusion and reorganization processes that occurred at the longer holding times and caused the larger indentation depths. In addition, the variation of the hardness with the sputtering powers for different hold times in Fig. 5(c) is not obvious when the powers range from 175 to 225 W. However, it appears a relatively large variation when the sputtering power of 150 W is used. This because the ZnO lm deposited at sputtering powers of 150 W has a larger roughness as listed in Table 1, and that induced a higher uncertainty and error of measurement. In order to reduce the measurement error, a longer hold time in the experiment may be used, such as 120 s. 5. Conclusion

thin lms are well ordered with a high (0 0 2)-orientation. The lms exhibited higher quality crystalline structures as the sputtering power was increased. At sputtering powers that ranged from 150 to 225 W during depth-sensing indentation recording, the Youngs modulus of the lms ranged from 61 to 125 GPa and the hardness ranged from 4 to 6 GPa. In addition, the nanoindentation characteristics affected by the indentation loads, loading rates and creep behaviors are presented. In summary, the results conrmed that various sputtering powers played an important role in the nanomechanical characteristics of the ZnO lm and that the lms deposited at 225 W appeared to have the best mechanical properties. Acknowledgements

The mechanical properties of ZnO lms deposited at various sputtering powers were investigated by nanoindentation. At higher sputtering powers, the crystalline structures of the ZnO

The author would like to thank Mr. Sheng-Rui Jian, ChunChin Chang and Shi-Cheng Liao for their technical support. This

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T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720 [12] K.H. Bang, D.K. Hwang, M.C. Jeong, K.S. Sohn, J.M. Myoung, Solid State Commun. 126 (2003) 623. [13] M. Fujita, N. Kawamoto, T. Tatsumi, K. Yamagishi, Y. Horikoshi, Jpn. J. Appl. Phys. 42 (2003) 67. [14] R. Bahl, A. Kumar, M. Vedawyas, D. Patel, Appl. Phys. A 69 (1999) S643. [15] M.J. Mayo, R.W. Siegel, Y.X. Liao, W.D. Nix, J. Mater. Res. 7 (4) (1992) 973. [16] S.O. Kucheyev, J.E. Bradby, J.S. Williams, C. Jagadish, M.V. Swain, Appl. Phys. Lett. 80 (2002) 956. [17] J.E. Bradby, S.O. Kucheyev, J.S. Williams, C. Jagadish, M.V. Swain, P. Munroe, M.R. Phillips, Appl. Phys. Lett. 80 (2002) 4537. [18] D.A. Lucca, M.J. Klopfstein, R. Ghisleni, G. Cantwell, Ann. CIRP 51 (2002) 483. [19] M.J. Klopfstein, D.A. Lucca, G. Cantwell, Phys. Status Solidi (a) 196 (2003) R1. [20] T.H. Fang, S.R. Jian, D.S. Chuu, J. Phys. D Appl. Phys. 36 (2003) 878. [21] T.H. Fang, W.J. Chang, Microelectron. J. 35 (2004) 595. [22] W.C. Oliver, G.M. Pharr, J. Mater. Res. 7 (1992) 1564. [23] B.D. Cullity, Elements of X-ray Diffraction, Addison-Wesley, Reading, MA, 1978, p. 102. [24] S.H. Seo, W.C. Shin, J.S. Park, Thin Solid Films 416 (2002) 190. [25] T. Chudoba, F. Richter, Surf. Coat. Technol. 148 (2001) 191.

work was partially supported by the National Science Council of Taiwan, under Grant Nos. NSC94-2212-E150-045, NSC942212-E150-046 and NSC95-2221-E-168-008. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] F. Hossein-Babaei, F. Taghibakhsh, Electron. Lett. 36 (2000) 1815. W. Water, S.Y. Chu, Mater. Lett. 55 (2002) 67. P. Sharma, S. Kumar, K. Sreenivas, J. Mater. Res. 18 (2003) 545. K.H. Kim, K.C. Park, T.Y. Ma, J. Appl. Phys. 81 (1997) 7764. Y.R. Park, K.J. Kim, Solid State Commun. 123 (2002) 147. T. Nagata, T. Shimura, A. Ashida, N. Fujimura, T. Ito, J. Cryst. Growth 237239 (2002) 533. H.M. Kim, S.K. Jung, J.S. Ahn, Y.J. Kang, K.C. Je, Jpn. J. Appl. Phys. 42 (2003) 223. K. Funk, T. Fabula, G. Flik, F. Larmer, J. Micromech. Microeng. 13 (2003) 353. J. Ebothe, A.El. Hichou, P. Vautrot, M. Addou, J. Appl. Phys. 93 (2003) 632. M. Sumiya, S. Fuke, A. Tsukazaki, K. Tamura, A. Ohtomo, M. Kawasaki, H. Koinuma, J. Appl. Phys. 93 (2003) 2562. K.H. Bang, D.H. Hwang, J.M. Myoung, Appl. Surf. Sci. 207 (2003) 359.