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Materials Science and Engineering A 452–453 (2007) 715–720 Nanoindentation characterization of ZnO thin films Te-Hua

Materials Science and Engineering A 452–453 (2007) 715–720

Science and Engineering A 452–453 (2007) 715–720 Nanoindentation characterization of ZnO thin films Te-Hua

Nanoindentation characterization of ZnO thin films

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 2–3 m thick ZnO films deposited on a Si(1 0 0) substrate were investigated by nanoindentation. The ZnO thin films were deposited under different sputtering powers by a radio frequency magnetron sputtering system. The crystallographic and surface properties of the films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). Results showed that Young’s modulus and the hardness of the films increased as the sputtering power was increased. The hardness and Young’s modulus slightly decreased as the indentation rate and creep time were increased. The best ZnO film mechanical properties were found at a sputtering power of 225 W. © 2006 Elsevier B.V. All rights reserved.

Keywords: Thin films; X-ray diffraction; Mechanical properties

1. Introduction

Recently, ZnO thin films have increasingly been used for various technological applications in sensor, surface acous- tic wave (SAW) and piezoelectric devices [1–4], due to their high transparency, piezoelectric properties, wide band-gap and electro-optical characteristics [5–8]. Many different deposition techniques, such as spray pyrol- ysis [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 films. Each method has its relative advantages for certain applica- tions. 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 films. It has been a chal- lenge to understand what effects the load, the loading rate and the creep behavior have on the mechanical properties of these films. The condition that will subject the ZnO thin films to tri-

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

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.

doi:10.1016/j.msea.2006.11.008

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 Young’s modu- lus of thin films [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 pro- vide finer grain sizes, tended to promote strain rate sensitivity [15]. Recently, a number of researchers have used the nanoinden- tation technique to study the indentation-produced deformation and dislocation mechanisms of bulk single-crystal ZnO [16–19], but the influence 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 poly- crystalline ZnO thin films deposited at various sputtering powers was investigated. The microstructural properties of ZnO films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The influence on a nanometer-scale that the indentation loads, the indentation-loading time, the creep behavior and the sputtering power had on the deposited films were also investigated.

2. Experimental details

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

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T.-H. Fang et al. / Materials Science and Engineering A 452–453 (2007) 715–720

using a 99.99% pure, 2 -diameter Zn target, and was deposited at sputtering powers of 150, 175, 200 and 225 W. The film’s thickness was measured using a stylus profiler (Tencor Alpha Step 200, USA). The thicknesses of the films were between 2 and 3 m. The detailed growth conditions of the ZnO films 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 films. Crys- tallographic orientation was determined by XRD rotation over θ–2θ degrees. The morphological properties of the ZnO film’s 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 films were charac- terized 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. Load–unloading 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 indentation- loading 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 Young’s modulus as a function of the displacement of the indenter were measured from the loading–unloading of the indenter. A loading–unloading curve is shown in Fig. 1. In the AFM micrograph of Fig. 1a, trian-

in Fig. 1 . In the AFM micrograph of Fig. 1 a, trian- Fig. 1. The

Fig. 1. The indentation loading–unloading curve and the associated ZnO thin film AFM indentation image.

gular indent can be clearly seen, with plastic behavior pile-up around the indentation. The hardness of a material is defined as its resistance to plastic deformation. Thus, hardness H is determined from maximum indentation load P max divided by the actual projected contact area A c and written as:

H = P max

(1)

A c

In depth-sensing nanoindentation, the composite modulus E * is calculated by [22]:

E =

πS

2β A c

(2)

where S is the measured stiffness and β is a shape constant of 1.034 for the Berkovich tip. Young’s modulus E m is defined by:

E m = (1 ν

m )

2

1

1 ν

2

i

E

E

i

1

(3)

where ν is Poisson’s ratio, E the Young’s modulus, and the subscripts i and m refer to indenter and test material, respec- tively. Indenter properties used in this study’s calculations were E i = 1141 GPa and ν i = 0.07 [22] and ν 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 des- ignated as W e . The area between the loading and unloading curve represents the energy dissipated into the film due to plastic deformation and is represented by the area designated as W p .

4. Results and discussion

4.1. Structural and surface characterizations

The XRD patterns for the ZnO films 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 film is more uniformly oriented at higher sputtering powers. In Fig. 2(a), the film deposited at 150 W had the poorest crys- tallinity. As the sputtering powers increased, the (0 0 2)-peaks of ZnO films became sharper. Base on the XRD data, the ZnO films started to gain better crystallization when the sputtering power was above 200 W. In addition, the best crystalline struc- ture 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 sput- tered atoms to pile-up on the surface of the film and to not have enough time to diffuse. The film also exhibited poor substrate adhesive properties at sputtering powers greater than 225 W. The average grain size (D) of the ZnO films 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 films 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

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Science and Engineering A 452–453 (2007) 715–720 717 Fig. 2. XRD spectra of ZnO thin films

Fig. 2. XRD spectra of ZnO thin films 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 gener- ally 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 film deposited at 225 W is shown in Fig. 3. Cone-like grains covering the ZnO surface can be seen. The average surface roughness (R a ) and root-mean-square surface roughness (RMS) are listed in Table 1. The average surface roughness of the ZnO films 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 spe- cial statistical differences between these surface roughness for films formed at different sputtering powers. The smoothest sur- face was created at the highest sputtering power of 225 W. High frequency surface acoustic wave devices function much better when the surface of the film is smoother [24]. This could be very useful in further SAW application development.

4.2. Investigation of loading–unloading behaviors

Fig. 4(a–c) shows the (Ph) curves and creep behavior (pen- etration depth versus indentation load) of ZnO films deposited at 225 W and indented at various loads, loading times and hold times. In this current study, pop-ins were not observed. How- ever, pop-ins have been observed in previous studies [15–18].

Table 1 Grain size (D) and surface roughness (R a , RMS) of ZnO films for different sputtering powers

Sputtering powers (W)

 

150

175

200

225

D

34 ± 5 12.7 ± 1.3 16.4 ± 1.6

37 ± 6 12.0 ± 1.0 15.7 ± 1.1

40 ± 6 12.4 ± 1.0 15.9 ± 1.1

42 ± 7 12.3 ± 0.8 14.3 ± 0.5

R a

RMS

Unit: nm.

 
0.8 14.3 ± 0.5 R a RMS Unit: nm.   Fig. 3. Three-dimensional AFM image of

Fig. 3. Three-dimensional AFM image of a ZnO film for a sputtering power of 225 W. The surface region: 1 m × 1 m, Z max = 97 nm.

This most likely can be attributed to the preparation methods of the different films used. In Fig. 4(a), it was found that as the indentation loads increased, the penetration depths, the plastic deformation and the area W p 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 film’s 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 defined 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 W p 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 h max as the hold times were increased. In this study, the maxi- mum indentation depth was less than 200 nm, i.e. approximately 1/10th of the films thickness and the mechanical properties were not influenced 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 W p increased as the hold time was increased. This implies that the longer hold times allowed for more energy to be dissi- pated and therefore caused the creep behavior to extend further out, which in turn created the larger indentation deformations

[25].

4.3.

Young’s modulus and hardness

Fig. 5(a) shows the Young’s modulus and the hardness of ZnO thin films measured under different indentation loads. The ZnO

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Science and Engineering A 452–453 (2007) 715–720 Fig. 4. Load–displacement curves of ZnO films sputtered

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

film’s Young’s modulus ranged from 68 to 125 GPa and the hard- ness ranged from 4 to 6 GPa. The hardness and Young’s modulus slightly decreased as the indentation loads were increased. Simi- lar 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 chemomechani- cally 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 Young’s modulus and hardness were achieved at the higher sputtering powers due to the ZnO films having had better crystalline structures. The ZnO film 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 films with higher E and H have greater wear resistance. The ZnO films Young’s modulus ranged from 61 to 123 GPa and the hardness ranged from 4 to 5 GPa at different indentation- loading times as shown in Fig. 5(b). As the indentation-loading time was decreased both the Young’s modulus and the hardness of the films increased. This was due to the longer indentation- loading times, and leading to dislocation slip to the material’s surface causing a larger degree of plastic deformation. Young’s modulus and hardness of the thin films under the different hold times of 30, 60 and 120 s are shown in Fig. 5(c). Young’s modulus and hardness ranged from 70 to 90 GPa, and from 4 to 6 GPa, respectively. As seen in Fig. 5(c), the indenta- tion creep tests showed that the hardness and Young’s modulus slightly decreased as the hold time was increased. These results

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Science and Engineering A 452–453 (2007) 715–720 719 Fig. 5. Young’s modulus and hardness for ZnO

Fig. 5. Young’s modulus and hardness for ZnO films subjected to various indentation: (a) loads, (b) loading times and (c) hold times.

might be due to the surface diffusion and reorganization pro- cesses 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 film 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

The mechanical properties of ZnO films deposited at vari- ous sputtering powers were investigated by nanoindentation. At higher sputtering powers, the crystalline structures of the ZnO

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

Acknowledgements

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

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T.-H. Fang et al. / Materials Science and Engineering A 452–453 (2007) 715–720

work was partially supported by the National Science Council of Taiwan, under Grant Nos. NSC94-2212-E150-045, NSC94- 2212-E150-046 and NSC95-2221-E-168-008.

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