Mat. Res. Soc. Symp. Proc. Vol.

648 2001 Materials Research Society

Surface Evolution of NiTi and NiTiHf Thin Films Chen Zhang*, Ralph H. Zee* and Paul E. Thoma** *Materials Research and Education Center, Auburn University, Auburn, AL 36849; **Corporate Technology, Johnson Controls, Inc., 1701 West Civic Dr., Milwaukee, WI 53209 ABSTRACT The microstructure evolution of Ti-rich NiTi thin films and (TiHf)-rich NiTiHf thin films containing 9at% Hf was investigated. These films were deposited from single NiTi and NiTiHf targets using a DC magnetron sputtering system. Free-standing films were obtained by using single crystal silicon substrates. The thickness of these films was controlled between 10-12 m. In this investigation, the effects of deposition temperature on the surface and cross-sectional microstructures of these films were studied. Substrate temperature during deposition was varied between 300C to 700C at 100C intervals. The influence of post deposition heat treatment (HT) temperature on the microstructure of these films was also studied. The post deposition HT temperature was varied between 300C and 800C at 100C intervals. Both surface and crosssectional microstructures were examined using a scanning electron microscope (SEM). The crystallinity and the phases present were determined using x-ray diffractometry. All the asdeposited films were found to be crystalline, even when the substrate temperature was as low as 300C. Results from the microstructure analysis show that all the films have a relatively fine grain size ranging from 0.2 m to 2.5 m, and the grain size increases with increasing substrate deposition temperature. The effect of post deposition HT on grain size was found to be minimal. INTRODUCTION Many investigations have been devoted to better understand the behavior of bulk shape memory alloys (SMAs) since their discovery in the 1960s. The achievements in development of SMAs have been significant. As a result, their commercial value has increased rapidly in the past few years. Many applications have been developed including actuators, electronic connectors, and medical implants such as stents and guidewires. Recently their applications have been extended to microactuators due to the increasing demands for miniature devices. Since shape memory alloys are used as an actuator element, by making it into a thin film, a new type of microactuator with high output stress and output strain becomes possible. Meanwhile, a drawback of bulk SMAs, such as slow response, can be overcome by increasing the actuator elements surface to volume ratio. NiTi thin films have been successfully fabricated and studied in the past ten years. Ternary NiTiHf SMA with high Hf concentration becomes more and more attractive due to its high transformation temperatures. The possibility of fabricating NiTiHf thin films, containing 10at% Hf, was first reported by Johnson et al. [1]. However, a reliable method for manufacturing micron-thick shape memory thin films, especially for high temperature shape memory thin films, is still not available. Further studies are needed to better understand the effect of processing. In this investigation, two specific shape memory thin films, a Ti-rich binary NiTi alloy and a ternary NiTiHf alloy containing around 9at% Hf, were successfully fabricated. Processing techniques for manufacturing these thin films were explored. The effects of processing

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conditions on the microstructure of these thin films and on their transformation properties are discussed. EXPERIMENTAL SETUP Ti-rich binary NiTi and ternary NiTiHf thin films were deposited from single targets of NiTi and NiTiHf respectively. The compositions of the targets are Ni47Ti53 and Ni42Ti48Hf10 (atomic ratio). A DC magnetron sputtering system equipped with a cryogenic pump was used to deposit the films. Base pressure of 5x10-7 torr was achieved prior to sputtering to prevent contamination. Both NiTi and NiTiHf ingots were arc melted and vacuum annealed at 900C for 100 hours by Johnson Controls, Inc. The ingots were then electrical-discharge machined into 2 inch (5.08cm) diameter targets. The thickness of the targets varied between 0.125 inch and 0.250 inch. The deposition process was described in authors previous papers [2,3]. Thickness of the films was controlled between 10 m 12 m. After deposition, the films were peeled from the silicon surface and cut into small pieces for heat treatment. The HT was conducted in an electron beam furnace and all films were heat treated for one hour. During heat treatment, the vacuum was maintained at around 5x10-7 torr to minimize oxidation. A K-type thermocouple was used to measure the temperature. The deposition temperatures and post deposition HT temperatures investigated in this study are listed in Table I. Both surface and cross-section microstructures of the thin films were studied using a Hitachi Scanning Electron Microscope (SEM) at room temperature. For cross-section microstructure analysis, thin film samples were first sandwiched between two stainless steel plates. The samples were cold mounted and then polished on 600 and 1000 grit abrasive paper consecutively. The rough polishing was followed by polishing on red cloth using 6 m and 1 m diamond paste. The final polishing was done using a 0.05 m SiO2 suspension on imperial cloth. Samples were then etched in a fresh etchant for 2 minutes prior to SEM examination. The etchant used was 50 ml glycerol, 18 ml HNO3 and 2 ml HF. Samples for surface structure analysis were directly etched without polishing. The same etchant was used on these samples. Table I. Target Composition, Substrate Temperature and Post Heat Treatment Temperature. Target Composition Substrate Temperature (Ts) 300C 400C 500C 300C 400C 500C 600C 700C Heat Treatment (HT)

Ni47Ti53

Ni42Ti48Hf10

300C 400C 500C 600C 700C 800C

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RESULTS As discussed in two previous papers by the authors [2,3], the martensite and austenite transformation temperatures of the NiTi and NiTiHf films are affected by the deposition temperature as well as post deposition HT temperature. This is also true for the microstructure of these films. The evolution of the surface and cross-sectional microstructure of these films with changes in substrate temperature and post deposition HT temperature are reviewed in the following sections. Films heat treated at 800C are not discussed in this paper due to the partial surface oxidization which made these films very difficult to examine. NiTi Thin Films All NiTi thin films with the various deposition temperatures and post HT temperatures show a fine grain structure. The grain size increases with increasing deposition temperature as shown in figures 1a and 1b. The film deposited on a 300C substrate has a grain size less than 0.2 m (figure 1a), while the film deposited on a 500C substrate shows a grain size several times larger. After HT, the grain size of these films remains the same despite the higher HT temperature used (700C) as shown in figure 1c. Figure 1c shows the surface microstructure of a film deposited on a 500C substrate and followed by a 700C HT. Compared with figure 1b, figure 1c shows more substructures inside the grains. No significant grain growth is observed in the microstructure shown in figure 1c. Figures 1d, 1e and 1f show the cross-sectional microstructure of NiTi thin films. All three films show a tapered structure except for the as-coated film at 300C. Figure 1d shows large Rphase grains with small tapered martensite grains starting to develop inside the R-phase grains. The presence of these phases is confirmed based on results from x-ray diffraction. These substructures (fine needles) can also be found in the cross-sectional views of the films as shown in figure 1f. Comparing figures 1e (as-coated) and 1f (heat treated), both films show tapered structures except that more substructures are revealed in the film. The substructures are observed in all the films heat treated at higher HT temperature. The substructures grow with increasing HT temperature and become most significant in the films heat treated at 700C. NiTiHf Thin Films The effect of deposition temperature and post deposition HT temperature on NiTiHf thin films is similar to that of NiTi films. In general, grain size increases with increasing deposition temperature while it remains the same for different post deposition HT temperature. Figures 2a to 2d show the surface microstructure of NiTiHf films deposited on substrates at temperatures from 300C to 700C. With elevated deposition temperature, the development of microstructure as a function of deposition temperature is obvious. In figure 2a, a martensite grain structure is just beginning to form, but is still surrounded by the retained austenite structure. This corresponds well with the x-ray and DSC results in the authors earlier publications [3,4]. During cooling, austenite transforms to martensite. With further cooling, austenite continues to transform to martensite. Detailed information can be found in authors previous papers [2-4]. With increasing deposition temperature, the martensite grain structure continues to develop. At 600C (figure 2c), the microstructure consists mainly of martensite as confirmed by XRD results. Figure 2d is the as-coated NiTiHf film deposited on a 700C substrate. It not only shows a larger grain size when compared with figures 2a - 2c, but also shows clear twin structures.
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(c)

(d)

(e)

(f)

Figure 1. Surface microstructure of NiTi films (a). as-coated at 300C, (b). as-coated at 500C, (c). as-coated at 500C followed by heat treatment at 700C for one hour. The reference line is 2 um. Cross-sectional microstructure of NiTi films (d). as-coated at 300C, (e). as-coated at 400C, (f) as-coated at 400C followed by heat treatment at 700C for one hour. The reference line is 5 um. The evolution of microstructure with increasing deposition temperature can also be observed from a cross-sectional examination of these films. Figures 2e and 2f are the cross-sectional microstructures of the as-coated NiTiHf films deposited at 300C and 600C. Figure 2e shows a coarse grain structure which is associated with the austenite structure. With increasing deposition temperature, a greater amount of the tapered martensite grain structure is observed. The film deposited at 600C is mainly composed of tapered martensite grains as shown in figure 2f. Similar to NiTi films, higher heat treatment temperature generates more substructure in the

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(b)

(c)

(d)

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Figure 2. Surface microstructure of NiTiHf films (a). as-coated at 300C, (b). as-coated at 500C, (c). as-coated at 600C. (d). as-coated at 700C. Cross-sectional microstructure of NiTiHf films (e). as-coated at 300C, (f). as-coated at 600C. The reference line is 10 um for (d) and 5 um for (a), (b), (c), (e), (f).

NiTiHf films. The size of substructures grows with increasing deposition temperature, similar to what is observed in the martensite grains. The substructure is found in all the films heat treated at higher HT temperatures. It becomes most distinct when the HT temperature is 700C. DISCUSSION The microstructures of both NiTi and NiTiHf thin films are presented above. All the asdeposited films are found to be crystalline, even when the substrate temperature is as low as 300C. It is found that grain size increases with increasing deposition temperature, but it is not affected by post deposition heat treatment temperature. This is related to the increased surface
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mobility of the atoms with increasing substrate temperature. As discussed in earlier papers [2-4], in the thin film growth process during sputtering, the adsorbed particles collide with one another and form clusters. The clusters continuously collide with incoming particles and grow in size until they reach a critical size at which they become thermodynamically stable. With increasing deposition temperature, the mobility of the particles increases and the possibility for particles and clusters interacting with one another also increases. As a result, large critical nuclei are formed. These critical nuclei continue to grow and eventually form grains. With increasing deposition temperature, the grains increase in size. It is interesting that grain size is not affected by post deposition heat treatment temperature, as observed in both the NiTi and NiTiHf thin films. This is because the as-coated films are already in the crystalline state and the mobility of the deposited atoms decreases significantly after the film is formed. Thermal diffusion is too slow to result in grain growth even when the post deposition HT temperature is higher than 700C. However, with increasing HT temperature, the available thermal energy does permit dislocations to move and form substructures as shown in figure 2d. It is found in both NiTi and NiTiHf thin films that martensite is primarily observed in the films heat treated and deposited at higher temperatures. It is believed that large amounts of dislocations formed at low deposition temperature and HT temperature might suppress the martensite transformation. With increasing deposition temperature and HT temperature, more and more dislocations are annealed out, therefore the martensite transformation temperature increases. However, the possibility of the existence of secondary phases such as Ti2Ni and (TiHf)2Ni formed in the films may also suppress the martensite by the development of internal stress, especially if these secondary phases are coherent. More research is needed to better understand the above observations. SUMMARY The microstructure analysis shows that all the NiTi and NiTiHf thin films have a fine grain size. The grain size increases with increasing deposition temperature, but no significant change was observed with elevated post deposition HT temperature. However, at higher post deposition HT temperature, more substructures were observed within the grains. This might be related to dislocation reorganization or formation of precipitates during the heat treatment. REFERENCES 1. A.D Johnson, V.V. Martynov and R.S, Minners, Journal de Physique IV Colloque C8 Supplement au Journal de Physique III vol. 5, C8-783-787 (1995). 2. C. Zhang, P.E. Thoma and R.H. Zee, Materials Processing Fundamentals, proceedings of 1999 EPD Congress, 139-145 (1999). 3. C. Zhang, P.E. Thoma and R.H. Zee, Materials for Smart Systems III, edited by Marilyn WunFogle, K. Uchino, Y. Ito and R. Gotthardt, Materials Research Society Proceedings vol. 604, 129-134 (1999). 4. C. Zhang, NiTi and NiTiHf Shape Memory Thin Films, PhD dissertation, 2000.
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