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Materials Transactions, Vol. 53, No. 6 (2012) pp.

1056 to 1061

2012 The Japan Institute of Metals

Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process
Hyun-Kuk Park1, Jung-Han Ryu1, Hee-Jun Youn1, Jun-Mo Yang2 and Ik-Hyun Oh1,+
1 2

Korea Institute of Industrial Technology (KITECH), Automotive Components Group, Gwang-Ju, 500-480 Korea Measurement & Analysis Team, National Nanofab Center, Daejeon, 305-806, Korea

Pure molybdenum compacts having a high density, purity and a ne-grained microstructure were fabricated by a spark plasma sintering process. Also, an optimized sintering condition was obtained by controlling process parameters such as temperature, pressure, and heating rate. Molybdenum compacts were prepared with diameters of 150 6.35 mm, and the characteristics of the compacts were analyzed by induction couple plasma (ICP), X-ray diffraction (XRD), and eld emission scanning electron microscopy (FE-SEM). In addition, molybdenum thin lms that were fabricated on a glass substrate by using sputtering equipment were analyzed by XRD, transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS). A relative density of up to 99% and the grain size of below 8 m were reached at the sintering temperature of 1473.15 K and the uniaxial pressure of 60 MPa. Also, molybdenum compacts having a uniform relative density and grain size were fabricated through an optimully redesigned mold and process control method. The resistivity (0.15 m) of the optimized spark plasma sintering (SPS) molybdenum thin lm showed properties that are similar to those of the lm prepared with conventional sintering. [doi:10.2320/matertrans.M2012039] (Received January 30, 2012; Accepted March 19, 2012; Published May 9, 2012) Keywords: spark plasma sintering process, molybdenum, sputtering target

1.

Introduction

Molybdenum is an important refractory metal that has a body-centered cubic crystal structure with a melting point of 2883.15 K and a density of 10.22 103 Mg/m3. The refractory properties of molybdenum reect the high strength of interatomic bonding resulting from an overlap of the 4d orbital and the number of available bonding electrons.1) Because of properties such as high corrosion resistance and weld-ability, it has been used for a wide scale of engineering applications. Some examples include ribbons and wires for lighting technology, semiconductor base plates for power electronics and electrodes for glass melting, parts for hightemperature furnaces, spray wires for automotive industry applications, and sputter targets or evaporation sources for coating technology. Components from pure molybdenum or its alloys are produced either by powder metallurgy or by melting processes. A ne-grained microstructure is obtained by the powder metallurgical route which improves the mechanical properties of nal products considerably. In addition, the powder route offers the exclusive possibility for production of molybdenum-copper alloys or for doping molybdenum with high-temperature resistant oxides.15) Most molybdenum materials are used as the above-mentioned alloys, but pure molybdenum material is used mostly as the molybdenum sputtering target for the back electrode of copper indium gallium selenide (CIGS) of solar cells and the gate electrode of organic light emitting diodes (OLED). Sputtering target materials require high purity, high density, and a ne-grained microstructure. Grain size and uniform distribution of the target, especially, are factors that inuence the electrical properties of wiring materials. Spark Plasma Sintering (SPS) could operate at a low temperature and for a short time duration because the powder
+

surface is activated by a high-voltage pulse current between gaps in powder. Key advantage of the SPS is that it fabricates microstructure compacts with high degree of densication. Recently, SPS has been studied and applied to the development of target materials. Compared to conventional sintering methods in which external pressure is applied, such as hot pressing (HP) or hot isostatic pressing (HIP), SPS densies powders extremely fast. Thus, the sintering temperatures can be lower, which allows for the limitation of grain growth.613) In this study, molybdenum was sintered using a rapid sintering process known as SPS. The method combined a pulsed DC current with the application of high pressure. The goal of this study is to produce a dense, ultrane molybdenum sputtering target in a very short sintering time (2440 s). Properties of the molybdenum sputtering target and the thin lm were investigated by X-ray diffraction (XRD), eld emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS), and the commercial target and thin lm were analyzed for comparison with the properties of the molybdenum target fabricated by SPS. 2. Experimental Procedure

Corresponding author, E-mail: ihoh@kitech.re.kr

In this study, 99.93% pure molybdenum powder (3 m, JMC Co, Japan) was used as raw material. Figure 1 shows an FE-SEM image of the pure molybdenum powder. The powders agglomerated, and the particles are distributed to a size of about 13 m. Purity of the raw material was analyzed by induction couple plasma (ICP) equipment (Xseries-II, ICP-MS), and the purity was 99.93%, as shown in Table 1. In this process, molybdenum powders were loaded into a graphite die (outside diameter, 250 mm; inside diameter, 150 mm; height, 80 mm) without any additives or binder and then placed into a spark plasma sintering (SPS) system made by Sumitomo

Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process

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Fig. 1

FE-SEM image of pure molybdenum powder.

Table 1 Results of induction couple plasma analysis for the raw Mo powder [99%]. O Raw material 1400 Cu Raw material 25 N 110 Ni 21 Si 410 Al 14 Fe 61 Ca 90 Cr 19 P 30 Pb 10 Fig. 3 Schematic diagram of time, temperature, pressure and shrinkage displacement prole during SPS process and different stages of consolidation.

Total (ppm) 680 (99.93%)

Fig. 2 Schematic diagram of the spark plasma sintering apparatus.

Coal Mining in Japan. A schematic diagram of this method is shown in Fig. 2. The SPS apparatus includes a 12 V, 30,000 A DC power supplies (which provides a pulsed current with 12 ms on time and 2 ms off time through the sample and the die) and a uniaxial press of 300 tons. The system was rst evacuated and a uniaxial pressure of 60 MPa was applied. DC current was then activated and maintained until the densication rate was negligible, as indicated by the observed shrinkage of the sample. Sample shrinkage is measured in real time by linear gauge that measures the vertical displacement. Temperature was measured by pyrometer focused on the surface of the graphite die hall.

Depending on the heating rate, the electrical and thermal conductivities of the compact, and on the relative density of the compact, there was a difference in temperature between the surface and the center of the sample. The heating rate was approximately 180480 K/s in the process. At the end of the process, the current was turned off and the sample was allowed to cool down to room temperature. The entire process of densication using the SPS process consists of four major control stages in Fig. 3. These are chamber evacuation, pressure application, power application, and cool down. The process was carried out under a vacuum of 6 Pa. Since there are different properties in the inner and outer parts of the fabricated compact, a graphite punch is designed to measure the temperature of the compact and fabricates molybdenum compact having a uniform properties. It has two holes at center and edge of the punch as shown in Fig. 4(a). Temperature of the inner and outer parts can be measured during the sintering. Also, temperature deviation can be reduced through process control as shown in Fig. 4(b). For example, temperature deviation of the two parts (inner and outer) is judged to occur owing to the thermal emission of the outer part during sintering. For this reason, temperature deviation can be minimized by maintaining each step or by adjusting the heating rate in the process. Fabricated compacts were cut into two parts, including the center and the edge for comparison of the properties (density and grain size), and the relative densities of the sintered samples were then calculated based on the theoretical density of 10.22 103 Mg/m3 by the Archimedean method. The Archimedean method was used to measure the density of the sintered samples for a zero min, holding time, (do), as well as for the particular sintering time, designated as d. Linear shrinkage was measured using a micrometer. Electron backscattered diffraction (EBSD)

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H.-K. Park, J.-H. Ryu, H.-J. Youn, J.-M. Yang and I.-H. Oh

Fig. 4

Shape of designed graphite mold (a) and detailed process diagram (b) to get uniform properties.

studies were carried out in an orientation imaging microscope (FEI Quanta 200HV) for specimens. The samples for the EBSD studies were prepared by grinding up a 1 m diamond nish and followed by electrolytic polishing (Struers LectroPol-5). Applying a potential of 5060 V, electrolytic polishing was performed in a bath consisting of 30 mL H2SO4, 6 mL HF, and 600 mL methanol, for 1020 s at below 273.15 K. The grain size measurements and orientation distributions of different grains were studied. The grain sizes were measured by the line intercept method. Initially, abnormal grains were identied for their larger size and orientation angles at the boundaries, and the average grain size was measured by drawing the lines in those areas where abnormal grains were absent and at least 60 normal grains were present. Also, X-ray diffraction (XRD) was recorded using Cu-K radiation to observe the phase change of the compacts.14) The fabricated compacts were surface ground to make the thin lm by forming them on a grinding machine. Worked surface of the molybdenum sputtering target was installed in the sputtering system (SRN-120), and the molybdenum thin lms were fabricated for 3.6 Ks at a mixed condition of high pressure (HP) and low pressure (LP). In general, this condition (HP + LP) is used to get outstanding adhesion (thin lm and substrate) and conductivity of thin lm. The HP and LP conditions were pressed with Ar gas 3.33 and 0.333 Pa, respectively. Also, a glass was used as the substrate. The thin lms were analyzed by transmission electron microscopy (TEM), SIMS, and specic resistivity. In addition, the molybdenum sputtering target fabricated by SPS and its thin lm were compared with that commercially fabricated by HIP (TASCO, USA). 3. 3.1 Results and Discussion

Fig. 5

XRD patterns of commercial and SPSed molybdenum target.

Analysis of Molybdenum compacts fabricated by SPS process Molybdenum compacts having temperature deviation of below 323.15 K were fabricated in two parts (inner and outer) through a designed mold and process control. The XRD (PANalytico, KPert PRO, Spectris Korea Ltd) result of molybdenum compacts is shown in Fig. 5. The contact of molybdenum powder with the graphite die and sheets results in diffusion of the carbon inside the samples, although the

SPS is a short time process. However, the lower sintering temperature can be prevented in order to generate Mo2C in the inside of compact, which differs from the conventional sintering method. Results of XRD analysis shows that all the peaks are only detected in the pure molybdenum phase, as shown in Fig. 5. Calculated relative densities and grain sizes of all sintered samples according to heating rate are listed in Table 2. For all samples, a high density of sample up to 99% can be obtained at a sintering temperature of 1473.15 K, under 60 MPa pressure. Also, the compact can be fabricated for a sintering time of 1500 to 3600 s. According to the rise in the heating rate of 180480 K/s, the grain size was decreased because the shorter sintering time inhibited grain growth. Also, the properties of the inner and outer parts can be used to equalize the heating rate because the temperature deviation was controlled below 323.15 K using the designed the mold. Also, because the temperature gap was shown to be up to 373.15 K at a higher heating rate, the maximum heating rate was set to 480 K/s. The sintered microstructures obtained through EBSD imaging are presented in Fig. 6. Figure 6 shows the comparison of grain size of the molybdenum compact fabricated by SPS and HIP processes. The grain of the molybdenum compact fabricated by the SPS process using the direct heating method is uniform below 0.4 m in two parts, and the average grain size is 4.2 m. However,

Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process Table 2 Grain size and density according to different heating rates (sintered at 2192 K under 60 MPa pressure). Compact Size (mm) Particle size (powder, m) Final Sintering Temperature () Pressure (MPa) Heating rate (/min) 86 37 Final relative density (%) Inner Outer Inner Outer Inner Outer Inner Outer 99.7 99.2 99.4 99.0 99.2 99.0 99.2 99.0

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Grain size (m) 7.9 6.2 4.9 4.9 4.4 4.1 43.8 64.4

150

2192

60

140

176

150

Commercial target (HIP)

Fig. 6 EBSD images of Mo sputtering targets fabricated by SPS and HIP; (a) SPS (176 K/min)-inner, insert inverse pole gure, (b) SPS (176 K/min)-outer, (c) HIP-inner, (d) HIP-outer.

the grain size of the molybdenum compact fabricated by HIP shows a difference between the inner and outer parts compared to the compact having a uniform microstructure. The molybdenum compact fabricated by HIP shows a different grain size about 20 m in inner and outer parts of the compact. As the indirect method is used for the HIP heating process, the temperature of the outer part is higher than that of the inner part during sintering. For the above reason, it is not easy to fabricate a uniform compact. However uniform compacts can be fabricated by SPS process at low temperature and as well as in a short time within 1440 s. So SPS process is considered as a means for the fabrication of high-density molybdenum compacts for two reasons. First, because high Joule heating occurs at the point of contact between particles due to an induced current, the spread of atoms is quickened. In addition, it is considered to be easier to perform sintering at a low temperature because the spread of atoms is quickened in an electric eld. And, second, when pressure is applied during sintering, the driving force of the sintering is increased; eq. (1) shows the increased driving force, FD.15)

FD Pa r= ;

where is the interfacial energy, and Pa and r are the applied pressure and radius of particle, respectively. Figure 7 shows the density as a function of the sintering temperature of the experiments compared with that obtained for the other sintering method.1518) When the compact was sintered by P2C until 1873.15 K with 40 MPa and 1923.15 K with 48 MPa external pressure, the densities of fabricated compacts were 96.0 and 98.5%, respectively.4,7,16) In addition, we can compare the densities obtained by SPS with those of isothermal sintering. The isothermal powder metallurgical route starts with the hydraulic or isostatic pressing of the molybdenum powder into rods and plates of various geometries and dimensions. The sintering process is carried out in furnaces at high temperatures (typically in the range of 2073.152473.15 K) and in a hydrogen atmosphere over long periods of time (7.210.8 ks) to obtain densities about 90% of the theoretical density. Figure 7 shows the relative densities published in,16,17) which were estimated after 3.6 ks isothermal sintering. For temperatures

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H.-K. Park, J.-H. Ryu, H.-J. Youn, J.-M. Yang and I.-H. Oh Table 4 Comparison of the resistivity of commercial and SPSed Mo thin lms. Scan size (2 m)-HP + LP Resistivity (cm) Commercial 15.9 SPS 176 K/min 15.7

Fig. 7 Relative density of spark plasma sintered molybdenum vs. sintering temperature, compared with other published data.

Table 3 Results of induction couple plasma analysis for the SPSed Mo target. O SPSed Mo 270 Cu SPSed Mo 10 N 30 Ni 10 Si 400 W 30 Al 10 Fe 77 Ca 10 Cr 17 P 10 Pb 10

Total (ppm) 584 (99.93%)

higher than 1673.15 K, the comparison shows that the relative densities of SPS are comparable with or higher than the relative densities generated by isothermal sintering, although the sintering time is very short for SPS. At lower temperature, isothermal sintered molybdenum bodies become denser, which is caused by the higher green density due to a higher compaction pressure. The molybdenum compact fabricated by SPS was cut into the shape of a chip to analyze the purity obtained by the ICP equipment. Since the purity of the compact was measured 99.93%, its purity is the same as that of the starting material. This result is shown in Table 3. Moreover the oxygen impurity of the sputtering target decreased from 1400 to 270 ppm, because the cleaning effect is generated by the spark phenomenon between particles during the sintering. 3.2 Evaluation of sputtered molybdenum thin lms After grinding on the surface of the molybdenum target, SPSed molybdenum target and HIP molybdenum target were installed in the sputtering system. Molybdenum thin lms were deposited on a glass substrate and used for the back electrode of the CIGS solar cell. As the detail process condition, Ar gas was rst applied at an initial pressure of 6.5 104 Pa (5 106 torr). When the thin lm was formed, the pressure was progressed under mixed condition of high pressure (3.33 Pa) and LP (0.33 Pa) for 3.6 ks at room temperature. Specic resistance was calculated through eq. (2) using the face resistance obtained by a 4 point probe. L R=A; 2 where is specic resistivity; L is length; and R and A are resistance and sectional area, respectively. The unit of

Fig. 8 SIMS depth proles of sputtered lms of the Mo targets according to mixed deposition condition (High and low pressure); (a) Commercial, (b) SPS (176 KC/min).

specic resistance is m at the CIGS unit system, and there is a countercurrent connection (specic resistance = 1/conductivity) with conductivity, demonstrating the ability of a material to conduct electricity.19) Measured values are shown in Table 4. Impurities analysis of the thin lm was carried out from the depth proles of SIMS, and the results are shown in Fig. 8. Figures 8(a) and 8(b) show nearly similar proles between commercial and SPS cases. Also, specic resistivity of SPS molybdenum thin lms showed properties similar to those of the lm prepared with the conventional target, as shown in Table 4. Figure 9 shows TEM images (cross-sectional view) of the sputtered lms deposited with a commercial HIP and SPS molybdenum target. Thickness of the thin lms was about 700 nm. The thin lms were closely deposited on glass substrate. It was found from TEM results that the grain size of both thin lms was nearly the same, and that second phases of defects, such as voids, were not formed in lms. Also, the molybdenum thin lms were grown with the (110) texture as show by electron diffraction patterns, and therefore, through investigation it was determined that the molybdenum target fabricated by SPS has approximately equal properties compared with the commercial one.

Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process

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Fig. 9

TEM images (cross-sectional view) of sputtered lms deposited with; (a) Commercial Mo, (b) SPS (80C/min) Mo.

4.

Conclusion

REFERENCES
1) E. R. Braithwaite and J. Harber: Molybdenum: An Outline of its Chemistry and Uses, (Elsevier, New York, 1994). 2) R. R. Freeman: Properties and applications of commercial molybdenum and molybdenum alloys, The Metal Molybdenum, ed. by J. H. Harwood, (American Society for Metals, 1956) pp. 1030. 3) E. F. Baroch, M. Ostermann and G. Patrick: Adv. Powder Metall. 5 (1991) 321331. 4) A. J. Herzig: The potential and future of molybdenum and its alloys, The Metal Molybdenum, ed. by J. H. Harwood, (American Society for Metals. 1956) pp. 49. 5) K. J. A. Mawella, D. J. Standing, K. G. Cowan, and J. S. Jones: TMS Annual Meeting, (TMS; 1998) pp. 183194. 6) M. Tokita: Proc. Int. Symp. on Microwave, Plasma and Thermochemical Processing of Advanced Materials, ed. by S. Miyake and M. Samandi, JWRI, Osaka Universities, Japan, (1997) pp. 6976. 7) R. Orru, R. Licheri, A. M. Locci, A. Cincotti and G. Cao: Mater. Sci. Eng. R 63 (2009) 127287. 8) Z. A. Munir, U. Anselmi-Tamburini and M. Ohyanagi: J. Mater. Sci. 41 (2006) 763777. 9) R. Chaim: Mater. Sci. Eng. A 443 (2007) 2532. 10) W. Chen, U. Anselmi-Tamburini, J. E. Garay, J. R. Groza and Z. A. Munir: Mater. Sci. Eng. A 394 (2005) 132138. 11) U. Anselmi-Tamburini, S. Gennari, J. E. Garay and Z. A. Munir: Mater. Sci. Eng. A 394 (2005) 139148. 12) U. Anselmi-Tamburini, J. E. Garay and Z. A. Munir: Mater. Sci. Eng. A 407 (2005) 2430. 13) M. Omori: Mater. Sci. Eng. A 287 (2000) 183188. 14) Database PDF-2 of the International Centre for Diffraction Data, (2006). 15) R. L. Coble: J. Appl. Psys. 41 (1970) 47984801. 16) T. S. Srivatsan, B. G. Ravi, A. S. Nauka, L. Riester, M. Petraroli and T. S. Sudarshan: Powder Technol. 114 (2001) 136144. 17) S. Majundar, S. Raveendra, I. Samajdar, P. Bhargava and I. G. Sharma: Acta Mater. 57 (2009) 41584168. 18) T. S. Srivatsan, B. G. Ravi, M. Petraroli and T. S. Sudarshan: Int. J. Refract. Met. Hard Met. 20 (2002) 181186. 19) D. William: Materials Science and Engineering, 6th Ed. (John Weily, 2004) p. 649.

A molybdenum sputtering target (150 mm 6.35 mm in diameter) was fabricated with molybdenum powder (grain size of 3 m and purity of 99.93%) using the SPS method. The designed mold was used for decreasing temperature deviation between the inner and outer parts; the temperature difference can be controlled below 323.15 K. From the results of the phase and purity analysis of the molybdenum compact, the other phase was not discovered, and the purity and grain size were 99.93% and 4 m, respectively. The purity of the molybdenum compact fabricated without grain growth was nearly equal to that of the raw powder having a purity of 99.93%. This result is considered to be due to sintering at a low temperature and a short time period, the advantages of the SPS process, and the nearly equal purity may be considered to be owing to the clean effect of particles by the spark phenomenon during the sintering process. The specic resistance (0.157 m) of the SPS molybdenum thin lm deposited with a compact fabricated by the heating rate of 4800 K/s showed properties similar to the lm prepared with a conventional sintering method (0.159 m). A high-quality molybdenum sputtering target can be fabricated by SPS in a short period of time, compared to the commercial HIP target. Because the SPS molybdenum target has properties that are similar to those of the commercial target and can be fabricated in a shorter amount of time, its application could be important because of the cost savings. Moreover, it can be utilized as sputtering target materials for the back electrode of CIGS solar cells and the gate electrode of organic emitting diodes (OLED).

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