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 fine-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 field emission scanning electron microscopy (FE-SEM). In addition, molybdenum thin films 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 µm 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 (³0.15 ®³m) of the optimized spark plasma sintering (SPS) molybdenum thin film showed properties that are similar to those of the film 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 reflect 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 fine-grained microstructure is obtained by the powder metallurgical route which improves the mechanical properties of final 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 fine-grained microstructure. Grain size and uniform distribution of the target, especially, are factors that influence 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 densification. 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 densifies 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, ultrafine molybdenum sputtering target in a very short sintering time (2440 s). Properties of the molybdenum sputtering target and the thin film were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS), and the commercial target and thin film 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 µm, 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 ³1­3 µm. 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

These are chamber evacuation. The heating rate was approximately ³180­480 K/s in the process. (do). temperature deviation can be minimized by maintaining each step or by adjusting the heating rate in the process. a graphite punch is designed to measure the temperature of the compact and fabricates molybdenum compact having a uniform properties. For this reason. the electrical and thermal conductivities of the compact. power application. temperature. designated as d. as well as for the particular sintering time. there was a difference in temperature between the surface and the center of the sample. pressure application. Coal Mining in Japan. 2 Schematic diagram of the spark plasma sintering apparatus. Electron backscattered diffraction (EBSD) . The system was first evacuated and a uniaxial pressure of 60 MPa was applied. and the relative densities of the sintered samples were then calculated based on the theoretical density of 10. A schematic diagram of this method is shown in Fig. It has two holes at center and edge of the punch as shown in Fig. At the end of the process. Linear shrinkage was measured using a micrometer. Fabricated compacts were cut into two parts. The SPS apparatus includes a 12 V. the current was turned off and the sample was allowed to cool down to room temperature. 2. The Archimedean method was used to measure the density of the sintered samples for a zero min. Also. Temperature was measured by pyrometer focused on the surface of the graphite die hall. 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. and on the relative density of the compact. Table 1 Results of induction couple plasma analysis for the raw Mo powder [99%]. 3. including the center and the edge for comparison of the properties (density and grain size). 4(b). as indicated by the observed shrinkage of the sample. holding time.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 entire process of densification using the SPS process consists of four major control stages in Fig. Temperature of the inner and outer parts can be measured during the sintering. DC current was then activated and maintained until the densification rate was negligible. temperature deviation can be reduced through process control as shown in Fig. The process was carried out under a vacuum of 6 Pa. Total (ppm) 680 (99. Sample shrinkage is measured in real time by linear gauge that measures the vertical displacement. 4(a). 3 Schematic diagram of time. pressure and shrinkage displacement profile during SPS process and different stages of consolidation. temperature deviation of the two parts (inner and outer) is judged to occur owing to the thermal emission of the outer part during sintering. 30. and cool down.Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process 1057 Fig. 1 FE-SEM image of pure molybdenum powder.93%) Fig.22 © 103 Mg/m3 by the Archimedean method. For example. Depending on the heating rate. Since there are different properties in the inner and outer parts of the fabricated compact.

In general.6 Ks at a mixed condition of high pressure (HP) and low pressure (LP).15 K. X-ray diffraction (XRD) was recorded using Cu-K¡ radiation to observe the phase change of the compacts.33 and 0. The sintered microstructures obtained through EBSD imaging are presented in Fig. for ³10­20 s at below 273. The grain sizes were measured by the line intercept method.-H.-K. abnormal grains were identified for their larger size and orientation angles at the boundaries. 3. and specific resistivity. under 60 MPa pressure. According to the rise in the heating rate of ³180­480 K/s. Also. Initially. Park. . 6. The samples for the EBSD studies were prepared by grinding up a 1 µm diamond finish and followed by electrolytic polishing (Struers LectroPol-5). a high density of sample up to 99% can be obtained at a sintering temperature of 1473.15 K. The thin films were analyzed by transmission electron microscopy (TEM). 3. The HP and LP conditions were pressed with Ar gas 3. Calculated relative densities and grain sizes of all sintered samples according to heating rate are listed in Table 2. 4 Shape of designed graphite mold (a) and detailed process diagram (b) to get uniform properties. as shown in Fig. Also. Also. Spectris Korea Ltd) result of molybdenum compacts is shown in Fig. Also. The XRD (PANalytico.4 µm in two parts. 5. studies were carried out in an orientation imaging microscope (FEI Quanta 200HV) for specimens. a glass was used as the substrate.1058 H. the maximum heating rate was set to 480 K/s.-M. although the SPS is a short time process.1 Results and Discussion Fig.-J. Ryu. In addition. the molybdenum sputtering target fabricated by SPS and its thin film were compared with that commercially fabricated by HIP (TASCO. However. However. which differs from the conventional sintering method. The grain of the molybdenum compact fabricated by the SPS process using the direct heating method is uniform below 0.15 K at a higher heating rate. USA). this condition (HP + LP) is used to get outstanding adhesion (thin film and substrate) and conductivity of thin film. 6 mL HF.2 µm. Also. The grain size measurements and orientation distributions of different grains were studied. Analysis of Molybdenum compacts fabricated by SPS process Molybdenum compacts having temperature deviation of below 323. Yang and I. the grain size was decreased because the shorter sintering time inhibited grain growth. and 600 mL methanol. For all samples. The contact of molybdenum powder with the graphite die and sheets results in diffusion of the carbon inside the samples. Worked surface of the molybdenum sputtering target was installed in the sputtering system (SRN-120).15 K were fabricated in two parts (inner and outer) through a designed mold and process control. Applying a potential of ³50­60 V. Figure 6 shows the comparison of grain size of the molybdenum compact fabricated by SPS and HIP processes. the properties of the inner and outer parts can be used to equalize the heating rate because the temperature deviation was controlled below 323. respectively.15 K using the designed the mold. SIMS. J. Youn. H. electrolytic polishing was performed in a bath consisting of 30 mL H2SO4. and the molybdenum thin films were fabricated for 3. 5.-H.333 Pa. because the temperature gap was shown to be up to 373. the compact can be fabricated for a sintering time of 1500 to 3600 s.14) The fabricated compacts were surface ground to make the thin film by forming them on a grinding machine. 5 XRD patterns of commercial and SPSed molybdenum target. Oh Fig. and the average grain size is 4. J. Results of XRD analysis shows that all the peaks are only detected in the pure molybdenum phase. the lower sintering temperature can be prevented in order to generate Mo2C in the inside of compact. K’Pert PRO. 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.

5%. (d) HIP-outer. the driving force of the sintering is increased.9 6. µm) Final Sintering Temperature (°) Pressure (MPa) Heating rate (°/min) 86 3­7 Final relative density (%) Inner Outer Inner Outer Inner Outer Inner Outer 99.8 64.15 K with 48 MPa external pressure. 6 EBSD images of Mo sputtering targets fabricated by SPS and HIP. Compact Size (mm) Particle size (powder.15­2473.0 99. As the indirect method is used for the HIP heating process. eq.16. (b) SPS (176 K/min)-outer.2 99.15 K with 40 MPa and 1923. However uniform compacts can be fabricated by SPS process at low temperature and as well as in a short time within 1440 s. it is not easy to fabricate a uniform compact. when pressure is applied during sintering. 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.0 1059 Grain size (µm) 7. The molybdenum compact fabricated by HIP shows a different grain size about 20 µm in inner and outer parts of the compact. For temperatures .0 and 98. the densities of fabricated compacts were 96.8 ks) to obtain densities about 90% of the theoretical density.15­18) When the compact was sintered by P2C until 1873. (c) HIP-inner.16) In addition. Figure 7 shows the relative densities published in.9 4. the spread of atoms is quickened. respectively. the temperature of the outer part is higher than that of the inner part during sintering. (a) SPS (176 K/min)-inner.9 4. So SPS process is considered as a means for the fabrication of high-density molybdenum compacts for two reasons. it is considered to be easier to perform sintering at a low temperature because the spread of atoms is quickened in an electric field.7 99. second. and Pa and r are the applied pressure and radius of particle.4 4. Figure 7 shows the density as a function of the sintering temperature of the experiments compared with that obtained for the other sintering method. we can compare the densities obtained by SPS with those of isothermal sintering.7.6 ks isothermal sintering. The sintering process is carried out in furnaces at high temperatures (typically in the range of ³2073.15 K) and in a hydrogen atmosphere over long periods of time (³7.1 43.2 99. FD.2­10. insert inverse pole figure. And. 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. (1) shows the increased driving force.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). because high Joule heating occurs at the point of contact between particles due to an induced current.15) FD ¼ £ þ ðPa r=³ Þ. In addition. ð1Þ where £ is the interfacial energy.4 150 2192 60 140 176 150 Commercial target (HIP) Fig.17) which were estimated after 3. For the above reason. respectively. First.4 99.2 99.0 99.4.2 4.

µ ¼ L Á R=A. This result is shown in Table 3. the comparison shows that the relative densities of SPS are comparable with or higher than the relative densities generated by isothermal sintering.19) Measured values are shown in Table 4. Impurities analysis of the thin film was carried out from the depth profiles of SIMS. were not formed in films. Park. specific resistance is ®³m at the CIGS unit system.6 ks at room temperature. When the thin film was formed. the pressure was progressed under mixed condition of high pressure (3. At lower temperature. which is caused by the higher green density due to a higher compaction pressure. and there is a countercurrent connection (specific resistance = 1/conductivity) with conductivity. Yang and I. as shown in Table 4. and that second phases of defects. respectively. Ar gas was first applied at an initial pressure of 6. Molybdenum thin films were deposited on a glass substrate and used for the back electrode of the CIGS solar cell. ð2Þ where µ is specific resistivity.93%. 8 SIMS depth profiles of sputtered films of the Mo targets according to mixed deposition condition (High and low pressure).5 © 10¹4 Pa (5 © 10¹6 torr). Moreover the oxygen impurity of the sputtering target decreased from 1400 to 270 ppm. 3. The thin films were closely deposited on glass substrate. Figures 8(a) and 8(b) show nearly similar profiles between commercial and SPS cases. demonstrating the ability of a material to conduct electricity. isothermal sintered molybdenum bodies become denser. sintering temperature. Also. Ryu.-K. because the cleaning effect is generated by the spark phenomenon between particles during the sintering. and therefore.-J. J. H. specific resistivity of SPS molybdenum thin films showed properties similar to those of the film prepared with the conventional target.15 K. compared with other published data. (2) using the face resistance obtained by a 4 point probe. The unit of Fig.33 Pa) and LP (0. J. Oh Table 4 Comparison of the resistivity of commercial and SPSed Mo thin films. 8.7 Fig.2 Evaluation of sputtered molybdenum thin films After grinding on the surface of the molybdenum target. L is length.-H. As the detail process condition. its purity is the same as that of the starting material.-H. The molybdenum compact fabricated by SPS was cut into the shape of a chip to analyze the purity obtained by the ICP equipment. through investigation it was determined that the molybdenum target fabricated by SPS has approximately equal properties compared with the commercial one. (a) Commercial.-M. such as voids. 7 Relative density of spark plasma sintered molybdenum vs. (b) SPS (176 K°C/min). Scan size (2 µm)-HP + LP Resistivity (µ³·cm) Commercial 15. . SPSed molybdenum target and HIP molybdenum target were installed in the sputtering system. Also. Since the purity of the compact was measured 99.1060 H. although the sintering time is very short for SPS.93%) higher than 1673. the molybdenum thin films were grown with the (110) texture as show by electron diffraction patterns. It was found from TEM results that the grain size of both thin films was nearly the same. and R and A are resistance and sectional area.33 Pa) for 3. Youn. 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. Figure 9 shows TEM images (cross-sectional view) of the sputtered films deposited with a commercial HIP and SPS molybdenum target. Specific resistance was calculated through eq. Thickness of the thin films was about 700 nm.9 SPS 176 K/min 15. and the results are shown in Fig. Table 3 Results of induction couple plasma analysis for the SPSed Mo target.

Plasma and Thermochemical Processing of Advanced Materials. Ravi. (Elsevier. 4­9. A. F. 20 (2002) 181­186. Refract. Riester. The specific resistance (0. S. A molybdenum sputtering target (150 mm © 6. R. Sci. Anselmi-Tamburini. A. J. Raveendra.157 ®³m) of the SPS molybdenum thin film deposited with a compact fabricated by the heating rate of 4800 K/s showed properties similar to the film prepared with a conventional sintering method (0. Eng. 69­76. (American Society for Metals. Omori: Mater.93% and ³4 µm. Eng. Groza and Z. Jones: TMS Annual Meeting. U. 18) T. J. (TMS. G. I. 5 (1991) 321­331. 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). M. Sci. 41 (2006) 763­777. (b) SPS (80°C/min) Mo.15 K. L. 649.35 mm in diameter) was fabricated with molybdenum powder (grain size of 3 µm and purity of 99. Osaka Universities. Freeman: Properties and applications of commercial molybdenum and molybdenum alloys. The purity of the molybdenum compact fabricated without grain growth was nearly equal to that of the raw powder having a purity of 99. Sci. JWRI. Harber: Molybdenum: An Outline of its Chemistry and Uses. G. the advantages of the SPS process. 12) U. Moreover. Patrick: Adv. (a) Commercial Mo. D. Munir. 15) R. Braithwaite and J. 41 (1970) 4798­4801. K. Ravi. (John Weily. Sudarshan: Powder Technol. B. 9) R. 57 (2009) 4158­4168. Mawella. on Microwave. 2004) p.93%. (1997) pp. Eng. and the purity and grain size were 99. Anselmi-Tamburini and M. 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. S. Tokita: Proc. Miyake and M. 114 (2001) 136­144. H. compared to the commercial HIP target. 1956) pp. by J.93%) using the SPS method. A 394 (2005) 132­138. A. Appl. A high-quality molybdenum sputtering target can be fabricated by SPS in a short period of time. Samandi. J. Standing. S. R. Munir: Mater. Licheri. 17) S. New York. Anselmi-Tamburini. Eng. 8) Z. Sudarshan: Int. R. Coble: J. Harwood. Symp. Munir: Mater. Eng. E. Chen.159 ®³m). Sharma: Acta Mater. B. Eng. Garay. William: Materials Science and Engineering. Chaim: Mater. Anselmi-Tamburini. ed. Int. Hard Met. Sci. L. A. Bhargava and I. P. E. M. 3) E. 1956) pp. G. U. J. R. by J. Garay and Z. 1994). J. 10­30. From the results of the phase and purity analysis of the molybdenum compact. A 407 (2005) 24­30. 5) K. and J. Sci. 10) W. 16) T. Powder Metall. A 443 (2007) 25­32. M. S. S. 1998) pp. Herzig: The potential and future of molybdenum and its alloys. H. 19) D. Met. S. Japan. R 63 (2009) 127­287. Locci. E. (American Society for Metals. J. S. Gennari. ed. G. 6) M. The designed mold was used for decreasing temperature deviation between the inner and outer parts. the temperature difference can be controlled below 323. A. ed. Garay and Z. Ohyanagi: J. Cao: Mater. 4. (2006). Psys. Petraroli and T. A 394 (2005) 139­148. J. Srivatsan. Baroch. Mater. S. Cincotti and G. Cowan. Ostermann and G. 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. Sci. . 183­194. 9 TEM images (cross-sectional view) of sputtered films deposited with. Conclusion REFERENCES 1) E. its application could be important because of the cost savings. Srivatsan. 14) Database PDF-2 of the International Centre for Diffraction Data. A. Sci. This result is considered to be due to sintering at a low temperature and a short time period. 7) R. The Metal Molybdenum. 11) U. The Metal Molybdenum. 6th Ed. Majundar. 13) M. Harwood. A. Orru. respectively. Samajdar.Fabrication and Property Evaluation of Mo Compacts for Sputtering Target Application by Spark Plasma Sintering Process 1061 Fig. Petraroli and T. 2) R. by S. A. M. Munir: Mater. the other phase was not discovered. A 287 (2000) 183­188. J. Nauka. 4) A.