Thin Solid Films 475 (2005) 202 207 www.elsevier.

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Deposition of tantalum nitride thin films by D.C. magnetron sputtering

S.K. Kim*, B.C. Cha
School of Materials Science and Engineering, University of Ulsan, Ulsan 680-749, South Korea Available online 28 September 2004

Abstract Thin films of tantalum nitride (TaN) were deposited on SKD11 tool steel substrate by a D.C. magnetron sputtering system. The influence of the N2/Ar gas ratio of the inlet gases on the structure, hardness, adhesion and wear resistance was investigated. The X-ray diffraction data showed that TaN deposited at low N2/Ar gas ratio, tetragonal h-Ta(330) and hexagonal TaN(101) were observed. Orthorhombic TaN(110) and orthorhombic Ta3N5 were formed with the increase of the N2/Ar gas ratio. High hardness of the films was observed at the low N2/Ar gas ratio. The films deposited at N2/Ar gas ratio of 0.3 showed good adhesion, wear resistance and hardness of Hv0.05 1450. The films deposited with etching time of 30 min at 133.32 Pa gave good adhesion. Thickness of the films decreased with applying the bias voltage. As the bias potential was increased, the hardness of the film increased and then decreased. The films with fine dome structure showed good wear resistance. D 2004 Elsevier B.V. All rights reserved.
Keywords: TaN; D.C. magnetron sputtering; Wear resistance; Adhesion

1. Introduction Transition metal nitrides are well known for their remarkable physical properties including high hardness and mechanical strength, chemical inertness, and high temperature stability. They are widely studied and have become technologically important for applications such as wear resistant coatings [1], protective coatings with functional optical properties [2] or for specific metallization properties in microelectronics [3]. Tantalum nitride (TaN) thin films are attractive for use as structural elements in integrated circuits. Most of the works on TaN have been done on their application in thin film resistors and diffusion barriers [4,5]. Very little work has been done on their application in hard wear resistant coatings. In this work, we report the effects of the N2/Ar gas ratio of inlet gases, the etching pressure and time and bias voltage on the structural and mechanical properties of magnetron-sputtered TaN thin films.

2. Experimental procedures The TaN films were produced in an unbalanced D.C. magnetron sputtering equipment. A circular sputter source

* Corresponding author. Tel.: +82 522592228; fax: +82 522591688. E-mail address: skim@ulsan.ac.kr (S.K. Kim). 0040-6090/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2004.08.059

Fig. 1. X-ray diffractograms of TaN films deposited with various N2/Ar gas ratios of inlet gases ((a) N2/Ar=0.1, (b) N2/Ar=0.2, (c) N2/Ar=0.3, (d) N2/Ar=0.4).

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Fig. 2. Hardness of TaN films deposited at various N2/Ar gas ratio.

was fixed to the lid of the chamber. A tantalum target (99.98% pure) of diameter 76.2 mm was attached to the sputter source. A sample holder, which can rotate and enabled bias voltage, was located at the center of the chamber. Substrate to target distance was 55 mm. After the chamber was evacuated to 1.3104 Pa using a rotary pump and a diffusion pump, argon was introduced to maintain working pressure. The SKD11 steel (1.5% C, 11.5% Cr, 0.8% Mo, 0.9% V) specimens were polished and degreased ultrasonically in alcohol. Before deposition, the specimens were plasma etched for 10 to 60 min with 370 V, 600 mA at the pressure of 133.32 Pa. To determine the effect of nitrogen partial pressure, the N2/Ar gas ratio of inlet gases was varied from 0.1 to 0.4. Target power was fixed to 200 W. Before the deposition of the TaN, an interlayer of tantalum was deposited at 0.8

Fig. 3. Optical micrographs of scratch tracks of TaN films deposited at various N2/Ar gas ratios ((a) N2/Ar=0.1, (b) N2/Ar=0.2, (c) N2/Ar=0.3, (d) N2/Ar=0.4).

Fig. 4. Optical micrographs of wear tracks of TaN films obtained at various N2/Ar gas ratios ((a) N2/Ar=0.1, (b) N2/Ar=0.2, (c) N2/Ar=0.3, (d) N2/Ar=0.4).

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Fig. 5. Micrographs of etched surface morphology of the substrate at various pressure ((a) 37.33 Pa, (b) 68 Pa, (c) 133.32 Pa).

Pa for 20 min. Then TaN layer was deposited at the same pressure for 60 min. X-ray diffractometer (Rigaku, RAD3C) was used to determine the phases of the films. Field emission scanning electron microscope (JSM-650F) was used to observe the surface morphology of the films. The hardness of films was measured by a Vickers hardness tester using a 50-g load. Adhesion was evaluated by a scratch tester (Revetest, CSEM). When wear resistance was measured by a ball-on-disc type wear tester, the test condition was a 3-N load, 121 rev./min, 6065% relative humidity. Test duration was up to 1000 cycle. Bearing steel ball which contained 10% Cr was used as a counterpart. Wear track was examined by an optical microscope.

3. Results and discussion X-ray diffractograms of TaN films deposited using various N2/Ar gas ratio of inlet gases are shown in Fig. 1 The other deposition parameters kept constant were the deposition pressure of 0.53 Pa and the target power of 220 W. At low N2/Ar gas ratio, tetragonal h-Ta(330) [JCPDS 251280] and hexagonal TaN(101) [JCPDS 39-1485] were observed. With the increase of the N2/Ar gas ratio, hexagonal TaN(110) [JCPDS 39-1485] and orthorhombic Ta3N5 [JCPDS 19-1291] were formed. At the N2/Ar gas ratio of 4, Ta3N5 phase was only present. Fig. 2 shows the hardness of TaN films deposited at various N2/Ar gas ratios. High hardness was observed at the N2/Ar gas ratio of 0.1 and 0.2

Fig. 6. Optical micrographs of scratch tracks of TaN films deposited with various etching time ((a) 20 min, (b) 30 min, (c) 40 min, (d) 60 min).

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Fig. 7. The hardness of the TaN films deposited at various bias potentials.

although the data fluctuated significantly. At the N2/Ar gas ratio of 0.3, hardness values did not fluctuate much and were very stable. The hardness of the films decreased significantly at the N2/Ar gas ratio of 0.4, this was due to the decrease of the deposition rate and the formation of Ta3N5 phase. Fig. 3 shows scratch tracks of thin films deposited at various N2/Ar gas ratio. The films deposited at N2/Ar gas ratio of 0.3 showed good adhesion whereas the films deposited at other gas ratios cracked due to the residual stress developed within the films. Wear tracks of TaN films obtained at various N2/Ar gas ratios are shown in Fig. 4. The films deposited at N2/Ar gas ratio of 0.3 showed best wear resistance. Although the films obtained at N2/Ar gas ratio of 0.1 exhibited good wear resistance, the films easily cracked with small shock due to high residual stress. Fig. 5 shows SEM micrographs of etched

Fig. 8. SEM micrographs of the surface morphology of TaN films deposited at various bias voltage ((a) 0 V, (b) 50 V, (c) 100 V, (d) 150 V, (e) 200 V, (f) 300 V).

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surface morphology of the substrate at various pressure. The pressure of 133.32 Pa produced very rough surface. The surface was etched very densely at the pressure of 37.33 Pa. The surface was relatively smooth at the pressure of 68 Pa. We cannot explain why such a smooth surface was obtained at this intermediate pressure. This increase in the etch rate with pressure is mainly due to the increase in the concentration of neutrals with increasing pressure. The scratch tracks of the TaN films deposited with various etching time at 133.32 Pa with N2/Ar gas ratio of 0.3 are shown in Fig. 6. TaN films deposited with etching time of 30 and 40 min gave good adhesion whereas 20- and 40-min etching time showed bad adhesion. Short etching time did not produce rough surface and prolonged etching time also made the surface smooth which resulted in bad adhesion. Effect of the bias voltage on the thickness and structure of the TaN films was studied. The thickness of the film deposited without

bias voltage was 4.5 Am. Thickness of the films deposited with 50-, 100-, 150-, 200- and 300-V bias voltage were 2.5, 2.5, 2.5, 2.0 and 2.8 Am, respectively. Thickness of the films decreased with applying the bias voltage. The increase of the bias voltage did not affect the thickness of the film significantly. Fig. 7 shows the hardness of the TaN films deposited at various substrate bias potentials. As the bias potential was increased, the hardness of the film increased and then decreased. SEM micrographs of the surface morphology of each film are shown in Fig. 8. At low bias potentials, coarse dome structures were developed. Fine dome structures were observed with the increase of the bias voltage. Further increase of the bias potential to 300 V collapsed the dome structure which resulted in low hardness of the film. Similar trend in the development of dome structures in the films deposited with the increase of the bias voltage was also observed previously at the NbN films deposited by D.C.

Fig. 9. Optical micrographs of wear track of TaN films obtained at various bias voltage ((a) 50 V, (b) 100 V, (c) 150 V, (d) 200 V, (e) 300 V).

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magnetron sputtering [6]. Fig. 9 shows wear tracks of TaN films deposited at various bias voltage. TaN films with fine dome structures (Fig. 8d) exhibited good wear resistance.

cantly. The films with fine dome structures exhibited good wear resistance.

Acknowledgment 4. Conclusion TaN thin films were deposited by D.C. magnetron sputtering method. There was transition from a mixture of h-Ta(330) and hexagonal TaN(101) to a mixture of orthorhombic TaN(110) and orthorhombic Ta3N5 and further to orthorhombic Ta3N5 with the increase of the nitrogen partial pressure of the inlet gas. The hardness of the film decreased significantly at high nitrogen gas ratio of the inlet gas. The films deposited at N2/Ar gas ratio of 0.3 showed good adhesion and wear resistance. The pressure of 133.32 Pa and etching time of 30 and 40 min gave good adhesion of the films. The thickness of the films decreased with applying the bias voltage. The increase of the bias voltage did not affect the thickness of the films signifiThis research was supported by the 2004 University of Ulsan Research Fund.

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