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Coating and ion implantation to the inner surface of a pipe by metal plasma-based ion implantation and deposition
Surface and Coatings Technology 169 – 170 (2003) 411–414
Coating and ion implantation to the inner surface of a pipe by metal plasma-based ion implantation and deposition Ken Yukimuraa,*, Eiji Kuzea, Masao Kumagaib,1, Mamoru Kohatac,2, Ken Numatad,3, Hidenori Saitod,3, Toshiro Maruyamae,4, Xinxin Maf,5 a
Department of Electrical Engineering, Faculty of Engineering, Doshisha University, 1-3 Tatara-Miyakodani, Kyotanabe, Kyoto 610-0321, Japan b Material Engineering Division, Kanagawa Industrial Technology Research Institute, 705-1 Shimo-Imaizumi, Ebina, Kanagawa 243-0435, Japan c Material and Component Development Department, Toshiba Tungaloy Co., Ltd., 2-7 Sugasawa-sho, Tsurumi-ku, Yokohama 230-0027, Japan d Material Characterization Laboratory, Kanagawa High-Technology Foundation, KSP Building, East 101, 3-2-1 Sakado, Takatsu-ku, Kawasaki 213-0012, Japan e Department of Chemical Engineering, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan f School of Material Science and Engineering, Harbin Institute of Technology, P.O. Box 433, 92 West Dazhi Street, Harbin 150001, PR China
Abstract This article describes the characteristics of the coating of the inner surface of a pipe using plasma-based ion implantation and deposition method with a d.c. titanium-cathodic-arc in nitrogen gas. It was confirmed that the coating of the inner surface of the pipe with titanium nitride film was possible by using this method. The film structure and preferential orientation can be controlled by the applied voltage to the pipe. The film on the inner surface of a pipe in its entrance region showed an oriented columnar grain structure oblique to the substrate. The surface morphology changed with the waveform of the applied voltage. These characteristics were closely related to the dynamic behavior of the ions. 䊚 2003 Elsevier Science B.V. All rights reserved. Keywords: Titanium nitride; Plasma-based ion implantation; deposition; preferred orientation
1. Introduction Plasma-based ion implantation (PBII) is applicable to the uniform surface modification of the material of a three-dimensional shape w1,2x. A hybrid process system, PBII-D, where the ion implantation and deposition onto the three-dimensional materials is simultaneously carried out, is promising for surface modification with low cost. The authors have developed the PBII-D method for *Corresponding author. Tel.: q81-774-65-6266; fax: q81-774-656816. E-mail addresses: [email protected] (K. Yukimura), [email protected] (M. Kumagai), [email protected] (M. Kohata), [email protected] (H. Saito), [email protected] (T. Maruyama), [email protected] (X. Ma). 1 Tel. q81-46-236-1500; fax: q81-46-236-1525. 2 Tel. q81-45-503-9018; fax: q81-45-503-9030. 3 Tel. q81-44-819-2105; fax: q81-44-819-2108. 4 Tel. q81-75-753-4853; fax: q81-75-761-7695. 5 Tel. q86-451-6413935; fax: q86-451-6413922.
preparing titanium nitride (TiN) films to the workpieces with a three-dimensional shape using a titanium-cathodic-arc in nitrogen gas w3x. Perry and Treglio w4x reported the preparation of the TiN films by using the line of sight system. PBII-D has an advantage that the inner surface of pipes can be coated with a thin film by immersing the pipe in plasma. The inner surface modification of the pipes has been studied by PBII using gaseous plasmas w5–7x. However, there have been only few reports about metallic and ceramic film preparations, i.e. PBII-D w8,9x. This article describes characteristics of TiN films prepared on the inner surface of pipes by PBII-D using titanium-cathodic-arc. 2. Experimental A schematic diagram of the experimental apparatus is shown in Fig. 1. The vacuum chamber had inner
0257-8972/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 7 - 8 9 7 2 Ž 0 3 . 0 0 1 4 0 - 3
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K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
Fig. 1. Schematic diagram of experimental facility.
dimensions of 350=350=600 mm3 and the titaniumcathodic-arc source was placed at one end of the chamber. The d.c. source voltage for generating the cathodic arc was 30 V and the arc voltage was approximately 20 V. The d.c. current was 80 A. The evacuated base pressure was 10y3 Pa. The nitrogen pressure in the chamber was maintained at 0.27 Pa during the process. The voltage applied to the sample was varied from y5 to y40 kV with a pulse duration of 20 ms and its repetition rate is 400 Hz. The processing durations were 5 and 40 min. A pipe of 50 mm in inner diameter and 150 mm length was used as a sample holder. A grounded rod with a diameter of 10 mm is set at the center axis of the pipe to make a voltage standard inside the pipe. Silicon single crystal substrates (size: 10=10 mm2, orientation: (111)) were attached on the inner surface of the pipe at four positions as shown in Fig. 1. Morphology, structure and composition were measured for the films deposited on the substrates at position (b) in Fig. 1. One of the openings of the pipe faced the cathodic arc source, so that the plasma species are directly diffused into the pipe.
The morphology and the thickness of the film were observed by a field-emission scanning electron microscope. The depth profile of the film components was obtained by X-ray photoelectron spectroscopy (XPS). The crystallinity of the film was analyzed by X-ray diffraction (XRD).
Fig. 2. XPS depth profile of the TiN film prepared on a silicon substrate at an applied voltage of y10 kV.
K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
413
Fig. 3. XRD pattern of the TiN film prepared at an applied voltage of y20 kV.
3. Results and discussion 3.1. Structure and composition of film Fig. 2 shows the XPS depth profile of the film deposited at an applied voltage of y10 kV. The film thickness was approximately 700 nm for the process time of 40 min. The fractions of titanium and nitrogen atoms do not vary in the film. The contaminant components are detected near the film surface. It was confirmed from the XPS spectrum of Ti2p that the prepared film is TiN, the ratio of nitrogen to titanium NyTi being approximately 4y5. Thus, the TiN film can be prepared on the inner surface of a pipe using a cathodic arc PBII-D method. 3.2. Crystalline structures Fig. 3 shows an example of the XRD pattern of the film. It was deposited at an applied voltage of y20 kV
Fig. 5. Sectional SEM image of the TiN film prepared at an applied voltage of y10 kV.
for the process time of 40 min. The pattern shows multiorientations such as TiN(1 1 1), TiN(2 0 0) and TiN(2 2 0). 3.3. Deposition rate of film The thickness distribution of the TiN film on the inner surface of the pipe is shown in Fig. 4 as a function of the axial distance of the pipe from the arc source. The deposition rate considerably decreases with increasing the distance. The deposition rate for y20 kV is larger than that for y10 kV at the inlet of the pipe, but they approach each other at a longer distance from the arc source. The deposition rate increased with increasing applied voltage to the target probably due to promoting the diffusion of the plasma species, i.e. titanium ions into the pipe. The deposition rate of the film prepared without voltage applied to the target was approximately 20% of that for y15 kV application. Thus, the deposition rate depends both on the applied voltage and on the distance. This fact suggests that the ions largely contribute to the deposition of the film. The dependence of the deposition rate on the axial distance is attributed to the axial distribution of plasma density diffused from the arc source. The ion density decreases by the collision between the ion and neutral particle and by the consumption of the ions by the deposition to the wall. 3.4. Direction of growth of grain
Fig. 4. Distribution of film thickness as a function of the distance from the arc source for applied voltages of y10 and y20 kV.
Fig. 5 shows the sectional SEM photograph of the TiN film deposited on the inner surface of a pipe. There appears an oriented columnar grain structure oblique to
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K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
the substrate, while the film on the disk shaped substrate showed a similar oriented columnar grain structure, but the structure is perpendicular to the substrate w10x. The difference in the direction of the film growth suggests a contribution of ions to the growth of the film. 4. Conclusions The PBII-D method using the metal plasma produced in nitrogen can prepare the TiN thin film on the inner surface of the pipe by immersing the pipe in the plasma. The deposition rate increases with increasing of the applied voltage to the target. The deposition rate of the film prepared without applying voltage is approximately 20% of that with application of voltage of y15 kV. The deposition rate on the inner surface of the pipe decreases with increasing distance from the arc source. This is caused by the decrease of the ion density due to the collision between the ion and neutral particle in addition to the consumption of the ions by the deposition to the wall. An oriented columnar grain structure oblique to the substrate appears on the inner surface of a pipe in
its entrance region. The dynamic behavior of ion is suggested to be closely related to the deposition of the TiN film. References w1x J.R. Conrad, J. Appl. Phys. 62 (1987) 777. w2x M.A. Lieberman, J. Appl. Phys. 66 (1989) 2926. w3x K. Yukimura, M. Sano, T. Teramoto, T. Maruyama, Surf. Coat. Technol. 131 (2000) 98. w4x A.J. Perry, J.R. Treglio, Surf. Coat. Technol. 76–77 (1995) 815. w5x M. Sun, S. Yang, J. Vac. Sci. Technol. A 16 (1998) 2718. w6x A. Liu, X. Wang, Q. Chen, B. Tang, P.K. Chu, Nucl. Instrum. Meth. Phys. Res. B 143 (1998) 306. w7x K. Baba, R. Hatada, Nucl. Instrum. Meth. Phys. Res. B 148 (1999) 69. w8x S.M. Malik, R.P. Fetherston, J.R. Conrad, J. Vac. Sci. Technol. A 15 (1997) 2875. w9x T. Kraus, P. Kern, B. Stritzker, W. Ensinger, Nucl. Instrum. Meth. Phys. Res. B 148 (1999) 912. w10x K. Yukimura, E. Kuze, M. Kumagai, T. Maruyama, M. Kohata, K. Numata, H. Saito, X. Ma, Surf. Coat. Technol., submitted for publication.
Coating and ion implantation to the inner surface of a pipe by metal plasma-based ion implantation and deposition Ken Yukimuraa,*, Eiji Kuzea, Masao Kumagaib,1, Mamoru Kohatac,2, Ken Numatad,3, Hidenori Saitod,3, Toshiro Maruyamae,4, Xinxin Maf,5 a
Department of Electrical Engineering, Faculty of Engineering, Doshisha University, 1-3 Tatara-Miyakodani, Kyotanabe, Kyoto 610-0321, Japan b Material Engineering Division, Kanagawa Industrial Technology Research Institute, 705-1 Shimo-Imaizumi, Ebina, Kanagawa 243-0435, Japan c Material and Component Development Department, Toshiba Tungaloy Co., Ltd., 2-7 Sugasawa-sho, Tsurumi-ku, Yokohama 230-0027, Japan d Material Characterization Laboratory, Kanagawa High-Technology Foundation, KSP Building, East 101, 3-2-1 Sakado, Takatsu-ku, Kawasaki 213-0012, Japan e Department of Chemical Engineering, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan f School of Material Science and Engineering, Harbin Institute of Technology, P.O. Box 433, 92 West Dazhi Street, Harbin 150001, PR China
Abstract This article describes the characteristics of the coating of the inner surface of a pipe using plasma-based ion implantation and deposition method with a d.c. titanium-cathodic-arc in nitrogen gas. It was confirmed that the coating of the inner surface of the pipe with titanium nitride film was possible by using this method. The film structure and preferential orientation can be controlled by the applied voltage to the pipe. The film on the inner surface of a pipe in its entrance region showed an oriented columnar grain structure oblique to the substrate. The surface morphology changed with the waveform of the applied voltage. These characteristics were closely related to the dynamic behavior of the ions. 䊚 2003 Elsevier Science B.V. All rights reserved. Keywords: Titanium nitride; Plasma-based ion implantation; deposition; preferred orientation
1. Introduction Plasma-based ion implantation (PBII) is applicable to the uniform surface modification of the material of a three-dimensional shape w1,2x. A hybrid process system, PBII-D, where the ion implantation and deposition onto the three-dimensional materials is simultaneously carried out, is promising for surface modification with low cost. The authors have developed the PBII-D method for *Corresponding author. Tel.: q81-774-65-6266; fax: q81-774-656816. E-mail addresses: [email protected] (K. Yukimura), [email protected] (M. Kumagai), [email protected] (M. Kohata), [email protected] (H. Saito), [email protected] (T. Maruyama), [email protected] (X. Ma). 1 Tel. q81-46-236-1500; fax: q81-46-236-1525. 2 Tel. q81-45-503-9018; fax: q81-45-503-9030. 3 Tel. q81-44-819-2105; fax: q81-44-819-2108. 4 Tel. q81-75-753-4853; fax: q81-75-761-7695. 5 Tel. q86-451-6413935; fax: q86-451-6413922.
preparing titanium nitride (TiN) films to the workpieces with a three-dimensional shape using a titanium-cathodic-arc in nitrogen gas w3x. Perry and Treglio w4x reported the preparation of the TiN films by using the line of sight system. PBII-D has an advantage that the inner surface of pipes can be coated with a thin film by immersing the pipe in plasma. The inner surface modification of the pipes has been studied by PBII using gaseous plasmas w5–7x. However, there have been only few reports about metallic and ceramic film preparations, i.e. PBII-D w8,9x. This article describes characteristics of TiN films prepared on the inner surface of pipes by PBII-D using titanium-cathodic-arc. 2. Experimental A schematic diagram of the experimental apparatus is shown in Fig. 1. The vacuum chamber had inner
0257-8972/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 7 - 8 9 7 2 Ž 0 3 . 0 0 1 4 0 - 3
412
K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
Fig. 1. Schematic diagram of experimental facility.
dimensions of 350=350=600 mm3 and the titaniumcathodic-arc source was placed at one end of the chamber. The d.c. source voltage for generating the cathodic arc was 30 V and the arc voltage was approximately 20 V. The d.c. current was 80 A. The evacuated base pressure was 10y3 Pa. The nitrogen pressure in the chamber was maintained at 0.27 Pa during the process. The voltage applied to the sample was varied from y5 to y40 kV with a pulse duration of 20 ms and its repetition rate is 400 Hz. The processing durations were 5 and 40 min. A pipe of 50 mm in inner diameter and 150 mm length was used as a sample holder. A grounded rod with a diameter of 10 mm is set at the center axis of the pipe to make a voltage standard inside the pipe. Silicon single crystal substrates (size: 10=10 mm2, orientation: (111)) were attached on the inner surface of the pipe at four positions as shown in Fig. 1. Morphology, structure and composition were measured for the films deposited on the substrates at position (b) in Fig. 1. One of the openings of the pipe faced the cathodic arc source, so that the plasma species are directly diffused into the pipe.
The morphology and the thickness of the film were observed by a field-emission scanning electron microscope. The depth profile of the film components was obtained by X-ray photoelectron spectroscopy (XPS). The crystallinity of the film was analyzed by X-ray diffraction (XRD).
Fig. 2. XPS depth profile of the TiN film prepared on a silicon substrate at an applied voltage of y10 kV.
K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
413
Fig. 3. XRD pattern of the TiN film prepared at an applied voltage of y20 kV.
3. Results and discussion 3.1. Structure and composition of film Fig. 2 shows the XPS depth profile of the film deposited at an applied voltage of y10 kV. The film thickness was approximately 700 nm for the process time of 40 min. The fractions of titanium and nitrogen atoms do not vary in the film. The contaminant components are detected near the film surface. It was confirmed from the XPS spectrum of Ti2p that the prepared film is TiN, the ratio of nitrogen to titanium NyTi being approximately 4y5. Thus, the TiN film can be prepared on the inner surface of a pipe using a cathodic arc PBII-D method. 3.2. Crystalline structures Fig. 3 shows an example of the XRD pattern of the film. It was deposited at an applied voltage of y20 kV
Fig. 5. Sectional SEM image of the TiN film prepared at an applied voltage of y10 kV.
for the process time of 40 min. The pattern shows multiorientations such as TiN(1 1 1), TiN(2 0 0) and TiN(2 2 0). 3.3. Deposition rate of film The thickness distribution of the TiN film on the inner surface of the pipe is shown in Fig. 4 as a function of the axial distance of the pipe from the arc source. The deposition rate considerably decreases with increasing the distance. The deposition rate for y20 kV is larger than that for y10 kV at the inlet of the pipe, but they approach each other at a longer distance from the arc source. The deposition rate increased with increasing applied voltage to the target probably due to promoting the diffusion of the plasma species, i.e. titanium ions into the pipe. The deposition rate of the film prepared without voltage applied to the target was approximately 20% of that for y15 kV application. Thus, the deposition rate depends both on the applied voltage and on the distance. This fact suggests that the ions largely contribute to the deposition of the film. The dependence of the deposition rate on the axial distance is attributed to the axial distribution of plasma density diffused from the arc source. The ion density decreases by the collision between the ion and neutral particle and by the consumption of the ions by the deposition to the wall. 3.4. Direction of growth of grain
Fig. 4. Distribution of film thickness as a function of the distance from the arc source for applied voltages of y10 and y20 kV.
Fig. 5 shows the sectional SEM photograph of the TiN film deposited on the inner surface of a pipe. There appears an oriented columnar grain structure oblique to
414
K. Yukimura et al. / Surface and Coatings Technology 169 – 170 (2003) 411–414
the substrate, while the film on the disk shaped substrate showed a similar oriented columnar grain structure, but the structure is perpendicular to the substrate w10x. The difference in the direction of the film growth suggests a contribution of ions to the growth of the film. 4. Conclusions The PBII-D method using the metal plasma produced in nitrogen can prepare the TiN thin film on the inner surface of the pipe by immersing the pipe in the plasma. The deposition rate increases with increasing of the applied voltage to the target. The deposition rate of the film prepared without applying voltage is approximately 20% of that with application of voltage of y15 kV. The deposition rate on the inner surface of the pipe decreases with increasing distance from the arc source. This is caused by the decrease of the ion density due to the collision between the ion and neutral particle in addition to the consumption of the ions by the deposition to the wall. An oriented columnar grain structure oblique to the substrate appears on the inner surface of a pipe in
its entrance region. The dynamic behavior of ion is suggested to be closely related to the deposition of the TiN film. References w1x J.R. Conrad, J. Appl. Phys. 62 (1987) 777. w2x M.A. Lieberman, J. Appl. Phys. 66 (1989) 2926. w3x K. Yukimura, M. Sano, T. Teramoto, T. Maruyama, Surf. Coat. Technol. 131 (2000) 98. w4x A.J. Perry, J.R. Treglio, Surf. Coat. Technol. 76–77 (1995) 815. w5x M. Sun, S. Yang, J. Vac. Sci. Technol. A 16 (1998) 2718. w6x A. Liu, X. Wang, Q. Chen, B. Tang, P.K. Chu, Nucl. Instrum. Meth. Phys. Res. B 143 (1998) 306. w7x K. Baba, R. Hatada, Nucl. Instrum. Meth. Phys. Res. B 148 (1999) 69. w8x S.M. Malik, R.P. Fetherston, J.R. Conrad, J. Vac. Sci. Technol. A 15 (1997) 2875. w9x T. Kraus, P. Kern, B. Stritzker, W. Ensinger, Nucl. Instrum. Meth. Phys. Res. B 148 (1999) 912. w10x K. Yukimura, E. Kuze, M. Kumagai, T. Maruyama, M. Kohata, K. Numata, H. Saito, X. Ma, Surf. Coat. Technol., submitted for publication.