Diamond & Related Materials 16 (2007) 220 224 www.elsevier.

com/locate/diamond

Diamond-like carbon films with End-Hall ion source enhanced chemical vapour deposition
Y.Q. Pan a , Y. Yin b,
a

Shaanxi Province Thin Film Technology and Optical Test Open Key Laboratory, Xi'an institute of Technology, Xi'an, China b School of Physics, University of Sydney, NSW 2006, Australia Received 29 August 2005; received in revised form 3 April 2006; accepted 9 May 2006 Available online 10 July 2006

Abstract A custom-designed End-Hall ion source was used to deposit diamond-like carbon (DLC) films in a plasma enhanced chemical vapour deposition (PECVD) mode. The deposition system was characterised and optimised for infrared transmission enhancement applications and large area deposition onto silicon or germanium substrates. Ion bombardment energy (in eV) on substrate was found to scale about 60% of the discharge voltage. Uniformity was about 2.5% and 5% for substrate diameters of 20 cm and 40 cm respectively. For the infrared enhancement applications the optimised ion bombardment energy was about 54 eV with a high deposition rate approximate 30 nm/min. Coating the DLC onto a single side of double-sided polished silicon wafers resulted in a transmission of 69.5% in the wavelength of about 4 m, very close to the ideal value. Mechanical and reliability properties of the DLC films on silicon wafers were analysed at different environmental conditions. It was found that the DLC films produced in the ion source PECVD deposition system were satisfied with the requirements for the infrared transmission enhancement applications. 2006 Elsevier B.V. All rights reserved.
Keywords: End-Hall ion source; PECVD; Diamond-like carbon films; Infrared transmission enhancement

1. Introduction Diamond-like carbon (DLC) thin films are unique because of a number of excellent properties, including infrared transparency, high mechanical hardness, very low friction coefficient, and chemical inertia. DLC films have been used in microelectronics, mechanical surface protection, optical devices, and biomedical applications. Extensive study has been done on its deposition method and material properties. Deposition methods include magnetron sputtering, reactive sputtering, plasma enhanced chemical vapour deposition (PECVD), vacuum arc, and vacuum arc assisted chemical vapour deposition [15]. In these methods, the ion energy during deposition is generally recognized as one of the most important parameters influencing the properties of DLC films. Unless a RF (or high frequency) source is applied to the substrate, however, the ion energy

Corresponding author. E-mail address: yyin@physics.usyd.edu.au (Y. Yin). 0925-9635/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.diamond.2006.05.003

control is not convenient in many deposition methods due to its electrically insulating property of DLC materials. Ion source can overcome this problem to provide the desired ion bombardment energy. Cold cathode ion source was used for PECVD deposition [6]. However, it is know that cold cathode ion source can only provide ion energy in the range between approximately 300 and 1000 eV. It is desirable in DLC deposition to extend the energy range to the region between 300 and a few tens of eV. It was reported that very hard and high sp3 content DLC films were reported to be deposited in this energy region [7]. It is also true that cold cathode ion source can only generate small ion current so that its plasma enhancement effect and thus the deposition rate is limited significantly. In this work, we proposed to use an End-Hall ion source for DLC PECVD deposition. End-Hall ion source can provide ion energy from approximately 30 eV to 200 eV, a useful extension of ion energy of the cold cathode ion sources. The ion current of an End-Hall ion source is approximately one order of magnitude higher than that of a typical cold cathode ion source. The technical design of the End-Hall ion source has been well developed, and its

Y.Q. Pan, Y. Yin / Diamond & Related Materials 16 (2007) 220224

221

operating mechanism is well understood. The End-Hall is named because the ion beam exists the acceleration region at the circular end of the magnetic field as described by Kaufman et al. [8]. Recently, the circular End-Hall ion sources were arranged to form a linear version for large area plasma treatment [9]. DLC films deposited in this work were aimed for applications of infrared transmittance enhancement in the wavelength region between 3 and 5 m. Infrared sensors or transducers for this window are usually made of materials such as Si and Ge. Those materials generally have high refractive index in the wavelength region, resulting in high reflection losses. It is thus necessary to deposit antireflection thin films to enhance the transmission. Unfortunately, conventional infrared antireflection thin films have some drawbacks such as poor mechanical property, low density, and moisture sensitive. DLC thin film is ideal for infrared transmission enhancement application, due to its infrared transparency, high mechanical hardness, moisture insensitive, chemical inertia, and ideal refractive index for silicon or germanium substrates [1012]. For the application in the wavelength region above 4 m, DLC films should be approximately thicker than 550 nm. This means a low mechanical stress DLC film is necessary. 2. Experimental setup and procedure Fig. 1 shows the schematic diagram of the custom-designed End-Hall ion source. End-Hall ion source designed in this work can form a glow discharge in the region as shown in the figure. The magnetic field lines cross the electric field lines so that the electrons can move in circular trajectories to generate the so called Hall current. Reactive gases were injected from bottom of the ion source as shown in the figure. The cathode was placed in front of the ion source. The electrons emitted from the cathode travel into the discharge region along the magnetic field lines to ionize gas molecules. Ions are extracted by the potential difference between the cathode and the anode and accelerated onto substrate. Base pressure of the system was 5 10 3 Pa. A grided ion energy analyser was used to measure the ion energy. It is known that the ion energy analysis method is problematic in plasmas with significant fraction of carbon species. In order to simplify the ion energy analysis, ion energy analysis was performed in argon atmosphere to avoid poisoning the grided ion energy

Fig. 2. Discharge current as a function of discharge voltage.

analyser. Methane (CH4) was used as reactive gas with purity of 4 N. All DLC experimental results presented in this paper were obtained at flow rate of 20 SCCM and operating pressure of 2.0 10 2 Pa. DLC films were deposited on to both sides of the polished p-type (100) silicon substrates. During deposition, the substrate temperature was about 50 C. All deposition and analysis in this work were conducted at distance of 20 cm from the ion source, unless specified in the text. Thin film thickness and optical constants were measured using J.A. Woollam M2000UI ellipsometer in the wavelength region from 400 to 1600 nm. Three incident angles, 65, 70, 75, were used in the ellipsometry analysis. Hardness was analysed using HXD-1000 microhardness instrument. Infrared transmission spectrum was obtained using P.E. Fourier transform infrared (FTIR) spectroscopy in the wave number range from 400 to 4000 cm 1. 3. Results Discharge current is a function of discharge voltage in the ion sources. Fig. 2 shows the dependence of the discharge current on the discharge voltage at argon pressure of 2 10 2 Pa. At the distance of 20 cm from the ion source, ion energy was measured using a grided ion energy analyser. The ions were generated in the discharge region as shown in Fig. 1. The ions coming out of the discharge region were then accelerated at the region between the cathode and the discharge region. The analysis showed that the ion energy was correlated to the discharge current and the ion energy in eV, which was approximately scaled as 60% of the discharge voltage with an energy window 5 eV.

Fig. 1. Schematic diagram of the custom-designed End-Hall ion source.

Fig. 3. Discharge current vs. cathode current.

222

Y.Q. Pan, Y. Yin / Diamond & Related Materials 16 (2007) 220224

Cathode current is an important parameter influencing the discharge current. Fig. 3 shows the dependence of the discharge current on the cathode current. The threshold cathode current was about 10 A. An approximately linear dependence of the discharge current was found for cathode current between 10 and 15 A, followed by a decrease of the discharge current. The linear range was resulted from that electron emission current from the cathode which enhanced the discharge. Further increasing the cathode current, the emitted electron current compensated the discharge current, resulting in decrease of the discharge current. The deposition rate was measured as a function of the discharge current and the distance from the substrate to the ion source as shown in Fig. 4. An approximately linear relationship of deposition rate was found for discharge current up to about 3 A as shown in Fig. 4(a). Beyond 3 A, it is expected that enhanced ion bombardment on substrate would result in etching deposited films. Increasing the substrate distance, the deposition rate decreased as shown in Fig. 4(b). The deposition rate was 30 nm/min for substrate distance about 20 cm, which is a reasonable rate for practical applications. Fig. 5 shows the hardness of DLC films as a function of discharge current. The hardest DLC film was correspondent to the discharge current about 2 A. As shown in Fig. 2, the discharge voltage corresponding to this discharge current was about 90 V, and thus the ion energy was about 54 eV (scaled about 60% of the discharge voltage). Energetic ion bombardment of DLC films during deposition is regarded as one of the most important factors affecting the hardness and intrinsic stress. Thornton schematically illustrated that thin films change from a porous or columnar to a dense structure as sputtering

Fig. 5. Hardness of DLC films vs. discharge current.

voltage increased [13]. The transition from a columnar to a dense material is often associated with changes in microstructure and preferred orientation. The hardness data in Fig. 5 was replotted in Fig. 6 as a function of ion energy. Experimentally, a universal behaviour is found in thin film materials showing intrinsic stress, reaching a maximum and then decreasing with increasing ion energy. Models were proposed by Davis [14] and other researchers [15] to explain the behaviour of compressive stress in thin films deposited with simultaneous ion bombardment. It was proposed that increasing compressive stress in DLC films resulted in increasing sp3 content and thus the hardness of the films [16]. The maximum position of the hardness in Fig. 6 is consistent with previous observations. The hardness dependence on ion energy suggested that the End-Hall ion source is very useful for ion source enhanced chemical vapour deposition of DLC films. Cold cathode ion source used in previous study [7] would be expected less effective to produce hard DLC films as its ion energy window was beyond 300 eV. In the infrared transmission enhancement application, optical refractive index is an important parameter. Ideally, one expected to have a relationship for the optical refractive index of a 2 material as nf = ns, where nf is the optical index of the thin film, and ns is the optical index of the substrate. In the infrared region, the optical index of silicon is equal to 3.5, thus the ideal optical index of the DLC films is 1.87 for this application when silicon is used as a substrate. Fig. 7 shows the refractive index of DLC films as a function of discharge current. A reasonable wide range of discharge current was found between 1 and 3 A.

Fig. 4. (a) Deposition rate as a function of discharge current, (b) deposition rate as a function of distance from substrate to ion source.

Fig. 6. Hardness of DLC films vs. ion energy.

Y.Q. Pan, Y. Yin / Diamond & Related Materials 16 (2007) 220224

223

Fig. 7. Effect of discharge current on refractive index of DLC films.

Considering the hardness effect in Fig. 6, we determined that the optimised condition of discharge current was 2 A. One of the advantages of the End-Hall ion source is its wide angle ion emission feature. We found that a large area uniform deposition can be obtained in the ion source enhanced PECVD mode. Fig. 8 shows the thickness profile for substrate distance of 20 cm. The uniformity was about 2.5% for a 20 cm diameter substrate. Increasing substrate diameter to 40 cm, the uniformity was still about 5%. Five hundred nanometer thick DLC film was deposited onto one side of a double-sided polished silicon substrate. A typical infrared transmission spectrum was shown in Fig. 9. At wavelength equal to 4 m, transmittance is about 69.4%, very close to the ideal value. Hydrogen was found to be incorporated into the DLC, evidenced by its associated absorption peaks in the region between 2800 and 3000 cm 1. The insert in Fig. 9 shows the details of these absorption peaks. The presence of these peaks was suggested as an indication of the carbon bonding states to be of predominantly sp3 type [17]. The bonding characteristics of the DLC films were studied further using Raman technique. Fig. 10 shows a Raman spectrum of a 500 nm thick as-deposited sample. The DLC was deposited with the optimised conditions at discharge current of 2 A. The Raman intensity spectrum showed a typical peak at 1350 cm 1 assigned as a D band overlapping with a peak at 1570 cm 1 assigned as a G band. The intensity ratio Id/ Ig is commonly used as a measure of the sp3 content in the films by deconvoluting and fitting to two Lorentzians [17]. For this sample, the fit resulted in a ratio Id/Ig of 2.06. The hardness and the Raman intensity of D band relative to that of G band appeared to be higher than expected. However, the observations in this work were not entirely contrary to results reported by other researchers. For example, Druz et al.

Fig. 9. Infrared spectrum of a DLC film coated on one side of silicon substrate.

[18] reported hardness higher than 30 GPa (or the hardness in this work). Their DLC films were obtained by using a Veeco RF ICP ion source with reactive gas methane or acetylene. However, Raman analysis on their films was not reported. Fang et al. reported both hardness and Raman absorption peaks of DLC films recently [19]. In their microwave plasma deposition, the substrate was biased to 30 V with mixture gas of methane and hydrogen. The relative absorption intensity of D band in their films appeared even higher than that in our result. Their hardness was about 27 GPa, very close to our result. Taking plasma potential as 25 V (which is very common for RF plasma), their ion energy should be approximately 55 eV, which is very close to our ion energy. Nevertheless, further investigation on this issue is required. The mechanical properties of the DLC coated samples were also analysed. The adhesion of the DLC film was very good. Adhesion of the DLC films on silicon substrate was analysed using a standard tape test. At the required thickness for applications in the 35 m region, all the DLC films survived the adhesion tests and their stresses were between 1 and 3 GPa. The DLC films on silicon substrates were also found thermally and chemically stable. At 200 C and 40 C in air for 8 h respectively, both hardness and infrared transmittance were not changed after 4 times repeating the experiment. We placed the DLC films into 5% NaCl, 5%HCl, and 5%NaOH aquatic solution respectively for one week. We found no evidence of degradation on mechanical and optical properties of the DLC films.

Fig. 8. Relative thickness vs. distance from ion source axis.

Fig. 10. Raman spectrum of an as-deposited DLC sample.

224

Y.Q. Pan, Y. Yin / Diamond & Related Materials 16 (2007) 220224

4. Conclusion A custom-designed End-Hall ion source was used to deposit diamond-like carbon (DLC) films in an ion source plasma enhanced chemical vapour deposition mode. The system was characterised and optimised for infrared transmission enhancement applications and for deposition of large area DLC onto silicon or germanium substrates. The ion energy range of the ion source was approximately between 30 and 200 eV. A large discharge current can be produced in this ion source. Ion bombardment energy (in eV) on substrate was found to scale about 60% of the discharge voltage, determined by using a grided ion energy analyser. Large area deposition was achieved with uniformity about 2.5% and 5% for substrate diameters of 20 cm and 40 cm respectively. Mechanical hardness and optical index of the DLC films were also analysed. For the infrared enhancement applications using silicon substrates the optimised ion bombardment energy was about 54 eV with a high deposition rate of 30 nm/min. Depositing DLC onto single side of double-sided polished silicon wafers resulted in a transmission of 69.5% in the wavelength of about 4 m, which was very close to the ideal value. Raman analysis was also conducted. Mechanical properties and reliability of DLC films on silicon wafers were analysed at different environmental conditions. We found that the DLC films produced in the ion source PECVD deposition system satisfied the requirements for the infrared transmission enhancement applications.

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] J. Robertson, Prog. Solid State Chem. 21 (1991) 199. J. Robertson, Surf. Coat. Technol. 50 (1992) 185. N. Fourches, G. Turban, Thin Solid Films 240 (1994) 28. J. Hong, A. Goullet, G. Turban, Thin Solid Films 352 (1999) 41. Y. Yin, R. McKenzie, J. Zhou, A. Das, J. Appl. Phys. 79 (1996) 1563. K.L. Enisherlova, Yu.A. Kontsevoi, et al., Mater. Sci. Eng. B46 (1997) 137. Y. Yin, D.R. McKenzie, Thin Solid Films 280 (1996) 90. H.R. Kaufman, R.S. Robinson, Vacuum 39 (1989) 1175. J. Madocks, Proceeding of 45th Annual Technical Conference of Society of Vacuum Coaters, Orlando, USA. ISSN :0737-592, 2002, p. 202. A.H. Lettington, C. Smith, Diamond Relat. Mater. 1 (1992) 805. M. Alaluf, J. Appelbaum, L. Kilbanov, D. Brinker, et al., Thin Solid Films 256 (1995) 1. E.J. Coad, C.S.J. Pickles, G.H. Jilbert, et al., Diamond Relat. Mater. 5 (1996) 640. J. Thornton, A. Penfold, in: J. Vossen, W. Kern (Eds.), Thin Film Processes, Academic Press, New York, 1978. C.A. Davis, Thin Solid Films 226 (1993) 30. Y. Yin, D. McKenzie, M. Bilek, Surf. Coat. Technol. 198 (2005) 156. D.R. McKenzie, Y. Yin, N.A. Marks, C.A. Davis, B.A. Pailthorpe, G.A.J. Amaratumga, V.S. Veerasamy, Diamond Relat. Mater. 3 (1994) 353. K. Sreejith, J. Nuwad, C.G.S. Pillai, Appl. Surf. Sci. 252 (2005) 296. B. Druz, I. Zaritskiy, J. Hoehn, V. Polyakov, A. Rukovishnikov, V. Novotny, Diamond Relat. Mater. 10 (2001) 931. T. Fang, W. Chang, Applied Surface Science, in press, online available since September 23, 2005.