Abstract
About 1.5-μm-thick single-layer TiN, CrN, TiAlN coatings and nanolayered TiN/CrN, TiAlN/CrN multilayer coatings were deposited on silicon (111) substrates using a reactive direct current magnetron sputtering process. Structural characterization of the coatings was done using x-ray diffraction (XRD) and micro-Raman spectroscopy. All the coatings exhibited NaCl B1 structure in the XRD data. Raman spectroscopy data of as-deposited coatings exhibited two broad bands centered at 230–250 and 540–630 cm−1. These bands have been assigned to acoustical and optical phonon modes, respectively. Thermal stability of the coatings was studied by heating the coatings in air in a resistive furnace for 30 min in the temperature range 400–900 °C. Structural changes as a result of heating were characterized using Raman spectroscopy and XRD. Raman data showed that TiN, CrN, TiN/CrN, TiAlN, and TiAlN/CrN coatings started to oxidize at 500, 600, 750, 800, and 900 °C, respectively. To isolate the oxidation-induced spectral changes as a result of heating of the coatings in air, samples were also annealed in vacuum at 800 °C under similar conditions. The Raman data of vacuum-annealed coatings showed no phase transformation, and intensity of the optical phonon mode increased and shifted to lower frequencies. The origin of these spectral changes is discussed in terms of defect structure of the coatings. Our results indicate that the thermal stability of nanolayered multilayer coatings is superior to the single-layer coatings.
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W.D. Munz: Titanium aluminium nitride films: A new alternative to TiN coatings. J. Vac. Sci. Technol. A 4, 2717 (1986).
H.C. Barshilia and K.S. Rajam: Characterization of Cu/Ni multilayer coatings by nanoindentation and atomic force microscopy. Surf. Coat. Technol. 155, 195 (2002).
H.C. Barshilia and K.S. Rajam: Deposition of TiN/CrN hard superlattices by reactive DC magnetron sputtering. Bull. Mater. Sci. 26, 233 (2003).
H.C. Barshilia, A. Jain, and K.S. Rajam: Structure, hardness and thermal stability of nanolayered TiN/CrN multilayer coatings. Vacuum 72/73, 241 (2004).
H.C. Barshilia and K.S. Rajam: Structure and properties of reactive DC magnetron sputtered TiN/NbN hard superlattices. Surf. Coat. Technol. 183, 174 (2004).
H.C. Barshilia, M.S. Prakash, A. Poojari, and K.S. Rajam: Corrosion behavior of nanolayered TiN/NbN multilayer coatings prepared by reactive DC magnetron sputtering process. Thin Solid Films 460, 133 (2004).
P. Panjan, B. Navinsek, A. Cvelbar, A. Zalar, and I. Milosev: Oxidation of TiN, ZrN, TiZrN, CrN, TiCrN and TiN/CrN multilayer hard coatings reactively sputtered at low temperature. Thin Solid Films 281–282, 298 (1996).
H. Ichimura and A. Kawana: High-temperature oxidation of ionplated TiN and TiAlN films. J. Mater. Res. 8, 1093 (1993).
M. Franck, J-P. Celis, and J.R. Roos: Microprobe Raman spectroscopy of TiN coatings oxidized by solar beam heat treatment. J. Mater. Res. 10, 119 (1995).
P.H. Mayrhofer, H. Willmann, and C. Mitterer: Oxidation kinetics of sputtered Cr-N coatings. Surf. Coat. Technol. 146–147, 222 (2001).
Jui-Neng Tu, Jenq-Gong Duh, and Shu-Yueh. Tsai: Morphology, mechanical properties, and oxidation behavior of reactively sputtered Cr-N films. Surf. Coat. Technol. 133–134, 181 (2000).
H. Ichimura and A. Kawana: High temperature oxidation of ionplated CrN films. J. Mater. Res. 9, 151 (1994).
D. McIntyre, J.E. Greene, G. Hakansson, J.E. Sundgren, and W.D. Munz: Oxidation of metastable single-phase polycrystalline Ti0.5Al0.5N films: Kinetics and mechanisms. J. Appl. Phys. 67, 1542 (1990).
P. Panjan, B. Navinsek, A. Cvelbar, A. Zalar, and J. Vlcek: High temperature oxidation of TiN/CrN multilayers reactively sputtered at low temperatures. Surf. Coat. Technol. 98, 1497 (1998).
I. Wadsworth, I.J. Smith, L.A. Donohue, and W.D. Munz: Thermal stability and oxidation resistance of TiAlN/CrN multilayer coatings. Surf. Coat. Technol. 94–95, 315 (1997).
H.C. Barshilia, M.S. Prakash, A. Jain, and K.S. Rajam: Structure, hardness and thermal stability of TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings. Vacuum (in press).
W. Spengler and R. Kaiser: First and second order Raman scattering in transition metal compounds. Solid State Commun. 18, 881 (1976).
E. Vancoille, B. Blanpain, Y. Xingpu, J.P. Celis, and J.R. Roos: Tribo-oxidation of a TiN coating sliding against corundum. J. Mater. Res. 9, 992 (1994).
N. Muraki, V. Sergo, G. Pezzotti, G. Katagiri, S. Meriani, and T. Nishida: Raman piezo-spectroscopic behavior of aluminum nitride. Appl. Spectro. 51, 1761 (1997).
R. Chowdhury, R.D. Vispute, K. Jagannadham, and J. Narayan: Characteristics of titanium nitride films grown by pulsed laser deposition. J. Mater. Res. 11, 1458 (1996).
A. Barata, L. Cunha, and C. Moura: Characterization of chromium nitride films produced by PVD techniques. Thin Solid Films 398–399, 501 (2001).
M. Bernard, A. Deneuville, O. Thomas, P. Gergaud, P. Sandstrom, and J. Birch: Raman spectra of TiN/AlN superlattices. Thin Solid Films 380, 252 (2000).
J.C. Parker and R.W. Siegel: Raman microprobe study of nanophase TiO2 and oxidation-induced spectral changes. J. Mater. Res. 5, 1246 (1990).
A. Misra, H.D. Bist, M.S. Navati, R.K. Thareja, and J. Narayan: Thin film of aluminum oxide through pulsed laser deposition: A micro-Raman study. Mater. Sci. Eng. B 79, 49 (2001).
W. Spengler, R. Kaiser, A.N. Christensen, and G. Muller-Vogt: Raman scattering, superconductivity and phonon density of states of stoichiometric and non-stoichiometric TiN. Phys. Rev. B 17, 1095 (1978).
C.P. Constable, J. Yarwood, and W.D. Munz: Raman microscopic studies of PVD hard coatings. Surf. Coat. Technol. 116–119, 155 (1999).
L. Hultman: Thermal stability of nitride thin films. Vacuum 57, 1 (2000).
I. Kosacki, T. Suzuki, H.U. Anderson, and P. Colomban: Raman scattering and lattice defets in nanocrystalline CeO2 thin films. Solid State Ionics 149, 99 (2002).
C.P. Constable, D.B. Lewis, J. Yarwood, and W.D. Munz: Raman microscopic studies of residual and applied stress in PVD hard ceramic coatings and correlation with x-ray diffraction (XRD) measurements. Surf. Coat. Technol. 184, 291 (2004).
I. Petrov, L. Hultman, U. Helmersson, J-E. Sundgren, and J.E. Greene: Microstructure modification of TiN by ion bombardment during reactive sputter deposition. Thin Solid Films 169, 299 (1989).
H. Ljungcrantz, L. Hultman, J.E. Sundgren, and L. Karlsson: Ion induced stress generation in arc-evaporated TiN films. J. Appl. Phys. 78, 832 (1995).
L. Hultman, U. Helmersson, S.A. Barnett, J-E. Sundgren, and J.E. Greene: Low-energy ion irradiation during film growth for reducing defect densities in epitaxial TiN (100) films deposited by reactive-magnetron sputtering. J. Appl. Phys. 61, 552 (1987).
M. Fujii, S. Hayashi, and K. Yamamoto: Raman scattering from quantum dots of Ge embedded in SiO2 thin films. Appl. Phys. Lett. 57, 2692 (1990).
Y. Tanaka, T.M. Gur, M. Kelly, S.B. Hagstrom, T. Ikeda, K. Wakihira, and H. Satoh: Properties of (Ti1-xAlx)N coatings for cutting tools prepared by the cathodic arc ion plating method. J. Vac. Sci. Technol. A 10, 1749 (1992).
R.A. Andrievski, I.A. Anisimova, V.P. Anisimov, V.P. Makarov, and V.P. Popova: Grain size and recrystallization of TiN, ZrN, NbN, and CrN alloyed and multilayer films. Thin Solid Films 261, 83 (1995).
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Barshilia, H.C., Rajam, K.S. Raman spectroscopy studies on the thermal stability of TiN, crN, TiAlN coatings and nanolayered TiN/CrN, TiAlN/CrN multilayer coatings. Journal of Materials Research 19, 3196–3205 (2004). https://doi.org/10.1557/JMR.2004.0444
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DOI: https://doi.org/10.1557/JMR.2004.0444