Chromium nitrides (CrN, Cr2N) from solid state metathesis reactions: effects of dilution and nitriding reagent

Abstract

The solid state metathesis (SSM) reaction of CrCl3 with Li3N in a sealed evacuated Pyrex ampoule at 445C produces a propagation wave and enables phase pure Cr2N to be isolated. The SSM reaction of CrCl2 and Mg3N2 at 350-500C with dilutant MgCl2 under similar conditions produces single phase CrN. Reaction of chromium oxide with Li3N at 500C produces CrN after 2h and Cr2N after 60h. This is the first report of a metal nitride being formed in a SSM reaction using an oxide starting material. The SSM nitrides were shown to have superior bulk nitridation levels (combustion analysis) and equivalent microscopic compositions (EELS, XRD) to commercial materials. The phases of chromium nitride produced were correlated with reaction enthalpy, dilution conditions and nitriding agent. The products were analysed by X-ray powder diffraction, FTIR, combustion microelemental analysis, SEM/EDAX, XPS and ELNES.

References

1. J. C. Bailar, H. J. Emeleus, R. Nyholm and A. F. Trotman, Comprehensive Inorganic Chemistry, Pergamon Press, Oxford, 1973, vol. 2, p. 233.
2. H. E. Hinterman, Thin Solid Films, 1981, 84, 215.
3. C. Masters, Adv. Organomet. Chem., 1979, 17, 16; G. I. Panov, Kinet. Katal., 1985, 54, 1623.
4. S. R. Kurtz and R. G. Gordon, Thin Solid Films, 1986, 140, 277.
5. W. D. Munz, D. Hofmann and K. Hartig, Thin Solid Films, 1982, 96, 79.
6. I. J. Raaijmakers, R. N. Vritis, J. Yang, S. Ramaswami, A. Lagendijk, D. A. Roberts and E. K. Broardbent, in Advanced Metallisation and Processing for Semiconductor Devices and Circuits II, ed. A. Katz, S. P. Murarka, Y. I. Nissim and J. M. E. Harper, Mater. Res. Soc. Symp. Proc. 260, Pittsburgh, PA, 1993, p. 99; C. Y. Ting, J. Vac. Sci. Technol, 1982, 21, 14.
7. J. N. Musher and R. G. Gordon, J. Mater. Res., 1996, 11, 989; R. Buhl, H. K. Pulker and E. Moll, Thin Solid Films, 1981, 80, 265.
8. J. W. Mellor, Inorganic and Theoretical Chemistry, Vol. VIII, supplement I, Nitrogen (part 1), Longmans, London, 1964, p. 150.
9. H. J. Goldschmidt, Interstitial Alloys, Butterworths, London, 1967, p. 214.
10. L. E. Toth, Transition Metal Carbides and Nitrides, Academic Press, New York, 1971.
11. Kirk-Othmer-Encyclopedia of Chemical Technology, ed. J. J. Kroschwitz, J. Wiley and Sons, Chichester, 4th edn., 1992, vol. 17.
12. D. Baxter, M. H. Chisholm, V. F. Distasi, G. Gama, A. Hector and I. P. Parkin, Chem. Mater., 1996, 15, 1741; D. M. Hoffman, Polyhedron, 1994, 13, 1169; C. G. Granquist, Thin Solid Films, 1990, 193/194, 455.
13. M. Azuma, Y. Nakato and H. Tsuboromura, J. Electroanal. Chem., 1988, 255, 179.
14. H. A. Johansen, Survey Prog. Chem., 1977, 8, 59.
15. I. P. Parkin and A. T. Rowley, Adv. Mater., 1994, 6, 780; I. P. Parkin and A. T. Rowley, J. Mater. Chem., 1995, 5, 909.
16. C. H. Winter, T. S. Lewkebandara, J. W. Proscia and A. L. Rheingold, Inorg. Chem., 1994, 33, 1227.
17. H. C. Yi and J. J. Moore, J. Mater. Sci., 1990, 25, 1159; H. Hirao, Y. Miyamoto and M. Koizumi, Materials (Jpn.), 1987, 36, 12; A. G. Merzhanov, Processing Technology, 1996, 56, 222.
18. P. R. Bonneau, R. F. Jarvis and R. B. Kaner, Nature, 1991, 349, 510.
19. E. Ponthieu, L. Rao, L. Gengembre, J. Grimblot and R. B. Kaner, Solid State Ionics, 1993, 63, 116; P. R. Bonneau, R. F. Jarvis and R. B. Kaner, Inorg. Chem., 1992, 31, 2127; R. E. Treece, G. S. Macala and R. B. Kaner, Chem. Mater., 1992, 4, 9; A. Hector and I. P. Parkin, J. Chem. Soc., Chem. Commun, 1993, 1095; J. C. Fitzmaurice, A. L. Hector and I. P. Parkin, Polyhedron, 1993, 12, 1295; A. L. Hector and I. P. Parkin, J. Chem. Soc., Dalton Trans., 1993, 2435; E. G. Gillan and R. B. Kaner, Inorg. Chem., 1994, 33, 235; A. L. Hector and I. P. Parkin, Polyhedron, 1995, 5, 909.
20. P. R. Bonneau, R. K. Shibao and R. B. Kaner, Inorg. Chem., 1990, 29, 2511; J. C. Fitzmaurice, A. L. Hector and I. P. Parkin, Main Group Metal Chem., 1994, 17, 537; J. Cotter, J. C. Fitzmaurice and I. P. Parkin, J. Mater. Chem., 1994, 4, 1603; J. C. Fitzmaurice and I. P. Parkin, New J. Chem., 1994, 18, 825; I. P. Parkin and A. T. Rowley, Polyhedron, 1993, 12, 2961; J. C. Fitzmaurice and I. P. Parkin, Main Group Metal Chem., 1994, 17, 7; I. P. Parkin, Chem. Soc. Rev., 1996, 199.
21. A. V. Komarov, I. P. Parkin and M. Odlyha, J. Mater. Sci., 1996, 31, 5033.
22. N. Schonberg, Acta. Chem. Scand., 1954, 8, 199.
23. C. D. Wagner, in Practical Surface Analysis, ed. D. Briggs and M. Peah, Wiley, Chicester, 2nd edn., 1990, vol. 1.
24. K. Frisk, A Thermochemical Evaluation of the Cr–N, Fe–N, Mo–N and Cr–Mo–N Systems, Report TRITA-MAC-0393, Materials Research Center, Royal Institute of Technology, Stockholm, 1989.
25. H. P. Klug and L. E. Alexander, X-Ray Diffraction Procedure for Polycrystalline and Amorphous Materials, J. Wiley, New York, 2nd edn., 1974.
26. A. J. Craven, J. Microsc., 1995, 180, 250.
27. A. L. Hector and I. P. Parkin, Chem. Mater., 1995, 7, 122.
28. I. P. Parkin and A. T. Nartowski, Polyhedron, in press.