Sol–gel synthesis and characterization of Ag₂S nanocrystallites in silica thin film glasses

Abstract

Silver sulfide particles embedded in thin coatings of transparent and homogeneous silica glass are promising materials for the development of optical devices. The optical properties are strongly dependent on the elemental composition and morphology of the coatings as well as on the size distribution of the nanoclusters. A sol–gel route has been used to achieve good control over film composition and morphology. The dip-coating procedure from alcoholic solutions containing tetraethoxysilane [Si(OEt)₄] and silver diethylthiourea complexes [Ag(EtNHCSNHEt)_n]⁺ has been adopted. The silver sulfide particles were directly generated in silica by decomposition of the silver complexes upon heating the coatings. Annealing was performed in a nitrogen atmosphere in order to prevent sulfide oxidation to sulfate. The sol–gel method has been shown to be a suitable procedure for controlling the size of the metal sulfide particles. Evolution of the system under heating has been studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), secondary-ion mass spectrometry (SIMS) and atomic force microscopy (AFM).

References

1. J. Warnock and D. D. Awschalom, Phys. Rev. B, 1985, 32, 5529.
2. N. F. Borrelli, D. W. Hall, H. J. Holland and D. W. Smith, J. Appl. Phys., 1987, 61, 5399.
3. G. Fuxi, J. Non-Cryst. Solids, 1991, 129, 299.
4. L. E. Brus, J. Chem. Phys., 1983, 79, 5566.
5. S. Schmitt-Rink, D. A. B. Miller and D. S. Chemla, Phys. Rev. B, 1987, 35, 8113.
6. H. Gleiter, Adv. Mater., 1992, 4, 474.
7. H. Nasu, K. Tsunetomo, Y. Tokumitsu and Y. Osaka, Jpn. J. Appl. Phys., 1989, 28, L862.
8. C. W. White, J. D. Budai, J. G. Zhu, S. P. Withrow, R. A. Zuhr, Y. Chen, D. H. Hembree Jr., R. H. Magruder and D. O. Henderson, Mater. Res. Soc. Symp. Proc., 1995, 358, 169.
9. J. G. Zhu, C. W. White, J. D. Budai, S. P. Withrow and Y. Chen, J. Appl. Phys., 1995, 78, 4386.
10. H. Meherzi-Magharoui, M. Dachraoui, S. Belgacem, K. D. Buhre, R. Kunst, P. Cowache and D. Lincot, Thin Solid Films, 1996, 288, 217.
11. R. Bertoncello, G. Battaglin, F. Caccavale, E. Cattaruzza, P. Colombo, S. Daolio, S. Gross, P. Mazzoldi and F. Trivillin, J. Mater. Res., 1999, 14, 1.
12. P. Mazzoldi, F. Caccavale, E. Cattaruzza, A. Boscolo-Boscoletto, R. Bertoncello, G. Battaglin and C. Gerardi, Nucl. Instrum. Methods B, 1992, 65, 367.
13. C. J. Brinker and G. W. Scherer, in Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing, Academic Press Inc., San Diego, CA, 1990.
14. M. Guglielmi, A. Martucci, E. Menegazzo, G. C. Righini, S. Pelli, J. Fick and G. Vitrant, J. Sol-Gel Sci. Technol., 1997, 8, 1017.
15. G. Henshaw, I. P. Parkin and G. Shaw, Chem. Commun., 1996, 1095.
16. R. G. Cope and H. J. Goldsmid, Br. J. Appl. Phys., 1965, 16, 1501.
17. G. Hodes, J. Manasen and D. Cahen, Nature (London), 1976, 261, 403.
18. T. Minami, J. Non-Cryst. Solids, 1987, 95–96, 107.
19. N. Tohge, M. Asuka and T. Minami, J. Non-Cryst. Solids, 1992, 147–148, 652.
20. R. D. Stramel, T. Nakamura and J. K. Thomas, J. Chem. Soc., Faraday Trans. 1, 1988, 84, 1287.
21. S. S. Dhumure and C. D. Lokhande, Thin Solid Films, 1994, 240, 1.
22. K. Bozhilov, V. Dimov, A. Panov and H. Haefke, Thin Solid Films, 1990, 190, 129.
23. Gmelins Handbuch der Anorganischen Chemie, 61 Ag B3, Verlag Chemie, Weinheim, 1973, pp. 8–56.
24. S. R. Barman, N. Shanthi, A. K. Shukla and D. D. Sarma, Phys. Rev. B, 1996, 53, 3746.
25. A. Boettcher, G. Haase and H. Treupel, Z. Angew. Phys., 1955, 7, 478.
26. Handbook of Chemistry and Physics, ed. R. C. Weast, CRC Press, Boca Raton, FL, 64th edn., 1984, B-137.
27. Gmelins Handbuch der Anorganischen Chemie, 61 Ag B7, Verlag Chemie, Weinheim, 1973, pp. 98–136.
28. W. L. Reynolds, Prog. Inorg. Chem., 1970, 12, 1.
29. A. Tavlaridis and R. Neeb, Naturwissenschaften, 1976, 63, 146.
30. R. Hesse, in Advances in the Chemistry of the Coordination Compounds, ed. S. Kirschner, New York, 1961, pp. 314–320.
31. L. Armelao, R. Bertoncello, S. Coronaro and A. Glisenti, Sci. Technol. Cultural Heritage, 1998, 7, 41.
32. M. P. Seah, in Practical Surface Analysis, ed. D. Briggs and M. P. Seah, J. Wiley & Sons, New York, 1990, vol. 1, p. 543.
33. J. F. Moulder, W. F. Stickle, P. E. Sobol and K. D. Bomben, in Handbook of X-Ray Photoelectron Spectroscopy, ed. J. Chastain, Perkin Elmer Corp., Eden Prairie, MN 1992.
34. C. D. Wagner, Anal. Chem., 1972, 44, 972.
35. S. Enzo, S. Polizzi and A. Benedetti, Z. Kristallogr., 1985, 170, 275.
36. C. Pagura, S. Daolio and B. Facchin, in Secondary-Ion Mass Spectrometry SIMS VIII, ed. A. Benninghoven, K. T. F. Jansen, J. Tumpner and H. W. Werner, John Wiley, Chichester, 1992, p. 239.
37. C. Pagura and S. Valcher, unpublished work.
38. O. Knacke, O. Kubaschewski and K. Hesselmann, in Thermochemical Properties of Inorganic Substances, Springer Verlag, Berlin, 1991, vol. 1.
39. C. D. Wagner, in Practical Surface Analysis, ed. D. Briggs and M. P. Seah, J. Wiley & Sons, New York, 1990, vol. 1, pp. 595–604.
40. J. Barrett and F. S. Deghaidy, Spectrochim. Acta, Part A, 1974, 31, 707.
41. H. Hosaya, J. Tanaka and S. Nagakura, Bull. Chem. Soc. Jpn., 1960, 33, 850.
42. V. K. Kaushik, J. Electron Spectrosc. Relat. Phenom., 1991, 56, 273.
43. XPS Photoelectron Spectroscopy Database, version 1.0, National Institute of Standards and Technology, Gaithersburg, MD, 1989.
44. A. N. Goldstein, C. M. Echer and A. P. Alivisatos, Science, 1992, 256, 1425.
45. Pattern 14-72 on Joint Committee on Powder Diffraction Standard, International Centre for Diffraction Data, Newton Square, PA, 1992.
46. Pattern 4-783 on Joint Committee on Powder Diffraction Standard, International Centre for Diffraction Data, Newton Square, PA, 1993.
47. K. L. Westra and D. J. Thomson, Thin Solid Films, 1995, 257, 15.
48. User's Guide to Autoprobe CP and LS, Park Scientific Instruments, Sunnyvale, CA, 1996.