Microscopic vs. macroscopic structural evolution of SiO2 sols and gels employing a tailor-made fluorescent reporter dye

Journal of Materials Chemistry

Volumn 15, Issue 30, 2005, Pages 3069-3083

  Unger, Brita ^a   Rurack, Knut ^b   Müller, Ralf ^a   Jancke, Harald ^b   Resch Genger, Ute ^b  

^a Div V4   (Germany)

^b Div 13   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

DYES; FLUORESCENCE; GRAVIMETRIC ANALYSIS; LIGHT SCATTERING; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS (CHEMICAL); TOPOLOGY;

FLUOROMETRY; FLUOROPHORES; PROTICITY; SOL AGING;

SOL-GELS;

EID: 23844462617     PISSN: 09599428     EISSN: None     Source Type: Journal    
DOI: 10.1039/b501622c     Document Type: Article

References (106)

1. Optical and Electronic Phenomena in Sol-Gel Glasses and Modern Application, ed. C. K. Jørgensen and R. Reisfeld, Springer, Berlin, 1996, vol. 85;
2. R. Reisfeld, Opt. Mater., 2001, 16, 1;
3. R. Reisfeld, J. Fluoresc., 2002, 12, 317.
4. J. M. McKiernan, S. A. Yamanaka, B. Dunn and J. I. Zink, J. Phys. Chem., 1990, 94, 5652;
5. B. Lebeau, N. Herlet, J. Livage and C. Sanchez, Chem. Phys. Lett., 1993, 206, 15;
6. Q. Zhang and Z. Jiang, Mater. Chem. Phys., 2001, 69, 95;
7. D. Lo, C. Ye and J. Wang, Appl. Phys. B: Lasers Opt., 2003, 76, 649;
8. A. A. Shaposhnikov, R. T. Kuznetsova, T. N. Kopylova, G. V. Maier, E. N. Tel'minov, T. A. Pavich and S. M. Arabei, Quantum Electron., 2004, 34, 715.
9. O. Ben-David, E. Shafir, I. Gilath, Y. Prior and D. Avnir, Chem. Mater., 1997, 9, 2255;
10. C. Malins, S. Fanni, H. G. Glever, J. G. Vos and B. D. MacCraith, Anal. Commun., 1999, 36, 3;
11. S. T. Lee, B. Aneeshkumar, P. Radhakrishnan, C. P. G. Vallabhan and V. P. N. Nampoori, Opt. Commun., 2002, 205, 253;
12. V. G. Andreou and Y. D. Clonis, Biosens. Bioelectron., 2002, 17, 61;
13. H.-C. Tsai, R.-A. Doong, H.-C. Chiang and K.-T. Chen, Anal. Chim. Acta, 2003, 481, 75.
14. D. Avnir, D. Levy and R. Reisfeld, J. Chem. Phys., 1984, 88, 5956;
15. D. Levy and D. Avnir, J. Phys. Chem., 1988, 92, 4734;
16. R. Reisfeld, V. Chernyak and C. K. Jørgensen, Chimia, 1992, 46, 148;
17. C. Burgdorff, H.-G. Löhmannsröben and R. Reisfeld, Chem. Phys. Lett., 1992, 197, 358;
18. M. Ueda, H.-B. Kim, T. Ikeda and K. Ichimura, J. Non-Cryst. Solids, 1993, 163, 125;
19. J. Samuel, Y. Polevaya, M. Ottolenghi and D. Avnir, Chem. Mater., 1994, 6, 1457;
20. F. Nishida, J. M. McKiernan, B. Dunn, J. I. Zink, C. J. Brinker and A. J. Hurd, J. Am. Ceram. Soc., 1995, 78, 1640;
21. L. Xu, L. Liu, J. Yu, W. Wang and F. Li, Appl. Phys. Lett., 1996, 69, 3791;
22. Z. He and L. D. Kispert, Chem. Mater., 2001, 13, 227;
23. C. Hellriegel, J. Kirstein, C. Bräuchle, V. Latour, T. Pigot, R. Olivier, S. Lacombe, R. Brown, V. Guieu, C. Payrastre, A. Izquierdo and P. Mocho, J. Phys. Chem. B, 2004, 108, 14699.
24. T. Basché, B. Sauter and C. Bräuchle, Ber. Bunsen-Ges. Phys. Chem., 1989, 93, 1055;
25. R. Gvishi and R. Reisfeld, J. Non-Cryst. Solids, 1991, 128, 69;
26. K. Matsui and K. Nozawa, Bull. Chem. Soc. Jpn., 1997, 70, 2331;
27. G. Hungerford and J. A. Ferreira, J. Lumin., 2001, 93, 155.
28. R. Gvishi, G. Ruland and P. N. Prasad, Opt. Mater., 1997, 8, 43.
29. E. Miller, B. Wandelt, S. Wysocki, D. Jozwik and A. Mielniczak, Biosens. Bioelectron., 2004, 20, 1196.
30. T. Suratwala, Z. Gardlund, K. Davidson, D. R. Uhlmann, J. Watson and N. Peyghambarian, Chem. Mater., 1998, 10, 190.
31. G. Qian, Z. Yang, Q. Yang and M. Wang, J. Appl. Phys., 2000, 88, 2503.
32. U. Narang, J. D. Jordan, F. V. Bright and P. N. Prasad, J. Phys. Chem., 1994, 98, 8101;
33. J. D. Brennan, S. Hartman, E. I. Ilnicki and M. Rakic, Chem. Mater., 1999, 11, 1853.
34. V. R. Kaufman and D. Avnir, Langmuir, 1986, 2, 717.
35. T. Mabuchi and T. Fujii, Bull. Chem. Soc. Jpn., 1993, 66, 2174.
36. F. Del Monte and D. Levy, J. Phys. Chem. B, 1998, 102, 8036.
37. M. Casalboni, F. De Matteis, V. Ferone, P. Prosposito, R. Senesi, R. Pizzoferrato, A. Bianco and A. De Mico, Chem. Phys. Lett., 1998, 291, 167.
38. B. Dunn and J. I. Zink, Chem. Mater., 1997, 9, 2280;
39. T. Keeling-Tucker and J. D. Brennan, Chem. Mater., 2001, 13, 3331.
40. D. J. Logan, C. S. Ashley, R. A. Assink and C. J. Brinker, Proc SPIE-Int. Soc. Opt. Eng., 1992, 1758, 519.
41. P. Innocenzi, H. Kozuka and T. Yoko, J. Non-Cryst. Solids, 1996, 201, 26.
42. T. Suratwala, Z. Gardlund, K. Davidson, D. R. Uhlmann, S. Bonilla and N. Peyghambarian, J. Sol-Gel Sci. Technol., 1997, 8, 953;
43. C. Rottman, A. Turniansky and D. Avnir, J. Sol-Gel Sci. Technol., 1998, 13, 17;
44. N. Leventis, I. A. Elder, D. R. Rolison, M. L. Anderson and C. I. Merzbacher, Chem. Mater., 1999, 11, 2837.
45. C. J. Brinker and G. W. Scherer, Sol-Gel Science. The Physics and Chemistry of Sol-Gel Processing, Academic, San Diego, 1990.
46. L. L. Hench and J. K. West, Chem. Rev., 1990, 90, 33.
47. C. L. Glaves, C. J. Brinker, D. M. Smith and P. J. Davis, Chem. Mater., 1989, 1, 34.
48. P. J. Davis, C. J. Brinker and D. M. Smith, J. Non-Cryst. Solids, 1992, 142, 189.
49. R. K. Her, The Chemistry of Silica, Wiley, New York, 1979;
50. G. Orcel, L. L. Hench, I. Artaki, J. Jonas and T. W. Zerda, J. Non-Cryst. Solids, 1988, 105, 223;
51. P. J. Davis, C. J. Brinker, D. M. Smith and R. A. Assink, J. Non-Cryst. Solids, 1992, 142, 197;
52. P. J. Davis, D. M. Smith, C. J. Brinker and R. A. Assink, J. Non-Cryst. Solids, 1994, 167, 295;
53. M. N. Logan, S. Prabakar and C. J. Brinker, Mater. Res. Soc. Symp. Proc., 1994, 346, 115.
54. L. M. Ilharco, A. M. Santos, M. J. Silva and J. M. G. Martinho, Langmuir, 1995, 11, 2419.
55. K. K. Flora, M. A. Dabrowski, S. P. Musson and J. D. Brennan, Can. J. Chem., 1999, 77, 1617.
56. R. A. Dunbar, J. D. Jordan and F. V. Bright, Anal. Chem., 1996, 68, 604;
57. R. Gupta, S. Mozumdar and N. K. Chaudhury, Biosens. Bioelectron., 2005, 20, 1358.
58. E. D. Cehelnik, K. D. Mielenz and R. A. Velapoldi, J. Res. Natl. Bur. Stand. A, 1975, 79A, 1;
59. H. Minato, M. Nanjo and Y. Nayatani, Color Res. Appl., 1983, 8, 238;
60. U. Resch-Genger, D. Pfeifer, C. Monte, W. Pilz, A. Hoffmann, M. Spieles, K. Rurack, J. Hollandt, D. Taubert, B. Schönenberger and P. Nording, J. Fluoresc., 2005, 15, 325.
61. K. Rurack, K. Hoffmann, W. Al-Soufi and U. Resch-Genger, J. Phys. Chem. B, 2002, 106, 9744.
62. B. Valeur, in Molecular Luminescence Spectroscopy, ed. S. G. Schulman, J. Wiley & Sons, New York, 1993, pp. 25;
63. W. Rettig and R. Lapouyade, in Probe Design and Chemical Sensing, ed. J. R. Lakowicz, Plenum, New York, 1994, pp. 109.
64. Whereas t is the time between synthesis and measurement for liquid samples and wet gels, it is the time between synthesis and the start of the drying procedure in the case of solid dried samples.
65. B. Unger, M. Hähnert and R. Nitzsche, J. Sol-Gel Sci. Technol., 1998, 13, 81.
66. B. Unger, P. Popp, U. Schade and M. Hähnert, J. Non-Cryst. Solids, 1993, 160, 152.
67. B. Unger, H. Jancke, H. Stade and M. Hähnert, J. Sol-Gel Sci. Technol., 1994, 2, 51.
68. r ≤ 0.01. Since at that stage, the absorption and fluorescence excitation spectra were identical, we relied on the latter type of spectra throughout the monitoring of the sol-gel process.
69. K. Rurack, J. L. Bricks, B. Schulz, M. Maus, G. Reck and U. Resch-Genger, J. Phys. Chem. A, 2000, 104, 6171.
70. K. H. Drexhage, J. Res. Natl. Bur. Stand., 1976, 80A, 421.
71. This is supported by small angle X-ray scattering studies of similar acid-catalyzed TEOS-derived sols which, in contrast to the strong increase in 〈s1〉 shown by DLS, found almost constant primary particle sizes of 1-2 nm during later aging stages: T. Gerber and B. Himmel, PhD Dissertation, University of Rostock, Rostock, 1987;
72. T. Gerber, B. Himmel and B. Unger, unpublished results.
73. W. Rettig, K. Rurack and M. Sczepan, in New Trends in Fluorescence Spectroscopy: Applications to Chemical and Life Sciences, ed. B. Valeur and J.-C. Brochon, Springer: Berlin, 2001, pp. 125.
74. B. Unger, K. Rurack, R. Müller, U. Resch-Genger and K. Buttke, J. Sol-Gel Sci. Technol., 2000, 19, 801.
75. S. Nigam and S. C. Rutan, Appl. Spectrosc., 2001, 55, 362A.
76. M. M. Martin, P. Plaza, Y. H. Meyer, F. Badaoui, J. Bourson, J.-P. Lefevre and B. Valeur, J. Phys. Chem., 1996, 100, 6879.
77. 2O: E. Lippert, Z. Naturforsch., 1955, 10a, 541;
78. E. Lippert, Z. Elektrochem., 1957, 61, 962;
79. N. Mataga, Y. Kaifu and M. Koizumi, Bull. Chem. Soc. Jpn., 1956, 29, 465.
80. Apparently, in the case of 1 with two potential protonation sites, doubly protonated species can also be present. With respect to the pH during sol synthesis and sol aging, and due to the fact that pH changes are still less pronounced after gel formation, ref. 11, no attempts were made to distinguish between mono- and doubly protonated molecules or to probe the behaviour of the dyes at lower pH.
81. In fact, self-aggregation was also not observed for 2 and 3 in saturated ethanol solution or ethanol/water mixtures.
82. 293, the only synthesis where a considerable amount of species II was found for the weakly doped samples.
83. Due to this fact, we refrained from intensive studies of 2-doped gels.
84. r ∼ 0.25, 0.5, and 0.75.
85. Note that the red-shifted excitation bands at 500 nm, corresponding to a 580 nm-centred emission, found by us in a previous study for long-term dried and aged coumarin 307-doped sol-gel monoliths, ref. 39, could not be observed during our recent studies.
86. F. Del Monte, J. D. Mackenzie and D. Levy, Langmuir, 2000, 16, 7377.
87. U. Brackmann, Lambdachrome® Laser Dyes, Lambda Physik GmbH, Göttingen, 1994.
88. Although the absolute fluorescence intensities of the gels and the dried monoliths are not comparable due to different measurement geometries, decomposition is also expected to occur for the concentrated samples, but does not lead to an almost complete loss of fluorescence.
89. r, ∼ 1), and probably in accordance with an apparent increase in viscosity upon formation of the three dimensional network, all the samples show a somewhat enhanced (<5%) type I fluorescence.
90. The constant decrease in the relative intensity of this species throughout the gelation and other wet-aging processes also does not favour such an assignment: whenever the sol-gel structure evolution is probed with potentially excimer-forming dyes such as pyrene derivatives, the narrowing of the pores during gelation has a dramatic influence and commonly enhances the excimer yield drastically, refs. 11,24.
91. T. Fujii, H. Nishikiori and T. Tamura, Chem. Phys. Lett., 1995, 233, 424.
92. G. Hungerford, K. Suhling and J. Ferreira, J. Photochem. Photobiol, A Chem., 1999, 129, 71.
93. G. Orcel, PhD Dissertation, University of Florida, Gainesville, FL, 1987.
94. C. D. Geddes and D. J. S. Birch, J. Non-Cryst. Solids, 2000, 270, 191.
95. r ∼ 0.8) for TMOS-derived sols byH. Kaji, K. Nakanishi, N. Soga, T. Inoue and N. Nemoto, J. Sol-Gel Sci. Technol., 1994, 3, 169. However, such behaviour was not observed during our studies.
96. J. Karolin, C. D. Geddes, K. Wynne and D. J. S. Birch, Meas. Sci. Technol., 2002, 13, 21.
97. A. J. Vega and G. W. Scherer, J. Non-Cryst. Solids, 1989, 99, 153.
98. S. Gits-Léon, F. LeFaucheux and M. C. Robert, J. Crystal Growth, 1987, 84, 155.
99. U. Narang, F. V. Bright and P. N. Prasad, Appl. Spectrosc., 1993, 47, 229;
100. L. L. Diaz-Flores, J. J. Pérez-Bueno, Y. V. Vorobiev, J. R. Martinez, F. Ruiz, F. Pérez-Robles and J. González-Hernández, Mater. Lett., 2000, 42, 25.
101. 29Si NMR experiments carried out by us for TEOS-derived samples with an extremely under-stoichiometric water content support these findings; H. Jancke and B. Unger, unpublished results.
102. J. L. Habib Jiwan, E. Robert and J.-P. Soumillion, J. Photochem. Photobiol., A Chem., 1999, 122, 61.
103. r ∼ 1.
104. T. Suratwala, Z. Gardlund, K. Davidson, D. R. Uhlmann, J. Watson, S. Bonilla and N. Peyghambarian, Chem. Mater., 1998, 10, 199;
105. L. L. Diaz-Flores, J. J. Pérez-Bueno, F. J. Espinoza-Beltrán, J. F. Pérez-Robles, R. Ramírez-Bon, Y. V. Vorobiev and J. González-Hernández, Microelectron. Eng., 2000, 51-52, 659.
106. 293 even to 100-70 nm) and 〈s1〉 from ∼ 70 to ∼ 20 nm. Only 2 h after sol dilution, the measured particle sizes remained virtually constant and these data are included here.