Ph. D. THESIS 2009

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6. Conclusions of part B In this work, we developed and optimized a direct and versatile pathway to fabricate metallic structures based on a metallic photo-reduction process induced by femtosecond laser irradiation. The fabrication process is very sensitive to the „writing” conditions, the chemical composition of the active layer as well as the laser power are found to have a strong influence on the fabricated structures. Continuous and regular metallic wires have been obtained in repeatedly and reproducible way. AFM and SEM measurements show that gold and silver wires are in fact constituted by two metallic lines –double-wire shape- centered on the area of engraving and generated by the thermal effect. The origin of the double-wire shape of the metallic wires has been demonstrated and we showed that optimized experimental conditions allow to generate a metallic single wire deposition. This method allowed us to fabricate regular and well-defined 3D gold microstructure embedded in a dielectric matrix as well as 3D self-standing silver microstructure. Optical and spectroscopic investigations highlighted that the metallic structures obtained by us exhibit very important plasmon resonances showing promising optical properties and challenging applications. This direct writing technique may be useful to fabricate highly efficient 3D gratings with spectral filtering properties due to the significant index contrast between polymer host and metallic parts. 19
Selected References 1. E. S. Wu, J. H. Strickler, W. R. Harrell, W. W. Webb, “Two-photon lithography for microelectronic application”, The Proceedings of SPIE 1992, 1674, 776-782. 2. S. Maruro, O. Nakamura, S. Kawata, “Three-dimensional microfabrication with two-photon-absorbed photopolymerization”, Optics Letters 1997, 22, 132- 134. 3. P.-W. Wu, W. Cheng, I. B. Martini, B. Dunn, B. J. Schwartz, E. Yablonovitch, “Two-Photon Photographic Production of Three-Dimensional Metallic Structures within a Dielectric Matrix”, Advanced Materials 2000, 12, 1438-1441. 4. C. A. Sacchi, “Laser-induced electric breakdown in water”, Journal of Optical Society of America B 1991, 8, 337-345 5. F. Stellacci, C. A. Bauer, T. Meyer-Friedrichsen, W. Wenseleers, V. Alain, S. M. Kuebler, S. J. K. Pond, Y. Zhang, S. R. Marder, J. W. Perry, “Laser and Electron-Beam Induced Growth of Nanoparticles for 2D and 3D Metal Patterning”, Advanced Materials 2002, 14, 194-198. 6. J. L. Elechiguerra, L. Larios-Lopez, C. Liu, D. Garcia-Gutierrez, A. Camacho-Bragado, and M. J. Yacaman, “Corosion at the Nanoscale: The Case of Silver Nanowires and Nanoparticles”, Chemistry of Materials 2005, 17, 6042-6052. 7. B. P. Donat, S. Panozzo, J. C. Vial, C. Beigne, R. Rieutord, “Increased field effect mobility from linear to branched tiophene-based polymers”, Synthetic- Metals, 2004, 146, 225-231. 8. S. J. Henley, J. D. Carey, S. R. P. Silva, “Laser-nanostructured Ag films as substrates for surface-enhanced Raman spectroscopy”, Applied Physics Letters 2006, 88, 1-3. 9. L. Rivas, S. Sanchez-Cortes, J. V. Garcia-Ramos, G. Morcillo, “Growth of silver Colloidal Particles Obtained by Citrate Reduction to Increase the Raman Enhancement Factor”, Langmuir 2001, 17, 574-577. 10. N. Tosa, G. Vitrant, P. L. Baldeck, O. Stephan, S. Astilean, I. Grosu, “Twophoton laser deposition of gold nanowires”, Journal of Optoelectronics and Advanced Materials 2007, 9, 641-645. 11. R. F. Karlicek, V. M. Donelly, G. J. Collins, “Laser-induced metal deposition on InP”, Journal of Applied Physics 1982, 53, 1084-1090. 12. a) A. N. Shipway, E. Katz, I. Willner, «Nanoparticle Arrays on Surfaces for Electronic, Optical, and Sensor Applications», ChemPhysChem 2000, 1, 18-25; b) K. Aslan, J.R. Lakowicz, C.D. Geddes, «Plasmon light scattering in biology 20
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“BABES-BOLYAI” UNIVERSITY CLUJ-
Page 3 and 4:
General Introduction OUTLINE Part A
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3.6.1. Dots 188 3.6.2. 3D structure
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Part A: Synthesis and Structural An
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H 3C H 3C O O O C C O O 1a O O C C
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The two forms are in equilibrium an
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Figu re 4 . Th e 13 C-NMR APT (CDCl
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set used , the anarmonicities that
Page 17 and 18: Figure 9. ORTEP diagram for the bic
Page 19 and 20: 1.5.1. Tetramethyl 3,7-dihydroxybic
Page 21 and 22: Table 7. The selected molecular par
Page 23 and 24: a b Figure 14. 1 H NMR spectrum (CD
Page 25 and 26: Figure 16. 13 C NMR spectrum APT (C
Page 27 and 28: Absorbance (a. u.) Absorbance (a.u.
Page 29 and 30: icyclo[3.3.1]nonane-3,7-dione solut
Page 31 and 32: m u lt ip let a t a t δ ==1 .7 6 p
Page 33 and 34: Figure 22. 13 C NMR APT spectrum of
Page 35 and 36: Figure 24. NMR investigation of the
Page 37 and 38: (mol·l -1 ) syn 8.8 x10 -3 1.4373
Page 39 and 40: a b Figure 29. 3D FTIR spectra in s
Page 41 and 42: Figure 32. ORTEP diagram for the cy
Page 43 and 44: H2 … N3 = 1.839 Å H5 … N6 = 1.
Page 45 and 46: 2. Conclusions of the part A Differ
Page 47: 20. L. J. Bellamy, “Advanced in I
Page 50 and 51: 2. Experimental part: fabrication a
Page 52 and 53: 3 m 30 m a b Figure 4. Optical imag
Page 54 and 55: (NA 1.25) in phase-contrast (a) and
Page 56 and 57: was chosen instead of an aqueous on
Page 58 and 59: Our goal is to develope a lasser as
Page 60 and 61: Figure 15. a Optical image of gold
Page 62 and 63: the power as parameter exhibits a m
Page 64 and 65: a b Figure 21 a) Optical image of g
Page 66: 4.5.3. 3D structures The 3D structu
Page 71: VIII. J. Bosson-Ehoomann, A. Mihut,
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Ph. D. THESIS 2009

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