The photoinduced formation of thin film structures from a Ti-alkoxide precursor (OPy)2Ti(TAP)2, where OPy = OC6H6N, TAP = OC6H2[CH2N(CH3)2]3-2,4,6, was demonstrated via direct deposition from a pyridine-based solution and by optical illumination of a solid-state spin-coated thin film of the compound. Photopatterned physical relief structures were produced using both of these deposition methods and feature sizes as small as ∼1 μm were readily achieved. Surface investigations of the material’s nanostructure revealed that films photo-deposited from solution exhibited nanometer-scale surface roughness with evenly distributed surface porosity (∼10 nm sized pores) while films produced through the illumination of spin-coated thin films exhibited, in comparison, a reduction in surface roughness. Vibrational spectra were compared with the results of quantum chemical computations (density-functional theory) of potential photoproducts in an attempt to identify and distinguish the dominant structural groups resulting from the optical processing of each precursor form (i.e., solution versus solid-state). It was determined that ultraviolet irradiation for both thin-film formation techniques resulted in a disruption of the ligand groups, facilitating the initiation of hydrolysis and condensation reactions in the films.
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H. Scmidt, H. Krug, R. Kasemann, and F. Tiefensee: Development of optical wave guide by sol-gel techniques for laser patterning. SPIE 1590, 36 (1991).
S. Najafi, T. Touam, R. Sara, M.P. Andrews, and M.A. Fardad: Sol-gel glass waveguide and grating on silicon. J. Lightwave Technol. 16, 1640 (1998).
N. Tohge, R. Ueno, F. Chiba, K. Kintaka, and J. Nishii: Characteristics of diffraction gratings fabricated by the two-beam interference method using photosensitive hybrid gel films. J. Sol-Gel Sci. Technol. 19, 119 (2000).
N. Tohge, G. Zhao, and F. Chiba: Photosensitive gel films prepared by the chemical modification and their application to surface-relief gratings. Thin Solid Films 351, 85 (1999).
M.R. Riley, D. DeRosa, J. Blaine, B.G. Potter Jr., P. Lucas, D. Le Coq, C. Juncker, D.E. Boesewetter, J.M. Collier, C. Boussard-Pledel, and B. Bureau: Biologically inspired sensing: Infrared spectroscopic analysis of cell responses to an inhalation health hazard. Biotechnol. Progr. 22, 24 (2006).
Z.V. Schneider, K. Simmons-Potter, and T.J. Boyle: Photomodification of heteroleptic titanium-based, complex metal alkoxides. J. Non-Cryst. Solids 355, 536 (2009).
K. Tadanaga, T. Owan, J. Morinaga, S. Urbanek, and T. Minami: Fine patterning of transparent, conductive SnO2 thin films by UV-irradiation. J. Sol-Gel Sci. Technol. 19, 791 (2000).
T. Imao, D. Hazama, N. Noma, and S. Ito: Photopatterning of titanium oxide gel films prepared from titanium alkoxide modified with hydroxl-substituted aromatic ketones. J. Ceram. Soc. Jpn. 114, 238 (2006).
K. Kikuta, K. Takagi, and S. Hirano: Photoreaction of titanium-based metal-organic compounds for ceramic fine patterning. J. Am. Ceram. Soc. 82, 1569 (1999).
N. Noma, S. Yamazaki, and N. Tohge: Preparation of new photosensitive ZrO2 gel films using hydroxyl-substituted aromatic ketones as chemical modification reagents and their patterning. J. Sol-Gel Sci. Technol. 31, 253 (2004).
K. Shinmou, N. Tohge, and T. Minami: Fine-patterning of ZrO2 thin films by the photolysis of chemically modified gel films. Jpn. J. Appl. Phys. 33, L1181 (1994).
H. Segawa, S. Adachi, Y. Arai, and K. Yoshida: Fine patterning of hybrid titania films by ultraviolet irradiation. J. Am. Ceram. Soc. 86, 761 (2003).
T. Imao, T. Horiuchi, N. Noma, and S. Ito: Preparation of new photosensitive TiO2 gel films using chemical additives including nitrogen and their patterning. J. Sol-Gel Sci. Technol. 39, 119 (2006).
H. Segawa, K. Tateishi, Y. Arai, K. Yoshida, and H. Kaji: Patterning of hybrid titania film using photopolymerization. Thin Solid Films 466, 48 (2004).
J.D. Musgraves, B.G. Potter Jr., R.M. Sewell, and T.J. Boyle: Photo-induced structural changes in titanium alkoxides for directing molecular assembly, in Self Assembly of Nanostructures Aided by Ion- or Photon-Beam Irradiation—Fundamentals and Applications, edited by R. Kalyanaraman, U. Valbusa, and Z. Zhang (Mater. Res. Soc. Symp. Proc. 960E, Warrendale, PA, 2007), p. N05–03.
J.D. Musgraves, B.G. Potter Jr., R.M. Sewell, and T.J. Boyle: Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly. J. Mater. Res. 22, 1694 (2007).
J.D. Musgraves, B.G. Potter Jr., and T.J. Boyle: Direct fabrication of physical relief structures via patterned photodeposition of a titanium alkoxide solution. Opt. Lett. 33, 1306 (2008).
B.G. Potter Jr., J.D. Musgraves, and T.J. Boyle: Photo-initiation of intermolecular bonding and oxide deposition in Ti-based alkoxide solutions. J. Non-Cryst. Solids 354, 2017 (2008).
J.D. Musgraves, B.G. Potter Jr., and T.J. Boyle: Nanostructure development in photodeposited, titania-based thin films. J. Mater. Res. 24, 3372 (2009).
T.J. Boyle, R.M. Sewell, L.A.M. Ottley, H.D. Pratt, C.J. Quintana, and S.D. Bunge: Controlled synthesis of a structurally characterized family of sterically constrained heterocyclic alkoxy-modified titanium alkoxides. J. Inorg. Chem. 46, 1825 (2007).
This research was supported by the United States Department of Energy, Office of Basic Energy Sciences. Partial support was also provided by the University of Arizona, State of Arizona, TRIF Optics Initiative program and by Sandia National Laboratories. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company for the United States Department of Energy’s National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.
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Schneider, Z., Musgraves, J., Simmons-Potter, K. et al. Photoinduced formation of thin-film structures in titanium alkoxides via direct deposition from solution and from spin-coated solid-state precursor films. Journal of Materials Research 26, 754–762 (2011). https://doi.org/10.1557/jmr.2010.34