Hostname: page-component-78c5997874-j824f Total loading time: 0 Render date: 2024-11-05T04:48:56.079Z Has data issue: false hasContentIssue false
  • English
  • Français

Photoinduced formation of thin-film structures in titanium alkoxides via direct deposition from solution and from spin-coated solid-state precursor films

Published online by Cambridge University Press:  11 March 2011

Z.V. Schneider ,
J.D. Musgraves ,
K. Simmons-Potter ,
B.G. Potter Jr.  and
T.J. Boyle
Z.V. Schneider
Affiliation:
University of Arizona, Tucson, Arizona 85721-0104
J.D. Musgraves
Affiliation:
University of Arizona, Tucson, Arizona 85721-0104
K. Simmons-Potter*
Affiliation:
University of Arizona, Tucson, Arizona 85721-0104
B.G. Potter Jr.
Affiliation:
University of Arizona, Tucson, Arizona 85721-0104
T.J. Boyle
Affiliation:
Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, New Mexico 87106
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

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.

Keywords

NanostructureSol-gelPhotochemical
Type
Articles
Information
Journal of Materials Research , Volume 26 , Issue 6 , 28 March 2011 , pp. 754 - 762
Copyright
Copyright © Materials Research Society 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Scmidt, H., Krug, H., Kasemann, R., and Tiefensee, F.: Development of optical wave guide by sol-gel techniques for laser patterning. SPIE 1590, 36 (1991).Google Scholar
2.Najafi, S., Touam, T., Sara, R., Andrews, M.P., and Fardad, M.A.: Sol-gel glass waveguide and grating on silicon. J. Lightwave Technol. 16, 1640 (1998).CrossRefGoogle Scholar
3.Tohge, N., Ueno, R., Chiba, F., Kintaka, K., and Nishii, J.: Characteristics of diffraction gratings fabricated by the two-beam interference method using photosensitive hybrid gel films. J. Sol-Gel Sci. Technol. 19, 119 (2000).CrossRefGoogle Scholar
4.Tohge, N., Zhao, G., and Chiba, F.: Photosensitive gel films prepared by the chemical modification and their application to surface-relief gratings. Thin Solid Films 351, 85 (1999).CrossRefGoogle Scholar
5.Riley, M.R., DeRosa, D., Blaine, J., Potter, B.G. Jr., Lucas, P., Le Coq, D., Juncker, C., Boesewetter, D.E., Collier, J.M., Boussard-Pledel, C., and Bureau, B.: Biologically inspired sensing: Infrared spectroscopic analysis of cell responses to an inhalation health hazard. Biotechnol. Progr. 22, 24 (2006).CrossRefGoogle Scholar
6.Schneider, Z.V., Simmons-Potter, K., and Boyle, T.J.: Photomodification of heteroleptic titanium-based, complex metal alkoxides. J. Non-Cryst. Solids 355, 536 (2009).CrossRefGoogle Scholar
7.Tadanaga, K., Owan, T., Morinaga, J., Urbanek, S., and Minami, T.: Fine patterning of transparent, conductive SnO2 thin films by UV-irradiation. J. Sol-Gel Sci. Technol. 19, 791 (2000).CrossRefGoogle Scholar
8.Imao, T., Hazama, D., Noma, N., and Ito, S.: Photopatterning of titanium oxide gel films prepared from titanium alkoxide modified with hydroxl-substituted aromatic ketones. J. Ceram. Soc. Jpn. 114, 238 (2006).CrossRefGoogle Scholar
9.Kikuta, K., Takagi, K., and Hirano, S.: Photoreaction of titanium-based metal-organic compounds for ceramic fine patterning. J. Am. Ceram. Soc. 82, 1569 (1999).CrossRefGoogle Scholar
10.Noma, N., Yamazaki, S., and Tohge, N.: 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).CrossRefGoogle Scholar
11.Shinmou, K., Tohge, N., and Minami, T.: Fine-patterning of ZrO2 thin films by the photolysis of chemically modified gel films. Jpn. J. Appl. Phys. 33, L1181 (1994).CrossRefGoogle Scholar
12.Segawa, H., Adachi, S., Arai, Y., and Yoshida, K.: Fine patterning of hybrid titania films by ultraviolet irradiation. J. Am. Ceram. Soc. 86, 761 (2003).CrossRefGoogle Scholar
13.Imao, T., Horiuchi, T., Noma, N., and Ito, S.: Preparation of new photosensitive TiO2 gel films using chemical additives including nitrogen and their patterning. J. Sol-Gel Sci. Technol. 39, 119 (2006).CrossRefGoogle Scholar
14.Segawa, H., Tateishi, K., Arai, Y., Yoshida, K., and Kaji, H.: Patterning of hybrid titania film using photopolymerization. Thin Solid Films 466, 48 (2004).CrossRefGoogle Scholar
15.Musgraves, J.D., Potter, B.G. Jr., Sewell, R.M., and Boyle, T.J.: 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 Kalyanaraman, R., Valbusa, U., and Zhang, Z. (Mater. Res. Soc. Symp. Proc. 960E, Warrendale, PA, 2007), p. N05–03.Google Scholar
16.Musgraves, J.D., Potter, B.G. Jr., Sewell, R.M., and Boyle, T.J.: Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly. J. Mater. Res. 22, 1694 (2007).CrossRefGoogle Scholar
17.Musgraves, J.D., Potter, B.G. Jr., and Boyle, T.J.: Direct fabrication of physical relief structures via patterned photodeposition of a titanium alkoxide solution. Opt. Lett. 33, 1306 (2008).CrossRefGoogle ScholarPubMed
18.Potter, B.G. Jr., Musgraves, J.D., and Boyle, T.J.: Photo-initiation of intermolecular bonding and oxide deposition in Ti-based alkoxide solutions. J. Non-Cryst. Solids 354, 2017 (2008).CrossRefGoogle Scholar
19.Musgraves, J.D., Potter, B.G. Jr., and Boyle, T.J.: Nanostructure development in photodeposited, titania-based thin films. J. Mater. Res. 24, 3372 (2009).CrossRefGoogle Scholar
20.Boyle, T.J., Sewell, R.M., Ottley, L.A.M., Pratt, H.D., Quintana, C.J., and Bunge, S.D.: Controlled synthesis of a structurally characterized family of sterically constrained heterocyclic alkoxy-modified titanium alkoxides. J. Inorg. Chem. 46, 1825 (2007).CrossRefGoogle ScholarPubMed