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Doctoral Thesis
DOI
https://doi.org/10.11606/T.43.2003.tde-05072012-162751
Document
Author
Full name
Fabio Furlan Ferreira
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2003
Supervisor
Committee
Fantini, Marcia Carvalho de Abreu (President)
Cotta, Mônica Alonso
Santos, Antonio Domingues dos
Scarmínio, Jair
Tabacniks, Manfredo Harri
Title in Portuguese
Eletrocromismo em filmes finos compósitos
Keywords in Portuguese
Eletrocromismo
Materiais compósitos
Óxidos Metálicos
Abstract in Portuguese
Neste trabalho calculamos inicialmente as propriedades ópticas de filmes compósitos de Me-NiO e Me-CoO, sendo os metais Me = Au, Ag, Cu, Ni, Pd e Pt, a partir da teoria de meio efetivo de Maxwell Garnett. Este estudo teórico possibilitou avaliar a viabilidade de se obter experimentalmente um material colorido na região do espectro visível, com absorção seletiva numa estreita faixa de comprimentos de onda. Os resultados mostraram que o candidato ideal para tal fim é o compósito a base de Au. A partir deste resultado iniciou-se o crescimento de filmes finos compósitos de Au-NiO e Au-CoO, utilizando diferentes estratégias experimentais: (i) deposição por DC magnetron sputtering reativo, (ii) deposição do filme de NiO, por DC magnetron sputtering reativo e Au pelos métodos de sol-gel e dip coating e (iii) deposição de ambos os filmes, NiOxHy e Au, por sol-gel e dip coating. Os resultados mostraram uma seletividade pequena (-5-10%) nos filmes crescidos pelo método de sputtering, devido ao caráter atomístico desse tipo de técnica, que conduz à formação de pequenos aglomerados de Au (menores que -3 nm), ao invés de agregados com tamanhos da ordem de algumas dezenas de nanômetros, obtidos facilmente pelo método sol-gel. O crescimento na forma de multicamadas proporciona uma melhor seletividade, em torno de 1 5%. Pós-tratamentos térmicos em filmes compósito s obtidos unicamente por sputtering induzem a aglomeração do Au, mas destroem as propriedades eletrocrôrnicas. No caso de filmes de Au crescidos por sol-gel, a seletividade espectral, decorrente da presença do Au aumenta, indo de 15% a 20% em filmes depositados sobre a matriz óxida crescida por sputtering e por sol-gel, respectivamente. Mediante processos eletroquímicos, os filmes de NiOxHy crescidos por sol-gel e dip coating apresentaram os melhores resultados de variação de transmitância (70%), devido à maior porosidade desses filmes.
Title in English
Electrochromism in thin film composites
Keywords in English
Composite materials
Electrochromism
Metal oxides
Abstract in English
In this work we initially calculated the optical properties of cermet films of Me-NiO and Me-CoO, being the metals Me = Au, Ag, Cu, Ni, Pd and Pt, by means of the Maxwell Garnett effective medium theory. This theoretical study allowed evaluating the viability to obtain, experimentally, a colored material in the visible spectrum region, with selective absorption in a narrow range of wavelengths. The results showed that the ideal candidate for such goal is the Au cermet. Looking at this result, the growth of Au-NiO and Au-CoO thin films was initiated using different experimental strategies: (i) deposition by reactive DC magnetron sputtering, (ii) deposition of the NiO, film by reactive DC magnetron sputtering and Au by the sol-gel and dip coating methods and (iii) deposition of both films, NiOxHy and Au, by sol-gel and dip coating. The films grown by sputtering showed a small selectivity (-5-10%), due to the atomistic character of this type of technique. It leads to the formation of small clusters of Au (smaller than -3 nrn), instead of aggregates with sizes of the order of some tenths of nanometers, easily obtained by the sol-gel method. Better selectivity, around 15%, is obtained in films deposited as multilayers. Post thermal annealing of the cermet films grown by sputtering induces the agglomeration of Au, but destroys the electrochromic properties. In the case of Au films grown by sol-gel, the spectral selectivity increases, due to the presence of Au, going from 15% to 20% in films deposited on the oxide matrix, deposited by sputtering and sol-gel, respectively. Under electrochemical processes, the NiOxHy films grown by sol-gel and dip coating presented the highest transmission variation (70%), due to larger porosity of these films.
 
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38559Ferreira2.pdf (66.68 Mbytes)
Publishing Date
2012-07-05
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • FERREIRA, F. F., and FANTINI, M. C. A. Theoretical optical properties of composite metal-NiO films [doi:10.1088/0022-3727/36/19/012]. Journal of Physics. D, Applied Physics [online], 2003, vol. 36, nº 19, p. 2386-2392.
  • HADDAD, P. S., et al. Gold-Nickel Hydroxide Multi-Layers with Selective Absorption in the Visible Range [doi:10.1023/b:jsst.0000039503.67720.2c]. Journal of Sol-Gel Science and Technology [online], 2004, vol. 30, nº 3, p. 179-185.
  • LOPES, L. B., et al. Reverse Hexagonal Phase Nanodispersion of Monoolein and Oleic Acid for Topical Delivery of Peptides: in Vitro and in Vivo Skin Penetration of Cyclosporin A [doi:10.1007/s11095-006-0143-7]. Pharmaceutical Research [online], 2006, vol. 23, p. 1332-1342.
  • PEREIRA, A. C., et al. Characterization of Electrochemically Co-deposited Metal−Molybdenum Oxide Films [doi:10.1021/cm040125t]. Chemistry of Materials [online], 2004, vol. 16, nº 13, p. 2662-2668.
  • URBANO, A., et al. Electrochromism in lithiated nickel oxide films deposited rf sputtering. Electrochimica Acta, 2001, vol. 46, p. 2269-2273.
  • FANTINI, M. C. A., FERREIRA, F. F., and GORENSTEIN, A. THEORETICAL TRANSMITTANCE OF COMPOSITE Au-NiOx AND Au-CoOx. In International Meeting on Electrochromism (IME4), 2000. Proceedings of the International Meeting on Electrochromism (IME4)., 2000. Abstract.
  • FERREIRA, F. F., et al. Composite Au-NiO films. In 5th International Meeting on Electrochromism (IME-5), GOLDEN, COLORADO, 2002. SOLID STATE IONICS., 2003.
  • FERREIRA, F. F., and FANTINI, M. C. A. Multi-layered composite Au-NiOx electrochromic films. In 14th International Solid State Ionics Conference, Monterey, California, USA, 2003. Solid State Ionics., 2003.
  • FERREIRA, F. F., FANTINI, M. C. A., and GORENSTEIN, A. ELECTROCHROMIC Au-NiOx THIN FILMS. In International Meeting on Electrochromism (IME4), 2000. Proceedings of the International Meeting on Electrochromism (IME4)., 2000. Abstract.
  • FERREIRA, F. F., FANTINI, M. C. A., and GORENSTEIN, A. Theoretical and experimental results on Au:NiO and Au:CoO electrochromic. In International Conference on Solid State Ionics - SSI 2001, Cairns, 2001. Solid State Ionics., 2002. Abstract.
  • HADDAD, P. S., et al. Chemical route and SAXS measurements to control gold nanoparticles size in nickel oxide/hydroxide films. In International Conference on Small Angle X-ray Scattering, Veneza, 2002. Proceedings SAS2002., 2002. Abstract.
  • URBANO, A., et al. ELECTROCHROMISM IN LIXNIOY THIN FILMS DEPOSITED RF SPUTTERING. In International Meeting on Electrochromism (IME4), 2000. Proceedings of the International Meeting on Electrochromism (IME4)., 2000. Abstract.
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