Fabrication and characterization of TiO2 thin film prepared by a layer-by-layer self-assembly method

Kim, Jin Ho; Fujita, Shiro; Shiratori, Seimei

doi:10.1016/j.tsf.2005.07.001

Cited by 55 publications

(30 citation statements)

References 26 publications

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“…3. Well-dispersed and homogeneous TiO2 nanoparticle thin films were obtained by the spray LbL method, in a similar manner as the conventional LbL method reported by Kim et al 19) The good dispersion and homogeneity in the films (even for a short processing time) are attributable to the narrow particle-size distribution and homogeneous dispersion of spherical-like TiO2 nanoparticles in the spray suspension, which facilitated the rearrangement of the nanoparticles on the substrate.…”

Section: )12)supporting

confidence: 63%

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Preparation and microstructure of titanate nanowire thin films by spray Layer-by-Layer assembly method

Suzuki

Pichon

D’Elia

et al. 2009

J. Ceram. Soc. Japan

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Hydrogen titanate nanowires were prepared by hydrothermal method in 10 M NaOH followed by ion-exchanging process. Titanate nanowire thin films were successfully obtained by spray Layer-by-Layer (spray LbL) method within a short time. Due to the good dispersion state of the nanowires in an aqueous suspension and their linear morphology, titanate nanowires effectively adsorbed on the glass substrate. As a reference, TiO2-anatase nanoparticle thin films were also prepared by spray LbL method.©2009 The Ceramic Society of Japan. All rights reserved.Key-words : Layer-by-Layer (LbL) method, Titanate nanowire, Thin film, Spray technique, TALH, Hydrothermal synthesis, Hightemperature X-ray diffraction (HT-XRD), Self assembly [Received November 17, 2008; Accepted January 15, 2009] Titanate and titania one-dimensional (1D) nanomaterials obtained by the hydrothermal method have attracted much attention since the innovative works by Kasuga et al. in 1998Kasuga et al. in -1999 1),2) Titanate nanowires, with typically 10-50 nm in diameter and 300-10000 nm (or more) in length, can be also prepared by hydrothermal method similarly to titanate nanotubes, but at slightly higher temperatures (~150-170°C, whereas typically ~110-130°C for nanotubes) and/or within stronger basic conditions (in 10 M KOH or 15 M NaOH, whereas typically 10 M NaOH for nanotubes).3),4) At higher hydrothermal temperatures and/or stronger basic (corrosive) conditions, nanosheet-like intermediate (which form scrolled nanotubes) 1),2) cannot exist stably, and hence, intrinsic one-dimensional oriented crystal growth of layered titanates becomes preferential. Titanate nanowires can be further converted into TiO2 (B) (a tunnelstructured TiO2 polymorph related to a bronze structure, NaxTiO2) nanowires or TiO2 anatase nanowires by ion-exchanging and post-heat treatment.3),5) The formation of titanate nanowires can be recognized as the "downsizing" of titanate microfibers, which were reported by Watanabe et al. in late 1970's. 6)-8)These titanate and TiO2 nanowires generally have smaller specific surface area than titanate nanotubes: e.g., ~150 m 2 /g for hydrogen titanate nanowires, 30-80 m 2 /g for TiO2 nanowires and ~300 m 2 /g for hydrogen titanate nanotubes. However, the nanowires have higher crystallinity (i.e., less defects) and higher thermal stability of 1D nanostructure. Hence, the titanate and TiO2 nanowires are suitable for photo-electro conversion applications, such as dye-sensitized solar cells (DSC) 9)-11) and photo-catalysts. 12) Our recent study revealed that TiO2 nanowires (obtained from the post-heat treatment of hydrogen titanate nanowires) showed much better hydrogen production ability due to their higher crystalinity. 12) In order to extend the application fields of these nanowires and other 1D nanomaterials, e.g. for electrodes, sensors, heterogeneous catalysts and so on, thin-film processing technologies must be established. In general, thin-film processing technologies tend to be required as rapid, precise (in nanometer order thickness), ...

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Section: )12)supporting

confidence: 63%

“…19) Hydrophilic, negatively charged glass substrates were obtained by 1 wt% KOH aq. treatment for 5 min and then rinsed with Milli-Q water (hereinafter, water).…”

Section: Jcs-japanmentioning

confidence: 99%

Preparation and microstructure of titanate nanowire thin films by spray Layer-by-Layer assembly method

Suzuki

Pichon

D’Elia

et al. 2009

J. Ceram. Soc. Japan

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“…With the increasing thickness of the film, larger TiO 2 crystallites were observed in the film, and hence the TiO 2 film had a greater roughness, whereas the absorption edge is red shifted. Therefore, as previously reported, an increase in the crystallite diameter, the thickness increment and the higher roughness of the TiO 2 films could be responsible for the red shift of the absorptionmaxima peak position as the number of PE bilayers in the organic template is increased from 7 to 17 [41][42].…”

Section: Figure 13 Uv-vis Absorption Spectra Of Tio 2 Films Fabricatsupporting

confidence: 60%

“…The extrapolated values of the band-gap energies in Figure 52 also show a decrease in the band-gap energy for the directly allowed transitions from 3.47eV to 3.25 eV as the TiO 2 film thickness is increased from 45 to 130 nm. Since a similar trend of decreasing the band-gap energy with increasing the PEM template thickness is observed in the case of direct and indirect transitions, due to the quantum-confinement effect, the blue-shift of the band-gap energy indicates an increase in the TiO 2 crystallite size with the increasing TiO 2 film thickness [41]. Since the average crystallite diameter about 10 nm in the TiO 2 film formed in the template of 17 PE bilayers is observed, the increase in the band-gap energy with decreasing the film thickness points to a decrease in the crystallite size below 10 nm as the TiO 2 films are formed in the templates composed of lower number of PE bilayers.…”

Section: Figure 13 Uv-vis Absorption Spectra Of Tio 2 Films Fabricatmentioning

confidence: 52%

Polyelectrolyte Multilayer Template Assisted in-Situ Synthesis of the Inorganic Nanostructures

Logar¹,

Jančar²,

Rečnik³

et al. 2010

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Apstract:Multilayers formed from weak polyions of polyallylamine (PAH) and polyacrylic acid (PAA), possessing ion-exchangeable carboxylic groups were used to bind the metal cations within the film. By subsequent wet chemical reaction process of the incorporated metal ions, pure zinc sulfide (ZnS) with a narrow size distribution was formed within the PEMs. The size and concentration of the inorganic nanoparticles in polyion matrix were controlled by the concentration of metal -binding carboxylic acid groups as determined by the multilayer assembly pH. Furthermore, the metal cation loading and reaction methodology could be repeatedly cycled to increase the size and volume density of the nanoparticles. Furthermore, the polyelectrolyte multilayer films were used as templates for the ceramic (TiO 2 ) thin film fabrication with a modified sol-gel reaction. Since the multilayer assembly is performed from the polyion aqueous solutions, the multilayers contain some water that, after infiltration of the organometallic precursor, enables in-situ reaction of hydrolysis and condensation reaction. After calcination, nanocrystalline TiO 2 thin films with thickness, controllable by the number of the polyion layers in the matrix, were formed. With the in-situ synthesis approach of inorganic nanstructures in polyelectrolyte multilayer matrix, the ability of obtaining the control over the film thickness and size of the inorganic particles has enabled the tuning of the optical properties of as fabricated inorganic-organic composite films, as well as nanocrystalline ceramic films.

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“…The spray LbL method in this study was the same as that in our previous study [11], which was based on the report by Kim et al on a conventional LbL method for colloidal TiO 2 [12]. Hydrophilic, negatively charged glass substrates were obtained by 1 wt% KOH aq.…”

Section: Spray-lbl Methodsmentioning

confidence: 99%

Preparation and Microstructure of Titanate Nanotube Thin Films by Spray Layer-by-Layer Assembly Method

Suzuki

Pichon

Grandcolas

et al. 2009

Trans. Mat. Res. Soc. Japan

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Titanate nanotubes prepared by a hydrothermal process in an alkali solution are promising for environmental and energy applications. A serious (but not-widely-recognized) problem of titanate nanotubes for potential device applications is their strong agglomeration (or even aggregation), which disturb thin-film processing in nanometer order thickness. The objective of this study is to demonstrate how the agglomerates/aggregates behave in an actual wet thin-film process, i.e., spray Layer-by-Layer (spray LbL) coating process. Under acidic (pH=2) and stirred conditions, apparently-dispersed titanate nanotube suspension actually contained plenty of micrometer-sized agglomerates/aggregates. The formation of the large agglomerates/aggregates disturbs the spray LbL process, suggesting an alternative dispersion method is necessary for wet processes of titanate nanotubes.

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Fabrication and characterization of TiO2 thin film prepared by a layer-by-layer self-assembly method

Cited by 55 publications

References 26 publications

Preparation and microstructure of titanate nanowire thin films by spray Layer-by-Layer assembly method

Preparation and microstructure of titanate nanowire thin films by spray Layer-by-Layer assembly method

Polyelectrolyte Multilayer Template Assisted in-Situ Synthesis of the Inorganic Nanostructures

Preparation and Microstructure of Titanate Nanotube Thin Films by Spray Layer-by-Layer Assembly Method

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