• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2271-2275
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• 2013

We report on the photoelectrochemical properties of partially reduced mesoporous titania thin films. The fabrication is achieved by synthesizing mesoporous titania thin films through the self-assembly of a titania precursor and a block copolymer, followed by aging and calcination, and heat-treatment under a $H_2$ (1 torr) environment. Depending on the temperature used for the reaction with $H_2$, the degree of the reduction (generation of oxygen vacancies) of the titania is controlled. The oxygen vacancies induce visible light absorption, and decrease of resistance while the mesoporosity is practically unaltered. The photoelectrochemical activity data on these films, by measuring their photocurrent-potential behavior in 1 M NaOH electrolyte under AM 1.5G 100 mW $cm^{-2}$ illumination, show that the three effects of the oxygen vacancies contribute to the enhancement of the photoelectrochemical properties of the mesoporous titania thin films. The results show that these oxygen deficient $TiO_2$ mesoporous thin films hold great promise for a solar hydrogen generation. Suggestions for the materials design for improved photoelectrochemical properties are made.

• Korean Chemical Engineering Research
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• 제44권4호
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• pp.399-403
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• 2006

현재 넓은 표면적과 메조기공 뿐만 아니라 $TiO_2$의 넓은 band gap과 그 광학 활성 등으로 인하여 크게 각광받고 있는 메조포러스 $TiO_2$ 박막을 합성하기 위해 여러 가지 합성방법이 제시되고 있으나, 그 합성이 습도나 온도 등의 여러조건에 따라 크게 영향을 받아 재현성이 떨어진다는 치명적인 문제점이 제기되어 왔다. 이는 합성 용액 내에서 $TiO_2$ 전구체가 가수분해 및 축합반응을 하면서 구조유도체와의 자기조립에 의한 나노구조물 형성하는 과정에서 $TiO_2$의 전구체가 온도나 습도 등 주변의 영향을 많이 받기 때문이다. 본 연구에서는 2차원 구조의 메조기공을 가진 $TiO_2$ 박막을 재현성 있게 얻을 수 있는 실험 조건을 찾고자 하였다. 이를 위해 촉매인 HCl과 $TiO_2$ 전구체의 몰비 그리고 $TiO_2$ 전구체와 P-123의 몰비 등의 합성 조건뿐 아니라 코팅과정 도중이나 이후의 습도와 온도가 미치는 영향에 대한 실험을 수행하였고 그 특성을 XRD와 TEM 등으로 분석하였다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.8.1-8.1
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• 2011

Nanocrystalline titanium dioxide ($TiO_2$) materials have been widely used as an electron collector in DSSC. This is required to have an extremely high porosity and surface area such that the dye can be sufficiently adsorbed and be electronically interconnected, resulting in the generation of a high photocurrent within cells. In particular, their geometrical structures and crystalline phase have been extensively investigated as important issues in improving its photovoltaic efficiency. In this study, we present a new strategy to fabricate a photoelectrode having a periodic structured $TiO_2$ film templated from 1D or 3D polystyrene (PS) microspheres array. Monodisperse PS spheres of various radiuses were used for colloidal array on FTO glasses and two types of photoelectrode structures with different $TiO_2$ materials were investigated respectively. One is the igloo-shaped electrode prepared by $TiO_2$ deposition by RF-sputtering onto 2D microsphere-templated substrates. At the interface between the film and substrate, there are voids formed by the decomposition of PS microspheres during the calcination step. These holes might be expected to play the predominant roles as scattering spherical voids to promote a light harvesting effect, a spacious structure for electrolytes with higher viscosity and effective paths for electron transfer. Additionally the nanocrystalline $TiO_2$ phase prepared by the RF-sputtering method was previously reported to improve the electron drift mobility within $TiO_2$ electrodes. This yields solar cells with a cell efficiency of 2.45% or more at AM 1.5 illumination, which is a very remarkable result, considering its $TiO_2$ electrode thickness (<2 ${\mu}m$). This study can be expanded to obtain higher cell efficiency by higher dye loading through the increase of surface area or multi-layered stacking. The other is the inverse opal photonic crystal electrode prepared by titania particles infusion within 3D colloidal arrays. To obtain the enlargement of ordered area and high quality of crystallinity, the synthesis of titania particles coated with a organic thin layer were applied instead of sol-gel process using the $TiO_2$ precursors. They were dispersed so well in most solvents without aggregates and infused successfully within colloidal array structures. This ordered mesoporous structure provides the large surface area leading to the enough adsorption of dye molecules and have an light harvesting effect due to the photonic band gap properties (back-and-forth reflection effects within structures). A major advantage of this colloidal array template method is that the pore size and its distribution within $TiO_2$ photoelectrodes are determined by those of latex beads, which can be controlled easily. These materials may have promising potentials for future applications of membrane, sensor and so on as well as solar cells.