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Synthesis of Anatase (Core)/Rutile (Shell) Nanostructured TiO <sub/>2</sub> Thin Films by Magnetron Sputtering Methods for Dye-Sensitized Solar Cell Applications

DOI:10.1021/acsaem.9b01910 期刊:ACS Applied Energy Materials 出版年份:2019 更新时间:2025-09-12 10:27:22
摘要: Currently, anatase/rutile core/shell structures are accepted as highly efficient building blocks for TiO2-based catalysts or photo-electrodes used in dye-sensitized solar cells (DSSCs). It is understood that a thin layer of rutile covering the core anatase pillar would improve the performance of DSSCs by retarding the charge recombination at the semiconductor/sensitizer/electrolyte interfaces. In this work, we report on the synthesis of core/shell nanostructured TiO2 thin films using reactive magnetron sputtering at a glancing angle with different power applying modes: well-separated pillars of pure anatase were synthesized using the DC mode, and then, high-pulse peak power was applied to the Ti target (high power impulse magnetron sputtering – HiPIMS) resulting in the covering of the anatase columns with a thin layer of rutile. The latter technique is well-known to increase the energy load during the growth of the film which is a key parameter to successfully obtain the TiO2 phase normally only achieved at high temperature, i.e. rutile. The peak current, the frequency and the pulse width were optimized in order to obtain the desired crystalline structure and thickness of the rutile top layer. Scanning Electron Microscopy (SEM) cross-section views of the synthesized films clearly show that the pillar-like structures are not affected by the energetic species striking the surface during the HiPIMS process. Grazing Incidence X-Ray Diffraction (GIXRD) suggests the presence of both anatase and rutile phases in the films. Further characterization of the anatase/rutile core/shell interface by electron transmission techniques such as Transmission Electron Microscopy (TEM) and Electron Energy Loss Spectroscopy (EELS) mapping confirm the hypothesis and reveal that the anatase pillars are partly covered by a rutile crust.
作者: Adriano Panepinto,Matthieu Michiels,Michael Dürrschnabel,Leopoldo Molina-Luna,Carla Bittencourt,Pierre-Antoine Cormier,Rony Snyders
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To synthesize anatase(core)/rutile(shell) nanostructured TiO2 thin films for dye-sensitized solar cell applications, aiming to improve the performance of DSSCs by retarding the charge recombination at the semiconductor/sensitizer/electrolyte interfaces.

The study successfully synthesized anatase(core)/rutile(shell) nano-pillars TiO2 thin films using a two-step strategy. The results demonstrated that the top of the pillars are fully covered with a rutile layer, while the covering of the middle edges is not completely conformational. The deposition time of the rutile shell layer was found to be critical for maintaining the open porosity of the thin films.

The deposition time of the rutile shell layer in HiPIMS regime is critical and should be monitored to avoid the merging of the nano-pillars, leading to the loss of the open porosity of the thin films.

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