【公開日：2025.06.10】【最終更新日：2025.05.12】

課題データ / Project Data

課題番号 / Project Issue Number

24NM5061

利用課題名 / Title

3D inverse opal inorganic film incorporated metal atom cluster for photocatalysis and optoelectronic devices

利用した実施機関 / Support Institute

物質・材料研究機構 / NIMS

機関外・機関内の利用 / External or Internal Use

内部利用（ARIM事業参画者以外）/Internal Use (by non ARIM members)

技術領域 / Technology Area

【横断技術領域 / Cross-Technology Area】（主 / Main）計測・分析/Advanced Characterization（副 / Sub）加工・デバイスプロセス/Nanofabrication

【重要技術領域 / Important Technology Area】（主 / Main）革新的なエネルギー変換を可能とするマテリアル/Materials enabling innovative energy conversion（副 / Sub）次世代ナノスケールマテリアル/Next-generation nanoscale materials

キーワード / Keywords

電子顕微鏡/ Electronic microscope,走査プローブ顕微鏡/ Scanning probe microscope,光学顕微鏡/ Optical microscope,赤外・可視・紫外分光/ Infrared/visible/ultraviolet spectroscopy,X線回折/ X-ray diffraction,電子分光/ Electron spectroscopy,スパッタリング/ Sputtering,太陽電池/ Solar cell,電極材料/ Electrode material,環境発電/ Energy Harvesting,ナノ粒子/ Nanoparticles,ナノ多孔体/ Nanoporuous material,メソポーラス材料/ Mesoporous material

利用者と利用形態 / User and Support Type

利用者名（課題申請者）/ User Name (Project Applicant)

グェン ティ キム ンガン(NGUYEN Thi Kim Ngan)

所属名 / Affiliation

物質・材料研究機構

共同利用者氏名 / Names of Collaborators in Other Institutes Than Hub and Spoke Institutes

ARIM実施機関支援担当者 / Names of Collaborators in The Hub and Spoke Institutes

利用形態 / Support Type

（主 / Main）機器利用/Equipment Utilization（副 / Sub）,技術補助/Technical Assistance

利用した主な設備 / Equipment Used in This Project

NM-220：紫外可視近赤外分光計（V-770）
NM-221：分光蛍光光度計（FP-8500DS）
NM-225：X線光電子分光分析装置（XPS-Quantera SXM）
NM-648：FE-SEM+EDX [SU8000]
NM-503：200kV電界放出形透過電子顕微鏡（JEM-2100F1）

報告書データ / Report

概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)

Today, the strategy of sustainable solar-driven research has been expanded on light-absorbing material characteristics and device technologies, aiming to utilize abundant, renewable, and green energy sources from solar light and enlarge scale in the practical industry. In this project, I have focused on optimizing light-absorption and energy-transferring efficiency of photosensitized heterogeneous semiconductors by applying chemical modifications and physical designs (1 or 3-dimensional (3D) photonic crystals). For the strategy concerning physical design, 1-3D artificial photonic crystal structures with beneficial photon management have attracted interest due to the delocalization of the light direction for enhancing the emitted or reflected light intensity. However, the scalability, mechanical stability, and reusability of previously researched materials have still inhibited for utilization of these materials at large scale. To address these disadvantages, I have successfully developed a new approach to fabricate 3D-porous semiconductor inverse opal films with high reproducibility, chemical stability, and large periodic area. The 3D porous inverse opal (IO) structure was fabricated from opal template film which was fabricated by optimized electrophoretic deposition process (1 min under applying a bias of 10V) coupled with thermal treatments. The 3D porous skeleton will be a potential strategy for immobilizing the photoactive materials, increasing specific areas, and favoring the light confinement phenomenon due to an efficient slow photon effect. Simultaneously, chemical modifications on the interfacial nanostructure of photosensitized octahedral molybdenum nanoclusters or plasmonic silver nanoparticles to improve the efficiency of charge transfer in redox reactions on the surface and restrict the charge carrier recombination rate have been investigated.

実験 / Experimental

The main objective of this project is to enhance tunable optical and electronic properties of metal clusters or nanoparticles integrated into 1D or 3D structured semiconductors for photocatalysis properties. Microstructure and structural analysis (TEM, SEM-EDX, XRD), chemical composition and bonding (FT-IR, XPS, EDS/EDX), and optical properties and spectroscopy (UV-Vis, Photoluminescence) were performed to optimize 3D porous CuO-TiO ₂ and Ag-immobilized TiO ₂ inverse opal structure, aiming to enhance photocatalytic efficiency for pollutant photodegradation.

結果と考察 / Results and Discussion

Plasmonic silver decorated TiO₂ inverse opal has shown an interesting potential for photocatalysis due to its physically tunable optical absorbance, highly active area, and flexible fabrication. In this study, electrophoretic deposition is used as a key technique to overcome the disadvantages of traditional inverse opal (IO)-fabricating methods, resulting in high reproducibility, chemical stability, and periodic area. The use of the IO structural engineering, beneficially delocalizing and enhancing the absorbed visible light accounted for 46% of total solar light, leads to the enhancement of the localized surface plasmonic resonance (LSPR) hot electrons of the Ag NPs and enhanced local electromagnetic (EM) field for the formation of photogenerated electrons on TiO₂. These enhancements in the Ag-deposited TiO₂ IO promoted the excellent photocatalytic kinetic constant of methylene blue degradation around 17.10^-3 min^-1, responding to tunable optical absorption at the stopband edge of TiO₂ IO containing 288-nm sized pores and low absorbance of Ag in the overlapped band. The explanation of the enhanced photocatalytic mechanism was studied on a high Ag deposition density, decrease of the photocurrent, increase of electron lifetime in electrolytes, and contribution of slow photon effect on these characteristics. The proposed photocatalysis mechanism concerned the enhancement of EM-generated electrons on TiO₂ that immigrate to the Ag surface for photoreduction while photooxidation occurred at the TiO₂ surface by the holes. The study provides an interesting strategy to improve the photocatalysis of semiconductor-metal composite systems.

図・表・数式 / Figures, Tables and Equations

その他・特記事項（参考文献・謝辞等） / Remarks(References and Acknowledgements)

成果発表・成果利用 / Publication and Patents

論文・プロシーディング（DOIのあるもの） / DOI (Publication and Proceedings)

1. Thi Kim Ngan Nguyen, Tunable slow photon effect and local surface plasmon in Ag-immobilized TiO₂ inverse opal films for enhancing pollutant photodegradation, Materials Advances, 5, 8615-8628(2024).
   DOI: 10.1039/D4MA00807C
   
2. Thi Kim Ngan Nguyen, Enhanced photoluminescence of hexamolybdenum cluster by anodic aluminum oxide photonic crystals, Materials Letters, 361, 136144(2024).
   DOI: 10.1016/j.matlet.2024.136144
   

口頭発表、ポスター発表および、その他の論文 / Oral Presentations etc.

特許 / Patents

特許出願件数 / Number of Patent Applications：0件
特許登録件数 / Number of Registered Patents：0件