【公開日：2024.07.25】【最終更新日：2024.05.13】

課題データ / Project Data

課題番号 / Project Issue Number

23NM5289

利用課題名 / Title

Visible photoconductivity response based on hexamolybdenum clusters integrated 3D inverse opal photonic crystal

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,蒸着・成膜/ Vapor deposition/film formation,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

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-503：200kV電界放出形透過電子顕微鏡（JEM-2100F1）
NM-648：FE-SEM+EDX [SU8000]
NM-627：イオンスパッタ [E-1045]
NM-641：スパッタ装置 [CFS-4EP-LL #2]
NM-647：FE-SEM+EDX [S-4800]

報告書データ / Report

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

In a dynamic of exploring new potential sensitizers, metal atom clusters were introduced as light-harvesting material for energy conversing applications due to high photostability, low cost, and feasible synthesis. Here, a different face-capped [(Mo₆Xⁱ₈)L^a₆]^-2 cluster (Xⁱ = halogen, L^a = halogen, functional groups, H₂O, etc.) family with a unique electron structure has been introduced as a broadly visible light absorber and large Stoke shift. Recently, a general study revealed the efficiency of the Mo₆ cluster as an absorber resulting in a performance efficiency of 0.44 % because the iodide apical groups limit the charge transfer inside the solar cell. The lack of knowledge of the photophysical and photoelectrochemical behavior of the metal cluster in optoelectronic devices obstructs the improvement of performance efficiency. The ARIM system can supply types of equipment for characterizing the photophysical and photoelectrochemical properties of the metal cluster for energy-related applicability.

実験 / Experimental

Morphology characterization: SEM, TEM, XPS, XRD, 3D microscopy, Dynamic Light Scattering, etc.Optical characterizations: UV-Vis Spectroscopy, Photoluminescence Spectroscopy, FT-IR Spectroscopy, Raman Spectroscopy, Photoluminescence lifetime decay, etc.Optoelectronic properties: Electrical Impedance Spectroscopy, solar cell efficiency measurements, etc.

結果と考察 / Results and Discussion

Achievement 1/ The optical properties of the atom cluster are tunable with electron and ionic conductivities of proton metallic phosphate conductors (MP₂O₇; M = Sn, Al, Mg, In, etc.) for photodetector application. A hexamolybdenum cluster compound (denoted as the Mo₆ cluster) was successfully functionalized on a tin pyrophosphate semiconductor (SnP₂O₇) integrated within an inverse opal photonic crystal to understand the tunable light absorption and electronic conduction properties. The size of the periodical pores, surface modification, and chemical composition of the infiltration material of the inverse opal film have been investigated to control the photonic bandgap in the visible range and the efficiency of the deposited Mo₆ cluster. The photoactive Mo₆ clusters act as a visible light harvester and generate an efficient photo-induced current upon light absorption that is enhanced by a slow photon effect occurring at the photonic stopband edges. Specific attention focused on the role of humidity and temperature regarding the reproducibility of the experiments and the photosensitivity of the nanocomposite. The suitable tunable photo-induced conduction property in organic-inorganic materials opens a new opportunity for the applicability of cluster-based compounds in visible optoelectronic devices. Reference had been published as“Thi Kim Ngan Nguyen et. al., Materials Today Chemistry. 27, 101351, 2022. Achievement 2/ A different face-capped [(Mo₆Xⁱ₈)L^a₆]^-2 cluster (Xⁱ = halogen, L^a = halogen, functional groups, H₂O, etc.) family with a unique electron structure has been introduced as a broadly visible light absorber and large Stoke shift for light-harvesting material in Metal Cluster-Sensitized Solar Cells (MCSSCs). For the first time, a functionalization of (^-OSO₂-C₁₀H₆-SO₃^-) aromatic sulfonate ligand (NS) which supports the delocalization of photoexcited electrons on the Mo₆ cluster and is beneficial for charge transfer in MCSSCs was studied. NS played a vital role in stabilizing the cluster in the redox mediator, increasing the distribution of the Mo₆-based photosensitizers in TiO₂, increasing the radiative de-excitation process as photoluminescence emission, and improving the charge transfer process in the redox mediator. Photovoltaic investigations can point out interesting information: i) NS can enhance photocurrent J_sc and fill factor that comes from the improvement of the electron transport by inducing band bending, and ii) control of the concentration of NS to obtain suitable emission lifetime for the {Mo₆Iⁱ₈}⁴⁺ core that accumulates the photocurrent. A deep understanding of photophysical and photoelectrical behaviors was the original step in targeting the improvement of the efficiency of photovoltaic devices based on octahedral transition metal clusters. The research result was submitted with the title Effect of Aromatic Sulfonate Ligand on the Photovoltaic Performance of Molybdenum Cluster-Sensitized Solar Cell (under revision).

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)

These studies were carried out under the continued financial support of the International Center for Young Scientists (ICYS-Sengen), NIMS, and the France-Japan International Collaboration Framework (IRL3629 LINK, ANR-22-CE09-0015). This study was supported by "Advanced Research Infrastructure for Materials and Nanotechnology in Japan (ARIM)" of the Ministry of Education, Culture, Sports, Science and Technology (MEXT); Proposal Number 23NM5289. https://doi.org/10.1016/j.mtchem.2022.101351 NGUYEN, Thi Kim Ngan, GRASSET Fabien, Stéphane Cordier, Noée Dumait, UCHIKOSHI, Tetsuo. "Zn-Al Layered Double Hydroxide Film Functionalized by Luminescent Octahedral Molybdenum Cluster: Ultraviolet-Visible Photoconductivity Response."The 7th International Conference on the Characterization and Control of Interfaces for High Quality Advanced Materials (ICCCI2022), Fujiyoshida, Japan, 15-18th November, 2022, oral.
DOI（Publication and Proceedings）：https://doi.org/10.1016/j.mtchem.2022.101351,https://doi.org/10.1080/14686996.2022.2119101,ICCCI2022

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)

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