【公開日：2025.06.10】【最終更新日：2025.03.24】
課題データ / Project Data
課題番号 / Project Issue Number
24AT0278
利用課題名 / Title
Hybrid halide semiconductors for optoelectronic applications
利用した実施機関 / Support Institute
産業技術総合研究所 / AIST
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）加工・デバイスプロセス/Nanofabrication（副 / Sub）計測・分析/Advanced Characterization
【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,太陽電池/ Solar cell,原子層薄膜/ Atomic layer thin film,スパッタリング/ Sputtering
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)
Turkevych Ivan
所属名 / Affiliation
国立研究開発法人産業技術総合研究所
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
鬼澤 敦子
利用形態 / Support Type
（主 / Main）機器利用/Equipment Utilization（副 / Sub）-
利用した主な設備 / Equipment Used in This Project
AT-025：スパッタ成膜装置(芝浦）
AT-004：電界放出形走査電子顕微鏡[S4800_FE-SEM]
報告書データ / Report
概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)
The rapid rise of power conversion efficiencies (PCE) of solar cells based on Pb hybrid perovskites with the general formula APbX3 (A=Cs, CH3NH3, H2NCHNH2, X=Br, I) from 3.8% to over 25% within a decade has made them superstars in photovoltaic community. Strong expectations are being placed on hybrid perovskite LEDs and X-ray detectors. At the same time, hybrid halides based on other transition metals are poorly explored. The aim of this project was to fabricate thin films of different transition metals (Zn, Ni, V, Nb, W, Mo, Ag, Cu, Bi, etc.), convert them to hybrid halides by using polyiodide-assisted method [Turkevych et.al., Nat. Nanotech 14, 57, 2019] and study their structural and optoelectronic properties.
実験 / Experimental
For the fabrication of thin films of various hybrid halides thin films of different metals (Sn, Ti, Zr, Nb, W, Bi, Bi/Ag and Bi/Cu) were deposited by r.f. sputtering or thermal evaporation on glass substrates. The polyiodide-assisted and iodination treatments were conducted by spin-coating of 0.5M MAI3 solution in isopropyl-alcohol (IPA) over the thin metal film and by annealing in iodine vapor at 30 ℃, respectively. A different synthetic route for the fabrication of ZrNI thin films started from the fabrication of ZrH2 thin films on fused silica substrates by using a custom built r.f. magnetron sputtering system and their subsequent conversion into ZrNI by annealing with NH4I at 600 ℃ in a quartz reactor under a constant flow of NH3 gas. Properties of the obtained thin films were studied by SEM, absorption spectroscopy and XRD.
結果と考察 / Results and Discussion
The conversion of metal thin films into corresponding semiconducting halides using a polyiodide-assisted or iodination approach has been demonstrated to be effective for pure Bi and Ag0.5Bi0.5 and Cu0.5Bi0.5 thin films. These methods yielded MA3Bi2I9 iodobismuthate (with an indirect bandgap of 1.96 eV), AgBiI4 and CuBiI4 rudorffites with direct bandgaps in the range of 1.83-1.84 eV, respectively. Conversion experiments using the polyiodide-assisted method were also carried out on thin films of Sn, Ti, Zr, Nb, and W. Under standard conditions, no substantial reaction was observed between these metals and spin-coated MAI3 polyiodide layers mostly due to formation of surface oxide layers upon contact of freshly deposited metal films with atmosphere. As for the ZrNI thin films fabricated by the different synthetic route, the XRD pattern confirmed the formation of a pure α-ZrNI phase, with no evidence of residual ZrH2, indicating complete conversion. The optical absorption spectrum revealed a direct bandgap of 2.04 eV for ZrNI, in excellent agreement with previous experimental and theoretical studies. The fabrication of thin films of the pure α-ZrNI phase has never been reported before and the future research will focus on development of a single-step deposition process using reactive r.f. magnetron sputtering with Zr and Ti targets in an N2 + I2 atmosphere to fabricate mixed ZrXTi1-XNI thin films with tunable bandgaps for integration into heterojunction solar cells.
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)
This work was partially supported by JSPS KAKENHI Grant No. 21K05250
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.
- Ivan Turkevych, "Synthesis Approaches for TiNX–ZrNX (X = Cl, Br, I) Semiconductors with Tunable Bandgaps for Pb-Free Optoelectronic Applications", Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP25), January 20-21, 2025, P051.
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