Large reverse saturable absorption at sunlight power level using ultralong lifetime of triplet excitons

• Project/Area Number: 26708010
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Functional solid state chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Hirata Shuzo 東京工業大学, 物質理工学院, 助教 (20552227)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2016: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2015: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2014: ¥16,510,000 (Direct Cost: ¥12,700,000、Indirect Cost: ¥3,810,000)
• Keywords: 三重項 / 非線形吸収 / 逆過飽和吸収 / 光制限効果 / オプティカルリミット / 室温りん光 / 多段階励起 / ステロイド / 励起三重項 / 三重項励起子 / 非制限効果 / 非線形光学 / 過飽和吸収 / 長寿命励起子 / 三重項三重項消滅 / 非コヒーレント光 / りん光 / 重水素化 / フォトクロミック材料

Outline of Final Research Achievements

Large reverse saturable absorption (RSA) at sunlight power level was observed from a host-guest amorphous material composed of d12-coronene as a guest and β-estradiol as a rigid amorphous host. Large highly symmetric two dimensional (2D) aromatic structure of d12-coronene doped into the rigid host causes ultralong triplet lifetime as well as high triplet yield, serving efficient accumulation of the triplet excitons of d12-coronene under weak excitation light. The high absorption coefficient of the triplet state (σ34) compared with that of the ground state (σ01) for d12-coronene is also caused by the highly symmetric 2D aromatic structure. The efficient accumulation of the triplet excitons and high σ34/σ01 led to an onset of the RSA characteristics under irradiance below 10-1 mW cm-2. An film of the amorphous material showed a large decrease of transmittance from 66% at 0.02 mW cm-2 to 24% at 50 mW cm-2 for continuous light at 405 nm.

Research Products

• [Journal Article] Recent advances in materials with room temperature phosphorescence: Photophysics for triplet exciton stabilization (2017)
  • Author(s): Ｓhuzo Hirata
  • Journal Title: Advanced Optical Materials Volume: 印刷中 Issue: 17 Pages: 1700116-1700116
  • DOI: 10.1002/adom.201700116
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] White Afterglow Room-Temperature Emission from an Isolated Single Aromatic Unit under Ambient Condition (2017)
  • Author(s): S. Hirata, M. Vacha
  • Journal Title: Adv. Opt. Mater. Volume: 5 Issue: 5 Pages: 1600996-1600996
  • DOI: 10.1002/adom.201600996
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Organic Light-Emitting Diodes: High-throughput virtual screening (2016)
  • Author(s): Shuzo Hirata, Katsuyuki Shizu
  • Journal Title: Nature Materials Volume: 15 Issue: 10 Pages: 1056-1057
  • DOI: 10.1038/nmat4750
  • Peer Reviewed
• [Journal Article] Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air (2016)
  • Author(s): S. Hirata, M. Vacha
  • Journal Title: J. Phys. Chem. Lett. Volume: 8 Issue: 8 Pages: 1539-1545
  • DOI: 10.1021/acs.jpclett.6b00554
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Large Transmittance Change Induced by Exciton Accumulation under Weak Continuous Photoexcitation (2016)
  • Author(s): S. Hirata, M. Vacha
  • Journal Title: Adv. Opt. Mater. Volume: 4 Issue: 2 Pages: 297-305
  • DOI: 10.1002/adom.201500378
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photoreversible On-off Recording of Persistent Room-temperature Phosphorescence (2015)
  • Author(s): Y. Katsurada, S. Hirata, T. Totani, T. Watanabe, M. Vacha
  • Journal Title: Adv. Opt. Mater. Volume: 3 Issue: 12 Pages: 1726-1737
  • DOI: 10.1002/adom.201500334
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] : Thermally activated delayed fluorescence with curcularly polarized luminescence characteristics (2015)
  • Author(s): T. Imagawa, S. Hirata, K. Totani, T. Watanabe, M. Vacha.
  • Journal Title: Chem. Commun. Volume: 51 Issue: 68 Pages: 13268-13271
  • DOI: 10.1039/c5cc04105h
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Long-lived Triplet Excitons Allowed by Intermolecular Hydrogen Bonding in Amorphous Matrix (2015)
  • Author(s): Yuichiro Tsubomoto, Kenro Totani, Toshiyuki Watanabe, Shuzo Hirata, Martin Vacha
  • Journal Title: Journal of Photopolymer Science and Technology Volume: 28 Issue: 4 Pages: 573-577
  • DOI: 10.2494/photopolymer.28.573
  • NAID: 130005101119
  • ISSN: 0914-9244, 1349-6336
  • Peer Reviewed
• [Journal Article] Material Degradation of Liquid Organic Semiconductors Analyzed by Nuclear Magnetic Resonance Spectroscopy (2015)
  • Author(s): T. Fukushima, J. Yamamoto, M. Fukuchi, S. Hirata, H. H. Jung, O. Hirata, Y. Shibano, C. Adachi, H. Kaji
  • Journal Title: AIP Advances Volume: 5 Issue: 8 Pages: 087124-087124
  • DOI: 10.1063/1.4928515
  • NAID: 120005666182
  • Peer Reviewed
• [Journal Article] [Paper] Meta-linking Strategy for Thermally Activated Delayed Fluorescence Emitters with a Small Singlet-Triplet Energy Gap (2015)
  • Author(s): K. Shizu, Y. Sakai, H. Tanaka, S. Hirata, C. Adachi, H. Kaji
  • Journal Title: ITE Transactions on Media Technology and Applications Volume: 3 Issue: 2 Pages: 108-113
  • DOI: 10.3169/mta.3.108
  • NAID: 130005064337
  • ISSN: 2186-7364
  • Peer Reviewed
• [Journal Article] Highly efficient blue electroluminescence based on thermally activated delayed fluorescence (2015)
  • Author(s): Shuzo Hirata, Yumi Sakai, Kensuke Masui, Hiroyuki Tanaka, Sae Youn Lee, Hiroko Nomura, Nozomi Nakamura, Mao Yasumatsu, Hajime Nakanotani, Qisheng Zhang, Katsuyuki Shizu, Hiroshi Miyazaki, Chihaya Adachi
  • Journal Title: Nat. Mater. Volume: 14 Issue: 3 Pages: 330-336
  • DOI: 10.1038/nmat4154
  • Peer Reviewed
• [Journal Article] Position-dependent three-dimensional diffusion in nematic liquid crystal monitored by single-particle fluorescence localization and tracking (2015)
  • Author(s): Seonik Lee, Koushi Noda, Shuzo Hirata, Martin Vacha
  • Journal Title: J. Phys. Chem. Lett. Volume: 6 Issue: 8 Pages: 1403-1407
  • DOI: 10.1021/acs.jpclett.5b00488
  • Peer Reviewed
• [Journal Article] Relationship between room temperature phosphorescence and duteration position in a purely aromatic compound (2014)
  • Author(s): Shuzo Hirata, Kenro Totani, Toshiyuki Watanabe,Hiroyuki Kaji, Martin Vacha
  • Journal Title: Chem. Phys. Lett Volume: 591 Pages: 119-125
  • DOI: 10.1016/j.cplett.2013.11.019
  • Peer Reviewed
• [Journal Article] Large reverse saturable absorption under weak continuous incoherent light (2014)
  • Author(s): Shuzo, Hirata, Martin Vacha, Kenro Totani, Takashi Yamashita, Chiaya Adachi
  • Journal Title: Nat. Mater. Volume: 13 Issue: 10 Pages: 938-946
  • DOI: 10.1038/nmat4081
  • Peer Reviewed
• [Journal Article] Bacteriochlorophyll aggregates self-assembled on functionalized gold nanorod cores as mimics of photosynthetic chlorosomal antennae (2014)
  • Author(s): S. Furumaki, F. Vacha, S. Hirata, M. Vacha
  • Journal Title: ACS Nano Volume: 8 Issue: 3 Pages: 2176-2182
  • DOI: 10.1021/nn500224v
  • Peer Reviewed
• [Journal Article] Single molecule electroluminescence and photoluminescence of polyfluorene unveils the photophysics behind the green emission band. (2014)
  • Author(s): Y. Honmou, S. Hirata, H. Komiyama, J. Hiyoshi, S. Kawauchi, T. Iyoda, M. Vacha
  • Journal Title: Nature Commun. Volume: 5 Issue: 1 Pages: 4666-4666
  • DOI: 10.1038/ncomms5666
  • Peer Reviewed
• [Presentation] Extraction of Unique Emission and Absorption Characteristics by Stabilization of Triplet Excitons (2017)
  • Author(s): Shuzo Hirata
  • Organizer: The 97th CSJ Annual Meeting, Asian International Symposium- Photochemistry
  • Place of Presentation: 慶応大学横浜キャンパス, 横浜, 日本
  • Year and Date: 2017-03-16
  • Invited
• [Presentation] 非共役系有機媒体の超剛直性を利用した芳香族分子の新規光機能, (2016)
  • Author(s): 平田修造
  • Organizer: 平成28年度繊維学会秋季研究発表会, 若手産学交流セッション
  • Place of Presentation: 山形大学米沢キャンパス, 山形, 日本
  • Year and Date: 2016-09-20
  • Invited
• [Presentation] Large Nonlinar Abosrption under Weak Conteneous Incoherent Light using Long-lived Room Tempeature Excitons (2016)
  • Author(s): 平田修造
  • Organizer: 2016 MRS spring meeting
  • Place of Presentation: Arizona, Phoenix Convention Center
  • Year and Date: 2016-03-28
  • Int'l Joint Research / Invited
• [Presentation] スーパーハードな環境下での芳香族化合物からの新規光機能の開拓 (2016)
  • Author(s): 平田修造
  • Organizer: 日本化学会代96春季年会
  • Place of Presentation: 京都, 同志社大学京田辺キャンパス
  • Year and Date: 2016-03-24
  • Invited
• [Presentation] 励起三重項を経由したルミネッセンスの科学と応用 (2016)
  • Author(s): 平田修造
  • Organizer: シンポジウム, 超短パルスレーザーと機能性材料; 物性評価と応用への新展開
  • Place of Presentation: 立命館大学大阪キャンパス, 大阪, 日本
  • Invited
• [Presentation] White afterglow room temperature emission from isolated single aromatic unit (2016)
  • Author(s): Shuzo Hirata
  • Organizer: International Symposium on Integrated Molecular/Materials Science and Engineering (IMSE2016),
  • Place of Presentation: Qingdao University of Science Technology, Qingdao, China
  • Int'l Joint Research / Invited
• [Presentation] キラルなドナーアクセプター分子からの熱活性化遅延蛍光と円偏光発光 (2015)
  • Author(s): 今川 拓郎・平田修造・戸谷健朗・渡辺敏行・バッハマーティン
  • Organizer: 有機EL討論会第21回例会
  • Place of Presentation: 福岡, 九州大学伊都キャンパス
  • Year and Date: 2015-11-12
• [Presentation] トリフェニルアミン部位を有するナフタセノン誘導体における光学活性と熱活性化遅延蛍光 (2015)
  • Author(s): 今川 拓郎・平田修造・戸谷健朗・バッハマーティン・渡辺敏行
  • Organizer: 2015年光化学討論会
  • Place of Presentation: 大阪, 大阪市立大学杉本キャンパス
  • Year and Date: 2015-09-09
• [Presentation] Large transmittance change induced by exciton accumulation under weak continuous photoexcitation (2015)
  • Author(s): 平田修造・バッハマーティン
  • Organizer: 2015年光化学討論会
  • Place of Presentation: 大阪, 大阪市立大学杉本キャンパス
  • Year and Date: 2015-09-09
• [Presentation] 熱活性化遅延蛍光と円偏光発光を両立する分子設計の考察 (2015)
  • Author(s): 平田修造・今川 拓郎・戸谷健朗・渡辺敏行・バッハマーティン
  • Organizer: 2015年光化学討論会
  • Place of Presentation: 大阪, 大阪市立大学杉本キャンパス
  • Year and Date: 2015-09-09
• [Presentation] 室温長寿命励起子を用いた光機能性材料の開発 (2015)
  • Author(s): 平田修造
  • Organizer: 第95回日本化学会春季年会
  • Place of Presentation: 日大船橋キャンパス（千葉県・船橋市）
  • Year and Date: 2015-03-28
  • Invited
• [Presentation] 室温長寿命励起子を利用した非コヒーレント光に応答する非線形吸収材料の開発 (2015)
  • Author(s): 平田修造
  • Organizer: 高分子同友会
  • Place of Presentation: 高分子学会事務局（東京都・中央区）
  • Year and Date: 2015-02-12
  • Invited
• [Presentation] 非コヒーレント光に応答する非線形吸収材料の三重項励起子の蓄積機構 (2014)
  • Author(s): 平田修造、バッハマーティン
  • Organizer: 2014年度光化学討論会
  • Place of Presentation: 北海道大学（北海道・札幌市）
  • Year and Date: 2014-10-12
• [Book] 分子性室温りん光と三重項の光物理化学, 光化学協会誌, Vol.47, No.2 (2016)
  • Author(s): 平田修造
  • Total Pages: 133
  • Publisher: 光化学協会
• [Book] 化学と工業3月号 (2015)
  • Author(s): 平田修造
  • Total Pages: 72
  • Publisher: 公益社団法人日本化学会
• [Book] 先端 有機半導体デバイス―基礎からデバイス物性まで― (2015)
  • Author(s): 平田修造
  • Total Pages: 788
  • Publisher: オーム社
• [Book] 高分子9月号 (2015)
  • Author(s): 平田修造, 伊都将司, Martin Vacha, 宮坂博
  • Total Pages: 48
  • Publisher: 公益社団法人高分子学会
• [Book] 機能材料4月号 (2015)
  • Author(s): 平田修造
  • Total Pages: 65
  • Publisher: シーエムシー出版
• [Book] 高分子 (2015)
  • Author(s): 平田修造, 伊都将司, VACHA Martin, 宮坂博
  • Publisher: 社団法人高分子学会
• [Book] 先端 有機半導体デバイス 基礎からデバイス物性まで- (2015)
  • Author(s): 平田修造
  • Publisher: 株式会社オーム社
• [Book] 飛躍する若手研究者 室温長寿命励起子を利用した光機能材料の創製 (2015)
  • Author(s): 平田修造
  • Publisher: 化学と工業
• [Book] 導電性ポリマー材の高機能化と用途開発最前線 (2014)
  • Author(s): 平田修造, 羽渕聡史, VACHA Martin
  • Total Pages: 265
  • Publisher: 株式会社エヌ・ティー・エス
• [Remarks] 2014年10月27日 Noteworthy Chemistry
  • URL: http://www.acs.org/content/acs/en/noteworthy-chemistry/2014-archive/october-27.html#nc3
• [Remarks] 2014年9月25日 日経産業新聞10面 強い光ほど透過しにくく
• [Remarks] 2014年10月3日 東工大ニュース
  • URL: http://www.titech.ac.jp/news/2014/028654.html
• [Remarks] News & Views, Nature Materials 13, 917-918 (2014)
  • URL: http://www.nature.com/nmat/journal/v13/n10/full/nmat4096.html
• [Patent(Industrial Property Rights)] 波長変換材料及びその応用 (2016)
  • Inventor(s): 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Holder: 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-03-18
• [Patent(Industrial Property Rights)] 波長変換材料及びその応用 (2016)
  • Inventor(s): 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Holder: 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-03-18
• [Patent(Industrial Property Rights)] 波長変換材料及びその応用 (2016)
  • Inventor(s): 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Holder: 平田修造, Martin Vacha, 村上陽一
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-03-18