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2014 Fiscal Year Annual Research Report

有機半導体電極界面のキャリア注入・取り出し機構の解明

Research Project

Project/Area Number 25288114
Research InstitutionChiba University

Principal Investigator

石井 久夫  千葉大学, 先進科学センター, 教授 (60232237)

Co-Investigator(Kenkyū-buntansha) 野口 裕  明治大学, 理工学部, 准教授 (20399538)
中山 泰生  千葉大学, 融合科学研究科(研究院), 助教 (30451751)
K.K. Rasika  千葉大学, 学内共同利用施設等, 助教 (90631557)
Project Period (FY) 2013-04-01 – 2016-03-31
Keywords光電子分光 / 光電子収量分光 / キャリア注入 / 有機EL素子 / 有機太陽電池 / ギャップ内準位
Outline of Annual Research Achievements

電極界面を通したキャリアの注入・取り出しは有機エレクトロニクスの性能を左右する重要なプロセスである。従来は有機半導体のHOMO(またはLUMO)準位と電極のフェルミ準位のエネルギー差に相当する”キャリアの注入障壁高さ”というパラメーターで一元的に解釈されてきた。しかしながら、HOMO準位とLUMO準位の間には低状態密度を有する準位(ギャップ内準位)が存在することが知られており、ギャップ内準位を介したキャリア注入の効果を考慮する必要がある。本研究では、(i)我々がこれまで開発を進めてきた低迷光・低エネルギー光電子分光と光電子収量分光を活用し、フェルミ準位直下の状態密度を5桁をこえるダイナミックレンジで直接観測し、(ii)電子構造測定と電気測定を同一試料・同一環境下で行い、界面の電気特性を解析し、キャリア注入機構の解明を目指す。
平成26年度は、電気特性をin-situで測定するための試料ホルダーを作成した。試料ホルダーには、ホルダー本体に加えて、2つの独立した電極を付加することができ、有機ELなどの2端子素子、トランジスタなどの3端子素子の電気測定を行えるようにした。また、光電子分光測定時に電場が撹乱されにくいように配慮した設計となっている。ex-situで作成した有機トランジスタを用いたテストは終了し、光電子分光とのin-situ測定を開始したところである。これと並行して、高感度光電子計測によるモデル系の電子構造測定を前倒しですすめ、(i)ITO/CuPc/C60/BCP型標準有機太陽電池において、C60/BCP界面にギャップ準位が形成されていることや、素子全体のポテンシャルプロファイルの解明に成功し、(ii)配向分極を示す有機EL材料系において表面に負イオンが蓄積しているなどの結果を見出した、これらの系のin-situ電気特性評価を平成27年度に進める予定である。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

in-situ電気測定のための装置改造が当初計画より遅れていたが、技術的な点はクリアした。並行して進めている、有機EL素子や有機太陽電池のモデル界面の電子構造の高感度測定に関しては、有機太陽電池系(ITO/CuPc/C60/BCP/Al)では、ギャップ内準位の観測と素子のポテンシャルプロファイルの決定に成功し、Advanced Energy Materials誌のinside coverに採用されるなどの評価を得ている。また、有機EL材料においては、膜の配向分極により生じる表面の分極電荷により捉えられた負イオンの高感度光電子計測に成功し、新しい電子親和力の評価法として期待出来る結果を得ている。

Strategy for Future Research Activity

これまでに先行して界面電子構造の高感度計測を進めてきた系について、実際に光電子分光測定と電気測定のin-situ測定をすすめ、キャリアの注入・取り出し機構の解明を進める。また、平成26年度に成功した負イオンの高感度光電子計測を発展させて、トランジスタ構造中の負性キャリア(負イオン)の直接観測もすすめ、有機半導体のキャリアに関する解明も進める予定である。

Causes of Carryover

in-situ電気測定の装置開発が当初予定より遅れたため、それを利用した実験が平成27年度にずれ込んだため。

Expenditure Plan for Carryover Budget

有機EL素子、太陽電池の電気特性・電子構造の同時測定を平成27年度にすすめ、予算を執行する予定である。

  • Research Products

    (28 results)

All 2015 2014 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Acknowledgement Compliant: 2 results) Presentation (18 results) (of which Invited: 10 results) Book (2 results) Remarks (1 results)

  • [Journal Article] Electronic Structures of a Well-Defined Organic Hetero-Interface: C60 on Pentacene Single Crystal2015

    • Author(s)
      Masayuki Yamamoto, Yasuo Nakayama, Yuki Uragami, Hiroumi Kinjo, Yuta Mizuno, Kazuhiko Mase, Kaveenga Rasika Koswattage, Hisao Ishii
    • Journal Title

      e-Journal of Surface Science and Nanotechnology

      Volume: 13 Pages: 59-64

    • DOI

      http://doi.org/10.1380/ejssnt.2015.59

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Charge carrier dynamics and degradation phenomena in organic light-emitting diodes doped by a thermally activated delayed fluorescence emitter2015

    • Author(s)
      Yutaka Noguchi, Hyung-Jun Kim, Ryuta Ishino, Kenichi Goushi, Chihaya Adachi, Yasuo Nakayama, Hisao Ishii
    • Journal Title

      Organic Electronics

      Volume: 17 Pages: 184-191

    • DOI

      doi:10.1016/j.orgel.2014.12.009

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] 極性分子の配向分極現象と有機薄膜素子の界面特性2015

    • Author(s)
      野口裕,中山泰生,石井久夫
    • Journal Title

      真空(Journal of the Vacuum Society of Japan)

      Volume: 58(3) Pages: 109-116

    • Peer Reviewed
  • [Journal Article] Determination of the highest occupied molecular orbital energy of pentacene single crystals by ultraviolet photoelectron and photoelectron yield spectroscopies2014

    • Author(s)
      Yasuo Nakayama, Yuki Uragami, Masayuki Yamamoto, Shin’ichi Machida, Hiroumi Kinjo, Kazuhiko Mase, Kaveenga Rasika Koswattage, Hisao Ishii
    • Journal Title

      Japanese Journal of Applied Physics

      Volume: 53(1S) Pages: 01AD03-1~4

    • DOI

      10.7567/JJAP.53.01AD03

    • Peer Reviewed
  • [Journal Article] Complete demonstration of the valence electronic structure inside a practical organic solar cell probed by low energy photoemission2014

    • Author(s)
      asuo Nakayama, Thanh Luan Nguyen, Yusuke Ozawa, Shin’ichi Machida, Tomoya Sato, Hiroshi Tokairin, Yutaka Noguchi, Hisao Ishii
    • Journal Title

      Advanced Energy Materials

      Volume: 4(7) Pages: 1301354-1~9

    • DOI

      10.1002/aenm.201470032

    • Peer Reviewed
  • [Journal Article] Evaluation of internal potential distribution and carrier extraction properties of organic solar cells through Kelvin probe and time-of-flight measurements2014

    • Author(s)
      Yuya Tanaka, Yutaka Noguchi, Keisuke Oda, Jun-ichi Takahashi, Hiroshi Tokairin, Hisao Ishii
    • Journal Title

      Journal of Applied Physics

      Volume: 116(11) Pages: 114503-1~7

    • DOI

      10.1063/1.4895712

    • Peer Reviewed
  • [Journal Article] Voc from a morphology point of view: The influence of molecular orientation on the open circuit voltage of organic planar heterojunction solar cells2014

    • Author(s)
      Ulrich Hoermann, (12名略) Yasuo Nakayama, Hisao Ishii, Norbert Koch, Ellen Moons, Frank Schreiber, Wolfgang Bruetting
    • Journal Title

      Journal of Physical Chemistry C

      Volume: 116 Pages: 26462-26470

    • DOI

      10.1063/1.4895712

    • Peer Reviewed
  • [Presentation] Direct Observation of Surface Anions Relaxed by Spontaneous Orientation Polarization in OLED Films by High Sensitivity Photoemission2015

    • Author(s)
      Hiroumi Kinjo, Tomoya Sato, Hirounjo, Junki Yamazaki, Yutaka Noguchi, Yasuo Nakayama, Hisao Ishii
    • Organizer
      SPIE Organic Photonics + Electronics
    • Place of Presentation
      San Diego, California, United States
    • Year and Date
      2015-08-09 – 2015-08-13
    • Invited
  • [Presentation] High Sensitivity Photoemission and Photoelectron Yield Spectroscopy of Weak Density of States of Organic Functional Films: Direct Detection of Gap States and Anion States2015

    • Author(s)
      Tomoya Sato, Hiroumi Kinjo, K. Rasika Koswattage, Yasuo Nakayama, Hisao Ishii
    • Organizer
      The 5th International Symposium on Organic and Inorganic Electronic Materials and Related Nanotechnologies (EM-NANO 2015)
    • Place of Presentation
      Niigata, Japan
    • Year and Date
      2015-06-16 – 2015-06-19
    • Invited
  • [Presentation] High Sensitivity Photoemission Study of Organic Molecules and Polymers: Direct Detection of Trap States and Charged States2015

    • Author(s)
      Tomoya Sato, Hiroumi Kinjo, K. Rasika Koswattage, Yasuo Nakayama,Hisao Ishii
    • Organizer
      SPIE Organic Photonics + Electronics
    • Place of Presentation
      Seoul, Korea
    • Year and Date
      2015-05-21 – 2015-05-22
    • Invited
  • [Presentation] Relaxed Anion-State in OLED Films Studied2015

    • Author(s)
      Hiroumi Kinjo, Tomoya Sato, Junki Yamazaki, Yutaka Noguchi, Yasuo Nakayama, Hisao Ishii
    • Organizer
      Korean Physics Society Meeting 2015
    • Place of Presentation
      Daejeon, Korea
    • Year and Date
      2015-04-23
    • Invited
  • [Presentation] Direct Determination of the Electric Potential in OLEDs: Influence of Orientation Polarization2014

    • Author(s)
      Christian S. Weigel, Rebecca Saive, Yutaka Noguchi, Hisao Ishii, Wolfgang Kowalsky
    • Organizer
      2014 MRS Fall Meeting
    • Place of Presentation
      Boston, United States
    • Year and Date
      2014-11-30 – 2014-12-05
  • [Presentation] Impact of Orientation Polarization in Alq3-based OLED on Carrier Injection Property2014

    • Author(s)
      Hiroumi Kinjo, Hyunsoo Lim, Hyungun Kim, T. Sato, Y. Noguchi, Y. Nakayama, and Hisao Ishii
    • Organizer
      6th Asian Conference on Organic Electronics (A-COE 2014)
    • Place of Presentation
      Tainan, Taiwan
    • Year and Date
      2014-11-12 – 2014-11-14
    • Invited
  • [Presentation] Direct Observation of Electronic Structure of Nylon-6, 6 Thin Film Studied by High Sensitivity Photoemission and Photoelectron Yield Spectroscopy2014

    • Author(s)
      Tomoya Sato, Kaveenga Rasika Koswattage, Yasuo Nakayama, Hisao Ishii
    • Organizer
      The 7th International Symposium on Surface Science
    • Place of Presentation
      Kunibiki Messe, Matsue, Japan
    • Year and Date
      2014-11-02 – 2014-11-06
  • [Presentation] Electronic fine structures inside organic devices probed by high-sensitivity ultraviolet photoemission2014

    • Author(s)
      Yasuo Nakayama, Yusuke Ozawa, Hiroumi Kinjo, Tomoya Sato, Thanh Luan Nguyen, Yuki Uragami, Shin’ichi Machida, K. Rasika Koswattage, Yutaka Noguchi, Hisao Ishii
    • Organizer
      The 2nd Workshop on Physics in Organic Optoelectronics
    • Place of Presentation
      Soochow (China)
    • Year and Date
      2014-10-28
    • Invited
  • [Presentation] 負イオン光電子分光で見た有機半導体配向分極膜の空準位電子状態2014

    • Author(s)
      金城 拓海,Lim Hyunsoo・佐藤友哉・大澤祐介・野口 裕・中山 泰生・石井 久夫
    • Organizer
      第4回CSJ化学フェスタ2014
    • Place of Presentation
      タワーホール船堀(東京)
    • Year and Date
      2014-10-14 – 2014-10-16
  • [Presentation] Charge Carrier Behaviors and Degradation Phenomena in Organic Light-Emitting Diodes Doped by a Thermally Activated Delayed Fluorescence Emitter2014

    • Author(s)
      Yutaka Noguchi, Hyung Jun Kim, Ryuta Ishino, Kenichi Goushi, Chihaya Adachi, Yasuo Nakayama, Hisao Ishii
    • Organizer
      The 14th International Discussion & Conference on Nano Interface Controlled Electronic Devices (IDC-NICE 2014)
    • Place of Presentation
      Samcheonggak, Seoul, Korea
    • Year and Date
      2014-10-10
    • Invited
  • [Presentation] Direct Observation of Negative Carrier States at Polarized Organic Semiconductor Surfaces Studied by High Sensitivity Photoemission and Photoelectron Yield Spectroscopy2014

    • Author(s)
      Hiroumi. Kinjo, Hyunsoo Lim, Yusuke Ozawa, Tomoya Sato, Yutaka Noguchi, Yasuo Nakayama and Hisao Ishii
    • Organizer
      KJF-ICOMEP 2014 International Conference on Organic Materials for Electronics and Photonics (KJF-ICOMEP 2014)
    • Place of Presentation
      Tsukuba, Japan
    • Year and Date
      2014-09-21 – 2014-09-24
  • [Presentation] 光電子分光および高感度光電子収量分光による Nylon-6,6 薄膜の電子構造観察2014

    • Author(s)
      佐藤 友哉, K.R. Koswattage, 中山 泰生, 石井 久夫
    • Organizer
      第75回応用物理学会秋季学術講演会
    • Place of Presentation
      札幌
    • Year and Date
      2014-09-17 – 2014-09-20
  • [Presentation] Anomalous photoemission by low-energy photo-excitation of a thermally activated delayed fluorescence material2014

    • Author(s)
      Yasuo Nakayama, Yusuke Ozawa, Hiroumi Kinjo, Tomoya Sato, Yutaka Noguchi, Kaveenga Rasika Koswattage, Hisao Ishii
    • Organizer
      The 10th International Conference on Electroluminescence and Optoelectronic Devices (ICEL10)
    • Place of Presentation
      Cologne, Germany
    • Year and Date
      2014-09-01 – 2014-09-03
  • [Presentation] Unusual photoemission by lower photon energy than ionization energy for organic EL materials with giant surface potential2014

    • Author(s)
      Hiroumi Kinjo, Hyunsoo Lim, Yusuke Ozawad, Tomoya Sato, Yasuo Nakayama, Hisao Ishii
    • Organizer
      SPIE Organic Photonics + Electronics
    • Place of Presentation
      San Diego, California, United States
    • Year and Date
      2014-08-18
    • Invited
  • [Presentation] 超高感度光電子計測によるAlq3薄膜における十分に緩和したLUMO準位の実測2014

    • Author(s)
      金城 拓海,Lim Hyunsoo,大澤 祐介,佐藤 友哉,野口 裕,中山 泰生,石井 久夫
    • Organizer
      有機EL討論会 第18回例会
    • Place of Presentation
      千葉
    • Year and Date
      2014-07-18
  • [Presentation] Photoemission from Organic Films by Visible Light Observed by High Sensitive UPS and PYS2014

    • Author(s)
      H. Kinjo, T. Sato, Y. Ozawa, H. Lim, Y. Nakayama, Hisao Ishii
    • Organizer
      The 7th Japanese-Swedish Workshop on Advanced Spectroscopy of Organic Materials for Electronic Applications
    • Place of Presentation
      Lund, Sweden
    • Year and Date
      2014-06-11
  • [Presentation] Electronic Structures of Organic Semiconductor Devices Studied by Photoemission Spectroscopy2014

    • Author(s)
      H. Ishii, S. Machida, H. Kinjo, T. Sato, and Y. Nakayama
    • Organizer
      15th International Krutyn Summer School
    • Place of Presentation
      Krutyn, Poland
    • Year and Date
      2014-06-09 – 2014-06-14
    • Invited
  • [Presentation] Displacement Current Measurement as a tool to investigate carrier behavior in organic semiconductor devices2014

    • Author(s)
      H. Ishii, , Y. Tanaka, H. Kim, H. Lim, M. Tamura, and Y. Noguchi
    • Organizer
      15th International Krutyn Summer School
    • Place of Presentation
      Krutyn, Poland
    • Year and Date
      2014-06-09 – 2014-06-14
    • Invited
  • [Book] Chapter 2 in Electronic processes in organic electronics: Bridging nanostructure, electronic states and device properties2015

    • Author(s)
      Yasuo Nakayama, Steffen Duhm, Qian Xin, Satoshi Kera, Hisao Ishii, Nobuo Ueno
    • Total Pages
      16
    • Publisher
      Springer
  • [Book] Chapter 8 in Electronic processes in organic electronics: Bridging nanostructure, electronic states and device properties2015

    • Author(s)
      Hisao Ishii, Hiroumi Kinjo, Tomoya Sato, Shin-ichi Machida, Yasuo Nakayama
    • Total Pages
      25
    • Publisher
      Springer
  • [Remarks] 千葉大学石井研究室のweb

    • URL

      http://ishii-lab.in.coocan.jp/pukiwiki/

URL: 

Published: 2016-06-01  

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