Transmission electron microscopy for soft materials with electron counting technique

• Project/Area Number: 20H02624
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 29020:Thin film/surface and interfacial physical properties-related
• Research Institution: National Institute for Materials Science
• Principal Investigator: KIMOTO Koji 国立研究開発法人物質・材料研究機構, 先端材料解析研究拠点, 拠点長 (90354399)
• Co-Investigator(Kenkyū-buntansha): 吉川 純 国立研究開発法人物質・材料研究機構, 先端材料解析研究拠点, 主任研究員 (20435754) ; Cretu Ovidiu 国立研究開発法人物質・材料研究機構, 先端材料解析研究拠点, 研究員 (60770112)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2022: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2021: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000); Fiscal Year 2020: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: electron microscopy / TEM / structure analysis / soft materials / EELS / electron counting / STEM / 透過電子顕微鏡法 / ソフトマテリアル / 材料評価 / 非晶質材料 / 走査透過電子顕微鏡 / 電子エネルギー損失分光法

Outline of Research at the Start

物質材料の微細構造評価は研究開発の基盤であり，数ある計測手法の中でも透過電子顕微鏡(TEM)は広範な材料に利用されている。しかしLi電池材料など軽元素を含む材料群や，原子レベルで制御されたナノ材料群では観察中の試料損傷が著しく，TEMの適用が大幅に制限されている。
本研究では，これらのいわゆるソフトマテリアル評価のため，電子を計数できる電子顕微鏡法のための要素技術開発し，広義のTEM（TEM・走査透過電子顕微鏡法・電子エネルギー損失分光法）への展開を行い，格段に高い検出精度と分析感度を目指す。

Outline of Final Research Achievements

Transmission electron microscopy (TEM) is effective for nano structure analysis; however, its application to so-called soft materials is limited due to electron beam damage during TEM observation. In this study, we developed basic techniques of electron-counting electron microscopy and applied them to various materials. First, we quantitatively measured the signal intensity produced by a single electron at various (6 types) cameras for TEM at different acceleration voltage (30-300 kV). Next, we incorporated these measurements into software that automatically converts the measured intensity from arbitrary units to the number of electrons. Using this equipment, local crystal structure analysis by STEM/TEM, local temperature measurement by EELS, and high-frequency STEM observation were performed.

Academic Significance and Societal Importance of the Research Achievements

電子計数型透過電子顕微鏡法にすることにより、STEM/TEM像観察やEELS分析等で様々な利点がある。電子を一つ一つ数えることができれば、ソフトマテリアルに対し有効な高感度計測となる。また、ドーズ量[e-/Å2]から電子線損傷を議論することが可能になり、ポアソン分布に基づき電子数Nから予想される量子ノイズ(√N/N)を議論できる。その結果、計測システムにおいて、計測ノイズと量子ノイズを個別に議論できる。本研究による電子計数型計測は、ソフトマテリアル計測における「試料損傷」「感度」「計測ノイズ」等の諸課題を解決するための基盤技術を確立したと言える。

Research Products

• [Journal Article] Nanometer-level temperature mapping of Joule-heated carbon nanotubes by plasmon spectroscopy (2023)
  • Author(s): Cretu Ovidiu、Tang Dai-Ming、Lu Da-Bao、Da Bo、Nemoto Yoshihiro、Kawamoto Naoyuki、Mitome Masanori、Ding Zejun、Kimoto Koji
  • Journal Title: Carbon Volume: 201 Pages: 1025-1029
  • DOI: 10.1016/j.carbon.2022.10.006
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Comparison of detection limits of direct-counting CMOS and CCD cameras in EELS experiments (2022)
  • Author(s): Haruta Mitsutaka、Kikkawa Jun、Kimoto Koji、Kurata Hiroki
  • Journal Title: Ultramicroscopy Volume: 240 Pages: 113577-113577
  • DOI: 10.1016/j.ultramic.2022.113577
  • Peer Reviewed
• [Journal Article] Nanoscale observation of subgap excitations in β-Si₃N₄ with a high refractive index using low-voltage monochromated STEM: a new approach to analyze the physical properties of defects in dielectric materials (2022)
  • Author(s): Asano Takanori、Tezura Manabu、Saitoh Masumi、Tanaka Hiroki、Kikkawa Jun、Kimoto Koji
  • Journal Title: Applied Physics Express Volume: 15 Issue: 7 Pages: 076501-076501
  • DOI: 10.35848/1882-0786/ac6e28
  • Peer Reviewed
• [Journal Article] Direct Observation of Thermal Vibration Modes Using Frequency-Selective Electron Microscopy (2022)
  • Author(s): Cretu Ovidiu、Zhang Han、Kimoto Koji
  • Journal Title: Nano Letters Volume: 22 Issue: 24 Pages: 10034-10039
  • DOI: 10.1021/acs.nanolett.2c03762
  • Peer Reviewed
• [Journal Article] Optical and acoustic phonon temperature measurements using electron nanoprobe and electron energy loss spectroscopy (2022)
  • Author(s): Kikkawa Jun、Kimoto Koji
  • Journal Title: Physical Review B Volume: 106 Issue: 19 Pages: 195431-195431
  • DOI: 10.1103/physrevb.106.195431
  • Peer Reviewed
• [Journal Article] Local structure analysis of disordered materials via contrast variation in scanning transmission electron microscopy (2022)
  • Author(s): Kimoto Koji、Shiga Motoki、Kohara Shinji、Kikkawa Jun、Cretu Ovidiu、Onodera Yohei、Ishizuka Kazuo
  • Journal Title: AIP Advances Volume: 12 Issue: 9 Pages: 095219-095219
  • DOI: 10.1063/5.0104798
  • Peer Reviewed / Open Access
• [Journal Article] Nanometric phonon spectroscopy for diamond and cubic boron nitride (2021)
  • Author(s): Kikkawa Jun、Taniguchi Takashi、Kimoto Koji
  • Journal Title: Physical Review B Volume: 104 Issue: 20
  • DOI: 10.1103/physrevb.104.l201402
  • Peer Reviewed
• [Journal Article] Heterostructuring Mesoporous 2D Iridium Nanosheets with Amorphous Nickel Boron Oxide Layers to Improve Electrolytic Water Splitting (2021)
  • Author(s): Kang Yunqing、Jiang Bo、Malgras Victor、Guo Yanna、Cretu Ovidiu、Kimoto Koji、Ashok Aditya、Wan Zhe、Li Hexing、Sugahara Yoshiyuki、Yamauchi Yusuke、Asahi Toru
  • Journal Title: Small Methods Volume: 5 Issue: 10 Pages: 2100679-2100679
  • DOI: 10.1002/smtd.202100679
  • Peer Reviewed
• [Journal Article] Intrinsic defect structures of polycrystalline CaKFe4As4 superconductors (2021)
  • Author(s): Sugali Pavan Kumar Naik、Ishida Shigeyuki、Kimoto Koji、Yanagisawa Keiichi、Kamiya Yoshihisa、Tsuchiya Yoshinori、Kawashima Kenji、Yoshida Yoshiyuki、Iyo Akira、Eisaki Hiroshi、Nishio Taichiro、Ogino Hiraku
  • Journal Title: Physical Chemistry Chemical Physics Volume: 23 Issue: 35 Pages: 19827-19833
  • DOI: 10.1039/d1cp02613e
  • Peer Reviewed / Open Access
• [Journal Article] Exfoliated Ferrierite-Related Unilamellar Nanosheets in Solution and Their Use for Preparation of Mixed Zeolite Hierarchical Structures (2021)
  • Author(s): Roth Wieslaw J.、Sasaki Takayoshi、Wolski Karol、Ebina Yasuo、Tang Dai-Ming、Michiue Yuichi、Sakai Nobuyuki、Ma Renzhi、Cretu Ovidiu、Kikkawa Jun、Kimoto Koji、Kalahurska Katarzyna、Gil Barbara、Mazur Michal、Zapotoczny Szczepan、Cejka Jiri、Grzybek Justyna、Kowalczyk Andrzej
  • Journal Title: Journal of the American Chemical Society Volume: 143 Issue: 29 Pages: 11052-11062
  • DOI: 10.1021/jacs.1c04081
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Atomic-Scale Electrical Field Mapping of Hexagonal Boron Nitride Defects (2021)
  • Author(s): Ovidiu Cretu, Akimitsu Ishizuka, Keiichi Yanagisawa, Kazuo Ishizuka, Koji Kimoto
  • Journal Title: ACS Nano Volume: 15 Issue: 3 Pages: 5316-5321
  • DOI: 10.1021/acsnano.0c10849
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides (2020)
  • Author(s): Takafumi Yamamoto, Akira Chikamatsu, Shunsaku Kitagawa
  • Journal Title: Nat. Commun. Volume: 11 Issue: 1 Pages: 5923-5923
  • DOI: 10.1038/s41467-020-19217-7
  • NAID: 120006936380
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Synthesis of Three-Layer Perovskite Oxynitride K2Ca2Ta3O9N・2H2O and Photocatalytic Activity for H2 Evolution under Visible Light (2020)
  • Author(s): Ya Tang, Kosaku Kato, Takayoshi Oshima, Hiroto Mogi, Akinobu Miyoshi, Kotaro Fujii, Kei-ichi Yanagisawa, Koji Kimoto, Akira Yamakata, Masatomo Yashima and Kazuhiko Maeda
  • Journal Title: Inorganic Chemistry Volume: 59 Issue: 15 Pages: 11122-11128
  • DOI: 10.1021/acs.inorgchem.0c01607
  • Peer Reviewed
• [Journal Article] Two-Dimensional Perovskite Oxynitride K2LaTa2O6N with an H+/K+ Exchangeability in Aqueous Solution to Form Stable Photocatalyst for Visible-Light H2 Evolution (2020)
  • Author(s): Takayoshi Oshima, Tom Ichibha,Kenji Oqmhula, Keisuke Hibino, Hiroto Mogi, Shunsuke Yamashita, Kotaro Fujii, Yugo Miseki, Kenta Hongo, Daling Lu,Ryo Maezono, Kazuhiro Sayama, Masatomo Yashima, Koji Kimoto,Hideki Kato, Masato Kakihana, Hiroshi Kageyama, Kazuhiko Maeda
  • Journal Title: Angewandte Chemie International Edition Volume: - Issue: 24 Pages: 9736-9743
  • DOI: 10.1002/anie.202002534
  • Peer Reviewed / Open Access
• [Journal Article] Responsive Four‐Coordinate Iron(II) Nodes in FePd(CN) 4 (2020)
  • Author(s): Ohtani Ryo、Matsunari Hiromu、Yamamoto Takafumi、Kimoto Koji、Isobe Masaaki、Fujii Kotaro、Yashima Masatomo、Fujii Susumu、Kuwabara Akihide、Hijikata Yuh、Noro Shin‐ichiro、Ohba Masaaki、Kageyama Hiroshi、Hayami Shinya
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Issue: 43 Pages: 19254-19259
  • DOI: 10.1002/anie.202008187
  • Peer Reviewed / Open Access
• [Presentation] 透過電子顕微鏡による微細構造解析の現状 (2023)
  • Author(s): 木本 浩司
  • Organizer: 2023年第70回応用物理学会春季学術講演会
  • Invited
• [Presentation] 透過電子顕微鏡による材料評価と解析データの取り扱い (2023)
  • Author(s): 木本 浩司
  • Organizer: マテリアル先端リサーチインフラ・マテリアルの高度循環のための技術領域セミナー
  • Invited
• [Presentation] 物質材料研究機構における透過電子顕微鏡を用いた研究 (2022)
  • Author(s): 木本 浩司
  • Organizer: 第17 回 SAT 研究情報交換会
  • Invited
• [Presentation] 走査透過電子顕微鏡法(STEM)やEELS/EDSを用いた分析法 (2022)
  • Author(s): 木本 浩司
  • Organizer: 応用物理学会東海支部基礎セミナー
  • Invited
• [Presentation] 走査透過電子顕微鏡法(STEM)入門 (2022)
  • Author(s): 木本 浩司
  • Organizer: 第32回(2022)電子顕微鏡大学
  • Invited
• [Presentation] 走査透過電子顕微鏡法(STEM)の基礎 (2021)
  • Author(s): 木本 浩司
  • Organizer: 第36回分析電子顕微鏡討論会,日本顕微鏡学会 分析電子顕微鏡討論会
  • Invited
• [Presentation] 走査透過電子顕微鏡法(STEM)入門 (2021)
  • Author(s): 木本 浩司
  • Organizer: 第31回電子顕微鏡大学
  • Invited
• [Presentation] NIMSでの電子顕微鏡による物質・材料評価（モノクロメーターおよびSTEMを用いた無機材料評価の現状） (2021)
  • Author(s): 木本 浩司
  • Organizer: 「次世代電子顕微鏡法」社会連携講座 第6回
  • Invited
• [Presentation] Material characterization using advanced transmission electron microscopy (2021)
  • Author(s): Koji Kimoto, Jun Kikkawa, Ovidiu Cretu
  • Organizer: The 10th International Workshop on Advanced Materials Science and Technology
  • Int'l Joint Research / Invited
• [Presentation] 複合アニオン化合物の透過電子顕微鏡による評価(14pC1-6) (2021)
  • Author(s): 木本浩司
  • Organizer: 日本物理学会第76回年次大会
  • Invited
• [Presentation] 走査透過電子顕微鏡法(STEM)入門 (2020)
  • Author(s): 木本 浩司、吉川 純、CRETU Ovidiu、柳澤 圭一、石塚 和夫
  • Organizer: 日本顕微鏡学会第63回シンポジウム
  • Invited
• [Book] 物質・材料研究のための透過電子顕微鏡 (2020)
  • Author(s): 木本 浩司、三石 和貴、三留 正則、原 徹、長井 拓郎
  • Total Pages: 400
  • Publisher: 講談社
  • ISBN: 9784065203866
• [Remarks] > DigitalMicrograph入門
  • URL: https://www.nims.go.jp/AEMG/DMindex.html
• [Remarks] 電子顕微鏡グループ > 研究
  • URL: https://www.nims.go.jp/AEMG/research_J.html
• [Remarks] AEMG of NIMS
  • URL: https://www.nims.go.jp/AEMG/research_E.html
• [Remarks] 電子顕微鏡グループ ＞ 研究
  • URL: https://www.nims.go.jp/AEMG/index.html
• [Remarks] AEMG of NIMS > Research
  • URL: https://www.nims.go.jp/AEMG/research_E.html
• [Remarks] 透過電子顕微鏡のデータ管理とDigitalMicrograph
  • URL: https://www.nims.go.jp/AEMG/recent/DigitalMicrographData_J.html
• [Remarks] 電子顕微鏡グループ ＞ 研究
  • URL: https://www.nims.go.jp/AEMG/research_J.html