Defect-free, Highly-luminescent and Non-blinking Perovskite Nanocrystals

2021 Fiscal Year Annual Research Report

• Project/Area Number: 19H02550
• Research Institution: Hokkaido University
• Principal Investigator: Biju V・Pillai 北海道大学, 電子科学研究所, 教授 (60392651)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Keywords: halide perovskites / single particle studies / blinking / vacancy filling

Outline of Annual Research Achievements

Highly luminescent nanocrystals and microcrystals of MAPbBr3 and MAPbI3, and nanocrystals of FAPbBr3 perovskites were prepared by solution processing under inverse temperature crystallization, antisolvent-assisted crystallization, hot injection synthesis, and ligand-assisted reprecipitation. FAPbBr3 nanocrystals synthesized showed well-defined emission switching in color and intensity by assembling into large nanostructures with intense green emission (ACS Nano 2022, and a Japanese patent filed). MAPbBr3 microcrystals and nanocrystals showed blinking due to halide defects. Defect passivation was accomplished by halide vacancy filing (Adv. Opt. Mater. 2021; Adv. Mater. Technol. 2021). Halide vacancy filling is confirmed from enhanced emission, long emission lifetime, and SEM-EDX. Also, blinking is modified by electron trapping (J. Phys. Chem. Lett. 2021) using newly synthesized electron acceptor-conjugated ligands. Electron donor ligands with amino groups were synthesized, which stabilized the perovskite nanocrystal emission. However, the donors and acceptors decreased the emission intensity. Thus, blinking suppression without emission quenching is achieved by halide vacancy filling (ACS Nano 2021).

Current Status of Research Progress

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

Reason

The synthesis of high-quality perovskite nanocrystals and microcrystals was completed. Electron acceptor (fullerene) and donor (amines) containing ligands were synthesized. Defects were suppressed and passivated by halide vacancy filling. Electron transfer was achieved using newly synthesized ligands. Blinking suppression and emission intensity and lifetime enhancements were achieved.

Strategy for Future Research Activity

Vacancy filling and blinking suppression were achieved and highly luminescent nanocrystals and microcrystals were developed. Although electron donors will be applied for post-synthesis defect passivation to characterize the nature of defects, electron transfer induced emission quenching was observed. However, the electron transfer will be valuable for solar cells. Also, electron donors will be used as ligands during the synthesis of nanocrystals and microcrystals. Therefore, electron transfer dynamics in perovskite-acceptor systems will be investigated and optimized. Also, electroluminescence blinking suppression will be investigated under the conditions of halide vacancy filling. Successively, photoluminescence and electroluminescence will be analyzed using steady-state and time-resolved methods. Defect-blinking relationships will be analyzed using single-molecule photoluminescence and electroluminescence microspectroscopy. An instrument for time-resolved electroluminescence will be developed. Photoluminescence and electroluminescence blinking will be suppressed, and highly photo- and electro-luminescent nanocrystals and microcrystals will be developed.

Research Products

• [Journal Article] Photoexfoliation Synthesis of 2D Materials (2022)
  • Author(s): P. Kumar, A. Dey, J. Roques, L. Assaud, S. Franger, P. Parida, V. Biju
  • Journal Title: ACS Materials Letters Volume: 4 Pages: 263-270
  • DOI: 10.1021/acsmaterialslett.1c00651
  • Peer Reviewed
• [Journal Article] Mechano-optical Modulation of Excitons and Carrier Recombination in Self-Assembled Halide Perovskite Quantum Dots (2022)
  • Author(s): Z. Zhang, S. Ghimire, T. Okamoto, B. M. Sachith, J. Sobhanan, C. Subrahmanyam, V. Biju
  • Journal Title: ACS Nano Volume: 16 Pages: 160-168
  • DOI: 10.1021/acsnano.1c04944
  • Peer Reviewed
• [Journal Article] Multimodal CTC detection using stem cell antigen-specific immunosilica particles and immunofluorescent quantum dots (2022)
  • Author(s): J. Sobhanan, Y. Takano, S. Sakiko, E. Hirata, Y. Shohei and V. P. Biju
  • Journal Title: NPG Asia Materials Volume: 14 Pages: 1-8
  • DOI: 10.1038/s41427-021-00353-5
  • Peer Reviewed
• [Journal Article] State of the Art and Prospects for Halide Perovskite Nanocrystals (2021)
  • Author(s): Dey, A., Ye, J., De, A., Debroye, E., Ha, S. K., Bladt, E., Kshirsagar, A. S., Wang, Z., Yin, J., Wang, Y., Quan, L. N., Yan, F., Gao, M., Li, X., Shamsi, J., Debnath, T., Cao, M., Scheel, M. A., Kumar, S., Steele, J. A., Gerhard, M., Chouhan, L., Xu, K., Wu, X., Li, Y., Zhang, Y., Biju, V., et al.
  • Journal Title: ACS nano Volume: 15 Pages: 10775-10981
  • DOI: 10.1021/acsnano.0c08903
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Shape-Dependent Kinetics of Halide Vacancy Filling in Organolead Halide Perovskites (2021)
  • Author(s): Okamoto, T., Shahjahan, M., Biju, V.
  • Journal Title: Advanced Optical Materials Volume: 9 Pages: 1
  • DOI: 10.1002/adom.202100355
  • Peer Reviewed
• [Journal Article] Photoluminescence investigations of sulfur quantum dots synthesized by a bubbling-assisted strategy (2021)
  • Author(s): Shuo Liu, S., Wang, H., Feng, A., Chang, J., Zhang, C., Shi, Y., Zhai, Y., Biju, V.
  • Journal Title: Nanoscale Adv. Volume: 14 Pages: 1-8
  • DOI: 10.1039/D1NA00282A
  • Peer Reviewed
• [Journal Article] Long-Range Interfacial Charge Carrier Trapping in Halide Perovskite-C60 and Halide Perovskite-TiO2 Donor-Acceptor Films (2021)
  • Author(s): Bhagyashree, M. S., Okamoto, T., Ghimire, S., Umeyama, T., Takano, Y., Imahori, H., Biju, V.
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 12 Pages: 8644-8651
  • DOI: 10.1021/acs.jpclett.1c01909
  • Peer Reviewed
• [Journal Article] Advances in photodynamic antimicrobial chemotherapy (2021)
  • Author(s): Anas, A., Sobhanan, J., Sulfiya, K. M., Jasmin, C., Sreelakshmi, P. K., Biju, V.
  • Journal Title: Journal of Photochemistry and Photobiology C Volume: 49 Pages: 100452
  • DOI: 10.1016/j.jphotochemrev.2021.100452
  • Peer Reviewed
• [Journal Article] Efficient solar water splitting using a CdS quantum dot decorated TiO2/Ag2Se photoanode (2021)
  • Author(s): B. Meena, P. Subramanyam, D. Suryakala, V. Biju, C. Subrahmanyam
  • Journal Title: International Journal of Hydrogen Energy Volume: 46 Pages: 34079-34088
  • DOI: 10.1016/j.ijhydene.2021.07.219
  • Peer Reviewed
• [Presentation] Charge Carrier and Exciton Dynamics in Semiconductors Nanocrystals (2022)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: Golden Jubilee International Conference NANOicon 2022
  • Int'l Joint Research / Invited
• [Presentation] Quantum confined nanomaterials living longer by charging and sleeping (2022)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: Trombay Symposium on Radiation & Photochemistry
  • Int'l Joint Research / Invited
• [Presentation] Photoinduced single-molecule electron transfer from halide perovskite quantum dots to molecular acceptors (2022)
  • Author(s): Zhang Zhijing、Vasudevan Pillai Biju
  • Organizer: 化学系学協会北海道支部2022年冬季研究発表会
• [Presentation] Visible fluorescent molecular sensors for singlet oxygen detection in solutions and cells (2022)
  • Author(s): H. Zhao, Y. Takano and V. P. Biju
  • Organizer: 化学系学協会北海道支部2022年冬季研究発表会
• [Presentation] Optimizing single crystal perovskite sizes, shapes and charge carrier properties for electroluminescence applications (2022)
  • Author(s): D. Zhang, V. P. Biju
  • Organizer: 化学系学協会北海道支部2022年冬季研究発表会
• [Presentation] 光治療化合物に向けたスルホンロサミンの分子機能解明 (2022)
  • Author(s): 吉田 和矢、髙野 勇太、Vasudevan Pillai Biju
  • Organizer: 化学系学協会北海道支部2022年冬季研究発表会
• [Presentation] Luminescent Nanomaterials: Chemistry and Applications (2022)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: National Science Day Lecture
  • Int'l Joint Research / Invited
• [Presentation] Transient Charging and Charge Carrier Trapping in Semiconductor Nanocrystals (2022)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: ICReDD-Hokkaido University Five Attached Institutes Joint Symposium
  • Int'l Joint Research / Invited
• [Presentation] Multimodal Detection of Circulating Tumor Cells Using Multifunctional Silica Particles (2022)
  • Author(s): Jeladhara Sobhanan, Y. Takano and V. P. Biju
  • Organizer: 日本化学会春季年会2022
• [Presentation] Control of the Excitons and Photoluminescence of Self-Assembled Lead Halide Perovskite Quantum Dots by Mechanical Force (2022)
  • Author(s): T. Okamoto, Z. Zhang and V. P. Biju
  • Organizer: 日本化学会春季年会2022
• [Presentation] Environmental Degradation of PbS and CdSe Quantum dots and the Related Toxicity (2022)
  • Author(s): Sobhanan Jeladhara、髙野 勇太、Vasudevan Pillai Biju
  • Organizer: 日本化学会春季年会2022
• [Presentation] The Tale of Two Blinking Nanocrystals (2021)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: Int'l Symposium on Photochemistry (ISP 2021)
  • Int'l Joint Research / Invited
• [Presentation] 「SPR induced photoluminescne quenching in quantum MAPbBr3-QD/TiO2 inteface」、Optical Devices and Materials for Solar Energy and Sol-id-state Lighting (2021)
  • Author(s): Seshaia K V、Chouhan Lata、Vasudevan Pillai Biju、Kumar Raavi Sai Santhosh
  • Organizer: Optical Society of America
  • Int'l Joint Research / Invited
• [Presentation] Multimodal Detection of Circulating Tumor Cells Using Multifunctional Silica Particles (2021)
  • Author(s): Jeladhara Sobhanan, Y. Takano and V. P. Biju
  • Organizer: 2021年光化学討論会
• [Presentation] Singlet Oxygen Caging, Releasing, and Optical Sensing by Photo-Excited State Engineering in an Aminomethyl anthracene-Coumarin Linked molecule (2021)
  • Author(s): Y. Takano, D. Sasikumar, H. Zhao, R. Kohara, M. Hamada, Y. Kobori and V. P. Biju
  • Organizer: 2021年光化学討論会
• [Presentation] A microspectroscopic Evaluation of Shape-Dependent Halide Vacancy Filling Kinetics in Lead Halide Perovskites (2021)
  • Author(s): T. Okamoto, Shahjahan MD and V. P. Biju
  • Organizer: 2021年光化学討論会
• [Presentation] Mechanically Modulated Emission from Perovskite Quantum Dot Assemblies (2021)
  • Author(s): Zhang Zhijing、岡本 拓也、Vasudevan Pillai Biju
  • Organizer: 2021年光化学討論会
• [Presentation] Spatiotemporal Photo-triggered Sensing of Singlet Oxygen by Rhodamine 6G-Anthracene Linked Molecule (2021)
  • Author(s): H. Zhao, Y. Takano, D. Sasikumar and V. P. Biju
  • Organizer: 2021年光化学討論会
• [Presentation] Long-Range Trapping of Photogenerated Electrons in Halide Perovskite Films (2021)
  • Author(s): S. Mahesha. Bhagyashree, S. Ghimire, T. Okamoto, T. Umeyama, Y. Takano, H. Imahori and V. P. Biju
  • Organizer: 2021年光化学討論会
• [Presentation] The Kinetics of Halide Vacancy Filling in Lead Halide Perovskite Microcrystals (2021)
  • Author(s): T. Okamoto, S. Ghimire and V. P. Biju
  • Organizer: Asian Photochemistry Conference
  • Int'l Joint Research
• [Presentation] The Release of Heavy Metal Ions from Engineered Nanomaterials: the Origin and Mechanism of Nanotoxicity (2021)
  • Author(s): Jeladhara Sobhanan, Y. Takano and V. P. Biju
  • Organizer: Asian Photochemistry Conference
  • Int'l Joint Research
• [Presentation] Ionic Vacancies and Luminescence Blinking in Halide Perovskite Nanocrystals and Quantum Dots (2021)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: Asian Photochemistry Conference
  • Int'l Joint Research / Invited
• [Presentation] uning the Structure and Emission Color of Self-Assembled Halide Perovskite Nanocrystals by Mechanical Distortions (2021)
  • Author(s): Z. Zhang, T. Okamoto and V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Coupled Charge Transfer Dynamics and Photoluminescence Quenching in Rational Designed ZCIS/Cs2SnCl6 Heterojunctions (2021)
  • Author(s): S. Palyam, V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Trapping and Accumulation of Photogenerated Charge Carriers in Bandgap Engineered Lead Halide Perovskite Heterostructures (2021)
  • Author(s): Shahjahan MD, T. Okamoto, S. Mahesha. Bhagyashree, L. Chouhan and V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Spatiotemporal Fluorescence Detection of Singlet Oxygen by Rhodamine 6G-Anthracene-Linked Molecules (2021)
  • Author(s): H. Zhao, Y. Takano and V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Sensor-Sensitizer-Loaded Mesoporous Silica Nanoparticles for Biosensing and Bioimaging (2021)
  • Author(s): Jeladhara Sobhanan, V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Homogenous Size and Shape MAPbBr3 Microcrystals and Their Optical Properties (2021)
  • Author(s): D. Zhang, T. Okamoto and V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Long-Range Trapping of Photogenerated Charge Carriers in Perovskite Nanocrystal Films (2021)
  • Author(s): S. Mahesha. Bhagyashree, Y. Takano and V. P. Biju
  • Organizer: the 22nd RIES-Hokudai International Symposium ‘癒’
  • Int'l Joint Research
• [Presentation] Photoluminescence and electroluminescence blinking of cadmium chalcogenide quantum dots and lead halide perovskite nanocrystals (2021)
  • Author(s): Vasudevan Pillai Biju
  • Organizer: PacifiChem 2021
  • Int'l Joint Research / Invited
• [Remarks]
  • URL: http://bijulab.main.jp/en/
• [Patent(Industrial Property Rights)] Mechano-Optical Modulation of Exciton or Carrier Recombination in Self-Assembled Halide Perovskite Quantum Dots (2022)
  • Inventor(s): Vasudevan Pillai Biju
  • Industrial Property Rights Holder: Vasudevan Pillai Biju
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: P2021-125-JP01