ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Uncovering the Origin of the Emitting States in Bi3+-Activated CaMO3 (M = Zr, Sn, Ti) Perovskites: Metal-To-Metal Charge Transfer Versus s–p Transitions

Cite this: J. Phys. Chem. C 2019, 123, 23, 14677–14688
Publication Date (Web):May 15, 2019
Copyright © 2019 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    After more than a century of studies on the optical properties of Bi3+ ions, the assignment of the nature of the emissions and the bands of the absorption spectra remain ambiguous. Here, we report an insight into the spectroscopy of Bi3+-activated CaMO3 perovskites (M = Zr, Sn, and Ti), discussing the factors driving the metal-to-metal charge transfer and sp → s2 transitions. With the aim to figure out the whole scenario, a combined experimental and theoretical approach is employed. The comparison between the temperature dependence of the photoluminescence emissions with the temperature dependence of the exciton energy of the systems has led to an unprecedented evidence of the charge-transfer character of the emitting states in Bi3+-activated phosphors. Low-temperature vacuum ultraviolet spectroscopy together with the design of the vacuum-referred binding energy diagram of the luminescent center is exploited to shed light on the origin of the absorption bands. In addition, the X-ray absorption near the edge structure unambiguously confirmed the stabilization of Bi3+ in the Ca2+ site in both CaSnO3 and CaZrO3 perovskites. This breakthrough into the understanding of the excited-state origin of Bi3+ could pave the way toward the design of a new generation of effective Bi3+-activated phosphors.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.9b03940.

    • Normalized temperature-dependent PL spectra, synchrotron-radiation VUV–vis PLE spectra deconvolution analysis (9 K) and experimental Bi L3-edge HERFD–XANES together with the results of FDMNES calculations, and partial DOS extracted for Bi in the Bi2O3 and NaBiO3 references (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 45 publications.

    1. Taisei Hangai, Takuya Hasegawa, Jian Xu, Takayuki Nakanishi, Takashi Takeda, Kosuke Nakano, Kenta Hongo, Ryo Maezono, Tomoyo Goto, Yasushi Sato, Ayahisa Okawa, Shu Yin. Key Role of Metal-to-Metal Charge Transfer Transition between Mo6+ and Bi3+ for Enhancement in NIR Luminescence of Gd2MoO6:Bi,Yb Nanophosphor. The Journal of Physical Chemistry C 2024, 128 (8) , 3351-3360.
    2. Hei-Yui Kai, Longbing Shang, Ka-Leung Wong, Chang-Kui Duan, Peter A. Tanner. Comment on “Charge Transfer-Triggered Bi3+ Near-Infrared Emission in Y2Ti2O7 for Dual-Mode Temperature Sensing”. ACS Applied Materials & Interfaces 2023, 15 (37) , 43226-43233.
    3. Hongbo Zhao, Ru Chen, Xiaoyan Li, Lifan Shen, Edwin Yue Bun Pun, Hai Lin. Surface Coating of Lead-free Perovskites to Break the Luminescence Threshold for Fluorescent Information Recognition. ACS Sustainable Chemistry & Engineering 2023, 11 (28) , 10534-10544.
    4. Xianli Wang, Forough Jahanbazi, Jialiang Wei, Carlo U. Segre, Wei Chen, Yuanbing Mao. Charge Transfer-Triggered Bi3+ Near-Infrared Emission in Y2Ti2O7 for Dual-Mode Temperature Sensing. ACS Applied Materials & Interfaces 2022, 14 (32) , 36834-36844.
    5. Jianyan Ding, Xufeng Zhou, Shitong Lin, Wenxin Zhang, Lizhen Shi, Jiangcong Zhou, Shanshan Ye, Dewu Wu, Quansheng Wu. Novel Orange-Emitting Phosphor Ba2LuGaO5:Bi3+ with High Efficiency and Thermal Robustness Induced by D-Band Emission. The Journal of Physical Chemistry C 2022, 126 (21) , 8978-8985.
    6. Matthias Hämmer, Jakoah Brgoch, Philip Netzsch, Henning A. Höppe. The Role of the Bi3+ Lone Pair Effect in Bi(H3O)(SO4)2, Bi(HSO4)3, and Bi2(SO4)3. Inorganic Chemistry 2022, 61 (9) , 4102-4113.
    7. Santosh K. Gupta, Brindaban Modak, Debarati Das, Ashok Kumar Yadav, Pampa Modak, Anil K. Debnath, Kathi Sudarshan. Light Harvesting from Oxygen Vacancies and A- and B-Site Dopants in CaSnO3 Perovskite through Efficient Photon Utilization and Local Site Engineering. ACS Applied Electronic Materials 2021, 3 (7) , 3256-3270.
    8. Fangying Ren, Yue Li, Edwin Yue Bun Pun, Hai Lin. Dual-Feedbacked Temperature Sensing of Er3+ in Fusiform-Polycrystalline-Implanted BaYF5/PAN Electrospun Fibers. The Journal of Physical Chemistry C 2021, 125 (22) , 12107-12117.
    9. Michele Back, Elisa Casagrande, Enrico Trave, Davide Cristofori, Emmanuele Ambrosi, Federico Dallo, Marco Roman, Jumpei Ueda, Jian Xu, Setsuhisa Tanabe, Alvise Benedetti, Pietro Riello. Confined-Melting-Assisted Synthesis of Bismuth Silicate Glass-Ceramic Nanoparticles: Formation and Optical Thermometry Investigation. ACS Applied Materials & Interfaces 2020, 12 (49) , 55195-55204.
    10. Zhenguo Shi, Shichao Lv, Guowu Tang, Junzhou Tang, Licheng Jiang, Qi Qian, Shifeng Zhou, Zhongmin Yang. Multiphase Transition toward Colorless Bismuth–Germanate Scintillating Glass and Fiber for Radiation Detection. ACS Applied Materials & Interfaces 2020, 12 (15) , 17752-17759.
    11. Michele Back, Jumpei Ueda, Emmanuele Ambrosi, Lorenzo Cassandro, Davide Cristofori, Riccardo Ottini, Pietro Riello, Gabriele Sponchia, Kazuki Asami, Setsuhisa Tanabe, Enrico Trave. Lanthanide-Doped Bismuth-Based Fluoride Nanocrystalline Particles: Formation, Spectroscopic Investigation, and Chemical Stability. Chemistry of Materials 2019, 31 (20) , 8504-8514.
    12. Shaolong Liu, Wenfeng Sun, Jingxuan He, Xia Xiang. Tunable cold/warm white light emission from Bi3+/Te4+ co-doped Cs2ZrCl6 perovskite phosphors. APL Materials 2024, 12 (3)
    13. Pieter Dorenbos. Effect of temperature on lanthanide charge transition levels and vacuum referred binding energies. Journal of Luminescence 2024, , 120443.
    14. Jianyan Ding, Ziyi An, Zheng Wang, Yongpeng Dai, Weifang Yu, Jianjun Deng, Yanbing Lai, Xinglin Huang, Quansheng Wu. Cationic substitution engineering induced Multi-Color light emitting of bismuth in Tantalate used for WLED. Chemical Engineering Journal 2023, 477 , 147122.
    15. Yangbo Wang, Yingdong Han, Runfa Liu, Cunping Duan, Huaiyong Li. Excitation-Controlled Host–Guest Multicolor Luminescence in Lanthanide-Doped Calcium Zirconate for Information Encryption. Molecules 2023, 28 (22) , 7623.
    16. Shuo Yang, Chuqi Wang, Xiaoxi Ma, Chuang Wang, Yujuan Dong, Enlai Dong, Ge Zhu, Shuangyu Xin. A metal-to-metal charge transfer induced green-yellow phosphor CsAlGe 2 O 6 :Bi 3+ for full-spectrum LED devices. Dalton Transactions 2023, 52 (30) , 10481-10488.
    17. Zutao Fan, Xiangyang Fan, Junpeng Xue, Yu Wang. Designing dual mode of non-contact optical thermometers in double perovskite Ca2LaTaO6:Bi3+, Eu3+ phosphors. Materials Today Chemistry 2023, 30 , 101528.
    18. Philippe Boutinaud. Luminescence–structure relationships in solids doped with Bi 3+. Physical Chemistry Chemical Physics 2023, 25 (16) , 11027-11054.
    19. Feng Du, Zuobin Tang, Qianqian Zhao, Longsheng Du, Wenqi Xia. Ba5GeO4Br6:Bi3+, a promising cyan phosphor for high-quality full-spectrum white light illumination. Journal of Luminescence 2023, 255 , 119592.
    20. Mükremin Yılmaz, Emre Alp. Low-cost Zn2(OH)BO3:Pb2+ phosphor for large-scale thermometric applications. Journal of Alloys and Compounds 2023, 934 , 167865.
    21. Zhaoyang Feng, Chang-Kui Duan. Understanding photoluminescence of bismuth-doped ternary alkaline earth d 10 metal oxides via first-principles calculations. Physical Review B 2023, 107 (8)
    22. Tengyue Wang, Jiaren Du, Xiaomeng Wang, Kai Jiang, Panqin Wang, Shaoxing Lyu, Hengwei Lin. Designing stimuli-responsive and color-tunable indicators via the coexistence of dual emitting centers. Materials Chemistry Frontiers 2023, 7 (3) , 535-544.
    23. Yangmin Tang, Mingxue Deng, Machao Wang, Xiaofeng Liu, Zhenzhen Zhou, Jiacheng Wang, Qian Liu. Bismuth‐Activated Persistent Phosphors. Advanced Optical Materials 2023, 11 (2)
    24. Anjun Huang, Mingzhe Liu, Chang-Kui Duan, Ka-Leung Wong, Peter A. Tanner. Understanding the ultraviolet, green, red, near infrared and infrared emission properties of bismuth halide double perovskite. Inorganic Chemistry Frontiers 2022, 9 (24) , 6379-6390.
    25. Xianli Wang, Yuanbing Mao. Emerging Ultraviolet Persistent Luminescent Materials. Advanced Optical Materials 2022, 10 (21)
    26. Yuanyuan Chen, Honghui Zhang, Kuili Liu, Xinying Zhu, Huanli Yuan. Luminescence performance of CaYGaO4:Bi3+, CaYGaO4:Mn4+ and CaYGaO4:Bi3+/Mn4+ phosphors. Journal of Alloys and Compounds 2022, 918 , 165759.
    27. A. M. Srivastava, M. G. Brik, W. W. Beers, W. Cohen. Chemical Pressure Effects on the Stokes Shift of Bi 3+ Luminescence in Orthorhombic Perovskites. ECS Journal of Solid State Science and Technology 2022, 11 (9) , 096003.
    28. Xiaoli Li, Yonglei Feng, Liwei Wang, Xianke Sun. Bi3+ → Mn2+ energy transfer and tunable luminescence in Ba9La2Si6O24:Bi3+/Mn2+ phosphors. Optical Materials 2022, 131 , 112593.
    29. Jianyan Ding, Yongwang Li, Xufeng Zhou, Wenjun Yuan, Weibin Zhang, ShanShan Ye, Jiangcong Zhou, Mengting Chen, Quansheng Wu. A novel Bi3+-Activated garnet phosphor with site-selected excitations and high temperature sensitivity. Ceramics International 2022, 48 (16) , 23784-23792.
    30. Hongzhi Zhang, Jing Zhang, Yuchang Su, Xinmin Zhang. Metal To Metal Charge Transfer Induced Efficient Yellow/Far‐Red Luminescence in Na 2 Ca 3 (Nb, Ta) 2 O 9 :Bi 3+ toward the Applications of White‐LEDs and Plant Growth Light. Advanced Optical Materials 2022, 10 (10)
    31. Xiuna Tian, Changjun Wang, Hongjian Dou, Lingyuan Wu. Photoluminescence origin and non-contact thermometric properties in Pb2+-activated CaZrO3 perovskite phosphor. Journal of Alloys and Compounds 2022, 892 , 162250.
    32. Shanshan Ye, Jianyan Ding, Quansheng Wu. MMCT-induced high-bright yellow light-emitting phosphor Bi3+-activated Ba2YGaO5 used for WLED. Chemical Engineering Journal 2022, 428 , 131238.
    33. Yan-Xun Chen, Meng-Hung Tsai, I-Wei Tseng, Hung-Chi Yen, Cheng-Liang Huang. The photoluminescence of single-phase warm white-light-emitting luminescence using CaSnO 3 : Ce 3+ / Mn 4+ / Dy 3+ phosphors. Journal of Asian Ceramic Societies 2021, 9 (3) , 1055-1066.
    34. Zehua Zhang, Xin He, Lili Wang, Peng Zhang. The 1S0 → 3P1 transition position shift of Bi3+ ion doped Ln2O3 (Ln = Lu, Gd, La) phosphors. Journal of Luminescence 2021, 234 , 117971.
    35. Xiaoqi Liu, Puxian Xiong, Huailu Liu, Sheng Wu, Quan Liu, Yubin Fu, Zhijun Ma, Mingying Peng, Qinyuan Zhang. Origin of D-band emission in a novel Bi 3+ -doped phosphor La 3 SnGa 5 O 14 :Bi 3+. Journal of Materials Chemistry C 2021, 9 (10) , 3455-3461.
    36. Bibo Lou, Jun Wen, Jiajia Cai, Yau-Yuen Yeung, Min Yin, Chang-Kui Duan. First-principles study of Bi 3 + -related luminescence and traps in the perovskites Ca M O 3 ( M = Zr , Sn , Ti ) . Physical Review B 2021, 103 (7)
    37. Guangting Xiong, Lifang Yuan, Yahong Jin, Haoyi Wu, Zhenzhang Li, Bingyan Qu, Guifang Ju, Li Chen, Shihe Yang, Yihua Hu. Aliovalent Doping and Surface Grafting Enable Efficient and Stable Lead‐Free Blue‐Emitting Perovskite Derivative. Advanced Optical Materials 2020, 8 (20)
    38. Renping Cao, Yuan Ren, Ting Chen, Wenhao Wang, Qingdong Guo, Qianglin Hu, Chenxing Liao, Ting Fan. Emission improvement and tunable emission properties of SrZrSi2O7:R (R = Sm3+ and Sm3+/Bi3+) phosphors. Journal of Luminescence 2020, 225 , 117350.
    39. Djamel Ghaffor, Zakia Lounis, Chawki Zegadi, Abdelkrim Mahfoud, Amira Derri, Amel Hadj-Kaddour, M’hamed Bouslama. Point defects behavior analysis in thin films and massif SnO2 by AES spectroscopy and photoluminescence. Journal of Materials Science: Materials in Electronics 2020, 31 (13) , 10213-10224.
    40. Philippe Boutinaud. On the spectroscopy of Bi3+ in d10 post-transition metal oxides. Journal of Luminescence 2020, 223 , 117219.
    41. K. Saidi, M. Dammak. Crystal structure, optical spectroscopy and energy transfer properties in NaZnPO 4 :Ce 3+ , Tb 3+ phosphors for UV-based LEDs. RSC Advances 2020, 10 (37) , 21867-21875.
    42. Michele Back, Jumpei Ueda, Jian Xu, Kazuki Asami, Mikhail G. Brik, Setsuhisa Tanabe. Effective Ratiometric Luminescent Thermal Sensor by Cr 3+ ‐Doped Mullite Bi 2 Al 4 O 9 with Robust and Reliable Performances. Advanced Optical Materials 2020, 8 (11)
    43. Aleksei Krasnikov, Eva Mihokova, Martin Nikl, Svetlana Zazubovich, Yaroslav Zhydachevskyy. Luminescence Spectroscopy and Origin of Luminescence Centers in Bi-Doped Materials. Crystals 2020, 10 (3) , 208.
    44. Philippe Boutinaud, Mikhail G. Brik. The optical properties of Bi 3+ and Sb 3+ in YNbTiO 6 analysed by means of DOS and semi-empirical calculations. Journal of Materials Chemistry C 2020, 8 (6) , 2086-2093.
    45. Mükremin Yılmaz, Ertuğrul Erdoğmuş. Luminescence properties of ZnB2O4:Pb2+ phosphors: Suppression of concentration quenching. Journal of Luminescence 2020, 218 , 116868.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect