Dynamic multicolor emissions of multimodal phosphors by Mn2+ trace doping in self-activated CaGa4O7

Yiqian Tang; Yiyu Cai; Kunpeng Dou; Jianqing Chang; Wei Li; Shanshan Wang; Mingzi Sun; Bolong Huang; Xiaofeng Liu; Jianrong Qiu; Lei Zhou; Mingmei Wu; Jun-Cheng Zhang

doi:10.1038/s41467-024-47431-0

Dynamic multicolor emissions of multimodal phosphors by Mn²⁺ trace doping in self-activated CaGa₄O₇

Nat Commun. 2024 Apr 13;15(1):3209. doi: 10.1038/s41467-024-47431-0.

Authors

Yiqian Tang^#^{1

2}, Yiyu Cai^#^{1

2}, Kunpeng Dou^{1

2}, Jianqing Chang^{1

2}, Wei Li^{1

2}, Shanshan Wang^{1

2}, Mingzi Sun³, Bolong Huang⁴, Xiaofeng Liu⁵, Jianrong Qiu⁵, Lei Zhou⁶, Mingmei Wu⁶, Jun-Cheng Zhang^{7

8}

Affiliations

¹ College of Physics and Optoelectronic Engineering, Faculty of Information Science and Engineering, Ocean University of China, Qingdao, 266100, China.
² Engineering Research Center of Advanced Marine Physical Instruments and Equipment of Education Ministry of China, and Key Laboratory of Optics and Optoelectronics of Qingdao, Ocean University of China, Qingdao, 266100, China.
³ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong SAR, China.
⁴ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong SAR, China. bhuang@polyu.edu.hk.
⁵ College of Optical Science and Engineering, State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou, 310027, China.
⁶ School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, China.
⁷ College of Physics and Optoelectronic Engineering, Faculty of Information Science and Engineering, Ocean University of China, Qingdao, 266100, China. zhangjuncheng@ouc.edu.cn.
⁸ Engineering Research Center of Advanced Marine Physical Instruments and Equipment of Education Ministry of China, and Key Laboratory of Optics and Optoelectronics of Qingdao, Ocean University of China, Qingdao, 266100, China. zhangjuncheng@ouc.edu.cn.

^# Contributed equally.

Abstract

The manipulation of excitation modes and resultant emission colors in luminescent materials holds pivotal importance for encrypting information in anti-counterfeiting applications. Despite considerable achievements in multimodal and multicolor luminescent materials, existing options generally suffer from static monocolor emission under fixed external stimulation, rendering them vulnerability to replication. Achieving dynamic multimodal luminescence within a single material presents a promising yet challenging solution. Here, we report the development of a phosphor exhibiting dynamic multicolor photoluminescence (PL) and photo-thermo-mechanically responsive multimodal emissions through the incorporation of trace Mn²⁺ ions into a self-activated CaGa₄O₇ host. The resulting phosphor offers adjustable emission-color changing rates, controllable via re-excitation intervals and photoexcitation powers. Additionally, it demonstrates temperature-induced color reversal and anti-thermal-quenched emission, alongside reproducible elastic mechanoluminescence (ML) characterized by high mechanical durability. Theoretical calculations elucidate electron transfer pathways dominated by intrinsic interstitial defects and vacancies for dynamic multicolor emission. Mn²⁺ dopants serve a dual role in stabilizing nearby defects and introducing additional defect levels, enabling flexible multi-responsive luminescence. This developed phosphor facilitates evolutionary color/pattern displays in both temporal and spatial dimensions using readily available tools, offering significant promise for dynamic anticounterfeiting displays and multimode sensing applications.

Abstract

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