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Cs2NaInCl6
JOURNAL OF MATERIALS SCIENCE · 2021 ·Vol. 56 ·期 13 ·8048-8059 · IF 4.22

Mn2+-doped Cs2NaInCl6 double perovskites and their photoluminescence properties

Chen Luming,Yang Weiyou,Fu Hui,Liu Wenna,Shao Gang,Tang Bin,Zheng Jinju

Abstract Lead-free double perovskites are emerging as an excellent candidate material for optoelectronic devices, owing to their unique properties such as widely adjustable band gap and markedly lower toxicity than the lead-halide counterparts. In this work, a series of Mn 2+ -doped Cs 2 NaInCl 6 (Mn 2+ :Cs 2 NaInCl 6 ) DP crystals with tailored Mn 2+ -doping concentrations are synthesized. The effects of the reaction temperatures and Mn/(In + Na) ratios in the raw materials on the Mn 2+ doping concentrations and their photoluminescence (PL) properties are investigated systematically. The resultant DP crystals exhibit well-resolved Mn 2+ 4 T 1  →  6 A 1 d − d emission with an optimal PL quantum yield of 16% and an extremely long excited state lifetime up to ~ 17 ms, which is the longest one of Mn 2+ emission among those of Mn 2+ -doped II–VI semiconductors or perovskite materials ever reported. Furthermore, the temperature-dependent PL and PL decay are studied in the temperatures range from 120 to 480 K. The decay lifetime decreased monotonously with the rise in temperatures, while the PL intensity gradually reaches a maximum and then keeps nearly constant, followed by a sharp decrease. Such abnormal phenomenon is mainly attributed to the combined effect of intrinsic property of octahedrally coordinated Mn 2+ in perovskite lattice and enhanced electron–phonon coupling at elevated temperature. Graphical abstract

研究领域: 材料科学 · 光学
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Nanomaterials · 2023 ·Vol. 13 ·期 3 ·549 · IF 5.3

Tb3+ and Bi3+ Co-Doping of Lead-Free Cs2NaInCl6 Double Perovskite Nanocrystals for Tailoring Optical Properties

Yang Yu,Wei Zhou,Cheng Li,Peigeng Han,Hui Li,Kun Zhao

Lead halide perovskites have achieved remarkable success in various photovoltaic and optoelectronic applications, especially solar cells and light-emitting diodes (LEDs). Despite the significant advances of lead halide perovskites, lead toxicity and insufficient stability limit their commercialization. Lead-free double perovskites (DPs) are potential materials to address these issues because of their non-toxicity and high stability. By doping DP nanocrystals (NCs) with lanthanide ions (Ln3+), it is possible to make them more stable and impart their optical properties. In this work, a variable temperature hot injection method is used to synthesize lead-free Tb3+-doped Cs2NaInCl6DP NCs, which exhibit a major narrow green photoluminescence (PL) peak at 544 nm derived from the transition of Tb3+ 5D4→7F5. With further Bi3+co-doping, the Tb3+-Bi3+-co-doped Cs2NaInCl6DP NCs are not only directly excited at 280 nm but are also excited at 310 nm and 342 nm. The latter have a higher PL intensity because partial Tb3+ions are excited through more efficient energy transfer channels from the Bi3+to the Tb3+ions. The investigation of the underlying mechanism between the intrinsic emission of Cs2NaInCl6NCs and the narrow green PL caused by lanthanide ion doping in this paper will facilitate the development of lead-free halide perovskite NCs.Keywords:lead-free double perovskite;lanthanide ion doping;Cs2NaInCl6;nanocrystals

研究领域: 材料科学 · 光学
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JOURNAL OF RARE EARTHS · 2023 · IF 4.9

Sb3+ and Sm3+ co-doped lead-free Cs2NaInCl6 double perovskite nanocrystals for single-component cold white emitter

Biao Zhou,Xiangtong Zhang,Ranran Hu,Ruixue Hou,William W. Yu

Metal halide perovskites exhibit promising prospect in light-emitting diodes, solar cells, photodetectors and bioimaging. However, the workhorse of metal halide perovskites relies on toxicity lead element, which severely damages human body and environment. Among lead-free perovskites, Cs 2 NaInCl 6 double perovskite is one of the most promising candidates because of its great stability and easy synthesis, but suffers inadequate optical performance. Here, we doped Sb 3+ and Sm 3+ into Cs 2 NaInCl 6 nanocrystals by a hot injection method. Cs 2 NaInCl 6 :Sb 3+ exhibits blue emission at 447 nm. Cs 2 NaInCl 6 :Sm 3+ ,Sb 3+ nanocrystals simultaneously generate the blue emission of Sb 3+ and the multiple emissions of Sm 3+ at 565, 602, 650 and 710 nm. With the increase of Sm 3+ feed ratio, the emission color of Cs 2 NaInCl 6 :Sm 3+ ,Sb 3+ gradually moves to cold white region at (0.27, 0.28) in CIE chromaticity diagram and correlated color temperature of 11,840 K. This work shows the potential application of Cs 2 NaInCl 6 :Sm 3+ ,Sb 3+ nanocrystals as a single-component cold white emitter.

研究领域: 材料科学 · 光学
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Thermochromic Cs2NaInCl6: Sb3+/Ln3+ (Ln = Er, Dy, Tb, Ho) phosphors for multifunctional applications

You Li,Sai Xu,Yuefeng Gao,Yongze Cao,Xizhen Zhang,Hongquan Yu,Yichao Wang,Tianshuo Liu,Baojiu Chen

The intrinsic challenge to thermally responsive photoluminescent materials is pertaining to the limited thermal stability and reproducibility. Most prevailing photoluminescent agents suffer from constraints imposed by their frail chemical structure , rendering them fail to work at elevated temperatures for a long time. This inherent limitation curtails their utility within domains in anti-counterfeiting and encoded information storage. Herein, a series of double perovskite Cs 2 NaInCl 6 : Sb 3+ /Ln 3+ (Ln = Er, Dy, Tb, Ho) phosphors were synthesized using the high-temperature hydrothermal method . Upon ultraviolet light illumination, the blue emission band of self-trapped excitons (STEs) and intrinsic emissions of Ln 3+ are observed. In light of the variations in thermal quenching levels of the two emission centers and the effect of temperature on the lifetime of Ln 3+ , multi-mode thermometers with superior sensitivity are established. Moreover, they also can be used in anti-counterfeiting and encoding information storage, relying on the significant temperature-dependent color variation, excellent thermal stability and repeatability. The unique thermochromic properties and satisfactory stability of Cs 2 NaInCl 6 : Sb 3+ /Ln 3+ (Ln = Er, Dy, Tb, Ho) phosphors bring forward a new concept of developing multi-mode thermometers and reliable information encryption systems with the application of thermochromic materials.

研究领域: 材料科学 · 光学
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OPTICAL MATERIALS · 2023 · IF 3.9

Bromide ions substitution-induced photoluminescence tuning in Cs2NaInCl6:Sb3+ double perovskite

Fan Chen,Xiao-Jun Wang,Xuehu Zhang,Changhua Zhang

Compositional tune and doping/alloying routes have become the research focus for tailoring optical features of lead-free metal halide double perovskites to advance the development of solid-state lighting and display applications. Cs 2 NaInCl 6 double perovskite is receiving tremendous attention owing to its excellent optical properties . In this paper, we have successfully obtained the lead-free Cs 2 NaInCl 6-x Br x :Sb 3+ perovskites using the hydrothermal method . Via the substitution of bromine ions for chloride ions in Cs 2 NaInCl 6 :Sb 3+ , a tunable emission from 445 nm to 480 nm was realized. The X-ray diffraction, scanning electron microscope , UV–vis absorption spectra , PL spectra, TRPL spectra, air stability and thermal stability were investigated in detail. The sample shows an admirable air stability and excellent thermal stability. The results demonstrate that the cyan-emitting Cs 2 NaInCl 6-x Br x :Sb 3+ perovskites can be applied to white LEDs, especially for the full-spectrum LED illumination.

研究领域: 材料科学 · 光学工程
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CHEMISTRY OF MATERIALS · 2022 · IF 10.508

Efficient Multicolor and White Photoluminescence in Erbium- and Holmium-Incorporated Cs2NaInCl6:Sb3+ Double Perovskites

Jingheng Nie,Bo Zhou,Shaofan Fang,Haizhe Zhong,Henan Li,Yumeng Shi

Inorganic lead-free halide perovskites with a broad-band emission of self-trapped excitons (STEs) have attracted great attention in lighting applications. However, it remains a fundamental challenge to expand the display color gamut because it is difficult to individually tune the emitting proportion at different wavelengths. Herein, we employ a doping route to incorporate Sb3+, Er3+, and Ho3+ ions into the Cs2NaInCl6, which enables multicolor emissions with narrow full width at half-maxima and high photoluminescence quantum yields (PLQYs). The blue emission (445 nm) originates from STEs in the [SbCl6]3– octahedrons, while the narrowband green (550 nm) and red (655 nm) emissions are mainly derived from the Er3+ and Ho3+ ions, respectively. An efficient energy transfer between multiple luminescent centers is the key point to achieve such an efficient and tunable emission. By controlling the lanthanide doping level, the emission color can be systematically modulated, and cold 10401 K (0.278, 0.286) to warm 4608 K (0.347, 0.298) adjustable white-light emission (PLQY of ∼70%) can be achieved successfully. The results provide inspiration for the material design of lead-free perovskites with efficient and tunable light-emitting properties for optoelectronic applications.

研究领域: 材料科学 · 光学
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INORGANIC CHEMISTRY · 2025 · IF 4.7

Cr3+/Yb3+ Codoped Cs2NaInCl6 Double Perovskites for Near-Infrared Light-Emitting Diodes

Xinyu Fu,Huwei Li,Hongxia Yue,Zheyu Li,Jing Feng,Hongjie Zhang

Near-infrared (NIR) light-emitting diodes (LEDs) are potential devices that could become the core components in biological imaging, security monitoring, etc., which are currently constrained by suboptimal luminous efficiency due to the absence of excellent luminescent materials. Here, we report a double perovskite Cs2NaInCl6 that is suitable for Cr3+ doping and exhibits broad NIR emission. Through direct absorption and energy transfer (ET) from the self-trapped excitons (STEs) induced in the Cs2NaInCl6 matrix, Cr3+ can be excited to 4T1(P), 4T1(F), and 4T2(F) levels. Then, the broad emission with a full width at half-maximum (FWHM) of ∼150 nm, spanning 800 to 1300 nm, and a high photoluminescence quantum yield (PLQY) of up to 70% can be realized, resulting from the 4T2→4A2 transition of Cr3+. Subsequently, the introduction of Yb3+ endows Cs2NaInCl6:Cr3+,Yb3+ with a higher PLQY of 76% at the optimal doping ratio than Cs2NaInCl6:Cr3+. Ultimately, a miniaturized NIR LED device packaged based on Cs2NaInCl6:15%Cr3+,15%Yb3+ has been fabricated, which demonstrates superior performance for night vision, traceless perspective detection, and biological imaging. This work not only screens out a suitable Cs2NaInCl6 matrix for Cr3+ doping with high PLQY but also promotes its luminescence performance through Yb3+ doping for NIR LED applications.

研究领域: 材料科学 · 光学工程
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

In Situ Fabrication of Highly Efficient and Stable Cs2NaInCl6: Sb3+@PVDF Composite Films for Optoelectronic Devices

Wen Li,Yongrun Dong,Ting Xie,Tongzhou Li,Chuang Ning,Tao Huang,Zequan Li,Wei Gao,Bingsuo Zou

Lead-free double perovskites (DPs) have superior phase stability and optical properties, which make them competitive for future applications in illumination and displays. However, the preparation of DPs was mainly based on high-temperature heating and hydrochloric acid as a solvent to form powders, which increased the risk and cost of the preparation process and limited its further application. In this study, the growth of Cs2NaInCl6: Sb3+ DPs in polyvinylidene difluoride (PVDF) films was achieved using an in situ fabrication strategy with DMSO as the solvent. The prepared Cs2NaInCl6: Sb3+@PVDF composite films (CFs) can achieve a bright blue emission under 302 nm irradiation. To achieve the optimal luminescent performance of CFs, the photoluminescence (PL) intensity of Cs2NaInCl6: Sb3+@PVDF CFs under various in situ preparation conditions was compared. In addition, the photoluminescence quantum yield (PLQY) of CFs was increased from 0.72% to 83.77% by adjusting the doping amount of Sb3+, and the fluorescence lifetimes t1 and t2 were 131.08 and 1048.52 ns, respectively. Temperature-dependent PL spectroscopy and density functional theory (DFT) calculations indicate that these excellent optical properties are derived from the self-trapped excitons (STEs) at the [SbCl6]3– octahedron and [InCl6]3– octahedron connected via Cl–Na–Cl. The CFs also demonstrated excellent environmental stability, maintaining a relatively stable PL intensity even under conditions of water immersion, high temperatures, and ultraviolet (UV) radiation. Finally, we used the CFs to assemble a blue light-emitting device (LED), which showed good and stable blue emission performance at different currents. This work can provide a new idea for preparing DPs, which is conducive to promoting their commercial application in high-performance optoelectronic devices.

研究领域: 材料科学 · 光学
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JOURNAL OF LUMINESCENCE · 2024 · IF 3.3

Tunable multicolor-emission in Eu3+ and Tb3+ codoped Cs2NaInCl6:Sb3+ double perovskite nanocrystals and its dual-model anti-counterfeiting and temperature-sensing applications

Xugang Cao,Yue Zhai,Diwen Guan,Xianwei Wang,Qiangqiang Zhu,Shuangqiang Fang,Hong Zhang,Le Wang

Lead-free metal halide double perovskites with non-toxicity and stable self-trapped excitons (STEs) have received considerable attention in the field of photoelectric applications. However, it is difficult to achieve independent control of its photoluminescence performance to meet the requirements of multi-band emission. Herein, a doping strategy was employed to introduce lanthanide ions (Ln 3+ ) into Cs 2 NaInCl 6 :Sb 3+ nanocrystals (NCs), enabling the multicolor emission modulation ranging from blue to red and even white light. Benefiting from the efficient energy transfer from Sb-related self-trapped excitons to Ln 3+ ions, green and red emissions originate from the 5 D 0 → 7 F J (J = 1, 2, 3, 4) transition of Eu 3+ ions and 5 D 4 - 7 F J (J = 6, 5, 4, 3) transition of Tb 3+ ions, respectively. According to the tunable polychromatic photoluminescence characteristics of doped NCs, the dual-mode fluorescent anti-counterfeiting applications were exhibited. Furthermore, the distinct temperature sensitivities exhibited by blue (453 nm) and red (617 nm) emission in Cs 2 NaInCl 6 :Sb 3+ /Eu 3+ NCs provide the opportunity for the optical thermometry, which demonstrates the maximum absolute and relative sensitivity are 0.0018 and 0.43 % K −1 , respectively. These results indicate that the synthesized codoped NCs have the potential applications in multifunctional fields, such as optical thermometer, fluorescence anti-counterfeiting, and multicolor-LEDs.

研究领域: 材料科学 · 光电子学 · 纳米技术 · 光子学
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Advanced Optical Materials · 2025 · IF 7.2

Ultra-Linear Power Dependency of Photon Release in Cs2NaInCl6: Ho3+/Yb3+ for Multifunctional Integration of Flexible Temperature Sensing and NIR Bioimaging

Xiaolong Dong,Xin Zhao,Lifan Shen,Maosen Hu,Edwin Yue Bun Pun,Hai Lin

The construction of perovskite-based luminescent systems for multifunctional integrated platforms via reciprocal energy transfer (ET) cascades emerges as a central focus, but the material design and photophysical control remain a significant challenge. Herein, a strong power-dependent quantum yield behavior is observed in Cs 2 NaInCl 6 : Ho 3+ -Yb 3+ (CNIC: Ho-Yb) phosphors with ultra-low phonon energy, and quantified multiphoton upconversion (UC) efficiencies exhibit ultra-linear enhancement with the increasing excitation power, ensuring practical applicability for UC-based temperature sensing. Moreover, an efficient quantum cutting process is unveiled in the CNIC: Ho-Yb, where a single high-energy photon of Ho 3+ is converted into multiple NIR emissions of Yb 3+ via energy redistribution under 453 nm laser excitation, offering significant potential for enhancing near-infrared (NIR) imaging capability in biological tissues. To address the inherent structural and functional limitations of powder-based materials, the CNIC: Ho-Yb/polyacrylonitrile (CNIC: Ho-Yb/PAN) nanofibers are synthesized by electrospinning, and the functional integration platform based on the efficient bidirectional ET is built by coupling 453 and 980 nm lasers to enable selective applications in flexible thermal monitoring and NIR bioimaging. These findings enable next-generation flexible thermometry platforms with higher sensitivity, signal fidelity, and device-level applicability, while also paving the way for non-invasive and high-contrast deep-tissue imaging in biomedical diagnostics.

研究领域: 材料科学 · 光学物理 · 纳米技术 · 生物医学工程 · 发光 · 能量传递 · 传感器 · 生物成像
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Cell Reports Physical Science · 2022 · IF 7.832

Efficient red photoluminescence in holmium-doped Cs2NaInCl6 double perovskite

Jingheng Nie,Henan Li,Shaofan Fang,Bo Zhou,Zexiang Liu,Fuming Chen,Ye Wang,Yumeng Shi

Metal halide perovskites with efficient and stable self-trapped exciton emission have attracted considerable attention for next-generation solid-state lighting owing to their ultrabroadband emission. However, it remains challenging to widen the color gamut and realize high color-rendering index due to the lack of highly saturated red color-emitting inorganic lead-free perovskite materials with narrow full width at half-maximum. Here, we report a lanthanide-codoped system (Cs 2 NaInCl 6 :Sb 3+ /Ho 3+ ) that enables efficient blue and red emissions with photoluminescence quantum yields of up to 99% and 72%, respectively. The energy transfer efficiency in Ho 3+ -doped Cs 2 NaInCl 6 :Sb is up to 73%, which can overcome the weak absorption cross-section of the f-f transition of lanthanide ion and improve its luminescence performance. Benefitting from the efficient energy-transfer channel from the self-trapped excitons to Ho 3+ , the emission color is continuously tuned from blue to red by controlling the Ho 3+ -doping concentration.

研究领域: 材料科学 · 光学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2025 · IF 6.3

Efficient white photoluminescence in manganese-doped Cs2NaInCl6:Sb3+ double perovskite single crystals

Pei Jiang,Hao Liang,Jie Sun,Yinhua Wang,Yi Zhang,Meng Zhou,Gang Yang,Yongsheng Zhu

Inorganic lead-free halide double perovskites are attracting significant attention for light-emitting diodes (LEDs), owing to their broad-band emission of self-trapped excitons (STEs) and exceptional environmental friendliness. However, it remains a challenge to modulate their spectra and enhance the photoluminescence quantum yield (PLQY) to meet different application requirements. Herein, a doping route was adopted to incorporate Sb 3+ ions into the Cs 2 NaInCl 6 for enhancing STEs density, and the highest PLQY of Cs 2 NaInCl 6 :3 %Sb 3+ single crystals (SCs) was up to about 84 %. By introducing Mn 2+ ions the emission color was flexibly modulated from blue to red. Especially, white light emission with high color rendering index and tunable correlated color temperature for Sb 3+ , Mn 2+ co-doped Cs 2 NaInCl 6 SCs were realized by high pressure treatment as well as doping commercial green phosphor. These findings provide new inspiration and strategies for the design and synthesis of novel inorganic halide double perovskites with enhanced optoelectronic properties.

研究领域: 材料科学 · 光学
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