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1. Synthesis of lead-free Cs ₄ (Cd _1−x Mn _x )Bi ₂ Cl ₁₂ (0 ≤ x ≤ 1) layered double perovskite nanocrystals with controlled Mn–Mn coupling interaction

   https://doi.org/10.1039/D0NR06771G  

   Yang, Hanjun; Shi, Wenwu; Cai, Tong; Hills-Kimball, Katie; Liu, Zhenyang; Dube, Lacie; Chen, Ou (November 2020, Nanoscale)

   null (Ed.)

   Lead-free perovskites and their analogues have been extensively studied as a class of next-generation luminescent and optoelectronic materials. Herein, we report the synthesis of new colloidal Cs 4 M( ii )Bi 2 Cl 12 (M( ii ) = Cd, Mn) nanocrystals (NCs) with unique luminescence properties. The obtained Cs 4 M( ii )Bi 2 Cl 12 NCs show a layered double perovskite (LDP) crystal structure with good particle stability. Density functional theory calculations show that both samples exhibit a wide, direct bandgap feature. Remarkably, the strong Mn–Mn coupling effect of the Cs 4 M( ii )Bi 2 Cl 12 NCs results in an ultra-short Mn photoluminescence (PL) decay lifetime of around 10 μs, around two orders of magnitude faster than commonly observed Mn 2+ dopant emission in NCs. Diluting the Mn 2+ ion concentration through forming Cs 4 (Cd 1−x Mn x )Bi 2 Cl 12 (0 < x < 1) alloyed LDP NCs leads to prolonged PL lifetimes and enhanced PL quantum yields. Our study provides the first synthetic example of Bi-based LDP colloidal NCs with potential for serving as a new category of stable lead-free perovskite-type materials for various applications. 

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2. Ultra-stable blue-emitting lead-free double perovskite Cs ₂ SnCl ₆ nanocrystals enabled by an aqueous synthesis on a microfluidic platform

   https://doi.org/10.1039/D2NR05510D  

   Tang, Xiaobing; Wen, Xiyu; Yang, Fuqian (December 2022, Nanoscale)

   Blue emitting Sn-based lead-free halide perovskite nanocrystals (NCs) are considered to be a promising material in lighting and displays. However, industrialised fabrication of blue-emitting NCs still remains a significant challenge due to the use of toxic solvents and optical instability, not mentioning in large-scale synthesis. In this work, a green-route synthesis of blue-emitting lead-free halide perovskite Cs 2 SnCl 6 powders is developed, in which deionized water with a small amount of inorganic acid is used as the solvent and the synthesis of the Cs 2 SnCl 6 powders is achieved on a microfluidic platform. Using the Cs 2 SnCl 6 powders, we prepare Cs 2 SnCl 6 NCs via an ultrasonication process. Changing the volume ratio of the ligands (oleic acid to oleylamine) can alter the photoluminescence (PL) characteristics of the prepared NCs, including the PL-peak wavelength, PL-peak intensity and quantum yield. The highest photoluminescence quantum yield (PLQY) of 13.4% is achieved by the Cs 2 SnCl 6 NCs prepared with the volume ratio of oleic acid to oleylamine of 40 μL to 10 μL. A long-term PL stability test demonstrates that the as-synthesized Cs 2 SnCl 6 NCs can retain a stable PLQY over a period of 60 days. This work opens up a new path for a large-scale green-route synthesis of blue-emitting Sn-based lead-free NCs, such as Cs 2 SnX 6 (Cl, Br and I), towards their applications in optoelectronics. 

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3. Tunable optical properties and stability of lead free all inorganic perovskites (Cs ₂ SnI _x Cl _6−x )

   https://doi.org/10.1039/c7ta10040j  

   Zhu, Weiguang; Xin, Guoqing; Wang, Yiping; Min, Xin; Yao, Tiankai; Xu, Wenqian; Fang, Minghao; Shi, Sufei; Shi, Jian; Lian, Jie (January 2018, Journal of Materials Chemistry A)

   Organic–inorganic hybrid lead-based perovskites experience significant environmental instability under ambient moist air and are not environmentally benign due to the usage of toxic Pb. Here, we report a new approach to synthesize lead-free all inorganic perovskites (Cs 2 SnI x Cl 6−x ) using hydriodic acid (HI) demonstrating greatly enhanced environmental stability and tunable optical properties by controlling the I − /Cl − ratios. Single phase perovskites can be achieved with a low iodine or chlorine content, and a phase separation occurs in the binary system with closer iodine and chlorine dopings. UV-vis diffuse reflectance and photoluminescence measurements reveal tunable band gaps of Cs 2 SnI x Cl 6−x perovskites from the UV to the infrared region. The mixed halide perovskite with a lower chloride content shows significantly higher photoluminescence intensity. The thermal stability of mixed halide all-inorganic perovskites is continuously improved as the Cl content increases. The synthesis of Sn-based perovskites with tunable optical properties and environmental stability represents one step further toward the realization of the stable lead-free all inorganic perovskites. 

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4. High-efficiency blue photoluminescence in the Cs ₂ NaInCl ₆ :Sb ³⁺ double perovskite phosphor

   https://doi.org/10.1039/D0TC01037E  

   Gray, Matthew B.; Hariyani, Shruti; Strom, T. Amanda; Majher, Jackson D.; Brgoch, Jakoah; Woodward, Patrick M. (May 2020, Journal of Materials Chemistry C)

   null (Ed.)

   In this paper, the photoluminescent properties of a lead-free double perovskite Cs 2 NaInCl 6 doped with Sb 3+ are explored. The host crystal structure is a cubic double perovskite with Fm 3̄ m symmetry, a = 10.53344(4) Å, and rock salt ordering of Na + and In 3+ . It is a wide bandgap compound ( E g ≈ 5.1 eV), and substitution with Sb 3+ leads to strong absorption in the UV due to localized 5s 2 → 5s 1 5p 1 transitions on Sb 3+ centers. Radiative relaxation back to the 5s 2 ground state, via a 3 P 1 → 1 S 0 transition, leads to intense blue luminescence, centered at 445 nm, with a photoluminescent quantum yield of 79%. The Stokes shift of 0.94 eV is roughly 33% smaller than it is in the related vacancy ordered double perovskite Cs 2 SnCl 6 . The reduction in Stokes shift is likely due to a change in coordination number of Sb 3+ from 6-coordinate in Cs 2 NaInCl 6 to 5-coordinate in Cs 2 SnCl 6 . In addition to the high quantum yield, Cs 2 NaInCl 6 :Sb 3+ exhibits excellent air/moisture stability and can be prepared from solution; these characteristics make it a promising blue phosphor for applications involving near-UV excitation. 

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5. Unconventional route to dual-shelled organolead halide perovskite nanocrystals with controlled dimensions, surface chemistry, and stabilities

   https://doi.org/10.1126/sciadv.aax4424  

   He, Yanjie; Yoon, Young Jun; Harn, Yeu Wei; Biesold-McGee, Gill V.; Liang, Shuang; Lin, Chun Hao; Tsukruk, Vladimir V.; Thadhani, Naresh; Kang, Zhitao; Lin, Zhiqun (November 2019, Science Advances)

   The past few years have witnessed rapid advances in the synthesis of high-quality perovskite nanocrystals (PNCs). However, despite the impressive developments, the stability of PNCs remains a substantial challenge. The ability to reliably improve stability of PNCs while retaining their individual nanometer size represents a critical step that underpins future advances in optoelectronic applications. Here, we report an unconventional strategy for crafting dual-shelled PNCs (i.e., polymer-ligated perovskite/SiO 2 core/shell NCs) with exquisite control over dimensions, surface chemistry, and stabilities. In stark contrast to conventional methods, our strategy relies on capitalizing on judiciously designed star-like copolymers as nanoreactors to render the growth of core/shell NCs with controlled yet tunable perovskite core diameter, SiO 2 shell thickness, and surface chemistry. Consequently, the resulting polymer-tethered perovskite/SiO 2 core/shell NCs display concurrently a stellar set of substantially improved stabilities (i.e., colloidal stability, chemical composition stability, photostability, water stability), while having appealing solution processability, which are unattainable by conventional methods. 

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