Lead-Free Cs4CuSb2Cl12 Layered Double Perovskite Nanocrystals

Cai, Tong; Shi, Wenwu; Hwang, Sooyeon; Kobbekaduwa, Kanishka; Nagaoka, Yosuke; Yang, Hanjun; Hills‐Kimball, Katie; Zhu, Hua; Wang, Junyu; Wang, Zhiguo; Liu, Yuzi; Su, Dong; Gao, Jianbo; Chen, Ou

doi:10.1021/jacs.0c04919

Cited by 161 publications

(189 citation statements)

References 74 publications

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“…Crystal structures of <100>‐oriented OIHPs, <100>‐oriented HDPs, and <111>‐oriented vacancy‐ordered layered HDPs with q = 2 and q = 3 are shown in Figure 3b. [ 123 ] A new layered quadruple HDP with <111> orientation Cs 4 CuSb 2 Cl 12 was first synthesized by Solis‐Ibarra and coworkers. [ 124 ] Layered <111>‐oriented HDPs with q = 3 can be obtained by replacing monovalent cations at the B′ site by a half‐and‐half mixture of bivalent cations and vacancies.…”

Section: Structural Diversity Of Hdpsmentioning

confidence: 99%

“…[ 119,125–127 ] Recently, Cai et al synthesized Cs 4 Cu x Ag 2−2 x Sb 2 Cl 12 (0 ≤ x ≤ 1) NCs with a uniform sphere‐like shape for the first time. [ 123 ] The vacancy‐ordered HDP NCs have electronic band structural transition from a wide indirect bandgap to a narrow direct bandgap with increased Cu content. Transmission electron microscopy (TEM) images show that the NCs have cubic shape with a HDP structure in the cubic phase ( x < 0.5) and then turn to a sphere‐like shape for the NCs with a layered quadruple HDP structure in the monoclinic phase ( x ≥ 0.5) with similar diameters.…”

Section: Structural Diversity Of Hdpsmentioning

confidence: 99%

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Lead‐Free Halide Double Perovskites: Structure, Luminescence, and Applications

Zeng

2020

Small Structures

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Organic–inorganic halide perovskites have attracted extensive attention due to their excellent optoelectronic properties. However, the toxicity of heavy atom Pb2+ and instability overshadow further commercial applications, motivating researchers to explore alternative analogues to overcome these disadvantages. Lead‐free halide double perovskites (HDPs), sharing similar crystal structures with organic–inorganic halide perovskites, are promising candidates for optoelectronic applications. However, HDPs possess unique properties that are uncommon in organic–inorganic halide perovskites deriving from feasible component engineering and strong electron–phonon interaction. Bright luminescence in HDPs originates from self‐trapped excitons (STEs) and sensitized dopants can cover the full visible and near‐infrared ray (NIR) gamut by modulating parity‐forbidden transitions and the energy‐transfer process. The superior optoelectronic characteristics of HDPs further extend applications on self‐assembly, white‐light phosphors, NIR bioimaging, and scintillators, in comparison to organic–inorganic halide perovskites. Herein, the structural diversity, tunable luminescence, photophysical mechanism of STEs, charge‐carrier dynamics, size effect, and stability issues of HDPs are discussed. The challenges and outlook for further investigations are also given, which may help in discovering new analogues and boosting the photoluminescence quantum yield and stability of HDPs.

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Section: Structural Diversity Of Hdpsmentioning

confidence: 99%

Section: Structural Diversity Of Hdpsmentioning

confidence: 99%

Lead‐Free Halide Double Perovskites: Structure, Luminescence, and Applications

Zeng

2020

Small Structures

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“…Unlike Cu 2+ in the Cs 4 CuSb 2 Cl 12 structure, Cd 2+ forms perfect CdCl 6 octahedra within the Cs 4 CdSb 2 Cl 12 structure, with Cd−Cl distances of 2.274 (17) Å. [25][26][27] The lack of distortion near the metal center is responsible for the higher-symmetry space group of Cs 4 CdSb 2 Cl 12 (R3̅ m) compared to Cs 4 CuSb 2 Cl 12 (C2/m). The PXRD results were also compared with results from the calculation based on the trigonal R3̅ m structure ( Figure S1, Supporting Information).…”

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confidence: 99%

Efficient Luminescent Halide Quadruple‐Perovskite Nanocrystals via Trap‐Engineering for Highly Sensitive Photodetectors

et al. 2021

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elements to replace lead due to the high toxicity. Lead-free halide perovskite NCs have recently received increasing attention for their low toxicity, high stability, and chemical diversity. [3-8] The most direct way is usually isovalent substitution of Pb 2+ with Sn 2+. [3] Unfortunately, lead-free CsSnX 3 (X = Cl, Br, and I) NCs is extremely unstable because of the easy oxidation of Sn 2+ into Sn 4+ in air. [3] Subsequently, A 3 M ' 2 X 9-type layer perovskite, A 2 MM ' X 6-type, and A 2 BX 6-type double perovskite (where A denotes alkali-metal ions; M, M' and B denotes monovalent-, trivalent-, and tetravalent-cations; X denotes halogen ions) with high stability have been reported. [9-20] However, optoelectronic devices based on these lead-free perovskite NCs have made limited progress. Such as, photodetectors based on lead-free perovskite NCs exhibited low responsivity (typically <1 A W −1). [17,18] This is mainly due to the low crystallinity, prominent charge-carrier trapping, and short charge-carrier lifetimes of these NCs. In this paper, we report, for the first time, the colloidal synthesis of a series of trigonal (R3̅ m) vacancy-ordered quadrupleperovskite NCs, i.e., Cs 4 CdSb 2 Cl 12 , Cs 4 MnSb 2 Cl 12 , Cs 4 CdBi 2 Cl 12 , and Cs 4 MnBi 2 Cl 12. The photoluminescence quantum yield (PLQY) can be enhanced by 96-fold while the PL lifetime can be enhanced by 77-fold in Cs 4 MnBi 2 Cl 12 NCs through metal alloying. Studies of the charge-carrier dynamics including temperature-dependent PL and femtosecond (fs) transient absorption (TA) measurements were performed to clarify the mechanism of the PL enhancement, which is due to the elimination of the charge-carrier trapping process and increased crystallinity. Besides, the PL-peak position can be tuned continuously from 590 to 640 nm by changing the MnCl bond distance via metal alloying. Finally, we fabricate photodetectors based on quadruple-perovskite NCs, which exhibit high responsivity (0.98 × 10 4 A W −1) and an EQE of 3 × 10 6 %. The responsivity is much higher than previous reported photodetectors base on lead-free perovskite NCs. These results show that quadruple-perovskite NCs open new possibilities for optoelectronic applications. The colloidal synthesis of halide quadruple-perovskite NCs was performed using a modified hot-injection method-for details see the Experimental Section. [14] As shown in Figure 1a,b, replacing M in A 2 MM'X 6 with one M'' (M'' denotes a +2 cation) The colloidal synthesis of a new type of lead-free halide quadruple-perovskite nanocrystals (NCs) is reported. The photoluminescence quantum yield and charge-carrier lifetime of quadruple-perovskite NCs can be enhanced by 96 and 77-fold, respectively, via metal alloying. Study of charge-carrier dynamics provide solid demonstrate that the PL enhancement is due to the elimination of ultrafast (1.4 ps) charge-carrier trapping processes in the alloyed NCs. Thanks to the high crystallinity, low trap-state density, and long carrier lifetime (193.4 μs), the alloyed quadruple-perovskite N...

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“…For instance, Cs 4 CuSb 2 Cl 12 layered HDP nanocrystals with spherical like shape and average diameter of 12.5 nm were prepared via modified hot‐injection method. [ 129 ]…”

Section: Strategies For Boosting the Efficiency Of Halide Double Peromentioning

confidence: 99%

Lead‐Free Halide Double Perovskite Nanocrystals for Light‐Emitting Applications: Strategies for Boosting Efficiency and Stability

et al. 2021

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Lead‐free halide double perovskite (HDP) nanocrystals are considered as one of the most promising alternatives to the lead halide perovskite nanocrystals due to their unique characteristics of nontoxicity, robust intrinsic thermodynamic stability, rich and tunable optoelectronic properties. Although lead‐free HDP variants with highly efficient emission are synthesized and characterized, the photoluminescent (PL) properties of colloidal HDP nanocrystals still have enormous challenges for application in light‐emitting diode (LED) devices due to their intrinsic and surface defects, indirect band, and disallowable optical transitions. Herein, recent progress on the synthetic strategies, ligands passivation, and metal doping/alloying for boosting efficiency and stability of HDP nanocrystals is comprehensive summarized. It begins by introducing the crystalline structure, electronic structure, and PL mechanism of lead‐free HDPs. Next, the limiting factors on PL properties and origins of instability are analyzed, followed by highlighting the effects of synthesis strategies, ligands passivation, and metal doping/alloying on the PL properties and stability of the HDPs. Then, their preliminary applications for LED devices are emphasized. Finally, the challenges and prospects concerning the development of highly efficient and stable HDP nanocrystals‐based LED devices in the future are proposed.

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Lead-Free Cs₄CuSb₂Cl₁₂ Layered Double Perovskite Nanocrystals

Cited by 161 publications

References 74 publications

Lead‐Free Halide Double Perovskites: Structure, Luminescence, and Applications

Lead‐Free Halide Double Perovskites: Structure, Luminescence, and Applications

Efficient Luminescent Halide Quadruple‐Perovskite Nanocrystals via Trap‐Engineering for Highly Sensitive Photodetectors

Lead‐Free Halide Double Perovskite Nanocrystals for Light‐Emitting Applications: Strategies for Boosting Efficiency and Stability

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