skip to main content


Title: Epitaxial Growth of Lead‐Free Double Perovskite Shell for CsPbX 3 /Cs 2 SnX 6 (X = Cl, Br, and I) Core/Shell Perovskite Nanocrystals with Enhanced Photoelectric Properties and Stability
Abstract

All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6(X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3and CsPbBr3NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.

 
more » « less
Award ID(s):
1944978
NSF-PAR ID:
10472191
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
34
Issue:
7
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Lead halide perovskites have recently attracted intensive attention as competitive alternative candidates of legacy compound materials CdTe, CdZnTe, and TlBr for high sensitivity energy‐resolving gamma‐ray detection at room temperature. However, the use of lead in these lead halide perovskites, which is necessary for increasing the stopping power of gamma radiation, poses a serious environmental concern due to the high toxicity of lead. In this regard, environmental‐friendly perovskite‐based gamma‐ray detector materials with key energy‐resolving capabilities are highly desired. Here, the gamma energy‐resolving performance of a new class of all‐inorganic and lead‐free Cs2AgBiBr6double perovskite single crystals (SCs) is reported. Two types of Cs2AgBiBr6SCs, prepared by Bi‐normal and Bi‐poor precursor solutions, respectively, have been grown. Their mobilities and response to gamma radiation are presented. Density of trap states in Bi‐poor Cs2AgBiBr6SCs (2.65 × 109 cm−3) is one order of magnitude lower than that in Bi‐normal Cs2AgBiBr6SCs (3.85 × 1010 cm−3). Using laser‐induced photocurrent measurements, the obtained mobility–lifetime (μ–τ) product in Bi‐poor Cs2AgBiBr6SCs is 1.47 × 10−3 cm2 V−1, indicating their great potentials for gamma‐ray detection. Further, the fabricated detector based on Bi‐poor Cs2AgBiBr6SC shows response to 59.5 keV gamma‐ray with an energy resolution of 13.91%.

     
    more » « less
  2. 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. 
    more » « less
  3. 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. 
    more » « less
  4. Abstract

    Compared to halides Cs2HfX6(X = Cl, Br, I) with a vacancy‐ordered cubic double perovskite structure, the halide Cs2HfF6(CHF), with a hexagonal Bravais lattice, possesses a higher mass density and chemical stability for radiation detection. Luminescence properties and energy transfer mechanisms of rare‐earths‐doped CHF materials are studied here. The structure of CHF is identified as a new type of vacancy‐ordered hexagonal perovskite, with the same type of building blocks of the double perovskite but stacked with single layers. Density‐functional theory calculations reveal a large bandgap of CHF. A broad emission is observed from the pristine CHF host, which is suggested to be associated with self‐trapped excitons (STEs). A series of rare‐earths‐doped materials are designed utilizing the STE emissions, and efficient energy transfers from STEs and Tb3+to Eu3+are achieved for tunable emissions. The codoped material shows stable emission under X‐ray irradiation, with 10.2% reduction from its initial emission intensity, associated with possible structural evolution by radiation‐induced deformation of the soft host. The radiation responses of singly and codoped materials are evaluated, and the codoped material is found to be more sensitive to the radiation energy than the singly doped or pristine CHF for radiation detection.

     
    more » « less
  5. Abstract

    Organometal halide perovskites have powerful intrinsic potential to drive next‐generation solar technology, but their insufficient thermomechanical reliability and unproven large‐area manufacturability limit competition with incumbent silicon photovoltaics. This work addresses these limitations by leveraging large‐area processing and robust inorganic hole transport layers (HTLs). Inverted perovskite solar cells utilizing NiOxHTLs deposited by rapid aqueous spray‐coating that outperform spin‐coated NiOxand lead to a 5× improvement in the fracture energy (Gc), a primary metric of thermomechanical stability, are presented. The morphology, chemical composition, and optoelectronic properties of the NiOxfilms are characterized to understand and optimize compatibility with an archetypal double cation perovskite, Cs.17FA.83Pb(Br.17I.83)3. Perovskite solar cells with sprayed NiOxshow higher photovoltaic performance, exhibiting up to 82% fill factor and 17.7% power conversion efficiency (PCE)—the highest PCE reported for inverted cell with scalable charge transport layers—as well as excellent stability under full illumination and after 4000 h aging in inert conditions at room temperature. By utilizing open‐air techniques and aqueous precursors, this combination of robust materials and low‐cost processing provides a platform for scaling perovskite modules with long‐term reliability.

     
    more » « less