skip to main content

Title: Near Unity PLQY and High Stability of Barium Thiocyanate Based All-Inorganic Perovskites and Their Applications in White Light-Emitting Diodes
All-inorganic lead halide perovskite (CsPbX3) nanocrystals (NCs) have emerged as a highly promising new generation of light emitters due to their extraordinary photophysical properties. However, the performance of these semiconducting NCs is undermined due to the inherent toxicity of lead and long-term environmental stability. Here, we report the addition of B-site cation and X-site anion (pseudo-halide) concurrently using Ba(SCN)2 (≤50%) in CsPbX3 NCs to reduce the lead and improve the photophysical properties and stability. The as-grown particles demonstrated an analogous structure with an almost identical lattice constant and a fluctuation of particle size without altering the morphology of particles. Photoluminescence quantum yield is enhanced up to near unity (~98%) by taking advantage of concomitant doping at the B- and X-site of the structure. Benefitted from the defect reductions and stronger bonding interaction between Pb2+ and SCN− ions, Ba(SCN)2-based NCs exhibit improved stability towards air and moisture compared to the host NCs. The doped NCs retain higher PLQY (as high as seven times) compared to the host NCs) when stored in an ambient atmosphere for more than 176 days. A novel 3D-printed multiplex color conversion layer was used to fabricate a white light-emitting diode (LED). The obtained white light shows a more » correlated color temperature of 6764 K, a color rendering index of 87, and luminous efficacy of radiation of 333 lm/W. In summary, this work proposes a facile route to treat sensitive lead halide perovskite NCs and to fabricate LEDs by using a low-cost large-scale 3-D printing method, which would serve as a foundation for fabricating high-quality optoelectronic devices for near future lighting technologies. « less
Authors:
; ; ; ;
Award ID(s):
1945558
Publication Date:
NSF-PAR ID:
10317154
Journal Name:
Photonics
Volume:
8
Issue:
6
ISSN:
2304-6732
Sponsoring Org:
National Science Foundation
More Like this
  1. All-inorganic halide perovskite nanocrystals (NCs) offer impressive optoelectronic properties for light harvesting, energy conversion, and photoredox applications, with two-dimensional (2D) perovskite NCs further increasing these prospects due to their improved photoluminescence (PL) tuneability, impressive color purity, high in-plane charge transport, and large lateral dimensions which is advantageous for device integration. However, the synthesis of 2D perovskites is still challenging, especially toward large-scale applications. In this study, through the control of surface ligand composition and concentration of a mixture of short (octanoic acid and octylamine, 8-carbon chain) and long (oleic acid and oleylamine, 18-carbon chain) ligands, we have developed an extremely facile ligand-mediated synthesis of 2D CsPbX 3 (X = Cl, Br, or mixture thereof) nanoplatelets (NPLs) at room temperature in an open vessel. In addition, the developed method is highly versatile and can be applied to synthesize Mn-doped CsPbX 3 NPLs, showing a systematic increase in the total PL quantum yield (QY) and the Mn-dopant emission around 600 nm with increasing Mn and Cl concentrations. The reaction occurs in toluene by the introduction of CsX, PbX 2 , and MnX 2 precursors under ambient conditions, which requires no harsh acids, avoids excessive lead waste, little thermal energy input, and ismore »potentially scalable toward industrial applications.« less
  2. Metal-halide perovskites, in particular their nanocrystal forms, have emerged as a new generation of light-emitting materials with exceptional optical properties, including narrow emissions covering the whole visible region with high photoluminescence quantum efficiencies of up to near-unity. Remarkable progress has been achieved over the last few years in the areas of materials development and device integration. A variety of synthetic approaches have been established to precisely control the compositions and microstructures of metal-halide perovskite nanocrystals (NCs) with tunable bandgaps and emission colors. The use of metal-halide perovskite NCs as active materials for optoelectronic devices has been extensively explored. Here, we provide a brief overview of recent advances in the development and application of metal-halide perovskite NCs. From color tuning via ion exchange and manipulation of quantum size effects, to stability enhancement via surface passivation, new chemistry for materials development is discussed. In addition, processes in optoelectronic devices based on metal-halide perovskite NCs, in particular, light-emitting diodes and radiation detectors, will be introduced. Opportunities for future research in metal-halide perovskite NCs are provided as well.
  3. The past decade has witnessed tremendous advances in synthesis of metal halide perovskites and their use for a rich variety of optoelectronics applications. Metal halide perovskite has the general formula ABX 3 , where A is a monovalent cation (which can be either organic ( e.g. , CH 3 NH 3 + (MA), CH(NH 2 ) 2 + (FA)) or inorganic ( e.g. , Cs + )), B is a divalent metal cation (usually Pb 2+ ), and X is a halogen anion (Cl − , Br − , I − ). Particularly, the photoluminescence (PL) properties of metal halide perovskites have garnered much attention due to the recent rapid development of perovskite nanocrystals. The introduction of capping ligands enables the synthesis of colloidal perovskite nanocrystals which offer new insight into dimension-dependent physical properties compared to their bulk counterparts. It is notable that doping and ion substitution represent effective strategies for tailoring the optoelectronic properties ( e.g. , absorption band gap, PL emission, and quantum yield (QY)) and stabilities of perovskite nanocrystals. The doping and ion substitution processes can be performed during or after the synthesis of colloidal nanocrystals by incorporating new A′, B′, or X′ site ions into themore »A, B, or X sites of ABX 3 perovskites. Interestingly, both isovalent and heterovalent doping and ion substitution can be conducted on colloidal perovskite nanocrystals. In this review, the general background of perovskite nanocrystals synthesis is first introduced. The effects of A-site, B-site, and X-site ionic doping and substitution on the optoelectronic properties and stabilities of colloidal metal halide perovskite nanocrystals are then detailed. Finally, possible applications and future research directions of doped and ion-substituted colloidal perovskite nanocrystals are also discussed.« less
  4. Metal halide perovskite nanocrystals (NCs) have emerged as new-generation light-emitting materials with narrow emissions and high photoluminescence quantum efficiencies (PLQEs). Various types of perovskite NCs, e.g., platelets, wires, and cubes, have been discovered to exhibit tunable emissions across the whole visible spectrum. Despite remarkable advances in the field of perovskite NCs, many nanostructures in inorganic NCs have not yet been realized in metal halide perovskites, and producing highly efficient blue-emitting perovskite NCs remains challenging and of great interest. Here, we report the discovery of highly efficient blue-emitting cesium lead bromide (CsPbBr 3 ) perovskite hollow NCs. By facile solution processing of CsPbBr 3 precursor solution containing ethylenediammonium bromide and sodium bromide, in situ formation of hollow CsPbBr 3 NCs with controlled particle and pore sizes is realized. Synthetic control of hollow nanostructures with quantum confinement effect results in color tuning of CsPbBr 3 NCs from green to blue, with high PLQEs of up to 81%.
  5. Halide perovskites, such as methylammonium lead halide perovskites (MAPbX3,X=I, Br, and Cl), are emerging as promising candidates for a wide range of optoelectronic applications, including solar cells, light-emitting diodes, and photodetectors, due to their superior optoelectronic properties. All-inorganic lead halide perovskitesCsPbX3are attracting a lot of attention because replacing the organic cations withCs+enhances the stability, and its halide-mixing derivatives offer broad bandgap tunability covering nearly the entire visible spectrum. However, there is evidence suggesting that the optical properties of mixed-halide perovskites are influenced by phase segregation under external stimuli, especially illumination, which may negatively impact the performance of optoelectronic devices. It is reported that the mixed-halide perovskites in forms of thin films and nanocrystals are segregated into a low-bandgap I-rich phase and a high-bandgap Br-rich phase. Herein, we present a critical review on the synthesis and basic properties of all-inorganic perovskites, phase-segregation phenomena, plausible mechanisms, and methods to mitigate phase segregation, providing insights on advancing mixed-halide perovskite optoelectronics with reliable performance.