Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
06 Aug 2015-Journal of the American Chemical Society (American Chemical Society)-Vol. 137, Iss: 32, pp 10276-10281
TL;DR: It is demonstrated that, via controlled anion exchange reactions using a range of different halide precursors, this approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs.
Abstract: We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
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TL;DR: N nanoscale phase stabilization of CsPbI3 quantum dots (QDs) to low temperatures that can be used as the active component of efficient optoelectronic devices and describe the formation of α-CsP bI3 QD films that are phase-stable for months in ambient air.
Abstract: We show nanoscale phase stabilization of CsPbI 3 quantum dots (QDs) to low temperatures that can be used as the active component of efficient optoelectronic devices. CsPbI 3 is an all-inorganic analog to the hybrid organic cation halide perovskites, but the cubic phase of bulk CsPbI 3 (α-CsPbI 3 )—the variant with desirable band gap—is only stable at high temperatures. We describe the formation of α-CsPbI 3 QD films that are phase-stable for months in ambient air. The films exhibit long-range electronic transport and were used to fabricate colloidal perovskite QD photovoltaic cells with an open-circuit voltage of 1.23 volts and efficiency of 10.77%. These devices also function as light-emitting diodes with low turn-on voltage and tunable emission.
2,103 citations
TL;DR: In this paper, a room-temperature (RT) synthesis of CsPbX3@X quantum-well band alignment is proposed to guarantee the excitons generation and high-rate radiative recombination at RT.
Abstract: Recently, Kovalenko and co-workers and Li and co-workers developed CsPbX3 (X = Cl, Br, I) inorganic perovskite quantum dots (IPQDs), which exhibited ultrahigh photoluminescence (PL) quantum yields (QYs), low-threshold lasing, and multicolor electroluminescence. However, the usual synthesis needs high temperature, inert gas protection, and localized injection operation, which are severely against applications. Moreover, the so unexpectedly high QYs are very confusing. Here, for the first time, the IPQDs' room-temperature (RT) synthesis, superior PL, underlying origins and potentials in lighting and displays are reported. The synthesis is designed according to supersaturated recrystallization (SR), which is operated at RT, within few seconds, free from inert gas and injection operation. Although formed at RT, IPQDs' PLs have QYs of 80%, 95%, 70%, and FWHMs of 35, 20, and 18 nm for red, green, and blue emissions. As to the origins, the observed 40 meV exciton binding energy, halogen self-passivation effect, and CsPbX3@X quantum-well band alignment are proposed to guarantee the excitons generation and high-rate radiative recombination at RT. Moreover, such superior optical merits endow them with promising potentials in lighting and displays, which are primarily demonstrated by the white light-emitting diodes with tunable color temperature and wide color gamut.
1,932 citations
TL;DR: Lead-halide perovskites have entered the family of colloidal nanocrystals, showing excellent optical properties and easy synthesizability, and insight is provided into their chemical versatility, stability challenges and use in optoelectronics.
Abstract: Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a 'soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.
1,430 citations
TL;DR: It is found that ligand binding to the NC surface is highly dynamic, and therefore, ligands are easily lost during the isolation and purification procedures, and when a small amount of both oleic acid and oleylamine is added, the NCs can be purified, maintaining optical, colloidal, and material integrity.
Abstract: Lead halide perovskite materials have attracted significant attention in the context of photovoltaics and other optoelectronic applications, and recently, research efforts have been directed to nanostructured lead halide perovskites. Collodial nanocrystals (NCs) of cesium lead halides (CsPbX3, X = Cl, Br, I) exhibit bright photoluminescence, with emission tunable over the entire visible spectral region. However, previous studies on CsPbX3 NCs did not address key aspects of their chemistry and photophysics such as surface chemistry and quantitative light absorption. Here, we elaborate on the synthesis of CsPbBr3 NCs and their surface chemistry. In addition, the intrinsic absorption coefficient was determined experimentally by combining elemental analysis with accurate optical absorption measurements. 1H solution nuclear magnetic resonance spectroscopy was used to characterize sample purity, elucidate the surface chemistry, and evaluate the influence of purification methods on the surface composition. We fi...
1,267 citations
TL;DR: Recent progress on hybrid perovskites is reviewed including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics.
Abstract: Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities.
1,200 citations
References
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TL;DR: In this paper, the rate data for the generalized nucleophilic displacement reaction were reviewed, and the authors presented a method to estimate the rate of the generalized displacement reaction in terms of the number of nucleophiles.
Abstract: Recently (1) the rate data for the generalized nucleophilic displacement reaction were reviewed.
8,433 citations
TL;DR: The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation.
Abstract: Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiativ...
6,170 citations
TL;DR: An approach for depositing high-quality FAPbI3 films, involving FAP bI3 crystallization by the direct intramolecular exchange of dimethylsulfoxide (DMSO) molecules intercalated in PbI2 with formamidinium iodide is reported.
Abstract: The band gap of formamidinium lead iodide (FAPbI3) perovskites allows broader absorption of the solar spectrum relative to conventional methylammonium lead iodide (MAPbI3). Because the optoelectronic properties of perovskite films are closely related to film quality, deposition of dense and uniform films is crucial for fabricating high-performance perovskite solar cells (PSCs). We report an approach for depositing high-quality FAPbI3 films, involving FAPbI3 crystallization by the direct intramolecular exchange of dimethylsulfoxide (DMSO) molecules intercalated in PbI2 with formamidinium iodide. This process produces FAPbI3 films with (111)-preferred crystallographic orientation, large-grained dense microstructures, and flat surfaces without residual PbI2. Using films prepared by this technique, we fabricated FAPbI3-based PSCs with maximum power conversion efficiency greater than 20%.
5,458 citations
TL;DR: This work combines the promising—but relatively unstable formamidinium lead iodide with FAPbI3 with methylammonium lead bromide as the light-harvesting unit in a bilayer solar-cell architecture and improves the power conversion efficiency of the solar cell to more than 18 per cent under a standard illumination.
Abstract: Inorganic–organic lead halide perovskite could be efficient when used as the light-harvesting component of solar cells; here incorporation of methylammonium lead bromide into formamidinium lead iodide stabilizes the perovskite and improves the power conversion efficiency of the solar cell up to 17.9 per cent. Inorganic–organic lead halide perovskites are currently attracting considerable interest for solar-cell applications. Most of the best performing perovskite solar cells to date have made use of methylammonium-based perovskites; formamidinium-based perovskites have also shown promise, but are not as stable. Now Nam Joong Jeon and colleagues show that the formamidinium-based perovskites can be stabilized by the addition of some methylammonium-based perovskite, and that solar cells incorporating the resulting compositionally tuned materials can reach new heights of efficiency. Of the many materials and methodologies aimed at producing low-cost, efficient photovoltaic cells, inorganic–organic lead halide perovskite materials1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17 appear particularly promising for next-generation solar devices owing to their high power conversion efficiency. The highest efficiencies reported for perovskite solar cells so far have been obtained mainly with methylammonium lead halide materials1,2,3,4,5,6,7,8,9,10. Here we combine the promising—owing to its comparatively narrow bandgap—but relatively unstable formamidinium lead iodide (FAPbI3) with methylammonium lead bromide (MAPbBr3) as the light-harvesting unit in a bilayer solar-cell architecture13. We investigated phase stability, morphology of the perovskite layer, hysteresis in current–voltage characteristics, and overall performance as a function of chemical composition. Our results show that incorporation of MAPbBr3 into FAPbI3 stabilizes the perovskite phase of FAPbI3 and improves the power conversion efficiency of the solar cell to more than 18 per cent under a standard illumination of 100 milliwatts per square centimetre. These findings further emphasize the versatility and performance potential of inorganic–organic lead halide perovskite materials for photovoltaic applications.
5,291 citations
TL;DR: This paper demonstrates highly efficient solar cells exhibiting 12.3% in a power conversion efficiency of under standard AM 1.5, for the most efficient device, as a result of tunable composition for the light harvester in conjunction with a mesoporous TiO2 film and a hole conducting polymer.
Abstract: Chemically tuned inorganic–organic hybrid materials, based on CH3NH3(═MA)Pb(I1–xBrx)3 perovskites, have been studied using UV–vis absorption and X-ray diffraction patterns and applied to nanostructured solar cells. The band gap engineering brought about by the chemical management of MAPb(I1–xBrx)3 perovskites can be controllably tuned to cover almost the entire visible spectrum, enabling the realization of colorful solar cells. We demonstrate highly efficient solar cells exhibiting 12.3% in a power conversion efficiency of under standard AM 1.5, for the most efficient device, as a result of tunable composition for the light harvester in conjunction with a mesoporous TiO2 film and a hole conducting polymer. We believe that the works highlighted in this paper represent one step toward the realization of low-cost, high-efficiency, and long-term stability with colorful solar cells.
4,065 citations