Cesium Lead Bromide Perovskite Research Articles

Precursor Chemistry of Lead Bromide Perovskite Nanocrystals.

We investigate the early stages of cesium lead bromide perovskite formation through absorption spectroscopy of stopped-flow reactions, high-throughput mapping, and direct synthesis and titration of potential precursor species. Calorimetric and spectroscopic measurements of lead bromide complex titrations combined with theoretical calculations suggest that bromide complexes with higher coordination numbers than previously considered for nonpolar systems can better explain observed behaviors. Synthesis mapping of binary lead halides reveals multiple lead bromide species with absorption peaks higher than 300 nm, including a previously observed species with a peak at 313 nm and two species with peaks at 345 and 370 nm that also appear as reaction intermediates during the formation of lead bromide perovskites. Based on theoretical calculations of excitonic energies that match within 50 meV, we give a preliminary assignment of these species as two-dimensional magic-sized clusters with side lengths of 2, 3, and 4 unit cells. Kinetic measurements of the conversion of benzoyl bromide precursor are connected to stopped-flow measurements of product formation and demonstrate that the formation of complexes and magic-sized clusters (i.e., nucleation) is controlled by precursor decomposition, whereas the growth rate of 2D and 3D perovskites is significantly slower.

CsPbBr3 NCs Confined and In Situ Grown in ZIF-8: A Stable, Sensitive, Reliable Fluorescent Sensor for Evaluating the Acid Value of Edible Oils.

Rapidly and sensitively evaluating the acid value (AV) of edible oils is significant to ensuring food quality and safety. Cesium lead bromide perovskite nanocrystals (CsPbBr3 NCs) are an effective candidate for AV detection; however, their instability restricts wide applications. Herein, CsPbBr3@ZIF-8 was prepared by confining and growing CsPbBr3 NCs in situ into zeolitic imidazolate framework-8 (ZIF-8) to improve the stability, and a fluorescence sensor was established to evaluate the AV of edible oils. The results present that CsPbBr3 NCs (below 5 nm) with excellent optical properties were confined and grown in situ in micropores and mesopores of ZIF-8. Meanwhile, CsPbBr3@ZIF-8 had better long-term storage, ultraviolet-irradiation, and water-exposure stabilities, compared with CsPbBr3 NCs. Given the fact that free fatty acids (the major contributor of AV) decrease the fluorescence of CsPbBr3 NCs, the fluorescence intensities of CsPbBr3@ZIF-8 were negative-linearly related to oil AV (R2 = 0.9902) in 0.04-6.00 mg of KOH/g with a 0.06 mg of KOH/g limit of detection. Besides, the practical AV recovery was 92-101% with an average relative standard deviation of 2%. Furthermore, the detection time was 20 min. The response mechanism revealed that free fatty acids could remove surface ligands and increase surface defects to prompt the aggregation of CsPbBr3 NCs and the formation of lattice fringe dislocations, inducing a decrease in the fluorescence. Thus, a stable, sensitive, reliable sensor was established to evaluate the AV of edible oils.

Surface-Engineered Cesium Lead Bromide Perovskite Nanocrystals for Enabling Photoreduction Activity.

In recent years, colloidal lead halide perovskite (LHP) nanocrystals (NCs) have exhibited such intriguing light absorption properties to be contemplated as promising candidates for photocatalytic conversions. However, for effective photocatalysis, the light harvesting system needs to be stable under the reaction conditions propaedeutic to a specific transformation. Unlike photoinduced oxidative reaction pathways, photoreductions with LHP NCs are challenging due to their scarce compatibility with common hole scavengers like amines and alcohols. In this contribution, it is investigated the potential of CsPbBr3 NCs protected by a suitably engineered bidentate ligand for the photoreduction of quinone species. Using an in situ approach for the construction of the passivating agent and a halide excess environment, quantum-confined nanocubes (average edge length = 6.0 ± 0.8 nm) are obtained with a low ligand density (1.73 ligand/nm2) at the NC surface. The bifunctional adhesion of the engineered ligand boosts the colloidal stability of the corresponding NCs, preserving their optical properties also in the presence of an amine excess. Despite their relatively short exciton lifetime (τAV = 3.7 ± 0.2 ns), these NCs show an efficient fluorescence quenching in the presence of the selected electron accepting quinones (1,4-naphthoquinone, 9,10-phenanthrenequinone, and 9,10-anthraquinone). All of these aspects demonstrate the suitability of the NCs for an efficient photoreduction of 1,4-naphthoquinone to 1,4-dihydroxynaphthalene in the presence of triethylamine as a hole scavenger. This chemical transformation is impracticable with conventionally passivated LHP NCs, thereby highlighting the potential of the surface functionalization in this class of nanomaterials for exploring new photoinduced reactivities.

Isobutyramide Additive to Improve the Performance of CsPbBr3 Perovskite Solar Cells Prepared by Green Solvent

The inorganic cesium lead bromide (CsPbBr3) perovskite solar cell (PSC) is considered as an attractive option for new solar cells due to its outstanding stability. Preparing CsPbBr3 PSCs with H2O can effectively save costs and reduce the harm of toxic solvents to the environment. However, the poor contact property of the PbBr2 layer to the CsBr/H2O solution and the ability of water to dissolve the CsPbBr3 phase has a significant impact on the performance of the CsPbBr3 devices. In this article, isobutyramide is introduced into the PbBr2 film in the first step to improve the wettability of the PbBr2 film to CsBr/H2O solution, followed by spin‐coating of the 150 mg mL−1 CsBr/H2O solution on the PbBr2 film. Using this strategy, the fabricated PSCs with the architecture of FTO/compact‐TiO2/mesoporous‐TiO2/CsPbBr3 film/carbon demonstrate outstanding performance with a maximum efficiency of 9.59%. Furthermore, after 45 days of storage at ambient temperatures, the unencapsulated device retains more than 96% of its original efficiency. Therefore, this work provides a good demonstration for the preparation of high‐efficiency and eco‐friendly CsPbBr3 PSCs.

Quantum‐Defect‐Minimized, Three‐Photon‐Pumped Ultralow‐Threshold Perovskite Excitonic Lasing

AbstractThree‐photon‐pumped (3PP) excitonic lasing in inorganic semiconductor quantum dots (QDs) is of particular importance for near‐infrared biophotonics and optical communications. However, the implementation of such lasers has been hindered severely by the required high pump thresholds. Here, 3PP excitonic lasing of all‐inorganic cesium lead bromide perovskite QDs (CsPbBr3 PQDs) embedded in a whispering‐gallery microcavity is demonstrated, and achieving a record low threshold of 3 mJ cm−2 by tuning the 3P pump energy in resonance with the S exciton state. Wavelength‐dispersive Z‐scan spectroscopy reveals that such reduced lasing threshold is attributed to the exciton resonance enhanced multiphoton absorption, which, as disclosed by the kinetics analysis of transient absorption spectroscopy (TAS), leads to the appearance of net gain at a pump fluence as low as 2.2 mJ cm−2, corresponding to an average S exciton population of 1.5. A microscopic model incorporating the quantum master equation reproduces the TAS results and provides the intrinsic parameters of biexciton relaxation for lasing. The 3PP resonant excitonic transition is the most favored multiphoton pumping process that minimizes quantum defect (6.8% of the pump photon energy) to realize optical gain at low threshold, marking a major step toward using all‐inorganic perovskite QDs for on‐chip integrated microlasers and multiphoton bioimaging.

Insight into the Interaction between Perovskite and Water via In Situ PL Measurement

Contrary to widely held view that water induces negative effect on lead halide perovskites, publications on active role of water in photoluminescence (PL) and stability of perovskites have been emerged recently. Until now, comprehensively understanding the interaction between perovskite and water is absolutely necessary for its highly correlation with the practical application and remains a significant challenge. In this study, we utilize in situ PL measurement, ex situ transmission electron microscopy, UV–vis spectroscopy and X-ray photoelectron spectroscopy to track and reveal the interaction of perovskite with water. For the organic-inorganic lead bromide perovskite, water induces amorphization, degradation of MAPbBr3, as well as formation of PbBrOH. As-obtained MAPbBr3@PbBrOH composites exhibit high PL quantum yield (QY) of 41.8–57.0% and robust water stability for the protection from PbBrOH. For cesium lead bromide perovskite, water facilitates the phase transition from non-luminescent Cs4PbBr6 to luminescent CsPbBr3, and could also instigate the formation of PbBrOH. However, the water-induced Ostwald maturation of CsPbBr3 and structure defects brought by the phase transition ultimately lead to the production of large CsPbBr3 crystals or CsPbBr3@PbBrOH composites with ultralow PLQY. This work provides valuable insights into the interaction between perovskite and water, and holds important implications for comprehending the instability of lead halide perovskites.

Enhanced Cyan Photoluminescence and Stability of CsPbBr3 Quantum Dots Via Surface Engineering for White Light‐Emitting Diodes

AbstractThe emission of cyan light (470‐500 nm) plays a vital role in the visible light spectrum and is essential for applications such as lighting, displays, and optical communication. Inorganic cesium lead bromide perovskite quantum dots (CsPbBr3 PQDs) have made significant progress in the field of luminescence materials and devices, however, the lack of techniques to obtain highly emissive and stable cyan‐emitting CsPbBr3 PQDs has limited their device applications. Here, it is demonstrated that the complete surface passivation by treatment of didodecyldimethylammonium bromide (DDAB) and lead bromide, which can enhance the photoluminescence and stability of cyan emitting CsPbBr3 PQDs. In particular, the photoluminescence quantum yield of CsPbBr3 QDs can be greatly improved from 10.5% to 83.8%. Through an effective PMMA passivation, the obtained stable and bright CsPbBr3 PQDs composite films as the cyan color converters can effectively emit the cyan light to fill the “cyan gap” of white light‐emitting diode (WLED). The color rendering index value of such WLED is remarkably enhanced from 73.6 to 82.5. This study paves the way for the application of PQD color converters in the next generation of full‐visible‐spectrum WLED lighting.

Cesium lead bromide perovskite nanocrystals synthesized via supersaturated recrystallization at room temperature: comparison of one-step and two-step processes.

Over more than a decade, lead halide perovskites (LHPs) have been popular as a next-generation semiconductor for optoelectronics. Later, all-inorganic CsPbX3 (X = Cl, Br, and I) nanocrystals (NCs) were synthesized via supersaturated recrystallization (SR) at room temperature (RT). However, compared to the hot injection (HI) method, the formation mechanism of NCs via SR-RT has not been well studied. Hence, this study will contribute to elucidating SR-RT based on the LaMer model and Hansen solubility parameter. Herein, we also demonstrate the entropy-driven mixing between two dissimilar polar-nonpolar (DMF-toluene) solvents. Next, we find that, in a poor solvent (toluene ≫ DMF in volume), ∼60 nm sized CsPbBr3 NCs were synthesized in one step, whereas in a marginal solvent (toluene ≈ DMF), ∼3.5 nm sized NCs were synthesized in two steps, indicating the importance of solvent polarity, specifically the 'solubility parameter'. In addition, in the presence of a CuBr2 additive, high-quality cubic NCs (with ∼3.8 nm and ∼21.4 nm edge sizes) were synthesized. Hence, through this study, we present a 'solubility parameter-based nanocrystal-size control model' for SR-RT processes.

Energy Funneling in a Noninteger Two-Dimensional Perovskite.

Energy funneling is a phenomenon that has been exploited in optoelectronic devices based on low-dimensional materials to improve their performance. Here, we introduce a new class of two-dimensional semiconductor, characterized by multiple regions of varying thickness in a single confined nanostructure with homogeneous composition. This "noninteger 2D semiconductor" was prepared via the structural transformation of two-octahedron-layer-thick (n = 2) 2D cesium lead bromide perovskite nanosheets; it consisted of a central n = 2 region surrounded by edge-lying n = 3 regions, as imaged by electron microscopy. Thicker noninteger 2D CsPbBr3 nanostructures were obtained as well. These noninteger 2D perovskites formed a laterally coupled quantum well band alignment with virtually no strain at the interface and no dielectric barrier, across which unprecedented intramaterial funneling of the photoexcitation energy was observed from the thin to the thick regions using time-resolved absorption and photoluminescence spectroscopy.

Crystal structures and photoluminescence characteristics of cesium lead bromide perovskite nanoplatelets depending on the antisolvent and ligand used in their syntheses

Cesium lead bromide (CsPbBr3) nanocrystals (NCs) with nanoplatelet shapes and different crystal structures were synthesized via the ligand-assisted reprecipitation (LARP) method using different pairs of ligands and antisolvents, namely oleic acid (OA) or linoleic acid (LA) as the ligand and toluene or chloroform as the antisolvent. The XRD data revealed that the obtained CsPbBr3 NCs have different crystal structures, namely orthorhombic, tetragonal, and cubic, depending on the ligand and antisolvent pair, which exhibited significantly different photoluminescence (PL) characteristics. From the XPS data, these CsPbBr3 nanoplatelets showed two doublet peaks of the Br-3d orbital at different binding energies, representing two different chemical environments of the Br bonds. The doublet peak apparent at a higher binding energy was associated with the Br chemical states at the crystal surface, which appeared because of the distorted crystal structure resulting from the interaction of the solvent and ligand with Br ions. The PL emission consists of three luminescence centers: a PL band peaked at 520 nm (A band), a PL band peaked at 540 nm (B band), and a PL band tail, which can be discussed in terms of exciton models. Stable and intense luminescence was observed in CsPbBr3 nanoplatelets synthesized using a pair of toluene antisolvent and LA ligand, namely CsPbBr3#(Tl/LA). The orthorhombic crystal structure and distorted crystal surface in this sample may lead to confinement of the photogenerated small exciton-polaron and weak phonon interactions, which effectively hinder exciton dissociation, particularly at the crystal surface, resulting in intense PL. The results of this study may provide additional important insights into the role of the antisolvent and ligand in the formation of CsPbBr3 NCs and the exciton behavior in their PL characteristics, which may also be found in other types of halide perovskites.

Investigation of the Amplified Spontaneous Emission Threshold of Cesium Lead Bromide Perovskite Quantum Dots at Different Excitation Wavelengths

The goal of this research is to see how excitation wavelength affects steady-state photoluminescence (PL), time-resolved photoluminescence (TRPL), and amplified spontaneous emission (ASE) in CsPbBr3 perovskite quantum dots (PQD). At PL and ASE, a plausible mechanism for explaining the excitation wavelength-dependent phenomena was proposed. The PL and ASE properties of CsPbBr3 PQD as optical materials were examined experimentally at excitation wavelengths of 355–450 nm. An optical parametric amplifier system was used to accomplish optical pumping utilizing a laser pulse with a pulse duration of 70 ps. The ASE threshold was explored and compared the ratio of photons in the pump pulse to band gap energies. The excitation wavelength (λ ex) has a considerable influence on the ASE behavior, with high optical densities correlating to optimal excitation, as evidenced by the absorption spectrum, which has a larger absorption coefficient. Furthermore, the energy density at the ASE threshold was closely correlated with the λ ex following the absorption spectrum. Also, it has been demonstrated that changing the excitation wavelength reduces the PQD PL lifetime. Finally, electron-hole pairs can be produced at a reasonable depth from the film’s surface using the appropriate excitation wavelength.

A facile, time-saving fabrication method of high purity CsPbBr3 films for efficient solar cells

All-brominated cesium lead bromide (CsPbBr3) perovskite solar cells (PSCs) have drawn growing attention owing to unprecedented stability in the family of perovskites. It usually employs a two-step method to prepare CsPbBr3 films owing to the low solubility of CsBr in the common solvents. The researchers have to provide enough Cs source through increasing the reaction time or repeat times of CsBr deposition so as to obtain the target CsPbBr3 films. The long preparation period and tedious process increase the time and economic cost, which may limit the practical application of CsPbBr3 solar cells. Herein, a facile method is proposed to prepare CsPbBr3 films, in which appropriate CsBr is pre-introduced into PbBr2 solutions in the first step, and CsBr/2-methoxyethanol solution (∼35 mg mL−1) is used as solution conversion medium in the second step. Benefitting from the pre-introduction of CsBr in the first step, a single phase of CsPbBr3 films with full coverage can be conversed for only once CsBr supplementation. After integrating the CsPbBr3 films into a solar cell, it delivers a power conversion efficiency (PCE) of 7.48% basing on the configuration of FTO/TiO2/CsPbBr3/Carbon. This work largely shortens the preparation time of CsPbBr3 films, which may provide a practical way for the large-scale production of CsPbBr3 based devices.

Correlation between Single-Photon Emission and Size of Cesium Lead Bromide Perovskite Nanocrystals.

Emission photon statistics of semiconductor nanocrystal quantum dots (QDs), including lead halide perovskite nanocrystals (PNCs), are important fundamental and practical optical properties. Single QDs exhibit high-probability single-photon emission owing to the efficient Auger recombination between generated excitons. Because the recombination rate depends on QD size, single-photon emission probability should be size-dependent. Previous studies have researched QDs smaller than their exciton Bohr diameters (twice the Bohr radius of excitons). Here, we investigated the relationship between the single-photon emission behavior and size of CsPbBr3 PNCs to elucidate their size threshold. Simultaneous single-nanocrystal spectroscopy and atomic force microscopy observations on single PNCs with approximately 5-25 nm edge length showed that those smaller than approximately 10 nm, which had size-dependent photoluminescence (PL) spectral shifts, exhibited high-probability single-photon emissions, which decreased linearly with PNC volume. Novel single-photon emission, size, and PL peak correlations of PNCs are important for understanding the relationship between single-photon emission and quantum confinement.

Optical and photoelectrical properties of low-concentration-Mn-doped CsPbBr3 nanocrystals

Doping of cesium lead bromide (CsPbBr3) perovskite nanocrystals offers effective control of their optical and optoelectrical properties, leading to possibilities of several new applications. Herein, cesium lead bromide perovskite nanocrystals are synthesized with doping of a low concentration of manganese (Mn) into the perovskite lattice using manganese (II) chloride (MnCl2) as a precursor. The shift in X-ray diffraction peaks toward higher angles indicates that manganese as a dopant is present inside the cesium lead bromide lattice. A change in the manganese (II) chloride precursor concentration from 5 to 10 mmol results in an increment in the atomic percentage of manganese from 0.3 to 0.5% in the cesium lead bromide crystal. Doping of a low concentration of manganese (0.3 at.%) into cesium lead bromide results in enhancement of green emission, while doping with a higher concentration of manganese (0.5 at.%) results in blue emission. The band gap of cesium lead bromide nanocrystals increases from 2.31 to 2.53 eV with an increase in the concentration of manganese. The dark and photoelectrical conductivity of cesium lead bromide nanocrystals is improved in the case of doping with a low concentration (0.3 at.%) of manganese. The ratio of photocurrent against dark current is found to be ∼182 in manganese-doped cesium lead bromide crystal film as compared with ∼101 for undoped cesium lead bromide crystal film. Doping with a low concentration of manganese improves the overall electrical and photoelectrical conductivity of cesium lead bromide perovskite nanocrystals.

Water-induced nucleation growth kinetics enhancement of cesium lead bromide perovskite nanocrystals

Water-induced nucleation growth kinetics enhancement of cesium lead bromide perovskite nanocrystals

Slower Auger Recombination in 12-Faceted Dodecahedron CsPbBr3 Nanocrystals.

Over the past two decades, intensive research efforts have been devoted to suppressions of Auger recombination in metal-chalcogenide and perovskite nanocrystals (PNCs) for the application of photovoltaics and light emitting devices (LEDs). Here, we have explored dodecahedron cesium lead bromide perovskite nanocrystals (DNCs), which show slower Auger recombination time compared to hexahedron nanocrystals (HNCs). We investigate many-body interactions that are manifested under high excitation flux density in both NCs using ultrafast spectroscopic pump-probe measurements. We demonstrate that the Auger recombination rate due to multiexciton recombinations are lower in DNCs than in HNCs. At low and intermediate excitation density, the majority of carriers recombine through biexcitonic recombination. However, at high excitation density (>1018 cm-3) a higher number of many-body Auger process dominates over biexcitonic recombination. Compared to HNCs, high PLQY and slower Auger recombinations in DNCs are likely to be significant for the fabrication of highly efficient perovskite-based photonics and LEDs.

Photostability of amine-free CsPbBr3 perovskite nanocrystals under continuous UV illumination

In this work, we verified that light induces a dynamic equilibrium between ligands and the inorganic surface in amine-free perovskite nanocrystals, and we demonstrated that oleylphosphate ligands can improve the photostability of cesium lead bromide perovskite nanocrystals.

Selective Detection of Folic Acid Using a Water-Stable Fluorescent CsPbBr3/Cs4PbBr6 Perovskite Nanocrystal Probe

A water-stable cesium lead bromide (CsPbBr3/Cs4PbBr6) perovskite nanocrystal (PNC) was synthesized and studied as a fluorescence probe for the selective detection of folic acid (FA). The as-prepared PNCs emitted strong green fluorescence at 525 nm, and their structure was systematically characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The interaction between the PNCs and small biological molecules was investigated and the results indicated that the fluorescence of the PNCs could be selectively quenched by FA. The quenching rate has a linear relationship with the concentration of FA in the concentration range from 10 to 800 μM, with a correlation coefficient R2 of 0.9841, and a limit of detection (LOD, 3σ) of 1.69 μM. The mechanism of the interaction between the PNCs and FA was discussed, and the reliability of the method for real sample detection was also verified by the standard addition method. The method proposed here, using a fluorescence PNCs probe, provided a simple alternative strategy for detecting FA that will play an important role in biochemical analysis.

Synthesis and characterization of cesium lead bromide perovskite quantum dots with photovoltaic applications

Synthesis and characterization of cesium lead bromide perovskite quantum dots with photovoltaic applications

Mechanochemistry-driven engineering of 0D/3D heterostructure for designing highly luminescent Cs–Pb–Br perovskites

Embedding metal-halide perovskite particles within an insulating host matrix has proven to be an effective strategy for revealing the outstanding luminescence properties of perovskites as an emerging class of light emitters. Particularly, unexpected bright green emission observed in a nominally pure zero-dimensional cesium–lead–bromide perovskite (Cs4PbBr6) has triggered intensive research in better understanding the serendipitous incorporation of emissive guest species within the Cs4PbBr6 host. However, a limited controllability over such heterostructural configurations in conventional solution-based synthesis methods has limited the degree of freedom in designing synthesis routes for accessing different structural and compositional configurations of these host–guest species. In this study, we provide means of enhancing the luminescence properties in the nominal Cs4PbBr6 powder through a guided heterostructural configuration engineering enabled by solid-state mechanochemical synthesis. Realized by an in-depth study on time-dependent evaluation of optical and structural properties during the synthesis of Cs4PbBr6, our target-designed synthesis protocol to promote the endotaxial formation of Cs4PbBr6/CsPbBr3 heterostructures provides key insights for understanding and designing kinetics-guided syntheses of highly luminescent perovskite emitters for light-emitting applications.