CsPbBr3 Perovskite Research Articles

Mesoporous silica stabilized perovskite quantum dots for the preparation of ultra-stable green flexible film.

CsPbBr3 perovskite quantum dots (QDs) have attracted much attention in the optical field because of their low band gap, wide absorption spectrum and high color purity. However, their poor stability in extreme environments such as water, light and heat severely limits their application in optical fields. Here, we prepared m-SiO2/CsPbBr3 composite luminescent material using an aqueous phase method combined with high temperature calcination. The material can retain 87% of the initial photoluminescence quantum efficiency after 60 days of storage under ambient conditions (humidity ∼80%; temperature ∼25 °C), its photoluminescence intensity only decreased by 33% after immersion in water for 90 min. This indicates that the material retains good stability under a high humidity environment. Finally, PMMA@m-SiO2/CsPbBr3 flexible films were prepared by aqueous solution polymerization. The flexible film has excellent green light emission properties and exhibits (0.092, 0.625) CIE coordinates.

Ultralow-Energy-Consumption Photosynaptic Transistor Utilizing Conjugated Polymers/Perovskite Quantum Dots Nanocomposites With Ligand Density Optimization.

The photosynaptic transistor stands as a promising contender for overcoming the von Neumann bottleneck in the realm of photo-communication. In this context, photonic synaptic transistors is developed through a straightforward solution process, employing an organic semiconducting polymer with pendant-naphthalene-containing side chains (PDPPNA) in combination with ligand-density-engineered CsPbBr3 perovskite quantum dots (PQDs). This fabrication approach allows the devices to emulate fundamental synaptic behaviors, encompassing excitatory postsynaptic current, paired-pulse facilitation, the transition from short-to-long-term memory, and the concept of "learning experience." Notably, the phototransistor, incorporating the blend of the PDPPNA and CsPbBr3 PQDs washed with ethyl acetate, achieved an exceptional memory ratio of 104. Simultaneously, the same device exhibited an impressive paired-pulse facilitation ratio of 223% at a moderate operating voltage of -4V and an extraordinarily low energy consumption of 0.215 aJ at an ultralow operating voltage of -0.1mV. Consequently, these low-voltage synaptic devices, constructed with a pendant side-chain engineering of organic semiconductors and a ligand density engineering of PQDs through a simple fabrication process, exhibit substantial potential for replicating the visual memory capabilities of the human brain.

Accuracy and limitations of the bond polarizability model in modeling of Raman scattering from molecular dynamics simulations.

Calculation of Raman scattering from molecular dynamics (MD) simulations requires accurate modeling of the evolution of the electronic polarizability of the system along its MD trajectory. For large systems, this necessitates the use of atomistic models to represent the dependence of electronic polarizability on atomic coordinates. The bond polarizability model (BPM) is the simplest such model and has been used for modeling the Raman spectra of molecular systems but has not been applied to solid-state systems. Here, we systematically investigate the accuracy and limitations of the BPM parameterized from the density functional theory results for a series of simple molecules, such as CO2, SO2, H2S, H2O, NH3, and CH4; the more complex CH2O, CH3OH, CH3CH2OH, and thiophene molecules; and the BaTiO3 and CsPbBr3 perovskite solids. We find that BPM can reliably reproduce the overall features of the Raman spectra, such as shifts of peak positions. However, with the exception of highly symmetric systems, the assumption of non-interacting bonds limits the quantitative accuracy of the BPM; this assumption also leads to qualitatively inaccurate polarizability evolution and Raman spectra for systems where large deviations from the ground state structure are present.

(Invited) Exploring and Manipulating Luminescence Centers in Lead Halide Perovskites through Hydrostatic Pressure

The application of hydrostatic pressure to materials induces changes in lattice constants, vibrational spectra, and electron-phonon interactions, thereby altering the optoelectronic properties of semiconductors. Consequently, hydrostatic pressure has become a widely utilized tool for investigating and enhancing the optical properties of organic/inorganic halide perovskites and their nanostructures. In this presentation, I will discuss the impact of hydrostatic pressure on two distinct types of luminescence centers in perovskite materials. The first type of luminescence centers originates from excitons within perovskite nanocrystals. I will discuss how hydrostatic pressure serves as a valuable tool for elucidating the origin of luminescence in low-dimensional perovskites, including 2D CsPb2Br5, 0D Cs4PbBr6, and 2D Ruddlesden-Popper Hybrid Perovskite Crystals. The second type of luminescence centers exhibit broadband optical emission from self-trapped excitons in low-dimensional perovskites. I will present our findings on the observation of strong exciton-phonon coupling and demonstrate how hydrostatic pressure can be employed to modulate electron-phonon coupling, offering a means to finely tune the broad emission spectrum.

Mapping and Characterization of Local Structures of CsPbBr3.

Inorganic perovskite CsPbBr3 is a promising material for optoelectronic applications and high-energy radiation detection due to its excellent photophysical properties, high carrier mobility, large carrier diffusion length, and higher stability than organic perovskite materials. Understanding phase transitions at the atomic level is crucial for optimizing its applications. Here, we employ experimental characterizations and molecular dynamics simulations to study the phase transitions in CsPbBr3 as a function of temperature. The simulation results are compared with the experimental results, which include X-ray diffraction (XRD). Our simulations provide new insights into the electronic structure and dynamic behavior of the Cs, Pb, and Br atoms as a function of temperature. We observe distinct phase transitions from monoclinic to cubic and analyze the associated changes in the local environment through atomic density contour maps. Our analysis of the atomic density distributions of the Pb, Br, and Cs atoms provides information about the crystal symmetry as a function of temperature. The tilt and rotation angles of [PbBr6] octahedra are increasing with the temperature increase and are found nonzero above 410 K when the structure is cubic, exhibiting the presence of dynamic tilting. Overall, our findings shed light on the thermal stability and structural dynamics of CsPbBr3, contribute to the fundamental understanding of its phase behavior, and provide a crucial pivot for guiding the design of next-generation optoelectronic and radiation detection devices.

Size Uniformity of CsPbBr3 Perovskite Quantum Dots via Manganese-Doping.

The achievement of size uniformity and monodispersity in perovskite quantum dots (QDs) requires the implementation of precise temperature control and the establishment of optimal reaction conditions. Nevertheless, the accurate control of a range of reaction variables represents a considerable challenge. This study addresses the aforementioned challenge by employing manganese (Mn) doping to achieve size uniformity in CsPbBr3 perovskite QDs without the necessity for the precise control of the reaction conditions. By optimizing the Mn:Pb ratio, it is possible to successfully dope CsPbBr3 QDs with the appropriate concentrations of Mn²⁺ and achieve a uniform size distribution. The spectroscopic measurements on single QDs indicate that the appropriate Mn²⁺ concentrations can result in a narrower spectral linewidth, a longer photoluminescence (PL) lifetime, and a reduced biexciton Auger recombination rate, thus positively affecting the PL properties. This study not only simplifies the size control of perovskite QDs but also demonstrates the potential of Mn-doped CsPbBr3 QDs for narrow-linewidth light-emitting diode applications.

Suppressed ion migration for high-performance X-ray detectors based on atmosphere-controlled EFG-grown perovskite CsPbBr3 single crystals

Suppressed ion migration for high-performance X-ray detectors based on atmosphere-controlled EFG-grown perovskite CsPbBr3 single crystals

Structural Disorder by Octahedral Tilting in Inorganic Halide Perovskites: New Insight with Bayesian Optimization

Structural disorder is common in metal‐halide perovskites and important for understanding the functional properties of these materials. First‐principles methods can address structure variation on the atomistic scale, but they are often limited by the lack of structure‐sampling schemes required to characterize the disorder. Herein, structural disorder in the benchmark inorganic halide perovskites CsPbI3 and CsPbBr3 is computationally studied in terms of the three octahedral‐tilting angles. The subsequent variations in energetics and properties are described by 3D potential‐energy surfaces (PESs) and property landscapes, delivered by Bayesian optimization as implemented in the Bayesian optimization structure search code sampling density functional theory (DFT) calculations. The rapid convergence of the PES with about 200 DFT data points in 3D searches demonstrates the power of active learning and strategic sampling with Bayesian optimization. Further analysis indicates that disorder grows with increasing temperature and reveals that the material bandgap at finite temperatures is a statistical mean over disordered structures.

Fluorescence based visual sensing of cesium ions enabled by space-confined converting enriched cesium ions to CsPbBr3 nanocrystals in crown ether functionalized mesoporous silica

Portable fluorescence-based Cs+ radionuclide sensing has received great concerns yet challenged by interference in complex sample matrices. Herein, a reliable method was established by in situ converting the preconcentrated Cs+ to CsPbBr3 perovskite nanocrystals in mesoporous silica modified with dibenzo 24-crown-8 ethers (DB24C8E-SiO2), which combined the selective extraction of Cs+ with in situ fluorescence derivatization to achieve good anti-interference ability. The high adsorption capacity (49.5 mg g−1) of DB24C8E-SiO2 for Cs+ and elution-free operation enabled enrichment factor up to 4500, which was conducive to reducing the limit of detection (LOD) for Cs+. By this method, the fluorescence intensity linearly increased with the Cs+ concentration from 0.050 μg mL−1 to 100 μg mL−1 with an LOD of 0.017 μg mL−1 (S/N = 3). The concentration of Cs+ in seawater sample was detected to be 0.056 μg mL−1. The recoveries of Cs+ in spiked samples remained above 88.90 % and the relative standard deviations were less than 12.06 %. In addition, the relative errors of this method were within ±13.2 % compared with the result from atomic absorption spectrometry. The study demonstrated the high potential of the method for removal and portable detection of Cs+.

Highly luminescent CsPbBr3 perovskite nanocrystal films via the ligand-assisted reaction

Via the ligand-assisted reaction, highly luminescent CsPbBr3 perovskite nanocrystal (PNC) films were synthesized by a simple centrifugal casting process based on the supersaturated recrystallization method. The structure, the optical properties, the morphology, the stability and the potential application of the PNC films were investigated in detail. The results show that under the joint use of OA, DDAB and APTES, the obtained PNC films with 1.5 M DDAB show the strong PL emission with highest quantum yield of 77.5 %, the pure CsPbBr3 structure, the smooth surface and the enhanced stability under UV irradiation. Additionally, the white LED device based on the PNC films obtained here and a commercial red phosphor layer shows excellent optical and color properties and working stability, demonstrating the potential of the PNC films in this study in the field of light-emitting and display.

Preparation of Highly Efficient and Stable All-Inorganic CsPbBr3 Perovskite Solar Cells Using Pre-Crystallization Multi-Step Spin-Coating Method

All-inorganic CsPbBr3 perovskite solar cells have garnered extensive attention in the photovoltaic domain due to their remarkable environmental stability. Nevertheless, CsPbBr3 prepared using the conventional sequential deposition method suffers from issues such as inferior crystallinity, low phase purity, and poor film morphology. Herein, we propose a pre-crystallization methodology by introducing a minute quantity of CsBr into the PbBr2 precursor solution to generate a small amount of CsPb2Br5 crystals within the PbBr2 film, leading to a porous PbBr2 film with enhanced crystallinity. Under the influence of more pores and CsPb2Br5 crystals as nucleation sites for inducing growth, a CsPbBr3 film with a larger crystal size, lower grain boundary density, stronger crystallinity, and higher phase purity is formed. Compared with untreated devices, photovoltaic devices prepared using the pre-crystallization method achieved a champion photovoltaic conversion efficiency (PCE) of 8.62%. Furthermore, pre-crystallized devices demonstrate higher stability than untreated ones and can still retain 94% of the original PCE after being exposed to air for 1000 h without encapsulating.

Nano-immuno-conjugates inspired by hydrophilic perovskite fluorescent spheres and magnetic assisted for detection of hepatitis B surface antigen.

The rampant hepatitis B virus (HBV) seriously endangers human health, and hepatitis B surface antigen (HBsAg) is its early diagnostic marker. Therefore, it is crucial to construct a fast and highly sensitive HBsAg detection method. Based on high-efficiency magnetic separation technology and fluorescent composite material labelling technology, an accurate, fast and sensitive fluorescent immunosensing system for HBsAg detectionwas developed. Immunomagnetic beads constructed from carboxyl-functionalized Fe3O4 nanoparticles (Fe3O4-COOH) with excellent magnetic response performance were used as efficient capture carriers for HBsAg. Immunofluorescence composite microspheres constructed based on ultra-stable polystyrene-coated CsPbBr3 perovskite nanocrystals (CPB@PSAA) with high hydrophilic properties, were excellent fluorescent markers for HBsAg. Using thissensitive sandwich fluorescence sensing system a good linear relationship within the range of 0.2-15ng/mL was established between HBsAg concentrationand fluorescence intensity with alimit of detection (LOD) of 0.05ng/mL. Thesystem obtained satisfactory results when tested on real human serum samples. The magnetic-assisted fluorescence immune-sandwich sensor system has broad application prospects in biomedicine such as rapid and early diagnosis and effective prevention of infectious diseases.

Understanding the emission behaviour of 0D Cs4PbBr6 perovskite nanocrystals at room temperature

We report 0D Cs4PbBr6 perovskite nanocrystals emitting at room temperature, synthesized by hot injection technique. Effect of injection temperature (TR) on the emission of Cs4PbBr6 nanocrystals (NCs) has been studied. High-quality NCs are synthesized in the 100 °C–180 °C temperature range. Pure phase Cs4PbBr6 nanocrystals are formed at lower temperatures (TR = 100 °C), while at higher temperatures, CsPbBr3 impurity phase appears along with Cs4PbBr6. Cs4PbBr6 nanocrystals emit blue light with broad emission spectra in the 400–500 nm wavelength range, while a green emission from CsPbBr3 impurities at 520 nm wavelength is observed. The emission spectra from Cs4PbBr6 NCs shows multiple radiative centers in the 400–500 nm range, unaffected by the change in excitation wavelength. The emission of pure Cs4PbBr6 is attributed to charge transfer states of Pb2+ ions and surface states incorporated by presence of ligands on NC surface. Further, it is to be emphasized that the Cs4PbBr6 perovskite NCs are highly stable and maintain their emission even after two years of synthesis.

Pressure-dependent band gap engineering with structural, electronic, mechanical, optical, and thermal properties of CsPbBr3: first-principles calculations.

In the renewable industry, pressure-dependent CsPbBr3 perovskite has a lot of potential due to its exceptional properties. Present work revealed the mechanical stability of CsPbBr3 between 0 to 50GPa. The bandgap of unstressed CsPbBr3 is 2.90eV, indicating a direct bandgap. Band gap values decrease by increasing external pressure. CsPbBr3 structure showed a direct band gap from 0 to 35GPa and in-direct from 40 to 50GPa. The unit cell volume and lattice constants are substantially decreased. Mechanical parameters, i.e., Young's modulus, bulk modulus, anisotropy factor, shear modulus, and poison's ratio are obtained. Under ambient conditions, the mechanical properties of CsPbBr3 showed ductile behavior and with induced pressure, their ductility has significantly improved. By applying stresses ranging from 0 to 50GPa, the considerable fluctuation in values of dielectric function (imaginary and real), absorption, reflectivity, loss function, refractive index (imaginary and real), and conductivity (imaginary and real), was also identified. When pressure rises, the optical parameters increase and drag in the direction of high energies. Response functions are used to predict the density of states and the phonon lattice dispersion to study the phonon properties. By using the quasi-harmonic Debye model, the thermal effect on the free energy, entropy, enthalpy, and heat capacity were predicted and compared. These results would be useful for theoretical research and indicate how external pressure significantly affects the physical characteristics of CsPbBr3 perovskites, which may open up new possibilities for use in optoelectronic, photonic, and solar cell applications. The structural, electrical, mechanical, optical, and thermal properties of cesium lead bromide (CsPbBr3) are investigated by applying external pressure from 0 to 50GPa, using generalized gradient approximations (GGA) and Perdew-Burke-Ernzerhof (PBE) with CASTEP code built-in material studio by density functional theory (DFT).

Luminescent Cs8PbBr64+ Quantum Dots Centered on the Octahedral PbBr64- Cluster within Zeolite LTA: Exploring the Edge of Three-Dimensional Crystal Structure and Its Stability.

The perovskite quantum dots (QDs) of CsPbX3 (X = Cl, Br, I) exhibit exceptional photoluminescent properties, but their sensitivity to moisture and heat poses a challenge. This study presents a solvent-free synthesis approach for incorporating CsPbBr3 perovskite QDs into zeolite A. The introduction of [Cs8PbBr6]4+ perovskite QDs into the zeolite framework resulted in a highly stable configuration, maintaining its initial luminescence properties even after being underwater or exposed to heat. The structure is determined by 3-dimensional single-crystal crystallography. Each octahedral PbBr64- ion is surrounded by Cs+ ions and [Cs8PbBr6]4+ perovskite QDs being formed at the 32% of the center of a large cavity. Further, [Na12CsBr8]5+ QDs are formed at the very center of another 46% large cavities by combining Cs+, Na+, and Br- ions. The peak in the emission spectrum of Pb,Br,Cs,Na-A is similar to those of the CsPbBr3 nanocrystal, Cs4PbBr6 0-dimensional perovskite QDs, and Pb,Br,H,Cs,Na-FAU(X and Y). This work demonstrates that Pb,Br,Cs,Na-A can be produced using a simplified solvent-free synthesis procedure, which exhibits excellent stability against moisture and heat. Moreover, through a straightforward process, various quantum dots (QDs) can be incorporated into zeolite cavities to develop materials with variety photoluminescent properties.

Spectator Exciton Effects in Nanocrystals III: Unveiling the Stimulated Emission Cross Section in Quantum Confined CsPbBr3 Nanocrystals.

Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of ∼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.

Reducing oxygen vacancies of MoO3 by polyaniline functionalization for stable and efficient inorganic tri-brominated perovskite solar cells

The photovoltaic performance of perovskite solar cells (PSCs) is closely dependent on the efficient carrier extraction and transport at the interface. Here, a polyaniline (PANI) functionalized MoO3 (PANI/MoO3) hole transport material (HTM) is exploited to perfect the interface between the perovskite layer and carbon electrode in all-inorganic CsPbBr3 PSCs. After functionalization with PANI, the p-type behavior and the hole mobility and conductivity of MoO3 are improved by reducing the oxygen vacancies, which boosts the hole extraction and transport, energy level arrangement at the interface of CsPbBr3 perovskite/(PANI/MoO3) HTM. Meanwhile, the PANI/MoO3 with rich C–N and N–H groups introduced by PANI passivates the ions trap states of perovskite films by the C–N⋯Pb2+ (Cs+) Lewis acid-base coordination and the N–H⋯Br− hydrogen bonding, leading to an effective suppression of non-radiative recombination for improved carrier extraction. As a result, the PANI/MoO3 HTMs-based CsPbBr3 PSCs obtain a remarkably increased power conversion efficiency of 10.41 %, in comparison with the efficiency of the original device (6.55 %). In addition, the unencapsulated device with PANI/MoO3 HTMs shows excellent long-term stability with 93.9 % maintenance of the initial efficiency after storing in air with 85 % relative humidity and at 85 °C for 30 days.

Growth and photoelectrical properties of CsPbBr3-xIx (0 ≤ x < 1) single crystals

The all-inorganic halide perovskite CsPbBr3 possesses excellent optoelectronic characteristics and has a high opportunity for application in a variety of photoelectric devices. CsPbBr3 is known for its relatively low ionic migration and higher resistivity compared to other perovskite compositions. In addition, the performance in X-ray detectors can be further improved by the addition of I- dopants. The addition of I- dopants has been shown to be an effective way to improve these properties. The vertical Bridgman method was used to grown I--doped CsPbBr3 crystals. The crystal structure, optical characteristics, electrical characteristics, and X-ray detection capabilities of CsPbBr3-xIx (0 ≤ x < 1) single crystals were all systematically investigated. The results indicate that I--doping can adjust the band gap, increase the resistivity and carrier mobility, and reduce the trap density and dark current, providing the possible application of halide perovskite in various optoelectronic devices.

Ultraviolet color image sensor based on CsPbBr3 inorganic perovskite nanocrystal film.

Ultraviolet and color imaging require different image sensors and optical channels, which results in large size, complex structure, and high cost of imaging systems. Here, we report a novel, to the best of our knowledge, image sensor that combines ultraviolet and color imaging functions. The fabrication of this image sensor is achieved by coating high-transparency CsPbBr3 perovskite nanocrystals in a polymer film on the color filter layer of a silicon-based detector. The film, serving as an ultraviolet photoluminescent layer, exhibits high transparency, exceeding 91.5% at wavelengths beyond the photoluminescence peak of 513 nm. During ultraviolet imaging, the film converts ultraviolet light into visible light, which passes through the green filter layer to reach the detector for imaging. During visible light imaging, red light, green light, and most of the blue light pass through the CsPbBr3 perovskite nanocrystal film and color filter layer to reach the detector for imaging. As a result, the image sensor can capture both 257 nm solar-blind ultraviolet images and color photos in the visible light.

Accessible New Non-Quantum Dot Cs2PbI2Cl2-Based Photocatalysts for Efficient Hole-Driven Photocatalytic Applications.

Efficient, low-cost photocatalysts with mild synthesis conditions and stable photocatalytic behavior have always been the focus in the field of photocatalysis. This study proves that non-quantum-dot Cs2PbI2Cl2-based materials, created by a simple method, can be successfully employed as new high-efficient photocatalysts. The results demonstrate that two-dimensional Cs2PbI2Cl2 perovskite can achieve over three times higher photocatalytic performance compared to three-dimensional CsPbBr3 perovskite. Moreover, the photocatalytic performance of Cs2PbI2Cl2 can be further improved by constructing a heterojunction structure, such as Cs2PbI2Cl2/CsPbBr3. Cs2PbI2Cl2 can connect well with CsPbBr3 through a simple method, resulting in tight bonding at the interface and efficient carrier transfer. Cs2PbI2Cl2/CsPbBr3 exhibits notable 5-fold and 10-fold improvements in photocatalytic performance and rate compared to CsPbBr3. Additionally, Cs2PbI2Cl2/CsPbBr3 demonstrates superb stable catalytic performance, with nearly no decrease in photocatalytic performance after 7 months (RH = 20% ± 10, T = 25 °C ± 5). This study also reveals that the photocatalytic process based on Cs2PbI2Cl2/CsPbBr3 can directly oxidize organic matter using holes, without relying on the generation of intermediate reactive oxygen species from water or oxygen (such as ·OH or ·O2-), showcasing further potential for achieving high photocatalytic efficiency and selectivity in anhydrous/anaerobic catalytic reactions and treating recalcitrant pollutants.