Brightening deep-blue perovskite light-emitting diodes: A path to Rec. 2020.

Deep-blue perovskite light-emitting diodes (PeLEDs) of high purity are highly sought after for next-generation displays complying with the Rec. 2020 standard. However, mixed-halide perovskite materials designed for deep-blue emitters are prone to halide vacancies, which readily occur because of the low formation energy of chloride vacancies. This degrades bandgap instability and performance. Here, we propose a chloride vacancy-targeting passivation strategy using sulfonate ligands with different chain lengths. The sulfonate groups have a strong affinity for lead(II) ions, effectively neutralizing vacancies. Our strategy successfully suppressed phase segregation, yielding color-stable deep-blue PeLEDs with an emission peak at 461 nanometers and a maximum luminance (Lmax) of 2707 candela per square meter with external quantum efficiency (EQE) of 3.05%, one of the highest for Rec. 2020 standard-compliant deep-blue PeLEDs. We also observed a notable increase in EQE up to 5.68% at Lmax of 1978 candela per square meter with an emission peak at 461 nanometers by changing the carbon chain length.

Self-Assembly of Delta-Formamidinium Lead Iodide Nanoparticles to Nanorods: Study of Memristor Properties and Resistive Switching Mechanism.

In the quest for advanced memristor technologies, this study introduces the synthesis of delta-formamidinium lead iodide (δ-FAPbI3) nanoparticles (NPs) and their self-assembly into nanorods (NRs). The formation of these NRs is facilitated by iodide vacancies, promoting the fusion of individual NPs at higher concentrations. Notably, these NRs exhibit robust stability under ambient conditions, a distinctive advantage attributed to the presence of capping ligands and a crystal lattice structured around face-sharing octahedra. When employed as the active layer in resistive random-access memory devices, these NRs demonstrate exceptional bipolar switching properties. A remarkable on/off ratio (105) is achieved, surpassing the performances of previously reported low-dimensional perovskite derivatives and α-FAPbI3 NP-based devices. This enhanced performance is attributed to the low off-state current owing to the reduced number of halide vacancies, intrinsic low dimensionality, and the parallel alignment of NRs on the FTO substrate. This study not only provides significant insights into the development of superior materials for memristor applications but also opens new avenues for exploring low-dimensional perovskite derivatives in advanced electronic devices.

Two-Dimensional Halide Perovskites: Approaches to Improve Optoelectronic Properties.

Three-dimensional (3D) halide perovskites (HPs) are in the spotlight of materials science research due to their excellent photonic and electronic properties suitable for functional device applications. However, the intrinsic instability of these materials stands as a hurdle in the way to their commercialization. Recently, two-dimensional (2D) HPs have emerged as an alternative to 3D perovskites, thanks to their excellent stability and tunable optoelectronic properties. Unlike 3D HPs, a library of 2D perovskites could be prepared by utilizing the unlimited number of organic cations since their formation is not within the boundary of the Goldschmidt tolerance factor. These materials have already proved their potential for applications such as solar cells, light-emitting diodes, transistors, photodetectors, photocatalysis, etc. However, poor charge carrier separation and transport efficiencies of 2D HPs are the bottlenecks resulting in inferior device performances compared to their 3D analogs. This minireview focuses on how to address these issues through the adoption of different strategies and improve the optoelectronic properties of 2D perovskites.

Organic Spacer Cation Assisted Modulation of the Structure and Properties of Bismuth Halide Perovskites.

ConspectusLead halide perovskites are under the spotlight of current research due to their potential for efficient and cost-effective next-generation optoelectronic devices. The unique photonic and electronic properties of these solution-processable materials brought them to the forefront of materials science. However, the toxicity and instability of lead-based perovskites are the major hurdles for their commercialization. These issues initiated an effort towards the development of environmentally friendly, lead-free perovskites. In this context, bismuth halide perovskites (BHPs) were ideal rivals for lead-based congeners due to their excellent chemical stability, lower toxicity, and structural versatility. Understanding the crystal structure and optoelectronic properties of BHPs is crucial for designing them for specific, tailor-made applications. This Account aims to review our recent research progress on the role of functional organic spacer cations in modulating the electronic confinements, optical properties, and photoconductivity of BHPs. We have employed a comprehensive experimental and theoretical investigation to probe the intriguing optical and electronic properties of these materials. Our findings on the structure-optoelectronic property correlations will be valuable guidelines for the rational selection of organic spacer cations in designing BHPs featuring low exciton binding energy, narrow optical bandgap, enhanced visible light absorption, and high photoconductivity. One of our key findings is that by increasing the electron affinity of the organic spacer ligands, photoconductivity and visible light absorption of BHPs could be significantly enhanced. We hope that the fundamental level understanding of the photophysical properties discussed in this Account will lead to new design rules for developing high-performance BHP materials.

Self-Assembled Organic Cations-Assisted Band-Edge Tailoring in Bismuth-Based Perovskites for Enhanced Visible Light Absorption and Photoconductivity.

Bismuth-based zero-dimensional perovskites garner high research interest because of their advantages, such as excellent moisture stability and lower toxicity in comparison to lead-based congeners. However, the wide optical bandgap (>2 eV) and poor photoconductivity of these materials are the bottlenecks for their optoelectronic applications. Herein, we report a combined experimental and theoretical study of the structural features and optoelectronic properties of two novel and stable zero-dimensional bismuth perovskites: (biphenyl bis(methylammonium))1.5BiI6·2H2O (BPBI) and (naphthalene diimide bis(ethylammonium))1.5BiI6·2H2O (NDBI). NDBI features a remarkably narrower bandgap (1.82 eV) than BPBI (2.06 eV) because of the significant orbital contribution of self-assembled naphthalene diimide cations at the band edges of NDBI. Further, the FP-TRMC analysis revealed that the photoconductivity of NDBI is about 3.7-fold greater than that of BPBI. DFT calculations showed that the enhanced photoconductivity in NDBI arises from its type-IIa band alignment, whereas type-Ib alignment was seen in BPBI.

Anisotropic Photoconductivity and Long-Lived Charge Carriers in Bismuth-Based One-Dimensional Perovskite with Type-IIa Band Alignment.

Bismuth-based perovskites are attracting intense scientific interest due to low toxicity and excellent moisture stability compared to lead-based analogues. However, high exciton binding energy, poor charge carrier separation, and transport efficiencies lower their optoelectronic performances. To address these issues, we have integrated an electronically active organic cation, naphthalimide ethylammonium, between the [BiI52-]n chains via crystal engineering to form a novel perovskite-like material (naphthalimide ethylammonium)2BiI5 (NBI). Single crystal analysis revealed a one-dimensional quantum-well structure for NBI in which inter-inorganic well electronic coupling is screened by organic layers. It exhibited anisotropic photoconductivity and long-lived charge carriers with milliseconds lifetime, which is higher than that of CH3NH3PbI3. Density functional theory calculations confirmed type-IIa band alignment between organic cations and inorganic chains, allowing the former to electronically contribute to the overall charge transport properties of the material.

Photoinduced photoluminescence enhancement in self-assembled clusters of formamidinium lead bromide perovskite nanocrystals.

Nanocrystals of formamidinium lead bromide perovskite (FAPbBr3) self-assemble into clusters in powder and film samples and provide a prolonged photoluminescence lifetime, which is attributed to the diffusion of charge carriers through interparticle states formed among nanocrystals. Interestingly, the photoluminescence lifetime decreases and the emission intensity increases for the clusters, which is with the increase in the intensity of excitation light. By doping the nanocrystal clusters with C60, we successfully harvested the photogenerated charge carriers. Nonetheless, at high intensities of excitation, the rate of radiative recombination becomes comparable to that of the electron transfer to C60. Thus, the optimum rate of electron transfer to C60 is accomplished by minimally exciting the self-assembled nanocrystals.

CH3 NH3 PbBr3 Perovskite Nanocrystals as Efficient Light-Harvesting Antenna for Fluorescence Resonance Energy Transfer.

Hybrid perovskites have created enormous research interest as a low-cost material for high-performance photovoltaic devices, light-emitting diodes, photodetectors, memory devices and sensors. Perovskite materials in nanocrystal form that display intense luminescence due to the quantum confinement effect were found to be particularly suitable for most of these applications. However, the potential use of perovskite nanocrystals as a light-harvesting antenna for possible applications in artificial photosynthesis systems is not yet explored. In the present work, we study the light-harvesting antenna properties of luminescent methylammonium lead bromide (CH3 NH3 PbBr3 )-based perovskite nanocrystals using fluorescent dyes (rhodamine B, rhodamine 101, and nile red) as energy acceptors. Our studies revealed that CH3 NH3 PbBr3 nanocrystals are an excellent light-harvesting antenna, and efficient fluorescence resonance energy transfer occurs from the nanocrystals to fluorescent dyes. Further, the energy transfer efficiency is found to be highly dependent on the number of anchoring groups and binding ability of the dyes to the surface of the nanocrystals. These observations may have significant implications for perovskite-based light-harvesting devices and their possible use in artificial photosynthesis systems.

Zero-Dimensional Methylammonium Bismuth Iodide-Based Lead-Free Perovskite Capacitor.

Symmetrical electrochemical capacitors are attracting immense attention because of their fast charging-discharging ability, high energy density, and low cost of production. The current research in this area is mainly focused on exploring novel low-cost electrode materials with higher energy and power densities. In the present work, we fabricated an electrochemical double-layer capacitor using methylammonium bismuth iodide (CH3NH3)3Bi2I9, a lead-free, zero-dimensional hybrid perovskite material. A maximum areal capacitance of 5.5 mF/cm2 was obtained, and the device retained 84.8% of its initial maximum capacitance even after 10 000 charge-discharge cycles. Impedance spectroscopy measurements revealed that the active layer provides a high surface area for the electrolyte to access. As a result, the charge transport resistance is reasonably low, which is advantageous for delivering excellent performance.

Channeling Exciton Migration into Electron Transfer in Formamidinium Lead Bromide Perovskite Nanocrystal/Fullerene Composites.

Hydrophobically capped nanocrystals of formamidinium lead bromide (FAPbBr3 ) perovskite (PNC) show bright and stable fluorescence in solution and thin-film states. When compared with isolated PNCs in a solution, close-packed PNCs in a thin film show extended fluorescence lifetime (ca. 4.2 µs), which is due to hopping or migration of photogenerated excitons among PNCs. Both fluorescence quantum efficiency and lifetime decrease in a PNC thin film doped with fullerene (C60 ), which is attributed to channeling of exciton migration into electron transfer to C60 . On the other hand, quenching of fluorescence intensity of a PNC solution is not accompanied by any change in fluorescence lifetime, indicating static electron transfer to C60 adsorbed onto the hydrophobic surface of individual PNCs. Exciton migration among close-packed PNCs and electron transfer to C60 places C60 -doped PNC thin films among cost-effective antenna systems for solar cells.