Band Gap Alteration of Halide Mixing in Hybrid Perovskites: A First-Principles Study with Statistical Analysis.

Despite numerous studies on the band gap of three-dimensional halide perovskites using the first-principles calculations, there are still significant discrepancies between theoretical and experimental values. Various solutions have been proposed, such as employing a system-specific hybrid functional with varying degrees of exact exchange and explicitly incorporating spin-orbit coupling effects. Our research involved a comprehensive investigation of three typical lead-containing three-dimensional perovskites MAPbI3, MAPbBr3, and MAPbCl3 (MA = CH3NH3). Through a statistical analysis comparing mean absolute error (MAE) with experimental results, we demonstrated that the nonlocal van der Waals (vdW) density functional corrections (i.e., optB86b) yielded the most approximate lattice parameters in comparison to experimental values. Furthermore, based on these lattice parameters, the HSE06 hybrid functional is the optimal estimation of the band gap among all the options. Moreover, we investigated three sets of mixed three-dimensional halide perovskites by varying the halide component. This exploration contributes to the identification of MAPb(Br0.333I0.667)3 and MAPb(Cl0.333I0.667)3 as exhibiting the smallest band gap of 1.315 (1.867) eV and 1.313 (1.885) eV for PBE (HSE06), respectively. These band gaps were determined using the HSE06 method with the optimized lattice by PBE considering the optB86b corrections. The approach employed in this work produced a band gap trend closely aligned with experimental observations, underscoring the importance of adopting a reliable and material-independent computational strategy when screening new halide perovskite materials for optoelectronic applications.

Regulating Exciton De-Trapping of Te4+ -Doped Zero-Dimensional Scandium-Halide Perovskite for Fluorescence Thermometry with Record High Time-Resolved Thermal Sensitivity.

Fluorescence thermometry has been propelled to the forefront of scientific attention due to its high spatial resolution and remote non-invasive detection. However, recent generations of thermometers still suffer from limited thermal sensitivity (Sr ) below 10% change per Kelvin. Herein, this work presents an ideal temperature-responsive fluorescence material through Te4+ -doped 0D Cs2 ScCl5 ·H2 O, in which isolated polyhedrons endow highly localized electronic structures, and the strong electron-phonon coupling facilitates the formation of self-trapped excitons (STEs). With rising temperature, the dramatic asymmetric expansion of the soft lattice induces increased defects, strong exciton-phonon coupling, and low thermal activation energy, which evokes a rapid de-trapping process of STEs, enabling several orders of magnitude changes in the fluorescence lifetime over a narrow temperature range. After regulating the de-trapping process with different Te4+ doping, a record-high Sr (27.36% K-1 ) of fluorescence lifetime-based detection is achieved at 325 K. The robust stability against multiple heating/cooling cycles and long-term measurements enables a low temperature uncertainty of 0.067 K. Further, the developed thermometers are demonstrated for the remote local monitoring of operating temperature on internal electronic components. It is believed that this work constitutes a solid step towards building the next generation of ultrasensitive thermometers based on low-dimensional metal halides.

High-Efficiency and Stable Long-Persistent Luminescence from Undoped Cesium Cadmium Chlorine Crystals Induced by Intrinsic Point Defects.

Application of long-persistent luminescence (LPL) materials in many technological fields is in the spotlight. However, the exploration of undoped persistent luminescent materials with high emission efficiency, robust stability, and long persistent duration remains challenging. Here, inorganic cesium cadmium chlorine (CsCdCl3 ) is developed, featuring remarkable LPL characteristics at room temperature, which is synthesized by a facile hydrothermal method. Excited by ultraviolet light, the CsCdCl3 crystals exhibit an intense yellow emission with a large photoluminescence quantum yield of ≈90%. Different from the reported systems with lanthanides or transition metals doping, the CsCdCl3 crystals without dopants perform yellow LPL with a long duration of 6000 s. Joint experiment-theory characterizations reveal the intrinsic point defects of CsCdCl3 act as the trap centers of excited electrons and the carrier de-trapping process from such trap sites to localized emission centers contributes to the LPL. Encouraged by the attractive fluorescence and persistent luminescence as well as good stability of CsCdCl3 against environment oxygen/moisture (75%), heat (100 °C for 10 h), and ultraviolet light irradiation, an effective dual-mode information storage-reading application is demonstrated. The results open up a new frontier for exploring LPL materials without dopants and provide an opportunity for advanced information storage compatible for practical applications.

Carbazole-Containing Polymer-Assisted Trap Passivation and Hole-Injection Promotion for Efficient and Stable CsCu2 I3 -Based Yellow LEDs.

Perovskite light-emitting diodes (LEDs) are emerging light sources for next-generation lighting and display technologies; however, their development is greatly plagued by difficulty in achieving yellow electroluminescence, environmental instability, and lead toxicity. Copper halide CsCu2 I3 with intrinsic yellow emission emerges as a highly promising candidate for eco-friendly LEDs, but the electroluminescent performance is limited by defect-related nonradiative losses and inefficient charge transport/injection. To solve these issues, a hole-transporting poly(9-vinlycarbazole) (PVK)-incorporated engineering into CsCu2 I3 emitter is proposed. PVK with carbazole groups is permeated at the grain boundaries of CsCu2 I3 films by interacting with the uncoordinated Cu+ , reducing the CuCs and CuI antisite defects to increase the radiative recombination and enhancing the hole mobility to balance the charge transport/injection, resulting in substantially enhanced device performances. Eventually, the yellow LEDs exhibit an 8.5-fold enhancement of external quantum efficiency, and the half-lifetime reaches 14.6 h, representing the most stable yellow LEDs based on perovskite systems reported so far.

Regulating the Singlet and Triplet Emission of Sb3+ Ions to Achieve Single-Component White-Light Emitter with Record High Color-Rendering Index and Stability.

The rapid development of solid-state lighting technology has attracted much attention for searching efficient and stable luminescent materials, especially the single-component white-light emitter. Here, we adopt a facile ion-doping technology to synthesize vacancy-ordered double perovskite Cs2ZrCl6:Sb. The introduction of Sb3+ ions with a 5s2 active lone pair into Cs2ZrCl6 host stimulates the singlet (blue) and triplet (orange) states emission of Sb3+ ions, and their relative emission intensity can be tuned through the energy transfer from singlet to triplet states. Benefiting from the dual-band emission as a pair of perfect complementary colors, the optimum Cs2ZrCl6:1.5%Sb exhibits a high-quality white emission with a color-rendering index of 96. By employing Cs2ZrCl6:1.5%Sb as the down-conversion phosphor, stable single-component white light-emitting diodes with a record half-lifetime of 2003 h were further fabricated. This study puts forward an effective ion-doping strategy to design single-component white-light emitter, making practical applications of them in lighting technologies a real possibility.

Revealing the Anisotropic Structural and Electrical Stabilities of 2D SnSe under Harsh Environments: Alkaline Environment and Mechanical Strain.

As a promising thermoelectric and semiconducting material, the stability of two-dimensional tin selenide (SnSe) under harsh environments is significant for its practical applications. Here, focusing on the key procedures in the device fabrication process, we report the anisotropic structural and electrical stabilities of SnSe under an alkaline environment and mechanical strain. Due to the anisotropic mechanical properties, the SnSe flakes can naturally form long-straight {011} edge planes during the mechanical exfoliation process. Such a cleavage tendency provides an effective crystal orientation identification method to uncover the orientation-dependent properties. We find that the single-crystalline SnSe flakes experience an anisotropic degradation process with the preferable {011} dissolution planes in the alkaline environment and can be gradually transformed to be polycrystalline consisting of SnSe2, Sn, and Se nanocrystals. SnSe flakes present an anisotropic electromechanical response with a gauge factor value that reaches ∼-460 under the uniaxial strain along the ⟨011⟩ directions. Our revealed structural and electrical stability of SnSe under harsh environments can provide guidance for the device design, fabrication, and performance evaluation.

Room-temperature synthesis of blue-emissive zero-dimensional cesium indium halide quantum dots for temperature-stable down-conversion white light-emitting diodes with a half-lifetime of 186 h.

Recently, the newly-emerging lead halide perovskite quantum dots (QDs) have attracted intensive research interest for lighting and display applications owing to their remarkable optoelectronic properties. It is regrettable that the toxicity and instability of lead largely hinder their practical applications. Here, zero-dimensional (0D) cesium indium halide (Cs3InX6) QDs were synthesized for the first time using a modified ligand-assisted reprecipitation method, and the emission wavelength can be tuned facilely via an anion exchange reaction. Typically, the Cs3InBr6 QDs showed broadband blue emission with a high photoluminescence (PL) quantum yield of 46%. First-principles calculations were performed and temperature-dependent PL was studied to investigate the emission mechanisms of the Cs3InBr6 QDs; the 0D nature of Cs3InBr6 enhances the localization of excitons, resulting in a large exciton binding energy. It is worth noting that the strong electron-phonon coupling of Cs3InBr6 indicates that the broadband emission comes from self-trapped exciton emission. Moreover, the Cs3InX6 QDs exhibit excellent stability against moisture, ultraviolet light and heat degradation, significantly better than for conventional lead halide perovskites. Subsequently, the white light-emitting diodes (WLEDs) prepared using blue-emissive Cs3InBr6 QD powder used as the phosphor showed an excellent working stability with a record half-life (T50) of 186 h. Even if the operating temperature is as high as 106.9 °C, the LED can still operate well and reach a T50 of 50 h. These results highlight the huge advantages and application potential of 0D Cs3InX6 QDs as an environmentally friendly emitter in the field of solid-state lighting.

High Color-Rendering Index and Stable White Light-Emitting Diodes by Assembling Two Broadband Emissive Self-Trapped Excitons.

White light-emitting diodes (WLEDs) are promising next-generation solid-state light sources. However, the commercialization route for WLED production suffers from challenges in terms of insufficient color-rendering index (CRI), color instability, and incorporation of rare-earth elements. Herein, a new two-component strategy is developed by assembling two broadband emissive materials with self-trapped excitons (STEs) for high CRI and stable WLEDs. The strategy addresses effectively the challenging issues facing current WLEDs. Based on first-principles thermodynamic calculations, copper-based ternary halides composites, CsCu2 I3 @Cs3 Cu2 I5 , are synthesized by a facile one-step solution approach. The composites exhibit an ideal white-light emission with a cold/warm white-light tuning and a robust stability against heat, ultraviolet light, and environmental oxygen/moisture. A series of cold/warm tunable WLEDs is demonstrated with a maximum luminance of 145 cd m-2 and an external quantum efficiency of 0.15%, and a record high CRI of 91.6 is achieved, which is the highest value for lead-free WLEDs. Importantly, the fabricated device demonstrates an excellent operation stability in a continuous current mode, exhibiting a long half-lifetime of 238.5 min. The results promise the use of the hybrids of STEs-derived broadband emissive materials for high-performance WLEDs.

Ultrastable Lead-Free Double Perovskite Warm-White Light-Emitting Devices with a Lifetime above 1000 Hours.

Recently, white light-emitting devices (WLEDs) based on halide perovskites has been extensively studied. However, the lead toxicity and poor stability of conventional lead halide perovskites severely hinder their commercial applications. In this study, lead-free double perovskite Cs2AgInCl6 with a broadband emission was fabricated by a heat-assisted solution evaporation method, in which a compositional engineering by sodium (Na+) alloying and bismuth (Bi3+) doping was performed. The photoluminescence quantum yield was promoted from ∼1.1 to 46.4% and then to 87.2% by Na+ alloying and subsequent Bi3+ doping. In addition, the theory calculation reveals that the diffusion barrier of Cl- vacancy in Cs2AgInCl6 can be increased by Na+ alloying, which would contribute to the stability of the material. Experimentally, the resulting Cs2Ag0.7Na0.3InCl6:Bi products demonstrate a remarkable stability under heat, ultraviolet light, and moisture conditions. The above advantages make it possible for this material to be used as solid-state phosphors for WLED applications, and the Commission International de I'Eclairage color coordinates at (0.38, 0.44), correlated color temperature of 4347 K, and high color rendering index of 87.8 were achieved. More importantly, the WLED demonstrates a remarkable operation stability in air ambient, and only 4.5% emission decay occurs after a long working time for 1000 h, the longest lifetime for perovskite-based WLEDs as far as we know.

Colloidal Synthesis of Ternary Copper Halide Nanocrystals for High-Efficiency Deep-Blue Light-Emitting Diodes with a Half-Lifetime above 100 h.

Currently, the blue perovskite light-emitting diodes (PeLEDs) suffer from a compromise in lead toxicity and poor operation stability, and most previous studies have struggled to meet the crucial blue NTSC standard. In this study, electrically driven deep-blue LEDs (∼445 nm) based on zero-dimensional (0D) Cs3Cu2I5 nanocrystals (NCs) were demonstrated with the color coordinates of (0.16, 0.07) and a high external quantum efficiency of ∼1.12%, comparable with the best-performing blue LEDs based on lead-halide perovskites. Encouraged by the remarkable stability of Cs3Cu2I5 NCs against heat and environmental oxygen/moisture, the proposed device was operated in a continuous current mode for 170 h, producing a record half-lifetime of ∼108 h. The device stability was further verified by an aggressive thermal cycling test (300-360-300 K) and a 35-day storage test. Together with the eco-friendly features and facile colloidal synthesis technique, the 0D Cs3Cu2I5 NCs can be therefore regarded as a promising candidate for deep-blue LEDs applications.

Water-induced MAPbBr3@PbBr(OH) with enhanced luminescence and stability.

Poor stability has long been one of the key issues that hinder the practical applications of lead-based halide perovskites. In this paper, the photoluminescence (PL) quantum yield (QY) of bromide-based perovskites can be increased from 2.5% to 71.54% by introducing water, and the PL QY of a sample in aqueous solution decreases minimally over 1 year. The enhanced stability and PL QY can be attributed to the water-induced methylamino lead bromide perovskite (MAPbBr3)@PbBr(OH). We note that this strategy is universal to MAPbBr3, formamidine lead bromide perovskite (FAPbBr3), inorganic lead bromide perovskite (CsPbBr3), etc. Light-emitting devices (LEDs) are fabricated by using the as-prepared perovskite as phosphors on a 365 nm UV chip. The luminance intensity of the LED is 9549 cd/m2 when the driven current is 200 mA, and blemishes on the surface of glass are clearly observed under the illumination of the LEDs. This work provides a new strategy for highly stable and efficient perovskites.

Stable Yellow Light-Emitting Devices Based on Ternary Copper Halides with Broadband Emissive Self-Trapped Excitons.

Great successes have been achieved in developing perovskite light-emitting devices (LEDs) with blue, green, red, and near-infrared emissions. However, as key optoelectronic devices, yellow-colored perovskite LEDs remain challenging, mainly due to the inevitable halide separation in mixed halide perovskites under high bias, causing undesired color change of devices. In addition to this color-missing problem, the intrinsic toxicity and poor stability of conventional lead-halide perovskites also restrict their practical applications. We herein report the fabrication of stable yellow LEDs based on a ternary copper halide CsCu2I3, addressing the color instability and toxicity issues facing current perovskite yellow LED's compromise. Joint experiment-theory characterizations indicate that the yellow electroluminescence originates from the broadband emission of self-trapped excitons centered at 550 nm as well as the comparable and reasonably low carrier effective masses favorable for charge transport. With a maximum luminance of 47.5 cd/m2 and an external quantum efficiency of 0.17%, the fabricated yellow LEDs exhibit a long half-lifetime of 5.2 h at 25 °C and still function properly at 60 °C with a half-lifetime of 2.2 h, which benefits from the superior resistance of CsCu2I3 to heat, moisture, and oxidation in ambient environmental conditions. The results obtained promise the copper halides with broadband light emission as an environment-friendly and stable yellow emitter for the LEDs compatible with practical applications.

Water-induced fluorescence enhancement of lead-free cesium bismuth halide quantum dots by 130% for stable white light-emitting devices.

Recently, the discovery and development of lead-free perovskite quantum dots (QDs) that are eco-friendly and stable has become an active research area in low-cost lighting and display fields. However, the low photoluminescence quantum yield (PLQY) caused by the residual surface states of such QDs severely hinders their practical applications and commercialization. In this work, a strategy of employing water-induced nanocomposites was proposed to improve the PLQY of cesium bismuth halide (Cs3Bi2X9) QDs, and a substantial enhancement by ∼130% (from 20.2% to 46.4%) was achieved by an optimized water treatment of Cs3Bi2Br9 QDs. A detailed analysis indicated that Cs3Bi2Br9/BiOBr nanocomposites, in which the Cs3Bi2Br9 QD core was encapsulated into a BiOBr matrix, can effectively suppress the surface defects of QDs, resulting in a longer PL lifetime and a larger exciton binding energy compared with the pristine sample. Finally, the Cs3Bi2Br9/BiOBr nanocomposites were used as the color-converting phosphors for down-conversion white light-emitting devices, which show a good operation stability in ambient air, significantly better than the reference device constructed with conventional lead-halide perovskites. We believe that the method used here provides an effective strategy to improve the fluorescence efficiency of lead-free perovskite QDs, which will create opportunities for their applications in lighting and displays.

Imaging of the Atomic Structure of All-Inorganic Halide Perovskites.

All-inorganic halide perovskites are promising materials for optoelectronic applications. The surface or interface structure of the perovskites plays a crucial role in determining the optoelectronic conversion efficiency, as well as the material stability. A thorough understanding of surface atomic structures of the inorganic perovskites and their contributions to their optoelectronic properties and stability is lacking. Here we show a scanning tunneling microscopy investigation on the atomic and electronic structure of CsPbBr3 perovskite. Two different surface structures with a stripe and an armchair domain are identified, which originates from a complex interplay between Cs cations and Br anions. Our findings are further supported and correlated with density functional theory calculations and photoemission spectroscopy measurements. The stability evaluation of photovoltaic devices indicates a higher stability for CsPbBr3 in comparison with MAPbBr3, which is closely related to the low volatility of Cs from the perovskite surface.

Trifluoroacetate induced small-grained CsPbBr3 perovskite films result in efficient and stable light-emitting devices.

Quantum efficiencies of organic-inorganic hybrid lead halide perovskite light-emitting devices (LEDs) have increased significantly, but poor device operational stability still impedes their further development and application. All-inorganic perovskites show better stability than the hybrid counterparts, but the performance of their respective films used in LEDs is limited by the large perovskite grain sizes, which lowers the radiative recombination probability and results in grain boundary related trap states. We realize smooth and pinhole-free, small-grained inorganic perovskite films with improved photoluminescence quantum yield by introducing trifluoroacetate anions to effectively passivate surface defects and control the crystal growth. As a result, efficient green LEDs based on inorganic perovskite films achieve a high current efficiency of 32.0 cd A-1 corresponding to an external quantum efficiency of 10.5%. More importantly, our all-inorganic perovskite LEDs demonstrate a record operational lifetime, with a half-lifetime of over 250 h at an initial luminance of 100 cd m-2.

Pressure-induced emission of cesium lead halide perovskite nanocrystals.

Metal halide perovskites (MHPs) are of great interest for optoelectronics because of their high quantum efficiency in solar cells and light-emitting devices. However, exploring an effective strategy to further improve their optical activities remains a considerable challenge. Here, we report that nanocrystals (NCs) of the initially nonfluorescent zero-dimensional (0D) cesium lead halide perovskite Cs4PbBr6 exhibit a distinct emission under a high pressure of 3.01 GPa. Subsequently, the emission intensity of Cs4PbBr6 NCs experiences a significant increase upon further compression. Joint experimental and theoretical analyses indicate that such pressure-induced emission (PIE) may be ascribed to the enhanced optical activity and the increased binding energy of self-trapped excitons upon compression. This phenomenon is a result of the large distortion of [PbBr6]4- octahedral motifs resulting from a structural phase transition. Our findings demonstrate that high pressure can be a robust tool to boost the photoluminescence efficiency and provide insights into the relationship between the structure and optical properties of 0D MHPs under extreme conditions.

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH3NH3PbI3: Implications on Solar Cell Degradation and Choice of Electrode.

Solar cells based on methylammonium lead triiodide (MAPbI3) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI3-based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current-voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI3. In addition to Au, many other metals have been used as electrodes in MAPbI3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI3 while having low resistivities and suitable work functions for carrier extraction.

Chlorine-Incorporation-Induced Formation of the Layered Phase for Antimony-Based Lead-Free Perovskite Solar Cells.

The environmental toxicity of Pb in organic-inorganic hybrid perovskite solar cells remains an issue, which has triggered intense research on seeking alternative Pb-free perovskites for solar applications. Halide perovskites based on group-VA cations of Bi3+ and Sb3+ with the same lone-pair ns2 state as Pb2+ are promising candidates. Herein, through a joint experimental and theoretical study, we demonstrate that Cl-incorporated methylammonium Sb halide perovskites (CH3NH3)3Sb2ClXI9-X show promise as efficient solar absorbers for Pb-free perovskite solar cells. Inclusion of methylammonium chloride into the precursor solutions suppresses the formation of the undesired zero-dimensional dimer phase and leads to the successful synthesis of high-quality perovskite films composed of the two-dimensional layered phase favored for photovoltaics. Solar cells based on the as-obtained (CH3NH3)3Sb2ClXI9-X films reach a record-high power conversion efficiency over 2%. This finding offers a new perspective for the development of nontoxic and low-cost Sb-based perovskite solar cells.

Doping Lanthanide into Perovskite Nanocrystals: Highly Improved and Expanded Optical Properties.

Cesium lead halide (CsPbX3) perovskite nanocrystals (NCs) have demonstrated extremely excellent optical properties and great application potentials in various optoelectronic devices. However, because of the anion exchange, it is difficult to achieve white-light and multicolor emission for practical applications. Herein, we present the successful doping of various lanthanide ions (Ce3+, Sm3+, Eu3+, Tb3+, Dy3+, Er3+, and Yb3+) into the lattices of CsPbCl3 perovskite NCs through a modified hot-injection method. For the lanthanide ions doped perovskite NCs, high photoluminescence quantum yield (QY) and stable and widely tunable multicolor emissions spanning from visible to near-infrared (NIR) regions are successfully obtained. This work indicates that the doped perovskite NCs will inherit most of the unique optical properties of lanthanide ions and deliver them to the perovskite NC host, thus endowing the family of perovskite materials with excellent optical, electric, or magnetic properties.

Highly Oriented Low-Dimensional Tin Halide Perovskites with Enhanced Stability and Photovoltaic Performance.

The low toxicity and a near-ideal choice of bandgap make tin perovskite an attractive alternative to lead perovskite in low cost solar cells. However, the development of Sn perovskite solar cells has been impeded by their extremely poor stability when exposed to oxygen. We report low-dimensional Sn perovskites that exhibit markedly enhanced air stability in comparison with their 3D counterparts. The reduced degradation under air exposure is attributed to the improved thermodynamic stability after dimensional reduction, the encapsulating organic ligands, and the compact perovskite film preventing oxygen ingress. We then explore these highly oriented low-dimensional Sn perovskite films in solar cells. The perpendicular growth of the perovskite domains between electrodes allows efficient charge carrier transport, leading to power conversion efficiencies of 5.94% without the requirement of further device structure engineering. We tracked the performance of unencapsulated devices over 100 h and found no appreciable decay in efficiency. These findings raise the prospects of pure Sn perovskites for solar cells application.