Over 21% Efficient Cesium Lead Triiodide Solar Cell Enabled by Molten Salt Accelerating the Crystallization Processes.

High-quality CsPbI3 with low defect density is indispensable for acquiring excellent photoelectric performance. Meticulous regulation of the CsPbI3 crystal growth processes is both feasible and efficacious in enhancing the quality of perovskite films. In this study, the cesium formate (CsFo) is introduced. On one hand, its low melting point can induce the crystallization processes at a low level of energy consumption. On the other hand, the pseudo-halide anion can participate in the passivation of iodide vacancies, as the formate anion exhibits a relatively higher affinity with iodide vacancies compared to other halides. Consequently, the introduction of CsFo enhances the quality of CsPbI3 thin films by altering the crystallization process and curbing defect formation. As a result, a steady-state output efficiency of 21.23% and an open-circuit voltage (Voc) as high as 1.25 V are achieved, with both parameters ranking among the highest for this type of solar cell.

Pseudohalide-Based Ionic Liquids: Advancing Crystallization Kinetics and Optoelectronic Properties in All-Inorganic Perovskite Solar Cells.

This study delves into the innovative approach of enhancing the efficiency and stability of all-inorganic perovskite solar cells (I-PSCs) through the strategic incorporation of thiocyanate (SCN-) ions via pseudohalide-based ionic liquid (IL) configurations. This straightforward methodology has exhibited captivating advancements in the kinetics of crystallization as well as the optoelectronic characteristics of the resulting perovskite films. These developments hold the promise of enhancing not only the quality and uniformity of the films but also aspects such as band alignment and the efficacy of charge transfer mechanisms. Calculation results corroborate that the incorporation of 1-butyl-3-methylimidazolium thiocyanate (BmimSCN) led to a significant redistribution of electron state density and enhanced electron-donating properties, indicating a substantial electron transfer between the perovskite material and the IL. Notably, the engineered devices demonstrate a remarkable efficiency surpassing 15%, a substantial enhancement attributed to the synergistic effects of the SCN- ion. Additionally, this approach offers inherent stability benefits, thereby addressing a significant challenge in I-PSC technology. This IL maintains >90% of the initial efficiency after 600 h, while the control device decreased to <20% of its initial value after only 100 h. 1-butyl-3-methylimidazolium iodide (BmimI) is also employed to further investigate the effects of SCN- ions on device performance.

All-Inorganic Perovskite NiTiO3/Cs3Sb2I9 Heterostructure for Photocatalytic CO2 Reduction to CH4 with High Selectivity.

Developing efficient and stable halide perovskite-based photocatalysts for highly selectivity reduction CO2 to valuable fuels remains a significant challenge due to their intrinsic instability. Herein, a novel heterostructure featuring 2D Cs3Sb2I9 nanosheets on a 3D flower-like mesoporous NiTiO3 framework using a top-down stepwise membrane fabrication technique is constructed. The unique bilayer heterostructure formed on the 3D mesoporous framework endowed NiTiO3/Cs3Sb2I9 with sufficient and close interface contact, minimizing charge transport distance, and effectively promoting the charge transfer at the interface, thus improving the reaction efficiency of the catalyst surface. As revealed by characterization and calculation, the coupling of Cs3Sb2I9 with NiTiO3 facilitates the hydrogenation process during catalytic, directing reaction intermediates toward highly selective CH4 production. Furthermore, the van der Waals forces inherent in the 3D/2D heterostructure with face-to-face contact provide superior stability, ensuring the efficient realization of photocatalytic CO2 reduction to CH4. Consequently, the optimized 3D/2D NiTiO3/Cs3Sb2I9 heterostructure demonstrates an impressive CH4 yield of 43.4 µmol g-1 h-1 with a selectivity of up to 88.6%, surpassing most reported perovskite-based photocatalysts to date. This investigation contributes to overcoming the challenges of commercializing perovskite-based photocatalysts and paves the way for the development of sustainable and efficient CO2 conversion technologies.

Tri-Step Water-Assisted Strategy for Suppressing Cs4PbBr6 Phase in Printable Carbon-Based CsPbBr3 Solar Cells to Achieve High Stability.

Often deemed the "natural nemesis" of perovskites, water molecules have been largely circumvented by the majority of researchers in the field of perovskite solar cells. This has resulted in significant hurdles in investigating the beneficial impacts of water molecules on perovskite crystallization. Herein, it is found that by utilizing ethanol with minimal water content and subjecting all-inorganic perovskite to three distinct annealing temperatures within the same solvent, the residual CsBr can be effectively removed, and the formation of the Cs4PbBr6 phase can be curtailed. By selecting an optimal water content, substantial improvements are observed in the crystalline quality of CsPbBr3, the perovskite/carbon interface, and the mesoporous filling effect. The Urbach energy (Eu) is reduced from 38.96 to 35.59 meV, and the defect density decreased from 4.16 × 1014 to 3.39 × 1014 cm-3. As a result, the power conversion efficiency (PCE) improved from 7.55% in the control group to 9.37%. Under severe environmental conditions with a temperature (T) of 85 °C and a relative humidity (RH) of 40%, tracking tests over 1200 h retained 89.3% of the initial PCE. This research signifies a breakthrough in the fabrication of highly stable and efficient all-inorganic printable mesoscopic perovskite solar cells.

Enhanced Absolute Recovered Energy under Low Electric Field in All-Inorganic 0-3 Nanocomposition Thick Films.

Inorganic thick-film dielectric capacitors with ultrahigh absolute recovered energy at low electric fields are extremely desired for their wide application in pulsed power systems. However, a long-standing technological bottleneck exists between high absolute energy and large recovered energy density. A new strategy is offered to fabricate selected all-inorganic 0-3 composite thick films up to 10 µm by a modified sol-slurry method. Here, the ceramic powder is dispersed into the sol-gel matrix to form a uniform suspension, assisted by powder, therefore, the 2 µm-thickness after single layer spin coating. To enhance the energy-storage performances, the composites process is thoroughly optimized by ultrafine powder (<50 nm) technique based on a low-cost coprecipitation method instead of the solid-state and sol-gel methods. 0D coprecipitation powder has a similar dielectric constant to the corresponding 3D films, thus uneven electrical field distributions is overcome. Moreover, the increase of interfacial polarization is realized due to the larger specific surface area. A maximum recoverable energy density of 14.62 J cm-3 is obtained in coprecipitation thick films ≈2.2 times that of the solid-state powder and ≈1.3 times for sol-gel powder. This study provides a new paradigm for further guiding the design of composite materials.

Defect Engineering of Metal Halide Perovskite Nanocrystals via Spontaneous Diffusion of Ag Nanocrystals.

Perovskite nanocrystals (NCs) have emerged as a promising building block for the fabrication of optic-/optoelectronic-/electronic devices owing to their superior characteristics, such as high absorption coefficient, rapid ion mobilities, and tunable energy levels. However, their low structural stability and poor surface passivation have restricted their application to next-generation devices. Herein, a drug delivery system (DDS)-inspired post-treatment strategy is reported for improving their structural stability by doping of Ag into CsPbBr3 (CPB) perovskite NCs; delivery to damaged sites can promote their structural recovery slowly and uniformly, averting the permanent loss of their intrinsic characteristics. Ag NCs are designed through surface-chemistry tuning and structural engineering to enable their circulation in CPB NC dispersions, followed by their delivery to the CPB NC surface, defect-site recovery, and defect prevention. The perovskite-structure healing process through the DDS-type process (with Ag NCs as the drug) is analyzed by a combination of theoretical calculations (with density functional theory) and experimental analyses. The proposed DDS-inspired healing strategy significantly enhances the optical properties and stability of perovskite NCs, enabling the fabrication of white light-emitting diodes.

Ultranarrow Line Width Room-Temperature Single-Photon Source from Perovskite Quantum Dot Embedded in Optical Microcavity.

Ultranarrow bandwidth single-photon sources operating at room-temperature are of vital importance for viable optical quantum technologies at scale, including quantum key distribution, cloud-based quantum information processing networks, and quantum metrology. Here we show a room-temperature ultranarrow bandwidth single-photon source generating single-mode photons at a rate of 5 MHz based on an inorganic CsPbI3 perovskite quantum dot embedded in a tunable open-access optical microcavity. When coupled to an optical cavity mode, the quantum dot room-temperature emission becomes single-mode, and the spectrum narrows down to just ∼1 nm. The low numerical aperture of the optical cavities enables efficient collection of high-purity single-mode single-photon emission at room-temperature, offering promising performance for photonic and quantum technology applications. We measure 94% pure single-photon emission in a single-mode under pulsed and continuous-wave (CW) excitation.

Theoretical Study and Analysis of CsSnX3 (X = Cl, Br, I) All-Inorganic Perovskite Solar Cells with Different X-Site Elements.

In this research, SCAPS-1D simulation software (Version: 3.3.10) was employed to enhance the efficiency of CsSnX3 (X = Cl, Br, I) all-inorganic perovskite solar cells. By fine-tuning essential parameters like the work function of the conductive glass, the back contact point, defect density, and the thickness of the light absorption layer, we effectively simulated the optimal performance of CsSnX3 (X = Cl, Br, I) all-inorganic perovskite solar cells under identical conditions. The effects of different X-site elements on the overall performance of the device were also explored. The theoretical photoelectric conversion efficiency of the device gradually increases with the successive substitution of halogen elements (Cl, Br, I), reaching 6.09%, 17.02%, and 26.74%, respectively. This trend is primarily attributed to the increasing size of the halogen atoms, which leads to better light absorption and charge transport properties, with iodine (I) yielding the highest theoretical conversion efficiency. These findings suggest that optimizing the halogen element in CsSnX3 can significantly enhance device performance, providing valuable theoretical guidance for the development of high-efficiency all-inorganic perovskite solar cells.

Influence of Donor Skeleton on Intramolecular Electron Transfer Amount for Efficient Perovskite Solar Cells.

The passivation of the defects derived from rapid-crystallization with electron-donating molecules is always a prerequisite to obtain desirable perovskite films for efficient and stable solar cells, thus, the in-depth understanding on the correlations between molecular structure and passivation capacity is of great importance for screening passivators. Here, we introduce the double-ended amide molecule into perovskite precursor solution to modulate crystallization process and passivate defects. By regulating the intermediate bridging skeletons with alkyl, alkenyl and benzene groups, the results show the passivation strength highly depends on the spin-state electronic structure that serves as an intrinsic descriptor to determine the intramolecular charge distribution by controlling orbital electron transfer from the donor segment to acceptor segment. Upon careful optimization, the benzene-bridged amide molecule demonstrates superior efficacy on improving perovskite film quality. As a physical proof-of-concept, the carbon-based, all-inorganic CsPbI2Br solar cell delivers a significantly increased efficiency of 15.51 % with a remarkably improved stability. Based on the same principle, a champion efficiency of 24.20 % is further obtained on the inverted (Cs0.05MA0.05FA0.9)Pb(I0.93Br0.07)3 solar cell. These findings provide new fundamental insights into the influence of spin-state modulation on effective perovskite solar cells.

Highly Durable Inverted Inorganic Perovskite/Organic Tandem Solar Cells Enabled by Multifunctional Additives.

Inverted perovskite/organic tandem solar cells (P/O TSCs) suffer from poor long-term device stability due to halide segregation in organic-inorganic hybrid wide-band gap (WBG) perovskites, which hinders their practical deployment. Therefore, developing all-inorganic WBG perovskites for incorporation into P/O TSCs is a promising strategy because of their superior stability under continuous illumination. However, these inorganic WBG perovskites also face some critical issues, including rapid crystallization, phase instability, and large energy loss, etc. To tackle these issues, two multifunctional additives based on 9,10-anthraquinone-2-sulfonic acid (AQS) are developed to regulate the perovskite crystallization by mediating the intermediate phases and suppress the halide segregation through the redox-shuttle effect. By coupling with organic cations having the desirable functional groups and dipole moments, these additives can effectively passivate the defects and adjust the alignment of interface energy levels. Consequently, a record Voc approaching 1.3 V with high power conversion efficiency (PCE) of 18.59 % could be achieved in a 1.78 eV band gap single-junction inverted all-inorganic PSC. More importantly, the P/O TSC derived from this cell demonstrates a T90 lifetime of 1000 h under continuous operation, presenting the most stable P/O TSCs reported so far.

Blue Long Afterglow and Ultra Broadband Vis-NIR Emission from All-Inorganic Copper-Doped Silver Halide Single Crystals.

All-inorganic metal halides with afterglow emission have attracted increasing attention due to their significantly longer afterglow duration and higher stability compared to their organic-inorganic hybrid counterparts. However, their afterglow colors have not yet reached the blue spectral region. Here, we report all-inorganic copper-doped Rb2AgBr3 single crystals with ultralong blue afterglow (>300 s) by modulating defect states through doping engineering. The introduction of copper(I) ions into Rb2AgBr3 facilitates the formation of bromine vacancies, thus increasing the density of trap states available for charge storage and enabling bright, persistent emission after ceasing the excitation. Moreover, cascade energy transfer between distinct emissive centers in the crystals results in ultra-broadband photoluminescence, not only covering the whole white light with near-unity quantum yield but also extending into the near-infrared region. This 'cocktail' of exotic light-emission properties, in conjunction with the excellent stability of copper-doped Rb2AgBr3 crystals, allowed us to demonstrate their implementation to solid-state lighting, night vision, and intelligent anti-counterfeiting.

Antisolvent-Free Heterogenous Nucleation Enabled by Employing 4-Tert-Butyl Pyridine Additive and Two-Step Annealing for Efficient CsPbI2 Br Perovskite Solar Cells.

All inorganic perovskite based on CsPbI2 Br has attracted significant attention due to its relatively thermal stable structure compare to its hybrid counterparts. With a wide bandgap of 1.9 eV and excellent light absorption capability, it has been extensively explored for applications in indoor photovoltaics and as a front absorber in tandem devices. However, the uncontrollable crystallization process during solvent evaporation and thermal annealing leads to both macroscopic defects like cracks and microscopic defects such as voids. In this study, a metastable adduct with lead (II) halides by incorporating 4-tert-butyl pyridine as a volatile Lewis base monodentate ligand in the precursor solution is formed. The strategic preferential decomposition of the adduct during the early-stage low-temperature annealing facilitated the desorption of lead (II) halides, inducing antisolvent-free heterogenous nucleation. This, in turn, promoted crystal growth during subsequent high-temperature annealing, resulting in dense films with low defect density. As a result, a maximum open-circuit voltage of 1.30 V is achieved with the champion power conversion efficiency of 16.5% in CsPbI2 Br-based perovskite solar cell. The work reveals a new mechanism of using Lewis acid-base adduct to obtain high quality perovskite films other than hindering crystallization in traditional way.

Improved Performance of All-Inorganic Perovskite Light-emitting Diodes via Nanostructured Stamp Imprinting.

Halide perovskites are emerging emitters with excellent optoelectronic properties. Contrary to the large grain fabrication goal in perovskite solar cells, perovskite light-emitting diodes (PeLEDs) based on small grain enable efficient radiative recombination because of relatively higher charge carrier densities due to spatial confinement. However, achieving small-sized grain growth with superior crystal quality and film morphology remains a challenge. In this work, we demonstrated a nanostructured stamp thermal imprinting strategy to boost the surface coverage and improve the crystalline quality of CsPbBr3 film, particularly confine the grain size, leading to the improvement of luminance and efficiency of PeLEDs. We improved the thermal imprinting process utilizing the nanostructured stamp to selectively manipulate the nucleation and growth in the nanoscale region and acquire small-sized grain accompanied by improved crystal quality and surface morphology of the film. By optimizing the imprinting pressure and the period of the nanostructures, appropriate grain size, high surface coverage, small surface roughness and improved crystallization could be achieved synchronously. Finally, the maximum luminance and efficiency of PeLEDs achieved by nanostructured stamp imprinting with a period of 320 nm are 67600 cd/m2 and 16.36 cd/A, respectively. This corresponds to improvements of 123 % in luminance and 100 % in efficiency, compared to that of PeLEDs without the imprinting.

Sr2+doped CsPbBrI2perovskite nanocrystals coated with ZrO2for applications as white LEDs.

Perovskite nanocrystals (NCs) feature adjustable bandgap, wide absorption range, and great color purity for robust perovskite optoelectronic applications. Nevertheless, the absence of lasting stability under continues energization, is still a major hurdle to the widespread use of NCs in commercial applications. In particular, the reactivity of red-emitting perovskites to environmental surroundings is more sensitive than that of their green counterparts. Here, we present a simple synthesis of ultrathin ZrO2coated, Sr2+doped CsPbBrI2NCs. Introducing divalent Sr2+may significantly eliminate Pb° surface traps, whereas ZrO2encapsulation greatly improves environmental stability. The photoluminescence quantum yield of the Sr2+-doped CsPbBrI2/ZrO2NCs was increased from 50.2% to 87.2% as a direct consequence of the efficient elimination of Pb° surface defects. Moreover, the thickness of the ZrO2thin coating gives remarkable heat resistance and improved water stability. Combining CsPbSr0.3BrI2/ZrO2NCs in a white light emitting diode (LED) with an excellent optical efficiency (100.08 lm W-1), high and a broad gamut 141% (NTSC) standard. This work offers a potential method to suppress Pb° traps by doping with Sr2+and improves the performance of perovskite NCs by ultrathin coating structured ZrO2, consequently enabling their applicability in commercial optical displays.

Managing Multiple Halide-Related Defects for Efficient and Stable Inorganic Perovskite Solar Cells.

Halide-related surface defects on inorganic halide perovskite not only induce charge recombination but also severely limit the long-term stability of perovskite solar cells. Herein, adopting density functional theory calculation, we verify that iodine interstitials (Ii ) has a low formation energy similar to that of the iodine vacancy (VI ) and is also readily formed on the surface of all-inorganic perovskite, and it is regarded to function as an electron trap. We screen a specific 2,6-diaminopyridine (2,6-DAPy) passivator, which, with the aid of the combined effects from halogen-Npyridine and coordination bonds, not only successfully eliminates the Ii and dissociative I2 but also passivates the abundant VI . Furthermore, the two symmetric neighboring -NH2 groups interact with adjacent halides of the octahedral cluster by forming hydrogen bonds, which further promotes the adsorption of 2,6-DAPy molecules onto the perovskite surface. Such synergetic effects can significantly passivate harmful iodine-related defects and undercoordinated Pb2+ , prolong carrier lifetimes and facilitate the interfacial hole transfer. Consequently, these merits enhance the power-conversion efficiency (PCE) from 19.6 % to 21.8 %, the highest value for this type of solar cells, just as importantly, the 2,6-DAPy-treated CsPbI3-x Brx films show better environmental stability.

Insights Into to the KX (X = Cl, Br, I) Adsorption-Assisted Stabilization of CsPbI2 Br Surface.

Despite the excellent optoelectronic properties, organic-inorganic hybrid perovskite solar cells (PSCs) still present significant challenges in terms of ambient stability. CsPbI2 Br, a member of all-inorganic perovskites, may respond to this challenge because of its inherent high stability against light, moisture, and heat, and therefore has gained tremendous attraction recently. However, the practical application of CsPbI2 Br is still impeded by the notorious phenomenon of photoinduced halide segregation. Herein, by applying first-principles calculations, the stability, electronic structure, defect properties, and ion-diffusion properties of the stoichiometric CsPbI2 Br (110) surface and that with the adsorption of KX (X = Cl, Br, I) are systematically investigated. It is found that the adsorbed KX can serve as an external substitute of the halogen vacancies on the surface, therefore inhibiting halogen segregation and improving the stability of the CsPbI2 Br surface. The KX can also eliminate deep-level defect states caused by antisites, thereby contributing to the promoted optoelectronic properties of CsPbI2 Br. The mechanistic understanding of surface passivation in this work can lay the foundation for the future design of CsPbI2 Br PSCs with optimized optoelectronic performance.

Schottky-Contacted High-Performance GaSb Nanowires Photodetectors Enabled by Lead-Free All-Inorganic Perovskites Decoration.

The surface Fermi level pinning effect promotes the formation of metal-independent Ohmic contacts for the high-speed GaSb nanowires (NWs) electronic devices, however, it limits next-generation optoelectronic devices. In this work, lead-free all-inorganic perovskites with broad bandgaps and low work functions are adopted to decorate the surfaces of GaSb NWs, demonstrating the success in the construction of Schottky-contacts by surface engineering. Benefiting from the expected Schottky barrier, the dark current is reduced to 2 pA, the Ilight /Idark ratio is improved to 103 and the response time is reduced by more than 15 times. Furthermore, a Schottky-contacted parallel array GaSb NWs photodetector is also fabricated by the contact printing technology, showing a higher photocurrent and a low dark current of 15 pA, along with the good infrared photodetection ability for a concealed target. All results guide the construction of Schottky-contacts by surface decorations for next-generation high-performance III-V NWs optoelectronics devices.

Phase Control of Cs-Pb-Br Derivatives to Suppress 0D Cs4 PbBr6 for High-Efficiency and Stable All-Inorganic CsPbBr3 Perovskite Solar Cells.

The precise phase control of Cs-Pb-Br derivatives from 3D CsPbBr3 to 0D Cs4 PbBr6 highly determines the photovoltaic performance of all-inorganic CsPbBr3 perovskite solar cells (PSCs). Herein, the preferred phase conversion from precursor to Cs-Pb-Br derivatives is revealed by theoretically calculating the Gibbs free energies (∆G) of various phase conversion processes, allowing for a simplified multi-step solution-processable spin-coating method to hinder the formation of detrimental 0D Cs4 PbBr6 phase and enhance the photovoltaic performance of a PSC because of its large exciton binding energy, which is regarded as a recombination center. By further accelerating the interfacial charge extraction with a novel 2D transition metal dichalcogenide ReSe2 , the hole-free CsPbBr3 PSC achieves a champion efficiency of 10.67% with an impressive open-circuit voltage of 1.622 V and an excellent long-term stability. This work provides an in-depth understanding on the precise Cs-Pb-Br perovskite phase control and the effect of derivatives on photovoltaic performance of advanced CsPbBr3 PSCs.

Stabilized High-Membered and Phase-Pure 2D All Inorganic Ruddlesden-Popper Halide Perovskites Nanocrystals as Photocatalysts for the CO2 Reduction Reaction.

In contrast to the 2D organic-inorganic hybrid Ruddlesden-Popper halide perovskites (RPP), a new class of 2D all inorganic RPP (IRPP) has been recently proposed by substituting the organic spacers with an optimal inorganic alternative of cesium cations (Cs+ ). Nevertheless, the synthesis of high-membered 2D IRPPs (n > 1) has been a very challenging task because the Cs+ need to act as both spacers and A-site cations simultaneously. This work presents the successful synthesis of stable phase-pure high-membered 2D IRPPs of Csn+1 Pbn Br3n+1 nanosheets (NSs) with n = 3 and 4 by employing the strategy of using additional strong binding bidentate ligands. The structures of the 2D IRPPs (n = 3 and 4) NSs are confirmed by powder X-ray diffraction and high-resolution aberration-corrected scanning transmission electron microscope measurements. These 2D IRPPs NSs exhibit a strong quantum confinement effect with tunable absorption and emission in the visible light range by varying their n values, attributed to their inherent 2D quantum-well structure. The superior structural and optical stability of the phase-pure high-membered 2D IRPPs make them a promising candidate as photocatalysts in CO2 reduction reactions with outstanding photocatalytic performance and long-term stability.

A computational study of electrical contacts to all-inorganic perovskite CsPbBr3.

All-inorganic halide perovskites are promising candidates for optoelectronic devices due to their excellent physicochemical properties and better thermal stability than their hybrid counterparts. The electrical contact to perovskite plays a crucial role in determining the device's performance. This paper investigated the contacts of two types of CsPbBr3surface to a series of metals (Pd, In, Pb, Zr, Ti, Zn, graphene, and Ti3C2) through first-principles calculations. On the PbBr2-terminated surface, all the studied metals form Schottky contacts with minimum barriers ranging from 0.63 to 0.97 eV. On the CsBr-terminated surface, Ti and Ti3C2forms n-type Ohmic contacts while others form Schottky contacts with minimum barriers ranging from 0.25 to 0.97 eV. Ti3C2, considering the small Schottky barrier, large tunneling barrier, and high electronic localization function, is found to be proper ohmic metal contacts with the CsBr-terminated surface. In addition, a -16.4% to 15.1% change in the size of the CsPbBr3band gap is found because of the interfacial interaction. The Fermi pinning factor of the CsPbBr3-metal contact is estimated via a modified method considering the gap change, and that of the PbBr2-terminated one is slightly larger than that of the CsBr-terminated one, indicating a more flexible Schottky barrier in the former through changing the metal work function. This work presents a comprehensive understanding of metal contacts to all-inorganic perovskite CsPbBr3and offers theoretical guidance for preparing high-performance inorganic perovskite photoelectric devices.