Precursor Engineering for Ambient‐Compatible Antisolvent‐Free Fabrication of High‐Efficiency CsPbI2Br Perovskite Solar Cells

High temperature stable inorganic CsPbX₃ (X: I, Br, or mixed halides) perovskites with their bandgap tailored by tuning the halide composition offer promising opportunities in the design of ideal top cells for high‐efficiency tandem solar cells. Unfortunately, the current high‐efficiency CsPbX₃ perovskite solar cells (PSCs) are prepared in vacuum, a moisture‐free glovebox or other low‐humidity conditions due to their poor moisture stability. Herein, a new precursor system (HCOOCs, HPbI₃, and HPbBr₃) is developed to replace the traditional precursors (CsI, PbI₂, and PbBr₂) commonly used for solar cells of this type. Both the experiments and calculations reveal that a new complex (HCOOH?Cs⁺) is generated in this precursor system. The new complex is not only stable against aging in humid air ambient at 91% relative humidity, but also effectively slows the perovskite crystallization, making it possible to eliminate the popular antisolvent used in the perovskite CsPbI₂Br film deposition. The CsPbI₂Br PSCs based on the new precursor system achieve a champion efficiency of 16.14%, the highest for inorganic PSCs prepared in ambient air conditions. Meanwhile, high air stability is demonstrated for an unencapsulated CsPbI₂Br PSC with 92% of the original efficiency remaining after more than 800 h aging in ambient air.     

A Temporary Barrier Effect of the Alloy Layer During Selenization: Tailoring the Thickness of MoSe2 for Efficient Cu2ZnSnSe4 Solar Cells

The influence of a prealloying process on the formation of MoSe₂ and thus on the performance of Cu₂ZnSnSe₄ (CZTSe) solar cells is investigated using sputtering deposition and post‐annealing approaches. The dense alloy layer, which is made by a low‐temperature prealloying process, acts as a temporary Se diffusion barrier during a subsequent high‐temperature selenization process. The formation of thick interfacial MoSe₂ can be suppressed effectively by this temporary barrier, cooperating with subsequent quick formation of compact CZTSe layer. The thickness of interfacial MoSe₂ layer in CZTSe solar cells can be tailored by adjusting the preannealing process during selenization. As a consequence, the series resistance of CZTSe solar cells is reduced to a low level (≈0.6 Ω cm²), and the performance of CZTSe solar cells is improved significantly. A CZTSe solar cell with efficiency of 8.7% is fabricated.     

Long‐Lasting Nanophosphors Applied to UV‐Resistant and Energy Storage Perovskite Solar Cells

Recently, considerable progress is achieved in lab prototype perovskite solar cells (PSCs); however, the stability of outdoor applications of PSCs remains a challenge due to the high sensitivity of perovskite material under moist and ultraviolet (UV) light conditions. In this work, the UV photostability of PSC devices is improved by incorporating a photon downshifting layer—SrAl₂O₄: Eu²⁺, Dy³⁺ (SAED)—prepared using the pulsed laser deposition approach. Light‐induced deep trap states in the photoactive layer are depressed, and UV light‐induced device degradation is inhibited after the SAED modification. Optimized power conversion efficiency (PCE) of 17.8% is obtained through the enhanced light harvesting and reduced carrier recombination provided by SAED. More importantly, a solar energy storage effect due to the long‐persistent luminescence of SAED is obtained after light illumination is turned off. The introduction of downconverting material with long‐persistent luminescence in PSCs not only represents a new strategy to improve PCE and light stability by photoconversion from UV to visible light but also provides a new paradigm for solar energy storage.     

Low Temperature Synthesis of Stable γ‐CsPbI3 Perovskite Layers for Solar Cells Obtained by High Throughput Experimentation

The structural phases and optoelectronic properties of coevaporated CsPbI₃ thin films with a wide range of [CsI]/[PbI₂] compositional ratios are investigated using high throughput experimentation and gradient samples. It is found that for CsI‐rich growth conditions, CsPbI₃ can be synthesized directly at low temperature into the distorted perovskite γ‐CsPbI₃ phase without detectable secondary phases. In contrast, PbI₂‐rich growth conditions are found to lead to the non‐perovskite δ‐phase. Photoluminescence spectroscopy and optical‐pump THz‐probe mapping show carrier lifetimes larger than 75 ns and charge carrier (sum) mobilities larger than 60 cm² V^?1 s^?1 for the γ‐phase, indicating their suitability for high efficiency solar cells. The dependence of the carrier mobilities and luminescence peak energy on the Cs‐content in the films indicates the presence of Schottky defect pairs, which may cause the stabilization of the γ‐phase. Building on these results, p–i–n type solar cells with a maximum efficiency exceeding 12% and high shelf stability of more than 1200 h are demonstrated, which in the future could still be significantly improved, judging on their bulk optoelectronic properties.     

Reliability of Small Molecule Organic Photovoltaics with Electron‐Filtering Compound Buffer Layers

Electron‐filtering compound buffer layers (EF‐CBLs) improve charge extraction in organic photovoltaic cells (OPVs) by blending an electron‐conducting fullerene with a wide energy gap exciton‐blocking molecule. It is found that devices with EF‐CBLs with high glass transition temperatures and a low crystallization rate produce highly stable morphologies and devices. The most stable OPVs employ 1:1 2,2′,2″‐(1,3,5‐benzenetriyl tris‐[1‐phenyl‐1H‐benzimidazole] TPBi:C₇₀ buffers that lose <20% of their initial power conversion efficiency of 6.6 ± 0.6% after 2700 h under continuous simulated AM1.5G illumination, and show no significant degradation after 100 days of outdoor aging. When exposed to 100‐sun (100 kW m^?2) concentrated solar illumination for 5 h, their power conversion efficiencies decrease by <8%. Moreover, it is found that the reliability of the devices employing stable EF‐CBLs has either reduced or no dependence on operating temperature up to 130 °C compared with BPhen:C₆₀ devices whose fill factors show thermally activated degradation. The robustness of TPBi:C₇₀ devices under extreme aging conditions including outdoor exposure, high temperature, and concentrated illumination is promising for the future of OPV as a stable solar cell technology.     

Stabilizing the Efficiency Beyond 20% with a Mixed Cation Perovskite Solar Cell Fabricated in Ambient Air under Controlled Humidity

Perovskite solar cells have evolved to have compatible high efficiency and stability by employing mixed cation/halide type perovskite crystals as pinhole‐free large grain absorbers. The cesium (Cs)–formamidium–methylammonium triple cation‐based perovskite device fabricated in a glove box enables reproducible high‐voltage performance. This study explores the method to reproduce stable and high power conversion efficiency (PCE) of a triple cation perovskite prepared using a one‐step solution deposition and low‐temperature annealing fully conducted in controlled ambient humidity conditions. Optimizing the perovskite grain size by Cs concentration and solution processes, a route is created to obtain highly uniform, pinhole‐free large grain perovskite films that work with reproducible PCE up to 20.8% and high preservation stability without cell encapsulation for more than 18 weeks. This study further investigates the light intensity characteristics of open‐circuit voltage (V_oc) of small (5 × 5 mm², PCE > 20%) and large (10 × 10 mm², PCE of 18%) devices. Intensity dependence of V_oc shows an ideality factor in the range of 1.7‐1.9 for both devices, implying that the triple cation perovskite involves trap‐assisted recombination loss at the hetero junction interfaces that influences V_oc. Despite relatively high ideality factor, perovskite device is capable of supplying high power conversion efficiency under low light intensity (0.01 Sun) whereas maintaining V_oc over 0.9 V.     

Performance Enhancement of Polymer‐Free Carbon Nanotube Solar Cells via Transfer Matrix Modeling

Polymer‐free (6,5) single‐walled carbon nanotubes (SWCNTs) prepared using the gel permeation approach are integrated into SWCNT:C₆₀ solar cells. Evaporation‐driven self‐assembly is used to form large‐area SWCNT thin films from the surfactant‐stabilized aqueous suspensions. The thicknesses of various layers within the solar cell are optimized by theoretical modeling using transfer matrix calculations, where the distribution of the electric field within the stack is matched to light absorption by the SWCNTs through either their primary (S₁₁) or secondary (S₂₂) absorption peaks, or a combination thereof. The validity of the model is verified experimentally through a detailed parameter study and then used to develop SWCNT:C₆₀ solar cells with high open‐circuit voltage (0.44 V) as well as a cutting‐edge internal quantum efficiency of up to 86% through the nanotube S₁₁ transition, over an active area of 0.105 cm².     

Efficient Plastic Perovskite Solar Cell with a Low‐Temperature Processable Electrodeposited TiO2 Compact Layer and a Brookite TiO2 Scaffold

Recent research on fabricating scaffold‐type perovskite solar cells on plastic substrates has reported noteworthy progress in replacing the high‐temperature processing of TiO₂ scaffolds and compact layers with various low‐temperature processes. Herein, recent progress in the laboratory is reported regarding the development of electrodeposited TiO_x compact layers and brookite TiO₂ scaffolds, both of which can be processed under 150 °C without greatly sacrificing their photovoltaic performance. Through systematic characterization of device properties and careful optimization of the fabrication conditions, a record‐high 15.76% power conversion efficiency of a plastic TiO₂ scaffold‐type perovskite solar cell is demonstrated. In addition, bending durability and preliminary stability tests on this plastic perovskite solar cell show promising results and indicate clear directions for future improvement.     

Efficient Nanostructured TiO2/SnS Heterojunction Solar Cells

Tin sulfide (SnS) is one of the most promising solar cell materials, as it is abundant, environment friendly, available at low cost, and offers long‐term stability. However, the highest efficiency of the SnS solar cell reported so far remains at 4.36% even using the expensive atomic layer deposition process. This study reports on the fabrication of SnS solar cells by a solution process that employs rapid thermal treatment for few seconds under Ar gas flow after spin‐coating a precursor solution of SnCl₂ and thiourea dissolved in dimethylformamide onto a nanostructured thin TiO₂ electrode. The best‐performing cell exhibits power conversion efficiency (PCE) of 3.8% under 1 sun radiation conditions (AM1.5G). Moreover, secondary treatment using SnCl₂ results in a significant improvement of 4.8% in PCE, which is one of the highest efficiencies among SnS‐based solar cells, especially with TiO₂ electrodes. The thin film properties of SnS after SnCl₂ secondary treatment are analyzed using grazing‐incidence wide‐angle X‐ray scattering, and high‐resolution transmittance electron microscopy.     

Bandgap Engineering Enhances the Performance of Mixed‐Cation Perovskite Materials for Indoor Photovoltaic Applications

Indoor photovoltaics (IPVs) are attracting renewed interest because they can provide sustainable energy through the recycling of photon energy from household lighting facilities. Herein, the Shockley–Queisser model is used to calculate the upper limits of the power conversion efficiencies (PCEs) of perovskite solar cells (PeSCs) for two types of artificial light sources: fluorescent tubes (FTs) and white light–emitting diodes (WLEDs). An unusual zone is found in which the dependence of the PCEs on the bandgap (E_g) under illumination from the indoor lighting sources follows trends different from that under solar irradiation. In other words, IPVs exhibiting high performance under solar irradiation may not perform well under indoor lighting conditions. Furthermore, the ideal bandgap energy for harvesting photonic power from these indoor lighting sources is ≈1.9 eV—a value higher than that of common perovskite materials (e.g., for CH₃NH₃PbI₃). Accordingly, Br^? ions are added into the perovskite films to increase their values of E_g. A resulting PeSC featuring a wider bandgap exhibits PCEs of 25.94% and 25.12% under illumination from an FT and a WLED, respectively. Additionally, large‐area (4 cm²) devices are prepared for which the PCE reaches ≈18% under indoor lighting conditions.     

Self‐Assembly Atomic Stacking Transport Layer of 2D Layered Titania for Perovskite Solar Cells with Extended UV Stability

A novel atomic stacking transporting layer (ASTL) based on 2D atomic sheets of titania (Ti_1?δO₂) is demonstrated in organic–inorganic lead halide perovskite solar cells. The atomically thin ASTL of 2D titania, which is fabricated using a solution‐processed self‐assembly atomic layer‐by‐layer deposition technique, exhibits the unique features of high UV transparency and negligible (or very low) oxygen vacancies, making it a promising electron transporting material in the development of stable and high‐performance perovskite solar cells. In particular, the solution‐processable atomically thin ASTL of 2D titania atomic sheets shows superior inhibition of UV degradation of perovskite solar cell devices, compared to the conventional high‐temperature sintered TiO₂ counterpart, which usually causes the notorious instability of devices under UV irradiation. The discovery opens up a new dimension to utilize the 2D layered materials with a great variety of homostructrual or heterostructural atomic stacking architectures to be integrated with the fabrication of large‐area photovoltaic or optoelectronic devices based on the solution processes.     

Ionic Liquid–Sulfolane Composite Electrolytes for High‐Performance and Stable Dye‐Sensitized Solar Cells

Ionic liquid electrolytes are prepared using sulfolane as a plasticizer for eutectic melts to realize highly stable and efficiently performing dye‐sensitized solar cells (DSCs) in hot climate conditions. Variations in the viscosity of the formulations with sulfolane content are measured and performance in DSCs is investigated using the ruthenium dye C106 as a sensitizer. A power conversion efficiency (PCE) of 8.2% is achieved under standard reporting conditions. Apart from lowering the viscosity, the addition of sulfolane induces a negative shift of the TiO₂ conduction band edge. Strikingly the device performance increases to 8.4% at 50 °C due to higher short circuit photocurrent and fill factor, over‐compensating the loss in open circuit voltage with increasing temperature. The PCE increases also upon decreasing the light intensity of the solar simulator, reaching up to 9% at 50 mW cm^?2. Devices based on these new electrolyte formulations show excellent stability during light soaking for 2320 h under full sunlight at 60 °C and also during a 1065 h long heat stress at 80 °C in the dark. A detailed investigation provides important information about the factors affecting the principal photovoltaic parameters during the aging process and the first results from a series of outdoor measurements are reported.     

In Situ Grain Boundary Functionalization for Stable and Efficient Inorganic CsPbI2Br Perovskite Solar Cells

The phase instability and large energy loss are two obstacles to achieve stable and efficient inorganic‐CsPbI_3?xBr_x perovskite solar cells. In this work, stable cubic perovskite (α)‐phase CsPbI₂Br is successfully achieved by Pb(Ac)₂ functioning at the grain boundary under low temperature. Ac^? strongly coordinates with CsPbI₂Br to stabilize the α‐phase and also make the grain size smaller and film uniform by fast nucleation. PbO is formed in situ at the grain boundary by decomposing Pb(Ac)₂ at high‐temperature annealing. The semiconducting PbO effectively passivates the surface states, reduces the interface recombination, and promotes the charge transport in CsPbI₂Br perovskite solar cells. A 12% efficiency and good stability are obtained for in situ PbO‐passivated CsPbI₂Br solar cells, while Pb(Ac)₂‐passivated device exhibits 8.7% performance and the highest stability, much better than the control device with 8.5% performance and inferior stability. This article highlights the extrinsic ionic grain boundary functionalization to achieve stable and efficient inorganic CsPbI_3?xBr_x materials and the devices.     

Inorganic CsPbI3 Perovskite Coating on PbS Quantum Dot for Highly Efficient and Stable Infrared Light Converting Solar Cells

Solution‐processed colloidal quantum dot (CQD) solar cells harvesting the infrared part of the solar spectrum are especially interesting for future use in semitransparent windows or multilayer solar cells. To improve the device power conversion efficiency (PCE) and stability of the solar cells, surface passivation of the quantum dots is vital in the research of CQD solar cells. Herein, inorganic CsPbI₃ perovskite (CsPbI₃‐P) coating on PbS CQDs with a low‐temperature, solution‐processed approach is reported. The PbS CQD solar cell with CsPbI₃‐P coating gives a high PCE of 10.5% and exhibits remarkable stability both under long‐term constant illumination and storage under ambient conditions. Detailed characterization and analysis reveal improved passivation of the PbS CQDs with the CsPbI₃‐P coating, and the results suggest that the lattice coherence between CsPbI₃‐P and PbS results in epitaxial induced growth of the CsPbI₃‐P coating. The improved passivation significantly diminishes the sub‐bandgap trap‐state assisted recombination, leading to improved charge collection and therefore higher photovoltaic performance. This work therefore provides important insight to improve the CQD passivation by coating with an inorganic perovskite ligand for photovoltaics or other optoelectronic applications.     

Hybrid Perovskite‐Organic Flexible Tandem Solar Cell Enabling Highly Efficient Electrocatalysis Overall Water Splitting

Perovskite‐organic tandem solar cells are attracting more attention due to their potential for highly efficient and flexible photovoltaic device. In this work, efficient perovskite‐organic monolithic tandem solar cells integrating the wide bandgap perovskite (1.74 eV) and low bandgap organic active PBDB‐T:SN6IC‐4F (1.30 eV) layer, which serve as the top and bottom subcell, respectively, are developed. The resulting perovskite‐organic tandem solar cells with passivated wide‐bandgap perovskite show a remarkable power conversion efficiency (PCE) of 15.13%, with an open‐circuit voltage (V_oc) of 1.85 V, a short‐circuit photocurrent (J_sc) of 11.52 mA cm^?2, and a fill factor (FF) of 70.98%. Thanks to the advantages of low temperature fabrication processes and the flexibility properties of the device, a flexible tandem solar cell which obtain a PCE of 13.61%, with V_oc of 1.80 V, J_sc of 11.07 mA cm^?2, and FF of 68.31% is fabricated. Moreover, to demonstrate the achieved high V_oc in the tandem solar cells for potential applications, a photovoltaic (PV)‐driven electrolysis system combing the tandem solar cell and water splitting electrocatalysis is assembled. The integrated device demonstrates a solar‐to‐hydrogen efficiency of 12.30% and 11.21% for rigid, and flexible perovskite‐organic tandem solar cell based PV‐driven electrolysis systems, respectively.     

Scalable Fabrication of Efficient Perovskite Solar Modules on Flexible Glass Substrates

Perovskite materials are good candidates for flexible photovoltaic applications due to their strong absorption and low‐temperature processing, but efficient flexible perovskite modules have not yet been realized. Here, a record efficiency flexible perovskite solar module is demonstrated by blade coating high‐quality perovskite films on flexible Corning Willow Glass using additive engineering. Ammonium chloride (NH₄Cl) is added into the perovskite precursor solution to retard the nucleation which prevents voids formation at the interface of perovskite and glass. The addition of NH₄Cl also suppresses the formation of PbI₂ and reduces the trap density in the perovskite films. The implementation of NH₄Cl enables the fabrication of single junction flexible perovskite solar devices with an efficiency of 19.72% on small‐area cells and a record aperture efficiency of 15.86% on modules with an area of 42.9 cm². This work provides a simple way to scale up high‐efficiency flexible perovskite modules for various applications.     

Relation of Nanostructure and Recombination Dynamics in a Low‐Temperature Solution‐Processed CuInS2 Nanocrystalline Solar Cell

The understanding and control of nanostructures with regard to transport and recombination mechanisms is of key importance in the optimization of the power conversion efficiency (PCE) of solar cells based on inorganic nanocrystals. Here, the transport properties of solution‐processed solar cells are investigated using photo‐CELIV (photogenerated charge carrier extraction by linearly increasing voltage) and transient photovoltage techniques; the solar cells are prepared by an in‐situ formation of CuInS₂ nanocrystals (CIS NCs) at the low temperature of 270 °C. Structural and morphological analyses reveal the presence of a metastable CuIn₅S₈ phase and a disordered morphology in the CuInS₂ nanocrytalline films consisting of polycrystalline grains at the nanoscale range. Consistent with the disordered morphology of the CIS NC thin films, the CIS NC devices are characterized by a low carrier mobility. The carrier density dynamic indicates that the recombination kinetics in these devices follows the dispersive bimolecular recombination model and does not fully behave in a diffusion‐controlled manner, as expected by Langevin‐type recombination. The mobility–lifetime product of the charge carriers properly explains the performance of the thin (200 nm) CIS NC solar cell with a high fill‐factor of 64% and a PCE of over 3.5%.     

Solar Rechargeable Batteries Based on Lead–Organohalide Electrolyte

A dye‐sensitized solar cell (DSC) with in situ energy storage capacity is demonstrated using a lead–organohalide electrolyte CH₃NH₃I·PbCl₂ (LOC) to replace the conventional I^?/I₃^? electrolyte. The coupling of lead and iodine in one electrolyte creates a dual‐function rechargeable solar battery that combines the working processes of photoelectrochemical cells with electrochemical batteries. Optimization of the H⁺ concentration in the electrolyte leads to increased photocharging efficiency and storage. The power conversion efficiency of the LOC–DSC is 8.6% under one sun illumination (AM 1.5, 100 mW cm^?2) as a DSC. When operating as a battery, Faraday efficiency can be achieved as high as 81.5% using a bromide‐based CH₃NH₃Br·PbBr₂ (LOB) electrolyte in a DSC configuration. This new cell design suggests a means of combining photovoltaic energy conversion and electrical energy storage.     

Hybrid Composite Coatings for Durable and Efficient Solar Hydrogen Generation under Diverse Operating Conditions

Safe and practical solar‐driven hydrogen generators must be capable of efficient and stable operation under diurnal cycling with full separation of gaseous H₂ and O₂ products. In this study, a novel architecture that fulfills all of these requirements is presented. The approach is inherently scalable and provides versatility for operation under diverse electrolyte and lighting conditions. The concept is validated using a 1 cm² triple‐junction photovoltaic cell with its illuminated photocathode protected by a composite coating comprising an organic encapsulant with an embedded catalytic support. The device is compatible with operation under conditions ranging from 1 m H₂SO₄ to 1 m KOH, enabling flexibility in selection of semiconductor, electrolyte, membrane, and catalyst. Stable operation at a solar‐to‐hydrogen conversion efficiency of >10% is demonstrated under continuous operation, as well as under diurnal light cycling for at least 4 d, with simulated sunlight. Operational characteristics are validated by extended time outdoor testing. A membrane ensures products are separated, with nonexplosive gas streams generated for both alkaline and acidic systems. Analysis of operational characteristics under different lighting conditions is enabled by comparison of a device model to experimental data.     

Toward High‐Temperature Stability of PTB7‐Based Bulk Heterojunction Solar Cells: Impact of Fullerene Size and Solvent Additive

The use of fullerene as acceptor limits the thermal stability of organic solar cells at high temperatures as their diffusion inside the donor leads to phase separation via Ostwald ripening. Here it is reported that fullerene diffusion is fully suppressed at temperatures up to 140 °C in bulk heterojunctions based on the benzodithiophene‐based polymer (the poly[[4,8‐bis[(2‐ethylhexyl)oxy]‐benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]‐thieno[3,4‐b]thiophenediyl]], (PTB7) in combination with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₀BM). The blend stability is found independently of the presence of diiodooctane (DIO) used to optimize nanostructuration and in contrast to PTB7 blends using the smaller fullerene derivative PC₇₀BM. The unprecedented thermal stability of PTB7:PC₇₀BM layers is addressed to local minima in the mixing enthalpy of the blend forming stable phases that inhibit fullerene diffusion. Importantly, although the nanoscale morphology of DIO processed blends is thermally stable, corresponding devices show strong performance losses under thermal stress. Only by the use of a high temperature annealing step removing residual DIO from the device, remarkably stable high efficiency solar cells with performance losses less than 10% after a continuous annealing at 140 °C over 3 days are obtained. These results pave the way toward high temperature stable polymer solar cells using fullerene acceptors.