Molecular Structure Tailoring of Organic Spacers for High‑Performance Ruddlesden–Popper Perovskite Solar Cells

Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.

Exploring Nanoscale Perovskite Materials for Next‑Generation Photodetectors:A Comprehensive Review and Future Directions

The rapid advancement of nanotechnology has sparked much interest in applying nanoscale perovskite materials for photodetection applications.These materials are promising candidates for next-generation photodetectors(PDs)due to their unique optoelectronic properties and flexible synthesis routes.This review explores the approaches used in the development and use of optoelectronic devices made of different nanoscale perovskite architectures,including quantum dots,nanosheets,nanorods,nanowires,and nanocrystals.Through a thorough analysis of recent literature,the review also addresses common issues like the mechanisms underlying the degradation of perovskite PDs and offers perspectives on potential solutions to improve stability and scalability that impede widespread implementation.In addition,it highlights that photodetection encompasses the detection of light fields in dimensions other than light intensity and suggests potential avenues for future research to overcome these obstacles and fully realize the potential of nanoscale perovskite materials in state-of-the-art photodetection systems.This review provides a comprehensive overview of nanoscale perovskite PDs and guides future research efforts towards improved performance and wider applicability,making it a valuable resource for researchers.

Low‑Temperature Fabrication of Stable Black‑Phase CsPbI_(3) Perovskite Flexible Photodetectors Toward Wearable Health Monitoring

Flexible wearable optoelectronic devices fabricated fromorganic–inorganic hybrid perovskites significantly accelerate the developmentof portable energy,biomedicine,and sensing fields,but their poor thermal stabilityhinders further applications.Conversely,all-inorganic perovskites possessexcellent thermal stability,but black-phase all-inorganic perovskite filmusually requires high-temperature annealing steps,which increases energy consumptionand is not conducive to the fabrication of flexible wearable devices.In this work,an unprecedented low-temperature fabrication of stable blackphaseCsPbI3perovskite films is demonstrated by the in situ hydrolysis reactionof diphenylphosphinic chloride additive.The released diphenyl phosphateand chloride ions during the hydrolysis reaction significantly lower the phasetransition temperature and effectively passivate the defects in the perovskitefilms,yielding high-performance photodetectors with a responsivity of 42.1 AW−1 and a detectivity of 1.3×10^(14)Jones.Furthermore,high-fidelity imageand photoplethysmography sensors are demonstrated based on the fabricated flexible wearable photodetectors.This work provides a newperspective for the low-temperature fabrication of large-area all-inorganic perovskite flexible optoelectronic devices.

Advances in the Fabrication of Perovskite Solar Cells by Roll-to-Roll Technology

In recent years,perovskite solar cells(PSCs)have garnered significant attention as a potential mainstream technology in the future photovol-taic(PV)market.This is primarily attributed to their salient advantages including high efficiency,low cost,and ease of preparation.Nota-bly,the power conversion efficiency(PCE)of PSCs has experienced a remarkable increase from 3.8%in 2009 to over 26%at present.Conse-quently,the adoption of roll-to-roll(R2R)technology for PSCs is considered a crucial step towards their successful commercialization.This arti-de reviews the diverse substrates,scalable deposition techniques(such as solution-based knife-coating and spraying technology),and optimiza.tion procedures employed in recent years to enhance device performance within the R2R process.Additionally,novel perspectives are presented to enrich the existing knowledge in this field.

A high entropy stabilized perovskite oxide La_(0.2)Pr_(0.2)Sm_(0.2)Gd_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)as a promising air electrode for reversible solid oxide cells

Reversible solid oxide cell(RSOC)is a new energy conversion device with significant applications,especially for power grid peaking shaving.However,the reversible conversion process of power generation/energy storage poses challenges for the performance and stability of air electrodes.In this work,a novel high-entropy perovskite oxide La_(0.2)Pr_(0.2)Gd_(0.2)Sm_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)(HE-LSCF)is proposed and investigated as an air electrode in RSOC.The electrochemical behavior of HE-LSCF was studied as an air electrode in both fuel cell and electrolysis modes.The polarization impedance(Rp)of the HE-LSCF electrode is only 0.25Ω·cm^(2) at 800℃ in an air atmosphere.Notably,at an electrolytic voltage of 2 V and a temperature of 800℃,the current density reaches up to 1.68 A/cm^(2).The HE-LSCF air electrode exhibited excellent reversibility and stability,and its electrochemical performance remains stable after 100 h of reversible operation.With these advantages,HE-LSCF is shown to be an excellent air electrode for RSOC.

Advances in flexible weak-light detectors based on perovskites:preparation,optimization,and application

Photodetectors with weak-light detection capabilities play an indispensable role in various crucial fields such as health monitors,imaging,optical communication,and etc.Nevertheless,the detection of weak light signals is often severely interfered by multiple factors such as background light,dark noise and circuit noise,making it difficult to accurately capture signals.While traditional technologies like silicon photomultiplier tubes excel in sensitivity,their high cost and inherent fragility restrict their widespread application.Against this background,perovskite materials have rapidly emerged as a research focus in the field of photodetection due to their simple preparation processes and exceptional optoelectronic properties.Not only are the preparation processes of perovskite materials straightforward and cost-effective,but more importantly,they can be flexibly integrated into flexible and stretchable substrates.This characteristic significantly compensates for the shortcomings of traditional rigid electronic devices in specific application scenarios,opening up entirely new possibilities for photodetection technology.Herein,recent advances in perovskite light detection technology are reviewed.Firstly,the chemical and physical properties of perovskite materials are discussed,highlighting their remarkable advantages in weak-light detection.Subsequently,the review systematically organizes various preparation techniques of perovskite materials and analyses their advantages in different application scenarios.Meanwhile,from the two core dimensions of performance improvement and light absorption enhancement,the key strategies of improving the performance of perovskite weak-light photodetectors are explored.Finally,the review concludes with a brief summary and a discussion on the potential challenges that may arise in the further development of perovskite devices.

Recent progress on stability and applications of flexible perovskite photodetectors

Flexible photodetectors have garnered significant attention by virtue of their potential applications in environmental monitoring,wearable healthcare,imaging sensing,and portable optical communications.Perovskites stand out as particularly promising materials for photodetectors,offering exceptional optoelectronic properties,tunable band gaps,low-temperature solution processing,and notable mechanical flexibility.In this review,we explore the latest progress in flexible perovskite photodetectors,emphasizing the strategies developed for photoactive materials and device structures to enhance optoelectronic performance and stability.Additionally,we discuss typical applications of these devices and offer insights into future directions and potential applications.

Self-polarized RGB device realized by semipolar micro-LEDs and perovskite-in-polymer films for backlight applications

In backlighting systems for liquid crystal displays,conventional red,green,and blue(RGB)light sources that lack polarization properties can result in a significant optical loss of up to 50%when passing through a polarizer.To address this inefficiency and optimize energy utilization,this study presents a high-performance device designed for RGB polarized emissions.The device employs an array of semipolar blueμLEDs with inherent polarization capabilities,coupled with mechanically stretched films of green-emitting CsPbBr3 nanorods and red-emitting CsPbI3-Cs4PbI6 hybrid nanocrystals.The CsPbBr3 nanorods in the polymer film offer intrinsic polarization emission,while the aligned-wire structures formed by the stable CsPbI3-Cs4PbI6 hybrid nanocrystals contribute to substantial anisotropic emissions,due to their high dielectric constant.The resulting device achieved RGB polarization degrees of 0.26,0.48,and 0.38,respectively,and exhibited a broad color gamut,reaching 137.2%of the NTSC standard and 102.5%of the Rec.2020 standard.When compared to a device utilizing c-plane LEDs for excitation,the current approach increased the intensity of light transmitted through the polarizer by 73.6%.This novel fabrication approach for polarized devices containing RGB components holds considerable promise for advancing next-generation display technologies.

Boosting MA-based two-dimensional Ruddlesden-Popper perovskite solar cells by incorporating a binary spacer

Two-dimensional Ruddlesden-Popper(2DRP)perovskite exhibits excellent stability in perovskite solar cells(PSCs)due to introducing hydrophobic long-chain organic spacers.However,the poor charge transporting property of bulky organic cation spacers limits the performance of 2DRP PSCs.Inspired by the Asite cation alloying strategy in 3D perovskites,2DRP perovskites with a binary spacer can promote charge transporting compared to the unary spacer counterparts.Herein,the superior MA-based 2DRP perovskite films with a binary spacer,including 3-guanidinopropanoic acid(GPA)and 4-fluorophenethylamine(FPEA)are realized.These films(GPA_(0.85)FPEA_(0.15))_(2)MA_(4)Pb_5I_(16)show good morphology,large grain size,decreased trap state density,and preferential orientation of the as-prepared film.Accordingly,the present 2DRP-based PSC with the binary spacer achieves a remarkable efficiency of 18.37%with a V_(OC)of1.15 V,a J_(SC)of 20.13 mA cm^(-2),and an FF of 79.23%.To our knowledge,the PCE value should be the highest for binary spacer MA-based 2DRP(n≤5)PSCs to date.Importantly,owing to the hydrophobic fluorine group of FPEA and the enhanced interlayer interaction by FPEA,the unencapsulated 2DRP PSCs based on binary spacers exhibit much excellent humidity stability and thermal stability than the unary spacer counterparts.

A short overview of the lead iodide residue impact and regulation strategies in perovskite solar cells

Lead iodide(PbI2) is a vital raw material for preparing perovskite solar cells(PSCs),and it not only takes part in forming the light absorption layer but also remains in the grain boundary as a passivator.In other words,the PbI2 content in the precursor and as formed film will affect the efficiency and stability of the PSCs.With moderate residual PbI2,it passivates the bulk/surface defects of perovskite,reduces the interfacial recombination,promotes the perovskite stability,minimizes the device hysteresis,and so on.Deficient PbI2 residue will reduce the interfacial passivation effect and device performance.In addition to facilitating the non-radiative recombination,over PbI2 residue can also lead to electronic insulation in the grain boundary and deteriorate the device performance.However,the impact and regulation of PbI2 residue on the device performance and stability is still not fully understood.Herein,a comprehensive and detailed review is presented by discussing the PbI2 residue impact and its regulation strategies(i.e., elimination,facilitation and conversion of the residue PbI2) to manipulate the PbI2 content,distribution and forms.Finally,we also show future outlooks in this field,with an aim to help further the progression of high-efficiency and stable PSCs.

Microwave shock motivating the Sr substitution of 2D porous GdFeO_(3) perovskite for highly active oxygen evolution

The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.

Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

High performance wide bandgap perovskite solar cell with low V_(OC) deficit less than 0.4 V

Wide bandgap perovskite solar cells(PSCs)have attracted significant attention because they can be applied to the top cells of tandem solar cells.However,high open-circuit voltage(V_(OC))deficit(>0.4 V)result from poor crystallization and high non-radiative recombination losses become a serious limitation in the pursuit of high performance.Here,the relevance between different Pbl_(2)proportions and performance parameters are revealed through analysis of surface morphology,residual stress,and photostability.The increase of Pbl_(2)proportion promotes crystal growth and reduces the work function of the perovskite film surface and promotes the energy level alignment with the carrier transport layer,which decreased the V_(OC)deficit.However,residual PbI_(2)exacerbated the stress level of perovskite film,and the resulting lattice disorder deteriorated the photostability of the device.Ultimately,after the synergistic passivation of residual PbI_(2)and PEAI,the V_(OC)achieves 1.266 V and V_(OC)deficit is less than 0.4 V,the record value in wide bandgap PSCs.

Enhancing the Performance of Perovskite Light-Emitting Diodes via Synergistic Effect of Defect Passivation and Dielectric Screening

Metal halide perovskites,particularly the quasi-two-dimensional perovskite subclass,have exhibited considerable potential for next-generation electroluminescent materials for lighting and display.Nevertheless,the presence of defects within these perovskites has a substantial influence on the emission efficiency and durability of the devices.In this study,we revealed a synergistic passivation mechanism on perovskite films by using a dual-functional compound of potassium bromide.The dual functional potassium bromide on the one hand can passivate the defects of halide vacancies with bromine anions and,on the other hand,can screen the charged defects at the grain boundaries with potassium cations.This approach effectively reduces the probability of carriers quenching resulting from charged defects capture and consequently enhances the radiative recombination efficiency of perovskite thin films,leading to a significant enhancement of photoluminescence quantum yield to near-unity values(95%).Meanwhile,the potassium bromide treatment promoted the growth of homogeneous and smooth film,facilitating the charge carrier injection in the devices.Consequently,the perovskite light-emitting diodes based on this strategy achieve a maximum external quantum efficiency of~21%and maximum luminance of~60,000 cd m^(-2).This work provides a deeper insight into the passivation mechanism of ionic compound additives in perovskite with the solution method.

Flexible perovskite light-emitting diodes for display applications and beyond

The flexible perovskite light-emitting diodes(FPeLEDs),which can be expediently integrated to portable and wearable devices,have shown great potential in various applications.The FPeLEDs inherit the unique optical properties of metal halide perovskites,such as tunable bandgap,narrow emission linewidth,high photoluminescence quantum yield,and particularly,the soft nature of lattice.At present,substantial efforts have been made for FPeLEDs with encouraging external quantum efficiency(EQE)of 24.5%.Herein,we summarize the recent progress in FPeLEDs,focusing on the strategy developed for perovskite emission layers and flexible electrodes to facilitate the optoelectrical and mechanical performance.In addition,we present relevant applications of FPeLEDs in displays and beyond.Finally,perspective toward the future development and applications of flexible PeLEDs are also discussed.

Two-Dimensional Perovskite Single Crystals for High-Performance X-ray Imaging and Exploring MeV X-ray Detection

Scintillation semiconductors play increasingly important medical diagnosis and industrial inspection roles.Recently,two-dimensional(2D)perovskites have been shown to be promising materials for medical X-ray imaging,but they are mostly used in low-energy(≤130 keV)regions.Direct detection of MeV X-rays,which ensure thorough penetration of the thick shell walls of containers,trucks,and aircraft,is also highly desired in practical industrial applications.Unfortunately,scintillation semiconductors for high-energy X-ray detection are currently scarce.Here,This paper reports a 2D(C_(4)H_(9)NH_(3))_(2)PbBr_(4)single crystal with outstanding sensitivity and stability toward X-ray radiation that provides an ultra-wide detectable X-ray range of between 8.20 nGy_(air)s^(-1)(50 keV)and 15.24 mGy_(air)s^(-1)(9 MeV).The(C_(4)H_(9)NH_(3))_(2)PbBr_(4)single-crystal detector with a vertical structure is used for high-performance X-ray imaging,delivering a good spatial resolution of 4.3 Ip mm^(-1)in a plane-scan imaging system.Low ionic migration in the 2D perovskite enables the vertical device to be operated with hundreds of keV to MeV X-ray radiation at high bias voltages,leading to a sensitivity of 46.90μC Gy_(air)-1 cm^(-2)(-1.16 Vμm^(-1))with 9 MeV X-ray radiation,demonstrating that 2D perovskites have enormous potential for high-energy industrial applications.

Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

Rational Design of Ruddlesden-Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells

Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7−δ)(SF)exhibits superior proton uptake and rapid ionic conduction,boosting activity.However,excessive proton uptake during RePCC operation degrades SF’s crystal structure,impacting durability.This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes,incorporating Sr-deficiency and Nb-substitution to create Sr_(2.8)Fe_(1.8)Nb_(0.2)O_(7−δ)(D-SFN).Nb stabilizes SF’s crystal,curbing excessive phase formation,and Sr-deficiency boosts oxygen vacancy concentration,optimizing oxygen transport.The D-SFN electrode demonstrates outstanding activity and durability,achieving a peak power density of 596 mW cm^(−2)in fuel cell mode and a current density of−1.19 A cm^(−2)in electrolysis mode at 1.3 V,650℃,with excellent cycling durability.This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.

Metal-Halide Perovskite Submicrometer-Thick Films for Ultra-Stable Self-Powered Direct X-Ray Detectors

Metal-halide perovskites are revolutionizing the world of X-ray detectors,due to the development of sensitive,fast,and cost-effective devices.Self-powered operation,ensuring portability and low power consumption,has also been recently demonstrated in both bulk materials and thin films.However,the signal stability and repeatability under continuous X-ray exposure has only been tested up to a few hours,often reporting degradation of the detection performance.Here it is shown that self-powered direct X-ray detectors,fabricated starting from a FAPbBr_(3)submicrometer-thick film deposition onto a mesoporous TiO_(2)scaffold,can withstand a 26-day uninterrupted X-ray exposure with negligible signal loss,demonstrating ultra-high operational stability and excellent repeatability.No structural modification is observed after irradiation with a total ionizing dose of almost 200 Gy,revealing an unexpectedly high radiation hardness for a metal-halide perovskite thin film.In addition,trap-assisted photoconductive gain enabled the device to achieve a record bulk sensitivity of 7.28 C Gy^(−1)cm^(−3)at 0 V,an unprecedented value in the field of thin-film-based photoconductors and photodiodes for“hard”X-rays.Finally,prototypal validation under the X-ray beam produced by a medical linear accelerator for cancer treatment is also introduced.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.