Recent Progress of Thin Crystal Engineering for Perovskite Solar Cells.

Metal halide perovskite single crystals hold promise for photovoltaics with high efficiency and stability due to their superior optoelectronic properties and weak bulk ion migration. The past several years have witnessed rapid development of single-crystal perovskite solar cells (PSCs) with efficiency rocketed from 6.5% to 24.3%, however, which still lags behind their polycrystalline counterparts. Moreover, the poor device stability under light illumination is contrary to the high ion migration barrier of perovskite single crystals. The key limiting factors should be the low crystalline quality and high surface defect density of solution-grown thin single crystals. Under this circumstance, a review paper summarizing the recent progress and challenges will be instructive for future development of this emerging field. In this manuscript, the crystal engineering used to enhance carrier transport and suppress carrier recombination in vertical single-crystal PSCs will be summarized initially, including crystal growth, component control, surface and interface modification. Subsequently, the application of perovskite single crystals in lateral single-crystal PSCs will be discussed and compared with the conventionally vertical structure. Finally, the challenges and proposed strategies for the development of single-crystal PSCs are provided.

Ultra-High-k Ferroelectric BaTiO3 Perovskite in the Gate Stack for Two-Dimensional WSe2 p-Type High-Performance Transistors.

The experimental demonstration of a p-type 2D WSe2 transistor with a ferroelectric perovskite BaTiO3 gate oxide is presented. The 30 nm thick BaTiO3 gate stack shows a robust ferroelectric hysteresis with a remanent polarization of 20 µC/cm2 and further enables a capacitance equivalent thickness of 0.5 nm in the hybrid WSe2/BaTiO3 stack due to its high dielectric constant of 323. We demonstrate one of the best ON currents for perovskite gate 2D transistors in the literature. This is enabled by high-quality epitaxial growth of BaTiO3 and a single 2D layer transfer based fabrication method that is shown to be amenable to silicon platforms. This demonstration is an important milestone toward the integration of crystalline complex oxides with 2D channel materials for scaled CMOS and low-voltage ferroelectric logic applications.

Suppressing Hole Accumulation Through Sub-Nanometer Dipole Interfaces in Hybrid Perovskite/Organic Solar Cells for Boosting Near-Infrared Photon Harvesting.

The potential of hybrid perovskite/organic solar cells (HSCs) is increasingly recognized owing to their advantageous characteristics, including straightforward fabrication, broad-spectrum photon absorption, and minimal open-circuit voltage (VOC) loss. Nonetheless, a key bottleneck for efficiency improvement is the energy level mismatch at the perovskite/bulk-heterojunction (BHJ) interface, leading to charge accumulation. In this study, it is demonstrated that introducing a uniform sub-nanometer dipole layer formed of B3PyMPM onto the perovskite surface effectively reduces the 0.24 eV energy band offset between the perovskite and the donor of BHJ. This strategic modification suppresses the charge recombination loss, resulting in a noticeable 30 mV increase in the VOC and a balanced carrier transport, accompanied by a 5.0% increase in the fill factor. Consequently, HSCs that achieve power conversion efficiency of 24.0% is developed, a new record for Pb-based HSCs with a remarkable increase in the short-circuit current of 4.9 mA cm-2, attributed to enhanced near-infrared photon harvesting.

Prospect for detecting magnetism in two-dimensional perovskite oxides by electron magnetic circular dichroism.

Two-dimensional (2D) magnets, especially strongly correlated 2D transition-metal perovskite oxides, have attracted significant attention due to their intriguing electromagnetic properties for potential applications in spintronic devices. Potentially electron magnetic circular dichroism (EMCD) under zone axis conditions can provide three-dimensional components of magnetic moments in 2D materials, but the collection efficiency and the signal-to-noise ratio for out-of-plane (OOP) components is limited due to the limited collection angle. Here we conducted a comprehensive computational simulation to optimize the experimental setting of EMCD for detecting the OOP components of magnetic moments in three beam conditions (3BCs) on 2D perovskite oxides La1-xSrxMnO3 (LSMO) in a TEM. The key parameters are sample thickness, accelerating voltage, Sr doping concentration, collection semi-angle and position, and sample orientation including systematic reflections excited and tilt angle. Our simulation results demonstrate that the relative dynamical diffraction coefficients of Mn OOP EMCD of LaMnO3 with a thickness ranging from 1 unit cell (uc) to 4 uc can be optimized in a 3BC with (110) systematic reflections excited and a relatively large collection semi-angle of 19 mrad at the relatively low accelerating voltage of 80 kV. In most cases, the relative dynamic diffraction coefficients for La1-xSrxMnO3 with the thickness ranging from 1 uc to 4 uc decrease with the increase of the Sr doping concentrations. The optimal tilt angle from a zone axis to a 3BC is 18° for the cases of the LSMO thickness of 2 uc, 3 uc and 4 uc, and 22° for the monolayer LSMO. Our work provides the theoretical simulation foundation for optimized EMCD experiments for measuring OOP components of magnetic moments in 2D transition-metal perovskite oxides.

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.

Ions-induced Assembly of Perovskite Nanocomposites for Highly Efficient Light-Emitting Diodes with EQE Exceeding 30.

Metal halide perovskites, a cost-effective class of semiconductos, hold great promise for display technologies that demand high-efficiency, color-pure light-emitting diodes (LEDs). Early research on three-dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non-radiative recombination. Here, an ions-induced growth method is employed to assembe lattice-anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr3 and its variant of zero-dimensional (0D) Cs4PbBr6, to feature significant low trap-assisted nonradiative recombination, enhanced light out-coupling with a corrugated surface, and well-balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half-maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach.

Deciphering the Effect of Defect Dipoles on the Polarization and Electrostrain Behavior in Perovskite Ferroelectrics.

Defect dipoles are crucial for regulating electromechanical properties in piezoelectric ceramics, but their effects on polarization and electrostrain behaviors are still unclear. Here, a reasonable theoretical model is proposed and evidenced by experiments to address a long-standing puzzle of the relationship between the internal bias field and defect dipoles. By incorporating the additional polarization induced by defect dipoles, we refine the classical theory to account for the recently reported asymmetric giant-strain behaviors. Phase-field simulation reveals the electrostrain evolution in response to defect dipole elastic distortion and additional polarization. This work not only elucidates the effect of defect dipoles on polarization and electrostrain but also advances the theoretical understanding of defects in piezoelectrics.

A Graded Redox Interfacial Modifier for High-Performance Perovskite Solar Cells.

Perovskite solar cells have emerged as a potential competitor to the silicon photovoltaic technology. The most representative perovskite cells employ SnO2 and spiro-OMeTAD as the charge-transport materials. Despite their high efficiencies, perovskite cells with such a configuration show unsatisfactory lifespan, normally attributed to the instability of perovskites and spiro-OMeTAD. Limited attention was paid to the influence of SnO2, an inorganic material, on device stability. Here we show that improving SnO2 with a redox interfacial modifier, cobalt hexammine sulfamate, simultaneously enhances the power-conversion efficiency (PCE) and stability of the perovskite solar cells. Redox reactions between the bivalent cobalt complexes and oxygen lead to the formation of a graded distribution of trivalent and bivalent cobalt complexes across the surface and bulk regions of the SnO2. The trivalent cobalt complex at the top surface of SnO2 raises the concentration of (SO3NH2)- which passivates uncoordinated Pb2+ and relieves tensile stress, facilitating the formation of perovskite with improved crystallinity. Our approach enables perovskite cells with PCEs of up to 24.91%. The devices retained 93.8% of their initial PCEs after 1000 hours of continuous operation under maximum power point tracking. These findings showcase the potential of cobalt complexes as redox interfacial modifiers for high-performance perovskite photovoltaics.

Computational screening two-dimensional conjugated microporous polymer applied in perovskite solar cells.

A two-dimensional (2D) conjugated microporous polymer with a structure of 2D nanosheets has been synthesized. Theoretical calculations and experimental results reveal that the Fermi level of this 2D polymer aligns well with perovskite absorber, and its conduction band is high enough to block electron transport to the anode. This 2D polymer is used to modify the hole transport layer, significantly improving its photoelectric properties, including enhanced hole mobility, matched energy level, and reduced recombination. Furthermore, the 2D polymer exhibits a mesoporous structure, allowing perovskite to fill into its loose framework, increasing the hole export area and providing a large hole transport flux. As a result, the efficiency of inverted perovskite solar cells enhances to 24.64% from 21.17% of control device without 2D conjugated microporous polymer. Given that this material can be synthesized on a large scale, this work has significant implications for the future development of 2D polymers in perovskite solar cells, potentially accelerating industrialization.

Enhanced Buried Interface Engineering for Efficient Inverted Perovskite Solar Cells Fabricated via Vapor-Solid Reaction.

Vapor-deposited inverted perovskite solar cells utilizing self-assembled monolayer (SAM) as hole transport material have gained significant attention for their high efficiencies and compatibility with silicon/perovskite monolithic tandem devices. However, as a small molecule, the SAM layer suffers low thermal tolerance in comparison with other metal oxide or polymers, rendering poor efficiency in solar device with high-temperature (> 160 °C) fabricating procedures. In this study, a dual modification approach involving AlOx and F-doped phenyltrimethylammonium bromide (F-PTABr) layers is introduced to enhance the buried interface. The AlOx dielectric layer improves the interface contact and prevents the upward diffusion of SAM molecules during the vapor-solid reaction at 170 °C, while the F-PTABr layer regulates crystal growth and reduces the interfacial defects. As a result, the AlOx/F-PTABr-treated perovskite film exhibits a homogeneous, pinhole-free morphology with improved crystal quality compared to the control films. This leads to a champion power conversion efficiency of 21.53% for the inverted perovskite solar cells. Moreover, the encapsulated devices maintained 90% of the initial efficiency after 600 h of ageing at 85 °C in air, demonstrating promising potential for silicon/perovskite tandem application.

High Sensitivity X-Ray Detectors with Low Degradation Based on Deuterated Halide Perovskite Single Crystals.

Methylammonium lead single crystal (MAPbI3 SC) possesses superior optoelectronic properties and low manufacturing cost, making it an ideal candidate for X-ray detection. However, the ionic migration of the perovskites usually leads to instability, dark current drift, and hysteresis of the detector, limiting their applications in well-established technologies. Here, a series of X-ray detectors of MAPbI3 SCs are reported with different degrees of deuteration (DxMAPbI3, x = 0, 0.15, 0.75, 0.99). By controlling the content of deuterium (D) in organic cations, the sensitivity, detection limits, ion migration, and resistivity of the detector can be controlled, thereby improving its performance. Due to stronger hydrogen bonds (N─D···I), the ion activation energy significantly increases to 886 meV. Consequently, the D0.99MAPbI3 SC detector shows more than five-fold enhancement, achieving a record-high mobility-lifetime (µτ) product of 5.39 × 10-2 cm2 V-1, with an ultrahigh sensitivity of 2.18 × 106 µC Gy-1 cm-2 under 120 keV hard X-ray and a low detection limit of 4.8 nGyair s-1, as well as long-term stability. The study provides a straightforward strategy for constructing ultrasensitive X-ray detection and imaging systems based on perovskite SCs.

Bright Structural-Phase-Pure CsPbI3 Core-PbSO4 Shell Nanoplatelets With Ultra-Narrow Emission Bandwidth of 77 meV at 630 nm.

Achieving a narrow emission bandwidth is long pursued for display applications. Among all primary colors, obtaining pure red emission with high visual perception is the most challenging. In this work, CsPbI3 halide perovskite nanoplatelets (NPLs) with rigorously controlled 2D  [PbI6]4- octahedron layer number (n) are demonstrated. A perovskite core-PbSO4 shell structure is designed to prevent aggregation and fusion between NPLs, enabling consistent thickness and quantum confinement strength for each NPL. Consequently, exact n = 4 CsPbI3 NPLs are demonstrated, exhibiting emission peaks around 630 nm, with very narrow spectral bandwidths of <24 nm and high absolute photoluminescence quantum yields up to 85%. The emission of n = 4 NPLs falls exactly within the pure-red region, closely aligning with the International Telecommunication Union Recommendation BT.2020  standard. Measurements suggest predominant stability and color homogeneity compared to traditional red-emitting CsPbIxBr3- x nanocrystals. Finally, proof-of-concept pure-red emissive light-emitting diodes (LEDs) are demonstrated by integrating n = 4 CsPbI3 NPLs films with a blue LED chip, showing an excellent external quantum efficiency of 18.3% and high brightness exceeding 3 × 106 nits. Stringent requirements for future display technologies, are satisfied based on the high color purity, stability, and brightness of CsPbI3 NPLs.

Direct detection of ethyl carbamate in baijiu by molecularly imprinted electrochemical sensors based on perovskite and graphene oxide.

Ethyl carbamate (EC), a carcinogen commonly found in Baijiu, requires an efficient detection method for quality control and monitoring. This study introduces a novel molecularly imprinted electrochemical sensor for sensitive and selective EC detection. We proposed a simple sol-gel method for the growth of perovskite-structured lanthanum manganate (LaMnO3) on graphene oxide (GO). A non-enzymatic electrochemical sensor was developed by coating a molecularly imprinted polymer synthesized via precipitation polymerization onto the surface of LaMnO3@GO. LaMnO3, with its superior three-dimensional nanocube structure, demonstrated excellent electrocatalytic activity, while the addition of GO provided a large specific surface area. The results indicate that the developed sensor exhibits exceptional recognition ability and electrochemical activity, which is attributed to the high affinity of LaMnO3@GO@MIP for EC. The sensor displays a broad linear range from 10 to 2000 µM, with a detection limit as low as 2.18 µM and long-term durability of 28 days. Notably, it demonstrates excellent selectivity, reproducibility, and stability even under different interference conditions. The sensor was successfully used to determine EC in real Baijiu samples. Overall, the sensor has broad application prospects for detecting trace contaminants in the field of food safety.

Recent Advances in Perovskite-Based Flexible Electroluminescent Devices.

Perovskite-based flexible electroluminescent (EL) devices are emerging as promising candidates in the display field due to their exceptional optoelectronic properties and potential for cost-effective production. However, simultaneously achieving high EL performance, excellent flexibility and stretchability, robust mechanical strength, and diverse applications remains a significant challenge. In this review, we provide a comprehensive overview of the latest developments in perovskite-based flexible EL devices, covering both direct-current (DC) and alternating-current (AC) electroluminescent formats. Our discussion encompasses the materials, working principles, device architectures, failure mechanisms, optimization strategies, and practical applications. Through this review, we aim to deepen our understanding of the current challenges and future directions of perovskite-based flexible light-emitting technologies, hoping to facilitate their potential commercial applications.

Regulating Functional Groups to Construct a Mild Passivator Enhancing the Efficiency and Stability of Carbon-Based Perovskite Solar Cells.

The abundant defects on the perovskite surface greatly impact the efficiency improvement and long-term stability of carbon-based perovskite solar cells. Molecules with electron-donating or electron-withdrawing functional groups have been cited for passivating various defects. However, few studies have investigated the potential adverse effects arising from the synergistic interactions among functional groups. Herein, we investigate the correlation between functional group configurations and passivation strength as well as the potential adverse impacts of strong electrostatic structures by methodically designing three distinct interface molecules functionalized with different ending groups, which both belong to biguanide derivatives, including 1-(3,4-dichlorophenyl) biguanide hydrochloride (DBGCl), metformin hydrochloride (MFCl), and biguanide hydrochloride (BGCl). The results indicate that DBGCl establishes comparatively mild active sites, not only passivates defects but also aids in forming a surface with a uniform potential. Conversely, MFCl exerts a more pronounced adverse effect on the perovskite surface, which is attributable to the electronic state perturbations induced by its functional groups. Due to the lack of hydrophobic groups, devices treated with BGCl demonstrate insufficient moisture resistance. Devices passivated with DBGCl demonstrate superior average efficiency, showcasing a 12% enhancement relative to the pristine. Furthermore, DBGCl-treated devices exhibit enhanced stability in three different environments, respectively, achieving the highest PCE retention rates under nitrogen conditions (25 °C), room-temperature air conditions (25 °C, RH = 40 ± 2%), and high-temperature air conditions (65 °C, RH = 40 ± 2%).

Regulation of Lead Iodide Crystallization and Distribution for Efficient Perovskite Solar Cells.

At present, the power conversion efficiency (PCE) of perovskite solar cells (PSCs) has reached 26.1%. Polycrystalline perovskite films prepared by sequential deposition are often accompanied by excess PbI2. Although excess PbI2 can reduce the internal defects of the perovskites and promote charge transfer, excess PbI2 is unevenly distributed in the perovskites and easily decomposed into the composite center of charge. Therefore, the growth and distribution of PbI2 crystals can be regulated by introducing 4-fluoroaniline (4-FLA) as an additive into the precursor of PbI2. We observe that the presence of an amino group in 4-FLA leads to a reduction in the strength of van der Waals forces between PbI2 layer structures, thereby facilitating the uniform dispersion of excess PbI2 within the perovskites. Additionally, 4-FLA is restricted from being embedded in the PbI2 layer due to the steric hindrance of 4-FLA and the hydrogen bond interaction between nitrogen atoms and PbI2. Therefore, it leads to better dispersion of PbI2, resulting in better passivation and device efficiency. Based on the hydrophobicity of the benzene ring, the modified perovskite film shows excellent hydrophobicity. Ultimately, we achieved 21.63% PCE and 1.16V VOC. This provides an effective strategy for regulating excess PbI2 to achieve efficient and stable PSCs.

Plasma-Based Modification of Tin Halide Perovskite Interfaces for Photovoltaic Applications.

Tin halide perovskites represent the most suitable alternative to their lead-based counterparts for sustainable photovoltaics. One of the most important drawbacks of this class of materials is the intrinsic tendency of tin (II) to oxidize under certain conditions and as a consequence of aging. Here, we explore plasma processing to gently treat the surface of the tin perovskite films. As shown by chemical, optical, and morphological analyses, this treatment by generating transient active species on the surface of the material impacts its aging, inhibiting the tendency of tin (II) to oxidize. Plasma-treated stored devices show a power conversion efficiency slightly higher and narrower in the distribution than that of the reference devices. The positive impact of this noninvasive technique, which can be easily implemented in large-area manufacturing facilities, increases the potential of lead-free alternative perovskite photovoltaics.

Efficient Semitransparent Solar Cells Enabled by Introducing N-Ethylbenzylamine Additives into Thin Layer of Halide Perovskites.

Semitransparent perovskite solar cells (ST-PSCs) have opened up new applications in tandem devices and building-integrated photovoltaics. Decreasing the thickness of the perovskite film makes it feasible to fabricate semitransparent perovskite layers. However, the formation of high-quality thin perovskite films has been a challenge during the film manufacturing process since the crystallization dynamics of thinner (<200 nm) films are different from that of thick films. In this article, we demonstrate a feasible method to fabricate a thinner layer of highly crystalline perovskites with low defect density for efficient ST-PSCs by introducing N-Ethylbenzylamine (EBA) to modify halide perovskites through Lewis acid-base interaction. As a result, a semitransparent solar cell based on EBA-treated perovskite with a film thickness of only ∼190 nm exhibits a high power conversion efficiency (PCE) of 14.77%, an average visible transmittance (AVT) of 13.2%, and an excellent light utilization efficiency (LUE) of 1.95%, which is the highest value in the ST-PSCs with Au as the electrode. Our findings highlight the effectiveness of the EBA additive in improving the photovoltaic performance of ST-PSCs, offering valuable insights into developing efficient and transparent photovoltaic technologies.

2D Printed Plasmonic Nanoparticle Array Incorporated Formamidinium-Based High-Performance Self-Biased Perovskite Photodetector.

Utilizing noble metal nanoparticles through novel technologies is a promising avenue for enhancing the performance of organic/inorganic photodetectors. This study investigates the performance enhancement of Formamidinium-based perovskite (Pe) photodetectors (PDs) through the incorporation of plasmonic silver nanoparticles (Ag NPs) arrays using a 2D printing technique. The incorporation of plasmonic Ag NPs leads to a major improvement in the performance of the planar PD device, which is attributed to increased light absorption, hot electron generation, and more efficient charge extraction and transport. The unique aspect of this study lies in the method of incorporating plasmonic NPs using a two-dimensional printing technology. This approach offers several advantages over traditional methods, including lower cost, nonvacuum operation, and compatibility with room temperature fabrication. The printed plasmon-enhanced optimized perovskite PD exhibits remarkable performance metrics, including a peak responsivity of 1.03 A/W at 5 V external bias, which is significantly high compared to the reported devices. Moreover, the PD demonstrates exceptional detectivity with a peak value of 3.7 × 1012 Jones at 5 V, highlighting its capability to detect ultralow light signals with high precision. The device can be reversibly switched between low and high conductance states, yielding a stable and repeatable Ilight/Idark ratio of 1.06 × 104. In addition, the integration of plasmonic nanoparticles imparts remarkable photovoltaic characteristics to the perovskite photodetector, enabling it to function as a self-biased device. The hybrid device demonstrates a peak responsivity of 15 mA/W, a high detectivity of 2.15 × 1011 Jones, and a significant on-off ratio of 2.23 × 103, all achieved at zero external bias. Overall, this study presents a significant advancement in the field of plasmon-enhanced Pe photodetection technology. By utilizing the benefits of printing technology to incorporate NPs, we have developed a high-performance PD that combines cost-effectiveness with exceptional performance. Thus, we believe that this study will pave the way for the development of a low-cost, high-performance plasmon-enhanced Pe-based PD.

Interface Engineering by Unsubstituted Pristine Nickel Phthalocyanine as Hole Transport Material for Efficient and Stable Perovskite Solar Cells.

Lead halide perovskite solar cells (PSCs) have been rapidly developed in the past decade. With the development of a PSC, interface engineering plays an increasingly important role in maximizing device performance and long-term stability. We report a simple and effective interface engineering method for achieving improvement of PSCs up to 20% by employing unsubstituted pristine nickel phthalocyanine (NiPc). Thermal annealing of NiPc improves the interface between NiPc and perovskite because of the incorporation of NiPc molecules into the perovskite grain boundaries, which creates improvements in hole extraction from the perovskite absorber layer, as evidenced by time-resolved photoluminescence measurements. This significantly improves the charge transfer and collection efficiency, which are closely related to the improvement of the interface between perovskite and NiPc.