Dion-Jacobson-Phase 2D Sn-Based Perovskite Comprising a High Dipole Moment of π-Conjugated Short-Chain Organic Spacers for High-Performance Solar Cell Applications.

The stability issue of Sn-based perovskite solar cells (PSCs) is expected to be resolved by involving a two-dimensional (2D) layered structure. However, Sn-based 2D PSCs, especially Dion-Jacobson (DJ)-phase ones with potentially good stability, have rarely been reported. Herein, superior DJ-phase Sn 2D perovskites with 3-aminobenzylamine (3ABA2+) or 4-aminobenzylamine (4ABA2+) π-conjugated short-chain ligands are reported to fabricate efficient 2D lead-free PSCs. Notably, the high dipole moment of the 3ABAI2 organic spacer is approved to possess faster charge transfer for forming (3ABA)FA4Sn5I16 2D perovskite with an extremely low exciton binding energy (only 84 meV). In combination with a diacetate partial substitution and methylamine iodide/bromide (MAI/MABr) post-treatment strategy to delay crystallization and improve compactness and coverage of the perovskite film, a record power conversion efficiency (PCE) of 6.81% and stability of 840 h (less than 5% degradation in a N2 atmosphere for unencapsulated devices) are acquired in eventual (3ABA)FA4Sn5I16 2D PSCs, which are among the highest PCE and the longest stability of Sn-based 2D PSCs reported to date. Our work provides a prospective molecule design and film preparation strategy of 2D Sn perovskites toward nontoxic high-performance tin-based PSCs, which pushes the almost stagnant research forward.

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.

Acceleration of radiative recombination for efficient perovskite LEDs.

The increasing demands for more efficient and brighter thin-film light-emitting diodes (LEDs) in flat-panel display and solid-state lighting applications have promoted research into three-dimensional (3D) perovskites. These materials exhibit high charge mobilities and low quantum efficiency droop1-6, making them promising candidates for achieving efficient LEDs with enhanced brightness. To improve the efficiency of LEDs, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, approaching levels close to those of single crystals3. However, the slow radiative (bimolecular) recombination has limited the photoluminescence quantum efficiencies (PLQEs) of 3D perovskites to less than 80% (refs. 1,3), resulting in external quantum efficiencies (EQEs) of LED devices of less than 25%. Here we present a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. This approach promotes the formation of tetragonal FAPbI3 perovskite, known for its high exciton binding energy, which effectively accelerates the radiative recombination. As a result, we achieve perovskite LEDs with a record peak EQE of 32.0%, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm-2. These findings provide valuable insights for advancing the development of high-efficiency and high-brightness perovskite LEDs.

Achieving Near-Unity Red Light Photoluminescence in Antimony Halide Crystals via Polyhedron Regulation.

Exploration of efficient red emitting antimony hybrid halide with large Stokes shift and zero self-absorption is highly desirable due to its enormous potential for applications in solid light emitting, and active optical waveguides. However, it is still challenging and rarely reported. Herein, a series of (TMS)2SbCl5 (TMS=triphenylsulfonium cation) crystals have been prepared with diverse [SbCl5]2- configurations and distinctive emission color. Among them, cubic-phase (TMS)2SbCl5 shows bright red emission with a large Stokes shift of 312 nm. In contrast, monoclinic and orthorhombic (TMS)2SbCl5 crystals deliver efficient yellow and orange emission, respectively. Comprehensive structural investigations reveal that larger Stokes shift and longer-wavelength emission of cubic (TMS)2SbCl5 can be attributed to the larger lattice volume and longer Sb⋅⋅⋅Sb distance, which favor sufficient structural aberration freedom at excited states. Together with robust stability, (TMS)2SbCl5 crystal family has been applied as optical waveguide with ultralow loss coefficient of 3.67 ⋅ 10-4 dB µm-1, and shows superior performance in white-light emission and anti-counterfeiting. In short, our study provides a novel and fundamental perspective to structure-property-application relationship of antimony hybrid halides, which will contribute to future rational design of high-performance emissive metal halides.

Vertically Concentrated Quantum Wells Enabling Highly Efficient Deep-Blue Perovskite Light-Emitting Diodes.

Deep-blue perovskite light-emitting diodes (PeLEDs) based on quasi-two-dimensional (quasi-2D) systems exist heightened sensitivity to the domain distribution. The top-down crystallization mode will lead to a vertical gradient distribution of quantum well (QW) structure, which is unfavorable for deep-blue emission. Herein, a thermal gradient annealing treatment is proposed to address the polydispersity issue of vertical QWs in quasi-2D perovskites. The formation of large-n domains at the upper interface of the perovskite film can be effectively inhibited by introducing a low-temperature source in the annealing process. Combined with the utilization of NaBr to inhibit the undesirable n=1 domain, a vertically concentrated QW structure is ultimately attained. As a result, the fabricated device delivers a narrow and stable deep-blue emission at 458 nm with an impressive external quantum efficiency (EQE) of 5.82 %. Green and sky-blue PeLEDs with remarkable EQE of 21.83 % and 17.51 % are also successfully achieved, respectively, by using the same strategy. The findings provide a universal strategy across the entire quasi-2D perovskites, paving the way for future practical application of PeLEDs.

The Role of Solution Aggregation Property toward High-Efficiency Non-Fullerene Organic Photovoltaic Cells.

In organic photovoltaic cells, the solution-aggregation effect (SAE) is long considered a critical factor in achieving high power-conversion efficiencies for polymer donor (PD)/non-fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D-benzodithiophene-based PDs and acceptor-donor-acceptor-type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well-known polymer-templated fibrillar network structures and superior PCEs. With the weakening of PDs' aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems.

Intermediate Phase Suppression with Long Chain Diammonium Alkane for High Performance Wide-Bandgap and Tandem Perovskite Solar Cells.

Wide bandgap (WBG) perovskite can construct tandem cells with narrow bandgap solar cells by adjusting the band gap to overcome the Shockley-Queisser limitation of single junction perovskite solar cells (PSCs). However, WBG perovskites still suffer from severe nonradiative carrier recombination and large open-circuit voltage loss. Here, this work uses an in situ photoluminescence (PL) measurement to monitor the intermediate phase evolution and crystallization process via blade coating. This work reports a strategy to fabricate efficient and stable WBG perovskite solar cells through doping a long carbon chain molecule octane-1,8-diamine dihydroiodide (ODADI). It is found that ODADI doping not only suppresses intermediate phases but also promote the crystallization of perovskite and passivate defects in blade coated 1.67 eV WBG FA0.7Cs0.25MA0.05Pb(I0.8Br0.2)3 perovskite films. As a result, the champion single junction inverted PSCs deliver the efficiencies of 22.06% and 19.63% for the active area of 0.07 and 1.02 cm2, respectively, which are the highest power conversion efficiencies (PCEs) in WBG PSCs by blade coating. The unencapsulated device demonstrates excellent stability in air, which maintains its initial efficiency at the maximum power points under constant AM 1.5G illumination in open air for nearly 500 h. The resulting semitransparent WBG device delivers a high PCE of 20.06%, and the 4-terminal all-perovskite tandem device delivers a PCE of 28.35%.

Boosting Luminescence Efficiency of Near-Infrared-II Aggregation-Induced Emission Luminogens via a Mash-Up Strategy of π-Extension and Deuteration for Dual-Model Image-Guided Surgery.

The simultaneous pursuit of accelerative radiative and restricted nonradiative decay is of tremendous significance to construct high-luminescence-efficiency fluorophores in the second near-infrared wavelength window (NIR-II), which is seriously hindered by the energy gap laws. Herein, a mash-up strategy of π-extension and deuteration is proposed to efficaciously ameliorate the knotty problem. By extending the π-conjugation of the aromatic fragment and introducing an isotope effect to the aggregation-induced emission luminogen (AIEgen), an improved oscillator strength (f), coupled with suppressed deformation and high-frequency oscillation in the excited state, are successively implemented. In this case, a faster rate of radiative decay (kr) and restricted nonradiative decay (knr) are simultaneously achieved. Moreover, the preeminent emissive property of AIEgen in the molecular state could be commendably inherited by the aggregates. The corresponding NIR-II emissive AIEgen-based nanoparticles display high brightness, large Stokes shift, and superior photostability simultaneously, which can be applied for image-guided cancer and sentinel lymph node (SLN) surgery. This work thus provides a rational roadmap to improve the luminescence efficiency of NIR-II fluorophores for biomedical applications.

Two-Dimensional Molybdenum Boride (MBene) Mo4/3B2Tx with Broadband and Termination-Dependent Ultrafast Nonlinear Optical Response.

Two-dimensional molybdenum borides (MBenes) comprise a new class of 2D transition metal borides that exhibit potential photonics applications. Recently, the synthesis of individual single-layer Mo4/3B2Tx (T = O, F, OH) MBene sheets has been realized, which attracted considerable attention in optoelectronics. However, there is still a lack of understanding and regulation of the photophysical processes of Mo4/3B2Tx MBene. Here, we demonstrate that Mo4/3B2Tx MBene exhibits a surface termination-dependent electronic structure, carrier dynamics, and nonlinear optical response over a wide wavelength range (500-1550 nm). As prepared 2D Mo4/3B2F2 MBene possesses a semimetal material property that exhibits a shorter intraband scattering process (<100 ps) and a considerable nonlinear optical response at a broadband cover optical communication C band at 1550 nm. These thrilling results are confirmed theoretically and experimentally. The analysis of these results adds to the regulating and understanding of the basic photophysical processes, which is anticipated to be beneficial for the further design of MBene-based photonics and nanoelectronics devices.

In Situ Hydrolysis of Phosphate Enabling Sky-Blue Perovskite Light-Emitting Diode with EQE Approaching 16.32.

The performance of blue perovskite light-emitting diodes (PeLEDs) lags behind the green and red counterparts owing to high trap density and undesirable red shift of the electroluminescence spectrum under operation conditions. Organic molecular additives were employed as passivators in previous reports. However, most commonly have limited functions, making it challenging to effectively address both efficiency and stability issues simultaneously. Herein, we reported an innovatively dynamic in situ hydrolysis strategy to modulate quasi-2D sky-blue perovskites by the multifunctional passivator phenyl dichlorophosphate that not only passivated the defects but also underwent in situ hydrolysis reaction to stabilize the emission. Moreover, hydrolysis products were beneficial for low-dimensional phase manipulation. Eventually, we obtained high-performance sky-blue PeLEDs with a maximum external quantum efficiency (EQE) of 16.32% and an exceptional luminance of 5740 cd m-2. More importantly, the emission peak of devices located at 485 nm remained stable under different biases. Our work signified the significant advancement toward realizing future applications of PeLEDs.

Modulation of Heterotypic and Homotypic Interactions to Visualize the Evolution of Organic Aggregates in a Fluorescence Turn-on Manner.

The abnormal evolution of membrane-less organelles into amyloid fibrils is a causative factor in many neurodegenerative diseases. Fundamental research on evolving organic aggregates is thus instructive for understanding the root causes of these diseases. In-situ monitoring of evolving molecular aggregates with built-in fluorescence properties is a reliable approach to reflect their subtle structural variation. To increase the sensitivity of real-time monitoring, we presented organic aggregates assembled by TPAN-2MeO, which is a triphenyl acrylonitrile derivative. TPAN-2MeO showed a morphological evolution with distinct turn-on emission. Upon rapid nanoaggregation, it formed non-emissive spherical aggregates in the kinetically metastable state. Experimental and simulation results revealed that the weak homotypic interactions between the TPAN-2MeO molecules liberated their molecular motion for efficient non-radiative decay, and the strong heterotypic interactions between TPAN-2MeO and water stabilized the molecular geometry favorable for the non-fluorescent state. After ultrasonication, the decreased heterotypic interactions and increased homotypic interactions acted synergistically to allow access to the emissive thermodynamic equilibrium state with a decent photoluminescence quantum yield (PLQY). The spherical aggregates were eventually transformed into micrometer-sized blocklike particles. Under mechanical stirring, the co-assembly of TPAN-2MeO and Pluronic F-127 formed uniform fluorescent platelets, inducing a significant enhancement in PLQY. These results decipher the stimuli-triggered structural variation of organic aggregates with concurrent sensitive fluorescence response and pave the way for a deep understanding of the evolutionary events of biogenic aggregates.

Metallopolymer strategy to explore hypoxic active narrow-bandgap photosensitizers for effective cancer photodynamic therapy.

Practical photodynamic therapy calls for high-performance, less O2-dependent, long-wavelength-light-activated photosensitizers to suit the hypoxic tumor microenvironment. Iridium-based photosensitizers exhibit excellent photocatalytic performance, but the in vivo applications are hindered by conventional O2-dependent Type-II photochemistry and poor absorption. Here we show a general metallopolymerization strategy for engineering iridium complexes exhibiting Type-I photochemistry and enhancing absorption intensity in the blue to near-infrared region. Reactive oxygen species generation of metallopolymer Ir-P1, where the iridium atom is covalently coupled to the polymer backbone, is over 80 times higher than that of its mother polymer without iridium under 680 nm irradiation. This strategy also works effectively when the iridium atom is directly included (Ir-P2) in the polymer backbones, exhibiting wide generality. The metallopolymer nanoparticles exhibiting efficient O2•- generation are conjugated with integrin αvß3 binding cRGD to achieve targeted photodynamic therapy.

Record high external quantum efficiency of 20% achieved in fully solution-processed quantum dot light-emitting diodes based on hole-conductive metal oxides.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been widely used as a hole injection material in quantum dot (QD) light-emitting diodes (QLEDs). However, it degrades the organic materials and electrodes in QLEDs due to its strong hydroscopicity and acidity. Although hole-conductive metal oxides have a great potential to solve this disadvantage, it is still a challenge to achieve efficient and stable QLEDs by using these solution-processed metal oxides. Herein, the state-of-the-art QLEDs fabricated by using hole-conductive MoOx QDs are achieved. The α-phase MoOx QDs exhibit a monodispersed size distribution with clear and regular crystal lattices, corresponding to high-quality nanocrystals. Meanwhile, the MoOx film owns an excellent transmittance, suitable valence band, good morphology and impressive hole-conductivity, demonstrating that the MoOx film could be used as a hole injection layer in QLEDs. Moreover, the rigid and flexible red QLEDs made by MoOx exhibit peak external quantum efficiencies of over 20%, representing a new record for the hole-conductive metal oxide based QLEDs. Most importantly, the MoOx QDs afford their QLEDs with a longer T95 lifetime than these devices made by PEDOT:PSS. As a result, we believe that the MoOx QDs could be used as efficient and stable hole injection materials used in QLEDs.

Turning Nonemissive CsPb2Br5 Crystals into High-Performance Scintillators through Alkali Metal Doping.

X-ray scintillators have utility in radiation detection, therapy, and imaging. Various materials, such as halide perovskites, organic illuminators, and metal clusters, have been developed to replace conventional scintillators due to their ease of fabrication, improved performance, and adaptability. However, they suffer from self-absorption, chemical instability, and weak X-ray stopping power. Addressing these limitations, we employ alkali metal doping to turn nonemissive CsPb2Br5 into scintillators. Introducing alkali metal dopants causes lattice distortion and enhances electron-phonon coupling, which creates transient potential energy wells capable of trapping photogenerated or X-ray-generated electrons and holes to form self-trapped excitons. These self-trapped excitons undergo radiative recombination, resulting in a photoluminescence quantum yield of 55.92%. The CsPb2Br5-based X-ray scintillator offers strong X-ray stopping power, high resistance to self-absorption, and enhanced stability when exposed to the atmosphere, chemical solvents, and intense irradiation. It exhibits a detection limit of 162.3 nGyair s-1 and an imaging resolution of 21 lp mm-1.

Synergistic Passivation With Phenylpropylammonium Bromide for Efficient Inverted Perovskite Solar Cells.

Inverted perovskite solar cells (PSCs) are a promising technology for commercialization due to their reliable operation and scalable fabrication. However, in inverted PSCs, depositing a high-quality perovskite layer comparable to those realized in normal structures still presents some challenges. Defects at grain boundaries and interfaces between the active layer and carrier extraction layer seriously hinder the power conversion efficiency (PCE) and stability of these cells. In this work, it is shown that synergistic bulk doping and surface treatment of triple-cation mixed-halide perovskites with phenylpropylammonium bromine (PPABr) can improve the efficiency and stability of inverted PSCs. The PPABr ligand is effective in eliminating halide vacancy defects and uncoordinated Pb2+ ions at both grain boundaries and interfaces. In addition, a 2D Ruddlesden-Popper (2D-RP) perovskite capping layer is formed on the surface of 3D perovskite by using PPABr post-treatment. This 2D-RP perovskite capping layer possesses a concentrated phase distribution ≈n = 2. This capping layer not only reduces interfacial non-radiative recombination loss and improves carrier extraction ability but also promotes stability and efficiency. As a result, the inverted PSCs achieve a champion PCE of over 23%, with an open-circuit voltage as high as 1.15 V and a fill factor of over 83%.

Large-n quasi-phase-pure two-dimensional halide perovskite: A toolbox from materials to devices.

Despite their excellent environmental stability, low defect density, and high carrier mobility, large-n quasi-two-dimensional halide perovskites (quasi-2DHPs) feature a limited application scope because of the formation of self-assembled multiple quantum wells (QWs) due to the similar thermal stabilities of large-n phases. However, large-n quasi-phase-pure 2DHPs (quasi-PP-2DHPs) can solve this problem perfectly. This review discusses the structures, formation mechanisms, and photoelectronic and physical properties of quasi-PP-2DHPs, summarises the corresponding single crystals, thin films, and heterojunction preparation methods, and presents the related advances. Moreover, we focus on applications of large-n quasi-PP-2DHPs in solar cells, photodetectors, lasers, light-emitting diodes, and field-effect transistors, discuss the challenges and prospects of these emerging photoelectronic materials, and review the potential technological developments in this area.

Persistent Charging of CsPbBr3 Perovskite Nanocrystals Confined in Glass Matrix.

Manipulation of persistent charges in semiconductor nanostructure is the key point to obtain quantum bits towards the application of quantum memory and information devices. However, realizing persistent charge storage in semiconductor nano-systems is still very challenge due to the disturbance from crystal defects and environment conditions. Herein, the two-photon persistent charging induced long-lasting afterglow and charged exciton formation are observed in CsPbBr3 perovskite nanocrystals (NCs) confined in glass host with effective lifetime surpassing one second, where the glass inclosure provides effective protection. A method combining the femtosecond and second time-resolved transient absorption spectroscopy is explored to determine the persistent charging possibility of perovskite NCs unambiguously. Meanwhile, with temperature-dependent spectroscopy, the underlying mechanism of this persistent charging is elucidated. A two-channel carrier transfer model is proposed involving athermal quantum tunneling and slower thermal-assisted channel. On this basis, two different information storage devices are demonstrated with the memory time exceeding two hours under low-temperature condition. These results provide a new strategy to realize persistent charging in perovskite NCs and deepen the understanding of the underlying carrier kinetics, which may pave an alternative way towards novel information memory and optical data storage applications.

Correlated Self-Trapped Excitons and Free Excitons with Intermediate Exciton-Phonon Coupling in 2D Mixed-Halide Perovskites.

Low-dimensional lead halides have attracted increasing attention due to their potential application as single-component white-light emitters. These materials exhibit a complex emission spectral structure, ranging from free exciton narrowband emissions to self-trapped exciton broadband emissions. However, there is still no consensus for the underlying physical mechanism, especially in the spectrum with both narrowband and broadband emissions. Here we aim to elucidate the correlation between the emission spectrum and the exciton-phonon coupling in the mixed halide perovskite BA2Pb(BrxCl1-x)4. Our findings reveal that the interplay between exciton localization and delocalization results in an intermediate exciton-phonon coupling, leading to line shapes beyond the Huang-Rhys model for the self-trapped exciton. By incorporating the exciton motional effect, we establish a unified photophysical model describing the emission spectrum from the self-trapped exciton type to the free exciton type. These results provide essential insights into the mechanisms governing exciton-phonon interactions and offer ways to control white-light emission in two-dimensional perovskites.