Precursor Engineering Induced High-Efficiency Electroluminescence of Quasi-Two-Dimensional Perovskites: A Synergistic Defect Inhibition and Passivation Approach.

Despite light-emitting diodes (LEDs) based on quasi-two-dimensional (Q-2D) perovskites being inexpensive and exhibiting high performance, defects still limit the improvement of electroluminescence efficiency and stability by causing nonradiative recombination. Here, an organic molecule, 1-(o-tolyl) biguanide, is used to simultaneously inhibit and passivate defects of Q-2D perovskites via in situ synchronous crystallization. This molecule not only prevents surface bromine vacancies from forming through hydrogen bonding with the bromine of intermediaries but also passivates surface defects through its interaction with uncoordinated Pb. Via combination of defect inhibition and passivation, the trap density of Q-2D perovskite films can be significantly reduced, and the emission efficiency of the film can be improved. Consequently, the corresponding LED shows an external quantum efficiency of 24.3%, and its operational stability has been increased nearly 15 times.

HCOO- Doping-Induced Multiexciton Emissions in Cs3Cu2I5 Crystals for Efficient X-Ray Scintillation.

Self-trapped exciton (STE) luminescence, typically associated with structural deformation of excited states, has attracted significant attention in metal halide materials recently. However, the mechanism of multiexciton STE emissions in certain metal halide crystals remains largely unexplored. This study investigates dual luminescence emissions in HCOO- doped Cs3Cu2I5 single crystals using transient and steady-state spectroscopy. The dual emissions are attributed to intrinsic STE luminescence originating from the host lattice and extrinsic STE luminescence induced by external dopants, respectively, each of which can be triggered independently at distinct energy levels. Theoretical calculations reveal that multiexciton emission originates from structural distortion of the host and dopant STEs within the 0D lattice in their respective excited states. By meticulously tuning the excitation wavelength and selectively exciting different STEs, the dynamic alteration of color change in Cs3Cu2I5:HCOO- crystals is demonstrated. Ultimately, owing to an extraordinarily high photoluminescence quantum yield (99.01%) and a diminished degree of self-absorption in Cs3Cu2I5:HCOO- crystals, they exhibit remarkable X-ray scintillation characteristics with light yield being improved by 5.4 times as compared to that of pristine Cs3Cu2I5 crystals, opening up exciting avenues for achieving low-dose X-ray detection and imaging.

Optimizing Energy Levels and Improving Film Compactness in PbS Quantum Dot Solar Cells by Silver Doping.

PbS quantum dot (QD) solar cells harvest near-infrared solar radiation. Their conventional hole transport layer has limited hole collection efficiency due to energy level mismatch and poor film quality. Here, how to resolve these two issues by using Ag-doped PbS QDs are demonstrated. On the one hand, Ag doping relieves the compressive stress during layer deposition and thus improves film compactness and homogeneity to suppress leakage currents. On the other hand, Ag doping increases hole concentration, which aligns energy levels and increases hole mobility to boost hole collection. Increased hole concentration also broadens the depletion region of the active layer, decreasing interface charge accumulation and promoting carrier extraction efficiency. A champion power conversion efficiency of 12.42% is achieved by optimizing the hole transport layer in PbS QD solar cells, compared to 9.38% for control devices. Doping can be combined with compressive strain relief to optimize carrier concentration and energy levels in QDs, and even introduce other novel phenomena such as improved film quality.

Band-Gap Narrowing and Electric Transport Regulation of Hybrid Perovskites via Pressure Engineering.

Lead-free organic-inorganic hybrid perovskites are one class of promising optoelectronic materials that have attracted much attention due to their outstanding stability and environmentally friendly nature. However, the intrinsic band gap far from the Shockley-Queisser limit and the inferior electrical properties largely limit their applicability. Here, a considerable band-gap narrowing from 2.43 to 1.64 eV with the compression rate up to 32.5% is achieved via high-pressure engineering in the lead-free hybrid perovskite MA3Sb2I9. Meanwhile, the electric transport process changes from the initial interaction of both ions and electrons to only the contribution of electrons upon compression. The alteration in electrical characteristics is ascribed to the vibration limitation of organic ions and the enhanced orbital overlap, resulting from the reduction of the Sb-I bond length through pressure-induced phase transitions. This work not only systematically investigates the correlation between the structural and optoelectronic properties of MA3Sb2I9 but also provides a potential pathway for optimizing electrical properties in lead-free hybrid perovskites.

Thermochromic Cs2 AgBiBr6 Single Crystal with Decreased Band Gap through Order-Disorder Transition.

Lead-free Cs2 AgBiBr6 double perovskite is considered to be a promising alternative to the traditional lead-based analogues due to its long carrier lifetime, high structural stability, and non-toxicity. However, the large band gap limits its absorption of visible light, which is not conducive to further optoelectronic applications. Herein, a thermochromic strategy is reported to decrease the band gap of Cs2 AgBiBr6 by approximately 0.36 eV, obtaining the smallest reported band gap of 1.69 eV under ambient conditions. The experimental data indicate that after annealing the Cs2 AgBiBr6 single crystals at 400 °C, the silver (Ag) and bismuth (Bi) atoms occupy the B-site in a random way and form a partially disordered configuration. The formation of the antisite defects broadens the band edges and decreases the band gap. This work offers new insights into the preparation of narrow band gap lead-free double perovskites, and a deep understanding of their structural and electronic properties for further development in photoelectric devices.

Hydration Intermediate Phase Regulated In-Plane and Out-Plane Epitaxy Growth of Oriented Nano-Array Structures on Perovskite Single Crystals.

Fabrication of organic-metal-halide perovskite micro-nano array structures draws attention to the potential application in polarized light, high-resolution X-ray imaging, light-emitting diodes, and lasers. However, it is still challenging to achieve the growth of controllable long-range ordered nanostructure arrays by chemical solution-based techniques. Herein, controllable epitaxial growth of long-range ordered micro-nano arrays on MAPbI3 single crystal (SC) surface is reported. A hydrated intermediate phase is found that can effectively regulate in-plane and out-plane orientated growth, respectively. This is attributed to the regulation of growth thermodynamics by hydration 0D perovskite intermediate phase enabling free recombination of PbI42- octahedral cages. Further, it is found that the degree of hydration is the key to the realization of in-plane and out-plane growth. Meanwhile, polarization emission and amplified spontaneous emission property are observed in highly oriented nanorod arrays with potential applications in anti-counterfeiting polarized emission.

Thermal Dynamic Self-Healing Supramolecular Dopant Towards Efficient and Stable Flexible Perovskite Solar Cells.

Flexible perovskite solar cells (FPSCs) have attracted great attention due to their advantageous traits such as low cost, portability, light-weight, etc. However, mechanical stability is still the weak point in their practical application. Herein, we prepared efficient FPSCs with remarkable mechanical stability by a dynamic thermal self-healing effect, which can be realized by the usage of a supramolecular adhesive. The supramolecular adhesive, which was obtained by random copolymerization of acrylamide and n-butyl acrylate, is amphiphilic, has a proper glass transition temperature and a high density of hydrogen-bond donors and receptors, providing the possibility of thermal dynamic repair of mechanical damage in FPSCs. The adhesive also greatly improves the leveling property of the precursor solution on the hydrophobic poly[bis(4-phenyl)(2,4,6-trimethylphenyl)]amine (PTAA) surface. PSCs containing this adhesive achieve more than a 20 % power conversion efficiency (PCE) on flexible substrates and a 21.99 % PCE on rigid substrates (certified PCE of 21.27 %), with improved electron mobility and reduced defect concentration.

Novel 2,3-Dialdehyde Cellulose-Based Films with Photodynamic Inactivation Potency by Incorporating the ß-Cyclodextrin/Curcumin Inclusion Complex.

Antibacterial packaging film mediated by photodynamic inactivation (PDI) is a new concept in food industry. The objective of this study was to fabricate a green 2,3-dialdehyde cellulose (DAC)-based antimicrobial film with PDI potency by incorporating the ß-cyclodextrin/curcumin (ß-CD/Cur) complex as a photosensitizer. The PDI-mediated films were characterized by evaluating the surface morphology, chemical structure, light transmittance, mechanical properties, photochemical and thermal stability, and water solubility. The results showed that the DAC-CD/Cur films were soluble in water and mechanically strong with a tensile strength of 63.87 MPa and an elongation break of 1.32%, which was attributed to the formation of hydrogen bonds between DAC and ß-CD/Cur molecules. Meanwhile, the composite films possessed a good light transmittance but impeded the penetration of ultraviolet light and efficiently delayed the degradation of curcumin. More importantly, the PDI-mediated films exhibited a broad-spectrum ability to kill Listeria monocytogenes, Vibrio parahaemolyticus, and Shewanella putrefaciens in pure culture. Notably, they also potently inactivated these harmful bacteria on ready-to-eat salmon with a maximum of ∼4 Log CFU/g (99.99%) reduction after 60 min irradiation (13.68 J/cm2). Therefore, the PDI-mediated DAC-CD/Cur films are novel and promising antimicrobial food packaging films in food industry.

Dynamic Passivation in Perovskite Quantum Dots for Specific Ammonia Detection at Room Temperature.

Perovskite structured CsPbX3 (X = Cl, Br, or I) quantum dots (QDs) have attracted considerable interest in the past few years due to their excellent optoelectronic properties. Surface passivation is one of the main pathways to optimize the optoelectrical performance of perovskite QDs, in which the amino group plays an important role for the corresponding interaction between lead and halide. In this work, it is found that ammonia gas could dramatically increase photoluminescence of purified QDs and effectively passivate surface defects of perovskite QDs introduced during purification, which is a reversible process. This phenomenon makes perovskite QDs a kind of ideal candidate for detection of ammonia gas at room temperature. This QD film sensor displays specific recognition behavior toward ammonia gas due to its significant fluorescence enhancement, while depressed luminescence in case of other gases. The sensor, in turn-on mode, shows a wide detection range from 25 to 350 ppm with a limit of detection as low as 8.85 ppm. Meanwhile, a fast response time of ≈10 s is achieved, and the recovery time is ≈30 s. The fully reversible, high sensitivity and selectivity characteristics make CsPbBr3 QDs ideal active materials for room-temperature ammonia sensing.

Large electrostrictive response in lead halide perovskites.

Lead halide perovskites have demonstrated outstanding performance in photovoltaics, photodetectors, radiation detectors and light-emitting diodes. However, the electromechanical properties, which are the main application of inorganic perovskites, have rarely been explored for lead halide perovskites. Here, we report the discovery of a large electrostrictive response in methylammonium lead triiodide (MAPbI3) single crystals. Under an electric field of 3.7 V µm-1, MAPbI3 shows a large compressive strain of 1%, corresponding to a mechanical energy density of 0.74 J cm-3, comparable to that of human muscles. The influences of piezoelectricity, thermal expansion, intrinsic electrostrictive effect, Maxwell stress, ferroelectricity, local polar fluctuation and methylammonium cation ordering on this electromechanical response are excluded. We speculate, using density functional theory, that electrostriction of MAPbI3 probably originates from lattice deformation due to formation of additional defects under applied bias. The discovery of large electrostriction in lead iodide perovskites may lead to new potential applications in actuators, sonar and micro-electromechanical systems and aid the understanding of other field-dependent material properties.

Publisher Correction: Large electrostrictive response in lead halide perovskites.

In the version of this Article originally published, the y axis of Fig. 1c was incorrectly labelled 'S (%)'; it should have been '-S (%)'. Also, the link for the Supplementary Video was missing from the online version of the Article. These errors have now been corrected.

Giant switchable photovoltaic effect in organometal trihalide perovskite devices.

Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V µm(-1). The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm(-2) under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by the formation of reversible p-i-n structures induced by ion drift in the perovskite layer. The demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

Ultrafast ion migration in hybrid perovskite polycrystalline thin films under light and suppression in single crystals.

Understanding the influence of light on ion migration in organic-inorganic halide perovskite (OIHP) materials is important to understand the photostability of perovskite solar cells. We reveal that light could greatly reduce the ion migration energy barrier in both polycrystalline and single crystalline OIHP. The activation energies derived from conductivity measurement under 0.25 Sun decrease to less than one half of the values in the dark. A typical ion drift velocity in CH3NH3PbI3 polycrystalline films is 1.2 µm s-1 under 1 Sun, compared with 0.016 µm s-1 under 0.02 Sun. Ion migration across the photoactive layers in most OIHP devices thus takes only subseconds under 1 Sun illumination, which is much shorter than what it was thought to take. Most important of all, ion migration through a single crystal surface is still too slow to be observed even after illumination for two days due to the large ion diffusion activation energy, >0.38 eV.

Chloride Incorporation Process in CH3NH3PbI(3-x)Cl(x) Perovskites via Nanoscale Bandgap Maps.

CH3NH3PbI(3-x)Cl(x) perovskites enable fabrication of highly efficient solar cells. Chloride ions benefit the morphology, carrier diffusion length, and stability of perovskite films; however, whether those benefits stem from the presence of Cl(-) in the precursor solution or from their incorporation in annealed films is debated. In this work, the photothermal-induced resonance, an in situ technique with nanoscale resolution, is leveraged to measure the bandgap of CH3NH3PbI(3-x)Cl(x) films obtained by a multicycle coating process that produces high efficiency (∼16%) solar cells. Because chloride ions modify the perovskite lattice, thereby widening the bandgap, measuring the bandgap locally yields the local chloride content. After a mild annealing (60 min, 60 °C) the films consist of Cl-rich (x < 0.3) and Cl-poor phases that upon further annealing (110 °C) evolve into a homogeneous Cl-poorer (x < 0.06) phase, suggesting that methylammonium-chrloride is progressively expelled from the film. Despite the small chloride content, CH3NH3PbI(3-x)Cl(x) films show better thermal stability up to 140 °C with respect CH3NH3PbI3 films fabricated with the same methodology.

Distinct exciton dissociation behavior of organolead trihalide perovskite and excitonic semiconductors studied in the same system.

The nonexcitonic character for organometal trihalide perovskites is demonstrated by examining the field-dependent exciton dissociation behavior. It is found that photogenerated excitons can be effectively dissociated into free charges inside perovskite without the assistance of charge extraction layer or external field, which is a stark contrast to the charge-separation behavior in excitonic materials in the same photovoltaic operation system.

Fabrication of carvacrol loaded cellulose acetate phthalate/shellac composite film and its application to mackerel fillets preservation.

In this research, the carvacrol (CAR) loaded cellulose acetate phthalate (CAP) /shellac (SH) films were prepared via electrostatic repulsion strategy and casting method. The CAP/SH-CAR films demonstrated excellent tensile strength, while also exhibiting good UV light barrier and thermal stability. The results showed that the addition of CAR significantly improved the barrier of the CAP film to water vapor and oxygen permeability. When the addition amount of CAR was 0.9 % (w/w) with respect to CAP content, the CAP/SH-CAR films exhibited good antibacterial activity and effectively reduced the growth of S. aureus and E. coli by approximately 47.9 % and 50.9 %, respectively. The presence of SH improved the retention rate of CAR in CAP/SH-CAR films, with the retention rate ranging from 45.2 to 56.8 %. Finally, the CAP/SH-CAR films were applied to preserve the mackerel fillets, indicating that the rate of freshness deterioration had been delayed and showing a good freshness preservation effect. Therefore, the CAP/SH-CAR films have the potential to be used as food packaging materials.

Sustained release, antimicrobial, and antioxidant properties of modified porous starch-based biodegradable polylactic acid/polybutylene adipate-co-terephthalate/thermoplastic starch active packaging film.

Porous starch (PS) is a modified starch with commendable biodegradable and adsorption properties. PS exhibits poor thermal stability, and the aqueous solution casting method is conventionally used for PS-activated packaging films. This approach limits the large-scale production of films and makes it difficult to play the functions of porous pores. In this study, PS was prepared by enzymatic digestion combined with freeze-drying and adsorbed with clove essential oil (CEO) after cross-linking with sodium trimetaphosphate. Subsequently, a novel PLA/PBAT/TPS/ScPS-CEO sustained release active packaging film was prepared by blending PLA, PBAT, TPS, and ScPS-CEO using industrial melt extrusion. Compared with PS, ScPS effectively slowed down the release of CEO from the film, with the maximum release of active substances at equilibrium increasing by approximately 100 %, which significantly enhanced the persistence of the antimicrobial and antioxidant properties. The polylactic acid/poly (butylene adipate-co-terephthalate)/thermoplastic starch/trimetaphosphate-crosslinked porous starch incorporated with clove essential oil (PLA/PBAT/TPS/ScPS-CEO) film could reduce the proteolysis, lipid oxidation and microbial growth of salmon, extending its shelf life by approximately 100 % at 4 °C. These results indicate that the ScPS can be used in fresh packaging material in practical applications.

Self-Trapped Exciton Emission Enhancement in 3D Cationic Lead Halide Hybrids Via Phase Transition Engineering.

Three-dimensional (3D) cationic lead halide hybrids constructed by organic ions and inorganic networks via coordination bonds are a promising material for solid-state lighting due to their exceptional environmental stability and broad-spectrum emission. Nevertheless, their fluorescence properties are hindered by the limited lattice distortion from extensive connectivity within the inorganic network. Here, a dramatic 100-fold enhancement of self-trapped exciton (STE) emission is achieved in 3D hybrid material [Pb2Br2][O2C(CH2)4CO2] via pressure-triggered phase transition. Notably, pressure-treated material exhibits a 110 nm redshift with 1.5-fold enhancement compared to the initial state after pressure was completely released. The irreversible structural phase transition intensifies the [PbBr3O3] octahedral distortion, which is highly responsible for the optimization of quenched emission. These findings present a promising strategy for improving the optical properties of 3D halide hybrids with relatively high stability and thus facilitate their practical applications by pressure-driven phase transition engineering.

Comparing tocilizumab biosimilar BAT1806/BIIB800 with reference tocilizumab in patients with moderate-to-severe rheumatoid arthritis with an inadequate response to methotrexate: a phase 3, randomised, multicentre, double-blind, active-controlled clinical trial.

BACKGROUND: Biosimilars provide an opportunity to address unmet medical need by expanding access to biological treatments. This study aimed to show equivalent efficacy, and comparable safety, immunogenicity, and pharmacokinetic profiles of a proposed tocilizumab biosimilar BAT1806/BIIB800, to reference tocilizumab, in participants with rheumatoid arthritis with an inadequate response to methotrexate. METHODS: This phase 3, multicentre, randomised, double-blind, active-controlled, equivalence study comprised a 24-week initial treatment period (results reported here) and a 24-week secondary treatment period. Participants were recruited at 54 centres across five countries (China, Ukraine, Poland, Georgia, and Bulgaria). Patients with active rheumatoid arthritis with an inadequate response to methotrexate were randomly assigned (1:1:2) to receive reference tocilizumab up to week 48, or reference tocilizumab up to week 24 followed by BAT1806/BIIB800 up to week 48 (the two reference tocilizumab groups were analysed as a single group in this analysis), or BAT1806/BIIB800 up to week 48 (the BAT1806/BIIB800 group), administered by intravenous infusion once every 4 weeks at a starting dose of 8 mg/kg. The primary endpoint was the proportion of participants who had a 20% improvement in American College of Rheumatology criteria (ACR20) at week 12 (for the European Medicines Agency [EMA]) or week 24 (for the US Food and Drug Administration [FDA] and China National Medical Products Administration [NMPA]) using prespecified equivalence margins (95% CI -14·5 to +14·5 [EMA], 90% CI -12·0 to +15·0 [FDA], and 95% CI -13·6 to +13·6 [NMPA]). The International Council for Harmonisation E9(R1) estimand framework, with strategies for addressing intercurrent events, was implemented for the efficacy evaluations with expected differences as per the predefined equivalence margins. This trial is registered at ClinicalTrials.gov (NCT03830203) and EudraCT (2018-002202-31), and is closed to new participants. FINDINGS: Between Dec 19, 2018, and Jan 5, 2021, we randomly assigned 621 participants: 309 to the reference tocilizumab group and 312 to the BAT1806/BIIB800 group. The mean age was 50·5 years (SD 12·0), 534 (86%) were women, 87 (14%) were men, and 368 (59%) were White. For the primary estimands, estimated ACR20 response rates were 64·8% in the reference tocilizumab group and 69·0% in the BAT1806/BIIB800 group (treatment difference 4·1% [95% CI -3·6 to 11·9]) at week 12, and 67·9% in the reference tocilizumab group and 69·9% in the BAT1806/BIIB800 group (treatment difference 1·9% [90% CI -4·0 to 7·9; 95% CI -5·2 to 9·1]) at week 24. All confidence intervals were contained within the predefined equivalence margins. Comparable pharmacokinetic and immunogenicity profiles were observed for the reference tocilizumab and BAT1806/BIIB800 groups. Adverse events were reported by 201 (65%) participants in the reference tocilizumab group and 206 (66%) in the BAT1806/BIIB800 group; 196 (63%) participants in the reference tocilizumab group and 201 (64%) participants in the BAT1806/BIIB800 group reported a treatment-emergent adverse event. Five participants had a fatal event (reference tocilizumab n=1; BAT1806/BIIB800 n=4). INTERPRETATION: BAT1806/BIIB800 showed equivalent efficacy, and comparable safety, immunogenicity, and pharmacokinetic profiles as reference tocilizumab. FUNDING: Bio-Thera Solutions and Biogen.

Metal-halide perovskites for high-efficiency radiation shielding applications.

The ionizing radiation possesses extremely strong penetration capability, which poses serious risk on the health of the human body and jeopardize electronics. Here the authors demonstrate that MAPbI3/epoxy composites prepared by a simple method show high radiation shielding performance.