Surface Reconstruction for Efficient NiOx-Based Inverted Perovskite Solar Cells.

Functional agents are verified to efficiently enhance device performance of perovskite solar cells (PSCs) through surface engineering. However, the influence of intrinsic characteristics of molecules on final device performance is overlooked. Here, a surface reconstruction strategy is developed to enhance the efficiency of inverted PSCs by mitigating the adverse effects of lead chelation (LC) molecules. Bathocuproine (BCP) is chosen as the representative of LC molecules for its easy accessibility and outstanding optoelectronic properties. During this strategy, BCP molecules on perovskite surface are first dissolved in solvents and then captured specially by undercoordinated Pb2+ ions, preventing adverse n-type doping by the molecules themselves. In this case, the BCP molecule exhibits outstanding passivation effect on perovskite surface, which leads to an obviously increased open-circuit voltage (VOC). Therefore, a record power conversion efficiency of 25.64% for NiOx-based inverted PSCs is achieved, maintaining over 80% of initial efficiency after exposure to ambient condition for ≈1500 h.

Aminoazanium of A-site Cations in Metal-Free Halide Perovskite Single Crystals to Reduce Thermal Expansion for Efficient X-ray Detection.

Metal-free perovskites (MFPs) have recently become a newcomer in X-ray detection due to their flexibility and low toxicity characteristics. However, their photoelectronic properties and stability should be further improved mainly through materials design. Here, the aminoazanium of DABCO2+ was developed for the preparation of NDABCO-NH4Br3 (NDABCO = N-amino-N'-diazabicyclo[2.2.2]octonium) single crystals (SCs), and its physical properties, intermolecular interactions, and device performance were systematically explored. Notably, NDABCO-NH4Br3 can achieve improved stability by enlarging defect formation energy and inducing abundant intermolecular forces. Moreover, the slight lattice distortion could ensure the weakening electron-phonon coupling for improving carrier transport. In particular, the slight lattice distortion after the long-chain NDABCO2+ introduction could retard thermal expansion for the preparation of high-quality crystals. Finally, the corresponding X-ray detector delivered a moderate sensitivity of 623.3 µC Gyair-1 cm-2. This work provides a novel strategy through rationally designed organic cations to balance the material stability and device performance.

Molecular Design of Layered Hybrid Silver Bismuth Bromine Single Crystal for Ultra-Stable X-Ray Detection With Record Sensitivity.

Nowadays, weak interlayer coupling and unclear mechanism in layered hybrid silver bismuth bromine (LH-AgBiBr) are the main reasons for limiting its further enhanced X-ray detection sensitivity and stability. Herein, the design rules for LH-AgBiBr and its influence on X-ray detection performance are reported for the first time. Although shortening amine size can enhance interlayer coupling, its detection performance is severely hampered by its easier defect formation caused by enlarged micro strain. In contrast, an appropriate divalent amine design endows the material with improved interlayer coupling and released micro strain, which benefits crystal stability and mechanical hardness. Another contribution is to increase material density and dielectric constant; thus, enhancing X-ray absorption and carrier transport. Consequently, the optimized parallel device based on BDA2 AgBiBr8 achieves a record sensitivity of 2638 µC Gyair -1 cm-2 and an ultra-low detection limit of 7.4 nGyair s-1 , outperforming other reported LH-AgBiBr X-ray detectors. Moreover, the unencapsulated device displays remarkable anti-moisture, anti-thermal (>150 °C), and anti-radiation (>1000 Gyair ) endurance. Eventually, high-resolution hard X-ray imaging is demonstrated by linear detector arrays under a benign dose rate (1.63 µGyair s-1 ) and low external bias (5 V). Hence, these findings provide guidelines for future materials design and device optimization.

Metal Halide Nanocrystals@Silica Aerogel Composite with Enhanced Dispersion Stability and Light Output for Efficient X-Ray Imaging in Harsh Environment.

Metal halide nanocrystals (MHNCs) embedded in a polymer matrix as flexible X-ray detector screens is an effective strategy with the advantages of low cost, facile preparation, and large area flexibility. However, MHNCs easily aggregate during preparation, recombination, under mechanical force, storage, or high operating temperature. Meanwhile, it shows an unmatched refractive index with polymer, resulting in low light yield. The related stability and properties of the device remain a huge unrevealed challenge. Herein, a composite screen (CZBM@AG-PS) by integrating MHNCs (Cs2ZnBr4: Mn2+ as an example) into silica aerogel (AG) and embedded in polystyrene (PS) is successfully developed. Further characterization points to the high porosity AG template that can effectively improve the dispersion of MHNCs in polymer detector screens, essentially decreasing nonradiative transition, Rayleigh scattering, and performance aging induced by aggregation in harsh environments. Furthermore, the higher light output and lower optical crosstalk are also achieved by a novel light propagation path based on the MHNCs/AG and AG/PS interfaces. Finally, the optimized CZBM@AG-PS screen shows much enhanced light yield, spatial resolution, and temperature stability. Significantly, the strategy is proven universal by the performance tests of other MHNCs embedded composite films for ultra-stable and efficient X-ray imaging.

Metal-Free Hydrazinium Halide Perovskitoid Single Crystals for X-ray Detection.

Metal-free perovskitoids (MFPs) with N2H5+ as B-site component possess higher crystal density and hydrogen bonding networks and have been recently expanded into X-ray detection. However, research on this material is in its infancy and lacks an understanding of the function of halide components on physical properties and device performance. Here, N2H5-based MFP single crystals (SCs) with different halides are fabricated, and the influence of halides on the crystal structure, band nature, charge transport characteristics, and final device performance is actively explored. Based on theory and experiments, the tolerance factor and octahedral factor jointly determine the octahedral composition. Further, halides with different electronegativities and ionic radii also affect octahedral distortion and energy band bending, further influencing carrier transport and device performance. Finally, a sensitivity of 1284 µC Gyair-1 cm-2 and low detection limits (LoD) of 5.62 µGyair s-1 were obtained by the Br-based device due to its superior physical properties.

Graphdiyne-polymer composites for a hybrid bound-state pulsed fiber laser.

In this paper, the graphdiyne (GDY)-polymethyl methacrylate (PMMA) films are prepared by a spin-coating method. The PMMA films have the function of isolating GDY from air and protecting the GDY from mechanical damage. The nonlinear optical properties of GDY-PMMA films are probed experimentally. The nonlinear optical responses of GDY-PMMA films with a modulation depth of ∼4.94% and saturated magnetization of ∼0.3M W/c m 2 are proved. When the GDY-PMMA films are applied to an erbium-doped hybrid passively mode-locked fiber laser (saturable absorber), the bound-state solitons, which are also called soliton molecules, can be obtained. The soliton molecule has a time separation of 13.31 ps, and the spectral modulation period of 0.58 nm. Along with the pump power increase, the separation of bound-state pulses becomes larger. When the pump power is fixed, stable bound solitons can be observed without any degeneration for more than 4.5 h. It is demonstrated that GDY-PMMA films have excellent nonlinear optical performance in a near-infrared regime, which we believe can be a novel type of photonics instrument and has a number of properties that are potentially promising in the ultrafast properties of laser.

Metal-Free Perovskites for X-Ray Detection.

Metal-free perovskites are a promising class of materials for X-ray detection due to their unique structural, optical, and electrical properties. Here, we first delve into the stoichiometry and geometric argument of metal-free perovskites. Followed, the alternative A/B/X ions and hydrogen-bonding are clearly introduced to further optimize the materials' stability and properties. Finally, we provide a comprehensive overview of their potential applications for flexible X-ray images and prospects for metal-free perovskite development. In conclusion, metal-free perovskite is a promising material for X-ray detection. Its stoichiometric and geometric parameters, ion, and hydrogen bond selection, and application prospects are worthy of further study.

Two-Dimensional Metal Halides for X-Ray Detection Applications.

Metal halide perovskites have recently emerged as promising candidates for the next generation of X-ray detectors due to their excellent optoelectronic properties. Especially, two-dimensional (2D) perovskites afford many distinct properties, including remarkable structural diversity, high generation energy, and balanced large exciton binding energy. With the advantages of 2D materials and perovskites, it successfully reduces the decomposition and phase transition of perovskite and effectively suppresses ion migration. Meanwhile, the existence of a high hydrophobic spacer can block water molecules, thus making 2D perovskite obtain excellent stability. All of these advantages have attracted much attention in the field of X-ray detection. This review introduces the classification of 2D halide perovskites, summarizes the synthesis technology and performance characteristics of 2D perovskite X-ray direct detector, and briefly discusses the application of 2D perovskite in scintillators. Finally, this review also emphasizes the key challenges faced by 2D perovskite X-ray detectors in practical application and presents our views on its future development.

Enhancement of Light and X-ray Charging in Persistent Luminescence Nanoparticle Scintillators Zn2SiO4:Mn2+, Yb3+, Li.

Persistent luminescence nanoparticle scintillators (PLNS) have been attempted for X-ray-induced photodynamic therapy (X-PDT) because persistent luminescence after ceasing radiation can make PLNS use less cumulative irradiation time and dose to generate the same amount of reactive oxygen species (ROS) compared with conventional scintillators to combat cancer cells. However, excessive surface defects in PLNS reduce the luminescence efficiency and quench the persistent luminescence, which is fatal to the efficacy of X-PDT. Herein, the PLNS of SiO2@Zn2SiO4:Mn2+, Yb3+, Li+ was designed by the energy trap engineering and synthesized by a simple template method, which has excellent X-ray and UV-excited persistent luminescence and continuously tunable emission spectra from 520 to 550 nm. Its luminescence intensity and afterglow time are more than 7 times that of the reported Zn2SiO4:Mn2+ used for X-PDT. By loading a Rose Bengal (RB) photosensitizer, an effective persistent energy transfer from the PLNS to photosensitizer is observed even after the removal of X-ray irradiation. The X-ray dose of nanoplatform SiO2@Zn2SiO4:Mn2+, Yb3+, Li+@RB in X-PDT of HeLa cancer cells was reduced to 0.18 Gy compared to the X-ray dose of 1.0 Gy for Zn2SiO4:Mn for X-PDT. This indicates that the Zn2SiO4:Mn2+, Yb3+, Li+ PLNS have great potential for X-PDT applications.

PF6 - Pseudohalides Anion Based Metal-Free Perovskite Single Crystal for Stable X-Ray Detector to Attain Record Sensitivity.

Metal-free perovskites (MFPs) possess excellent photophysical properties of perovskites while avoiding the introduction of toxic metal ions and organic solvents, and have been expanded to X-ray detection. However, iodine-based high-performance MFPs are tended to oxidation, corrosion, and uncontrolled ion migration, resulting in poor material stability and device performance. Herein, the strongly electronegative PF6 - pseudohalide is used to fabricate the large-size MDABCO-NH4 (PF6 )3 (MDBACO = methyl-N'-diazabicyclo[2.2.2]octonium) single crystals (SCs) for solving the problems of iodine ions. After the introduction of PF6 - pseudohalides, the Coulomb interaction and hydrogen bonding strength are enhanced to alleviate the ion-migration and stability problems. Moreover, combined with theoretical calculations, PF6 - pseudohalides increase the ion-migration barrier, and affect the contribution of its components to the energy band for a broadening bandgap. Meanwhile, the improved physical properties, such as large activation energy of ionic migration, high resistivity, and low current drift, further expand its application in low-dose and sensitive X-ray detection. Finally, the X-ray detector based on MDABCO-NH4 (PF6 )3 SCs achieves a sensitivity of 2078 µC Gyair -1 cm-2 (highest among metal-free SCs-based detectors) and the lowest detectable dose rate (16.3 nGyair s-1 ). This work has expanded the selection of MFPs for X-ray detectors and somewhat advanced the development of high-performance devices.

Hydrogen Bonds Strengthened Metal-Free Perovskite for Degradable X-ray Detector with Enhanced Stability, Flexibility and Sensitivity.

Metal-free perovskites (MFPs) with flexible and degradable properties have been adopted in flexible X-ray detection. For now, figuring out the key factors between structure and device performance are critical to guide the design of MFPs. Herein, MPAZE-NH4 I3 ⋅ H2 O was first designed and synthesized with improved structural stability and device performance. Through theoretical calculations, the introducing methyl group benefits modulating tolerance factor, increases dipole moment and strengthens hydrogen bonds. Meanwhile, H2 O increases the hydrogen bond formation sites and synergistically realizes the band nature modulation, ionic migration inhibition and structural stiffness optimization. Spectra analysis also proves that the improved electron-phonon coupling and carrier recombination lifetime contribute to enhanced performance. Finally, a flexible and degradable X-ray detector was fabricated with the highest sensitivity of 740.8 µC Gyair -1 cm-2 and low detection limit (0.14 nGyair s-1 ).

Manipulate energy transport via fluorinated spacers towards record-efficiency 2D Dion-Jacobson CsPbI3 solar cells.

Two-dimensional (2D) Dion-Jacobson (D-J)-type cesium lead iodide CsPbI3 perform remarkably in terms of stability. However, the complex interactions between spacer and inorganic layers limit its excellent progress in perovskite solar cells (PSCs). Herein, starting from the considerable structural diversity of organic spacers, we engineer 2D CsPbI3 with fine-tuning functionalities. Specifically, for the first time we embedded fluorinated aromatic cations in 2D D-J CsPbI3, and successfully applied it into construction of high-performance PSCs. Compared with constitutive 1,4-diaminobenzene (PDA), the fluorinated 2-fluorobenzene-1,4-diamine (F-PDA) component greatly expands the dipole moment from 0.59D to 3.47D, which reduces the exciton binding energy of the system. A theoretical study shows that the spacer layer and inorganic plane are more enriched with charge accumulation in (F-PDA)Csn-1PbnI3n+1. The results show that (F-PDA)Csn-1PbnI3n+1 demonstrates more significant charge transfer between organic and inorganic layers than (PDA)Csn-1PbnI3n+1, and it is confirmed in the femtosecond transient absorption experiment. Moreover, the interactions of the fluorinated spacer with the [PbI6]4- plane effectively manipulate the crystallization quality, and thus the ion migration and defect formation of target 2D CsPbI3 are inhibited. As a result, we obtained a record power conversion efficiency (PCE) beyond 15% for 2D D-J (F-PDA)Cs3Pb4I13 (n = 4) PSCs with significantly improved environmental stability compared with the three-dimensional (3D) counterparts.

Vertically Oriented Porous PET as Template to Integrated Metal Halide for High-Performance Large-Area and Ultra-Flexible X-Ray Detector.

High-performance X-ray detectors have immense potential in medical and security inspections. However, the current X-ray detectors are limited in flexible, high-spatial-resolution large-scale detection, and integration for imaging. Here, nuclear track-etched porous polyethylene terephthalate (PET) is developed as the template for preparing uniform, large-area (≥105 cm2 ), and flexible metal halide (MH)-based X-ray detectors. Adjustable high-density vertically oriented porous PET with adjustable thickness can provide proper physical support for flexible thick absorption film, thus improving X-ray absorption ability with excellent bending stability. Moreover, vertical channels can block the ion migration, lateral charge diffusion, and water/oxygen attacks, increasing activation energy for ionic transport, charge collection rate of electrodes, and environmental stability. Hence, the related detectors eventually obtain large sensitivity (6722 µC Gyair -1 cm-2 ), low detection limit (1.87 nGyair s-1 ), and high spatial resolution (5.17 lp mm-1 ) compared to the detectors without porous PET template. Meanwhile, the device shows no degradation after storage or working under various thermal attacks. MH-filled-PET is also monolithically integrated on the bottom circuit with different MHs and it is applied to single-pixel mode and fast linear-array imaging in a broad range of X-rays photon energy (20 to 160 keV).

Novel PHA Organic Spacer Increases Interlayer Interactions for High Efficiency in 2D Ruddlesden-Popper CsPbI3 Solar Cells.

The two-dimensional (2D) Ruddlesden-Popper (RP) CsPbI3 with hydrophobic organic spacers can significantly improve the environmental and phase stability of photovoltaic devices by suppressing ion migration and inducing steric hindrance. However, due to the multiple-quantum-well structure, these spacer cations lead to weak interactions in 2D RP CsPbI3, which seriously affect the carrier transport. Here, a novel N-H-group-rich phenylhydrazine spacer, namely, PHA, was developed for 2D RP CsPbI3 perovskite solar cells (PSCs). A series of characterizations confirm that the 2D perovskites using PHA spacers enhanced the N-H···I hydrogen-bonding interaction between the organic spacer cations and the [PbI6]4- inorganic layer and accelerated the crystallization rate of the perovskite film, which was beneficial to the preparation of high-quality films with preferred vertical orientation, large grain size, and dense morphology. Meanwhile, the trap state density of the as-prepared 2D RP perovskite films is significantly reduced to enable efficient charge carrier transport. As a result, the (PHA)2Cs4Pb5I16 PSCs achieved a performance of 16.23% with good environmental stability. This work provides a simple organic spacer selection scheme to realize interaction optimization in 2D RP CsPbI3 to develop efficient and stable PSCs.

Metal-Free PAZE-NH4 X3 ⋠H2 O Perovskite for Flexible Transparent X-ray Detection and Imaging.

Metal-free perovskites are of interest for their chemical diversity and eco-friendly properties, and recently have been used for X-ray detection with superior carrier behavior. However, the size and shape complexity of the organic components results in difficulties in evaluating their stability in high-energy radiation. Herein, we introduce multiple hydrogen-bond metal-free PAZE-NH4 X3 ⋅H2 O perovskite, where H2 O leads to more hydrogen bonds appearing between organic molecules and the perovskite host. As suggested by the theoretical calculations, multiple hydrogen bonds promote stiffness of the lattice, and increase the diffusion barrier to inhibit ionic migration. Then, low trap density, high µτ products and structural flexibility of PAZE-NH4 Br3 ⋅H2 O give a flexible X-ray detector with the highest sensitivity of 3708 µC Gyair -1 cm-2 , ultra-low detection limit of 0.19 µGyair -1 s-1 and superior spatial resolution of 5.0 lp mm-1 .

Ordered Element Distributed C3 N Quantum Dots Manipulated Crystallization Kinetics for 2D CsPbI3 Solar Cells with Ultra-High Performance.

Two-dimensional (2D) CsPbI3 is developed to conquer the phase-stability problem of CsPbI3 by introducing bulky organic cations to produce a steric hindrance effect. However, organic cations also inevitably increase the formation energy and difficulty in crystallization kinetics regulation. Such poor crystallization process modulation of 2D CsPbI3 leads to disordered phase-arrangement, which impedes the transport of photo-generated carriers and worsens device performance. Herein, a type of C3 N quantum dots (QDs) with ordered carbon and nitrogen atoms to manipulate the crystallization process of 2D CsPbI3 for improving the crystallization pathway, phase-arrangement and morphology, is introduced. Combination analyses of theoretical simulation, morphology regulation and femtosecond transient absorption (fs-TA) characterization, show that the C3 N QDs induce the formation of electron-rich regions to adsorb bulky organic cations and provide nucleation sites to realize a bi-directional crystallization process. Meanwhile, the quality of 2D CsPbI3 film is improved with lower trap density, higher surface potential, and compact morphology. As a result, the power conversion efficiency (PCE) of the optimized device (n = 5) boosts to an ultra-high value of 15.63% with strengthened environmental stability. Moreover, the simple C3 N QDs insertion method shows good universality to other bulky organic cations of Ruddlesden-Popper and Dion-Jacobson, providing a good modulation strategy for other optoelectronic devices.

Low-Trap-Density CsPbX3 Film for High-Efficiency Indoor Photovoltaics.

The continuous advancement of the Internet of Things (IoT) and photovoltaic technology has promoted the development of indoor photovoltaics (IPVs) that powers wireless devices. Nowadays, the CsPbX3 perovskite has received widespread attention because of its high power conversion efficiency (PCE) in an indoor environment and suitable band gap for IPVs. In this work, we regulated the thickness of the photoactive layer (to optimize the carrier transport process without affecting indoor absorption) and bromine substitution (to adjust the band gap and improve the quality of the film) to reduce trap-assisted carrier recombination. A CsPbI2.7Br0.3 perovskite cell with excellent performance was obtained, which is superior to c-Si cells in a low-light environment. The optimized device achieved PCE values of 32.69 and 33.11% under a 1000 lux fluorescent lamp and white light-emitting diode (WLED) illumination. The J-V hysteresis of the device is also effectively suppressed. Moreover, it has a steady-state output power of 7.76 µW (0.09 cm2, and can be enhanced by enlarging the areas), which can meet the consumption of many small wireless devices. It is worth noting that the optimized device has excellent applicability to be used in a complex indoor environment.

Copper-based metal halides for X-ray and photodetection.

Copper-based metal halides have become important materials in the field of X-ray and photodetection due to their excellent optical properties, good environmental stability and low toxicity. This review presents the progress of research on crystal structure/morphology, photophysics/optical properties and applications of copper-based metal halides. We also discuss the challenges of copper-based metal halides with a perspective of their future research directions.

Origin, Influence, and Countermeasures of Defects in Perovskite Solar Cells.

Defects are considered to be one of the most significant factors that compromise the power conversion efficiencies and long-term stability of perovskite solar cells. Therefore, it is urgent to have a profound understanding of their formation and influence mechanism, so as to take corresponding measures to suppress or even completely eliminate their adverse effects on device performance. Herein, the possible origins of the defects in metal halide perovskite films and their impacts on the device performance are analyzed, and then various methods to reduce defect density are introduced in detail. Starting from the internal and interfacial aspects of the metal halide perovskite films, several ways to improve device performance and long-term stability including additive engineering, surface passivation, and other physical treatments (annealing engineering), etc., are further elaborated. Finally, the further understanding of defects and the development trend of passivation strategies are prospected.