Glass Disorder Modulated Luminescence in Zero-Dimensional Antimony-Chloride Coplanar Dimers for Optical Anti-counterfeiting.

Zero-dimensional metal halides have received wide attention due to their structural diversity, strong quantum confinement, and associated excellent photoluminescence properties. A reversible and tunable luminescence would be desirable for applications such as anti-counterfeiting, information encryption, and artificial intelligence. Yet, these materials are underexplored, with little known about their luminescence tuning mechanisms. Here we report a pyramidal coplanar dimer, (TBA)Sb2Cl7 (TBA = tetrabutylammonium), showing broadband emission wavelength tuning (585-650 nm) by simple thermal treatment. We attribute the broad color change to structural disorder induced by varying the heat treatment temperatures. Increasing the heating temperature transitions the material from long-range ordered crystalline phase to highly disordered glassy phase. The latter exhibits stronger electron-phonon coupling, enhancing the self-trapped exciton emission efficiency. The work provides a new material platform for manifold optical anti-counterfeiting applications and sheds light on the emission color tuning mechanisms for further design of stimuli-responsive materials.

Regulating Surface-Passivator Binding Priority for Efficient Perovskite Light-Emitting Diodes.

Suppressing trap-assisted nonradiative losses through passivators is a prerequisite for efficient perovskite light-emitting diodes (PeLEDs). However, the complex bonding between passivators and perovskites severely suppresses the passivation process, which still lacks comprehensive understanding. Herein, the number, category, and degree of bonds between different functional groups and the perovskite are quantitatively assessed to study the passivation dynamics. Functional groups with high electrostatic potential and large steric hindrance prioritize strong bonding with organic cations and halides on the perfect surface, leading to suppressed coordination with bulky defects. By modulating the binding priorities and coordination capacity, hindrance from the intense interaction with perfect perovskite is significantly reduced, leading to a more direct passivation process. Consequently, the near-infrared PeLED without external light out-coupling demonstrates a record external quantum efficiency of 24.3% at a current density of 42 mA cm-2. In addition, the device exhibits a record-level-cycle ON/OFF switching of 20 000 and ultralong half-lifetime of 1126.3 h under 5 mA cm-2. An in-depth understanding of the passivators can offer new insights into the development of high-performance PeLEDs.

Charge Injection and Auger Recombination Modulation for Efficient and Stable Quasi-2D Perovskite Light-Emitting Diodes.

The inefficient charge transport and large exciton binding energy of quasi-2D perovskites pose challenges to the emission efficiency and roll-off issues for perovskite light-emitting diodes (PeLEDs) despite excellent stability compared to 3D counterparts. Herein, alkyldiammonium cations with different molecular sizes, namely 1,4-butanediamine (BDA), 1,6-hexanediamine (HDA) and 1,8-octanediamine (ODA), are employed into quasi-2D perovskites, to simultaneously modulate the injection efficiency and recombination dynamics. The size increase of the bulky cation leads to increased excitonic recombination and also larger Auger recombination rate. Besides, the larger size assists the formation of randomly distributed 2D perovskite nanoplates, which results in less efficient injection and deteriorates the electroluminescent performance. Moderate exciton binding energy, suppressed 2D phases and balanced carrier injection of HDA-based PeLEDs contribute to a peak external quantum efficiency of 21.9%, among the highest in quasi-2D perovskite based near-infrared devices. Besides, the HDA-PeLED shows an ultralong operational half-lifetime T50 up to 479 h at 20 mA cm‒2, and sustains the initial performance after a record-level 30 000 cycles of ON-OFF switching, attributed to the suppressed migration of iodide anions into adjacent layers and the electrochemical reaction in HDA-PeLEDs. This work provides a potential direction of cation design for efficient and stable quasi-2D-PeLEDs.

Boosting exciton mobility approaching Mott-Ioffe-Regel limit in Ruddlesden-Popper perovskites by anchoring the organic cation.

Exciton transport in two-dimensional Ruddlesden-Popper perovskite plays a pivotal role for their optoelectronic performance. However, a clear photophysical picture of exciton transport is still lacking due to strong confinement effects and intricate exciton-phonon interactions in an organic-inorganic hybrid lattice. Herein, we present a systematical study on exciton transport in (BA)2(MA)n-1PbnI3n+1 Ruddlesden-Popper perovskites using time-resolved photoluminescence microscopy. We reveal that the free exciton mobilities in exfoliated thin flakes can be improved from around 8 cm2 V-1 s-1 to 280 cm2V-1s-1 by anchoring the soft butyl ammonium cation with a polymethyl methacrylate network at the surface. The mobility of the latter is close to the theoretical limit of Mott-Ioffe-Regel criterion. Combining optical measurements and theoretical studies, it is unveiled that the polymethyl methacrylate network significantly improve the lattice rigidity resulting in the decrease of deformation potential scattering and lattice fluctuation at the surface few layers. Our work elucidates the origin of high exciton mobility in Ruddlesden-Popper perovskites and opens up avenues to regulate exciton transport in two-dimensional materials.

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.

Uncovering the mechanisms of efficient upconversion in two-dimensional perovskites with anti-Stokes shift up to 220 meV.

Phonon-assisted photon upconversion holds great potential for numerous applications, e.g., optical refrigeration. However, traditional semiconductors face energy gain limitations due to thermal energy, typically achieving only ~25 milli-electron volts at room temperature. Here, we demonstrate that quasi-two-dimensional perovskites, with a soft hybrid organic-inorganic lattice, can efficiently upconvert photons with an anti-Stokes shift exceeding 200 milli-electron volts. By using microscopic transient absorption measurements and density functional theory calculations, we explicate that the giant energy gain stems from strong lattice fluctuation leading to a picosecond timescale transient band energy renormalization with a large energy variation of around ±180 milli-electron volts at room temperature. The motion of organic molecules drives the deformation of inorganic framework, providing energy and local states necessary for efficient upconversion within a time constant of around 1 ps. These results establish a deep understanding of perovskite-based photon upconversion and offer previously unknown insights into the development of various upconversion applications.

Photon-recycling effect in perovskites for photovoltaic applications: a Monte Carlo study.

Photon recycling has been shown to play an important role in the optoelectronic properties and device performance of perovskite solar cells recently. However, there lacks an analytical method to accurately predict the dynamics of charge carriers and photons and the device performance with photon recycling due to the complexity of multiple electron-photon conversion processes involved in photon recycling. We propose a model based on the Monte Carlo simulation method that combines charge carrier diffusion and photon radiation transport to analyze the effects of photon recycling on electron-photon dynamics and device performance of perovskite solar cells. We show that the carrier lifetime can be significantly boosted by photon recycling in the radiative limit, which yields a 37 meV increase in the open-circuit voltage for a 500 nm thick perovskite solar cell. Our results provide insights for the working mechanisms of perovskite solar cells, and the new model can be further applied to other types of solar cells with photon recycling.

3D DCT Based Image Compression Method for the Medical Endoscopic Application.

This paper proposes a novel 3D discrete cosine transform (DCT) based image compression method for medical endoscopic applications. Due to the high correlation among color components of wireless capsule endoscopy (WCE) images, the original 2D Bayer data pattern is reconstructed into a new 3D data pattern, and 3D DCT is adopted to compress the 3D data for high compression ratio and high quality. For the low computational complexity of 3D-DCT, an optimized 4-point DCT butterfly structure without multiplication operation is proposed. Due to the unique characteristics of the 3D data pattern, the quantization and zigzag scan are ameliorated. To further improve the visual quality of decompressed images, a frequency-domain filter is proposed to eliminate the blocking artifacts adaptively. Experiments show that our method attains an average compression ratio (CR) of 22.94:1 with the peak signal to noise ratio (PSNR) of 40.73 dB, which outperforms state-of-the-art methods.

The compatibility of methylammonium and formamidinium in mixed cation perovskite: the optoelectronic and stability properties.

The methylammonium (MA) and formamidinium (FA) are the most commonly used organic cations in perovskite solar cells (PSCs), whereas the impact of size and polarity differences between these two on the photovoltaic performances has been rarely revealed. Herein, we systematically investigated the phase distribution, optoelectronic and stability properties of FA-MA mixed perovskites. To identify the phase homogeneity, depth-dependent grazing-incidence wide-angle x-ray scattering measurements were employed, which demonstrates that the mixed cation perovskite possesses a FA-rich phase on the film surface and the bottom is comprised of MA-rich phase. Additionally, upon long-time illumination, a new PL peak is appeared at 778 nm, representing the generation of MA-rich phase induced by ion migration. It is worth noting that the phase splitting and inhomogeneous phase distribution would not bring any obvious detrimental effects to the photovoltaic performances and stability properties. Through judiciously tuning the cation proportion in pure-iodide perovskite, the additive-free PSCs achieve an efficiency as high as 20.7%. Furthermore, the PSCs with a broad range of FA/MA ratios show improved humidity/thermal/light stability despite the phase inhomogeneity. Therefore, the work shows that the MA and FA cations have a high compatibility in perovskite structure and the precise ratio control can further improve the performances.

Green perovskite light-emitting diodes with simultaneous high luminance and quantum efficiency through charge injection engineering.

Metal halide perovskite light emitting diodes (PeLEDs) have recently experienced rapid development due to the tunable emission wavelengths, narrow emission linewidth and low material cost. To achieve state-of-the-art performance, the high photoluminescence quantum yield (PLQY) of the active emission layer, the balanced charge injection, and the optimized optical extraction should be considered simultaneously. Multiple chemical passivation strategies have been provided as controllable and efficient methods to improve the PLQY of the perovskite layer. However, high luminance under large injection current and high external quantum efficiency (EQE) can hardly be achieved due to Auger recombination at high carrier density. Here, we decreased the electron injection barrier by tuning the Fermi-level of the perovskite, leading to a reduced turn on voltage. Through molecular doping of the hole injection material, a more balanced hole injection was achieved. At last, a device with modified charge injection realizes high luminance and quantum efficiency simultaneously. The best device exhibits luminance of 55,000 cd m-2, EQE of 8.02% at the working voltage of 2.65 V, current density of 115 mA cm-2, and shows EQE T50 stability around 160 min at 100 mA cm-2 injection current density.

Graphene controlled Brewster angle device for ultra broadband terahertz modulation.

Terahertz modulators with high tunability of both intensity and phase are essential for effective control of electromagnetic properties. Due to the underlying physics behind existing approaches there is still a lack of broadband devices able to achieve deep modulation. Here, we demonstrate the effect of tunable Brewster angle controlled by graphene, and develop a highly-tunable solid-state graphene/quartz modulator based on this mechanism. The Brewster angle of the device can be tuned by varying the conductivity of the graphene through an electrical gate. In this way, we achieve near perfect intensity modulation with spectrally flat modulation depth of 99.3 to 99.9 percent and phase tunability of up to 140 degree in the frequency range from 0.5 to 1.6 THz. Different from using electromagnetic resonance effects (for example, metamaterials), this principle ensures that our device can operate in ultra-broadband. Thus it is an effective principle for terahertz modulation.

Adaptive Image Enhancement Based on Guide Image and Fraction-Power Transformation for Wireless Capsule Endoscopy.

Good image quality of the wireless capsule endoscopy (WCE) is the key for doctors to diagnose gastrointestinal (GI) tract diseases. However, the poor illumination, limited performance of the camera in WCE, and complex environment in the GI tract usually result in low-quality endoscopic images. Existing image enhancement methods only use the information of the image itself or multiple images of the same scene to accomplish the enhancement. In this paper, we propose an adaptive image enhancement method based on guide image and fraction-power transformation. First, intensities of endoscopic images are analyzed to assess the illumination conditions. Second, images captured under poor illumination conditions are enhanced by a brand-new image enhancement method called adaptive guide image based enhancement (AGIE). AGIE enhances low-quality images by using the information of a good quality image of the similar scene. Otherwise, images are enhanced by the proposed adaptive fraction-power transformation. Experimental results show that the proposed method improves the average intensity of endoscopic images by 64.20% and the average local entropy by 31.25%, which outperforms the state-of-art methods.

Abnormal Synergetic Effect of Organic and Halide Ions on the Stability and Optoelectronic Properties of a Mixed Perovskite via In Situ Characterizations.

The mixed cation lead mixed halide perovskite (MLMP) Csx FA1-x PbIy Br3-y is one of the most promising candidates for both single-junction and tandem solar cells due to its high efficiency and remarkable stability. However, the composition effect on thermal stability and photovoltaic performances has not yet been comprehensively investigated. Therefore, the interplay between composition, crystal structure, morphology, and optoelectronic properties under heat stress, is systematically elucidated here through a series of in situ characterizations. It is revealed for the first time that the FA+ and Br- release synchronously at first even under mild annealing. This leads to a serious FA- and Br-deficiency issue, with only 88.3% of Br and 90.2% of FA retained after annealing at 100 °C, which significantly magnifies the hysteresis, phase segregation, and instability issues. Finally, a trace amount of FA+ and Br- is introduced onto the post-annealed MLMP surface to compensate for the deficiency through vacancy filling. The degradation lifetime to 80% of the initial efficiency (t80 ) is improved from 504 to 1056 h and the hysteresis issue is also well resolved. This work highlights the importance of the synergetic composition effect of the organic cation and halide anion on stability and efficiency optimization for long-term applications.

Flexible Piezoelectric-Induced Pressure Sensors for Static Measurements Based on Nanowires/Graphene Heterostructures.

The piezoelectric effect is widely applied in pressure sensors for the detection of dynamic signals. However, these piezoelectric-induced pressure sensors have challenges in measuring static signals that are based on the transient flow of electrons in an external load as driven by the piezopotential arisen from dynamic stress. Here, we present a pressure sensor with nanowires/graphene heterostructures for static measurements based on the synergistic mechanisms between strain-induced polarization charges in piezoelectric nanowires and the caused change of carrier scattering in graphene. Compared to the conventional piezoelectric nanowire or graphene pressure sensors, this sensor is capable of measuring static pressures with a sensitivity of up to 9.4 × 10-3 kPa-1 and a fast response time down to 5-7 ms. This demonstration of pressure sensors shows great potential in the applications of electronic skin and wearable devices.

Synergistic Effects of Plasmonics and Electron Trapping in Graphene Short-Wave Infrared Photodetectors with Ultrahigh Responsivity.

Graphene's unique electronic and optical properties have made it an attractive material for developing ultrafast short-wave infrared (SWIR) photodetectors. However, the performance of graphene SWIR photodetectors has been limited by the low optical absorption of graphene as well as the ultrashort lifetime of photoinduced carriers. Here, we present two mechanisms to overcome these two shortages and demonstrate a graphene-based SWIR photodetector with high responsivity and fast photoresponse. In particular, a vertical built-in field is employed in the graphene channel for trapping the photoinduced electrons and leaving holes in graphene, which results in prolonged photoinduced carrier lifetime. On the other hand, plasmonic effects were employed to realize photon trapping and enhance the light absorption of graphene. Thanks to the above two mechanisms, the responsivity of this proposed SWIR photodetector is up to a record of 83 A/W at a wavelength of 1.55 µm with a fast rising time of less than 600 ns. This device design concept addresses key challenges for high-performance graphene SWIR photodetectors and is promising for the development of mid/far-infrared optoelectronic applications.

Facet-Dependent Property of Sequentially Deposited Perovskite Thin Films: Chemical Origin and Self-Annihilation.

Quantification of intergrain length scale properties of CH3NH3PbI3 (MAPbI3) can provide further understanding of material physics, leading to improved device performance. In this work, we noticed that two typical types of facets appear in sequential deposited perovskite (SDP) films: smooth and steplike morphologies. By mapping the surface potential as well as the photoluminescence (PL) peak position, we revealed the heterogeneity of SDP thin films that smooth facets are almost intrinsic with a PL peak at 775 nm, while the steplike facets are p-type-doped with 5-nm blue-shifted PL peak. Considering the reaction process, we propose that the smooth facets have well-defined crystal lattices that resulted from the interfacial reaction between MAI and PbI2 domains containing low trap states density. The steplike facets are MAI-rich originated from the grain boundaries of PbI2 film and own more trap states. Conversion of steplike facets to smooth facets can be controlled by increasing the reaction time through Ostwald ripening. The improved stability, photoresponsivity up to 0.3 A/W, on/off ratio up to 3900, and decreased photo response time to ∼160 µs show that the trap states can be annihilated effectively to improve the photoelectrical conversion with prolonged reaction time and elimination of steplike facets. Our findings demonstrate the relationship between the facet heterogeneity of SDP films and crystal growth process for the first time, and imply that the systematic control of crystal grain modification will enable amelioration of crystallinity for more-efficient perovskite photoelectrical applications.

Nonstoichiometric acid-base reaction as reliable synthetic route to highly stable CH3NH3PbI3 perovskite film.

Perovskite solar cells have received worldwide interests due to swiftly improved efficiency but the poor stability of the perovskite component hampers the device fabrication under normal condition. Herein, we develop a reliable nonstoichiometric acid-base reaction route to stable perovskite films by intermediate chemistry and technology. Perovskite thin-film prepared by nonstoichiometric acid-base reaction route is stable for two months with negligible PbI2-impurity under ∼65% humidity, whereas other perovskites prepared by traditional methods degrade distinctly after 2 weeks. Route optimization involves the reaction of PbI2 with excess HI to generate HPbI3, which subsequently undergoes reaction with excess CH3NH2 to deliver CH3NH3PbI3 thin films. High quality of intermediate HPbI3 and CH3NH2 abundance are two important factors to stable CH3NH3PbI3 perovskite. Excess volatile acid/base not only affords full conversion in nonstoichiometric acid-base reaction route but also permits its facile removal for stoichiometric purification, resulting in average efficiency of 16.1% in forward/reverse scans.

Ultrathin efficient perovskite solar cells employing a periodic structure of a composite hole conductor for elevated plasmonic light harvesting and hole collection.

We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure composite (PMC) HTM in combination with the conformal Au electrode could promote the absorption through the enhanced cavity effects, leading to comparable absorption even using much thinner perovskite (240 nm). We identified that the cavity was the combination of Fabry-Pérot interferometer and surface plasmonic resonance, with light harvesting enhancement through surface plasmon polariton or waveguide modes that propagate in the plane of the perovskite layer. On the other hand, the PMC HTM increased hole conductivity by one order of magnitude with respect to standard spiro-OMeTAD HTM due to molecular packing and self-assembly, embodying traceable hole mobility and density elevation up to 3 times, and thus the hysteresis was greatly avoided. Owing to dual optical and electronic enhancement, the PMC PSC afforded high efficiency PSC using as thin as 240 nm perovskite layer, delivering a V(oc) of 1.05 V, J(sc) of 22.9 mA cm(-2), FF of 0.736, and efficiency amounting to 17.7% PCE, the highest efficiency with ultrathin perovskite layer.

Hybrid halide perovskite solar cell precursors: colloidal chemistry and coordination engineering behind device processing for high efficiency.

The precursor of solution-processed perovskite thin films is one of the most central components for high-efficiency perovskite solar cells. We first present the crucial colloidal chemistry visualization of the perovskite precursor solution based on analytical spectra and reveal that perovskite precursor solutions for solar cells are generally colloidal dispersions in a mother solution, with a colloidal size up to the mesoscale, rather than real solutions. The colloid is made of a soft coordination complex in the form of a lead polyhalide framework between organic and inorganic components and can be structurally tuned by the coordination degree, thereby primarily determining the basic film coverage and morphology of deposited thin films. By utilizing coordination engineering, particularly through employing additional methylammonium halide over the stoichiometric ratio for tuning the coordination degree and mode in the initial colloidal solution, along with a thermal leaching for the selective release of excess methylammonium halides, we achieved full and even coverage, the preferential orientation, and high purity of planar perovskite thin films. We have also identified that excess organic component can reduce the colloidal size of and tune the morphology of the coordination framework in relation to final perovskite grains and partial chlorine substitution can accelerate the crystalline nucleation process of perovskite. This work demonstrates the important fundamental chemistry of perovskite precursors and provides genuine guidelines for accurately controlling the high quality of hybrid perovskite thin films without any impurity, thereby delivering efficient planar perovskite solar cells with a power conversion efficiency as high as 17% without distinct hysteresis owing to the high quality of perovskite thin films.