Symmetry‐Reduction Enhanced Polarization‐Sensitive Photodetection in Core–Shell SbI3/Sb2O3 van der Waals Heterostructure

Structural symmetry is a simple way to quantify the anisotropic properties of materials toward unique device applications including anisotropic transportation and polarization‐sensitive photodetection. The enhancement of anisotropy can be achieved by artificial symmetry‐reduction design. A core–shell SbI₃/Sb₂O₃ nanowire, a heterostructure bonded by van der Waals forces, is introduced as an example of enhancing the performance of polarization‐sensitive photodetectors via symmetry reduction. The structural, vibrational, and optical anisotropies of such core–shell nanostructures are systematically investigated. It is found that the anisotropic absorbance of a core–shell nanowire is obviously higher than that of two single compounds from both theoretical and experimental investigations. Anisotropic photocurrents of the polarization‐sensitive photodetectors based on these core–shell SbI₃/Sb₂O₃ van der Waals nanowires are measured ranging from ultraviolet (UV) to visible light (360–532 nm). Compared with other van der Waals 1D materials, low anisotropy ratio (I_max/I_min) is measured based on SbI₃ but a device based on this core–shell nanowire possesses a relatively high anisotropy ratio of ≈3.14 under 450 nm polarized light. This work shows that the low‐symmetrical core–shell van der Waals heterostructure has large potential to be applied in wide range polarization‐sensitive photodetectors.     

Highly‐Anisotropic Dion–Jacobson Hybrid Perovskite by Tailoring Diamine into CsPbBr3 for Polarization‐Sensitive Photodetection

2D materials with inherent attributes of structural anisotropy have been well applied in the field of polarization‐sensitive photodetection. However, to explore new 2D members with strong polarized‐light responses still remains a challenge. Herein, by alloying diamine molecule into the 3D prototype of CsPbBr₃, a new Dion–Jacobson (DJ) type 2D perovskite of (HDA)CsPb₂Br₇ ( 1 , where HDA²⁺ is 1,6‐hexamethylenediammonium), containing both inorganic Cs metal and organic cations is designed. The natural anisotropy characteristics of 1 are solidly elucidated by analyzing crystal structure, electric conductivity, and optical properties. Strikingly, distinct polarization‐sensitive responses are observed in 1 , owing to its strong anisotropy of optical absorption (the ratio of α_c/α_b ≈ 2.2). Consequently, crystal‐based detectors of 1 exhibit fascinating photo‐activities to polarized‐light, including high detectivity (1.5 × 10⁹ Jones), large dichroism ratio (I_ph^c/I_ph^b ≈ 1.6) and fast responding rate (200 µs). All these polarization‐sensitive performances along with intriguing phase stability make 1 a potential candidate for polarized‐light detection. This work paves a pathway toward new functionalities of DJ‐type 2D hybrid perovskites for their future optoelectronic device applications.     

Fabry–Pérot Oscillation and Room Temperature Lasing in Perovskite Cube‐Corner Pyramid Cavities

Recently, organometal halide perovskite‐based optoelectronics, particularly lasers, have attracted intensive attentions because of its outstanding spectral coherence, low threshold, and wideband tunability. In this work, high‐quality CH₃NH₃PbBr₃ single crystals with a unique shape of cube‐corner pyramids are synthesized on mica substrates using chemical vapor deposition method. These micropyramids naturally form cube‐corner cavities, which are eminent candidates for small‐sized resonators and retroreflectors. The as‐grown perovskites show strong emission ≈530 nm in the vertical direction at room temperature. A special Fabry–Pérot (F–P) mode is employed to interpret the light confinement in the cavity. Lasing from the perovskite pyramids is observed from 80 to 200 K, with threshold ranging from ≈92 µJ cm^?2 to 2.2 mJ cm^?2, yielding a characteristic temperature of T₀ = 35 K. By coating a thin layer of Ag film, the threshold is reduced from ≈92 to 26 µJ cm^?2, which is accompanied by room temperature lasing with a threshold of ≈75 µJ cm^?2. This work advocates the prospect of shape‐engineered perovskite crystals toward developing micro‐sized optoelectronic devices and potentially investigating light–matter coupling in quantum optics.     

Two‐Photon Up‐Conversion Photoluminescence Realized through Spatially Extended Gap States in Quasi‐2D Perovskite Films

A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D perovskite films [(PEA)₂(MA)₄Pb₅Br₁₆ with n = 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.     

Anisotropic Broadband Photoresponse of Layered Type‐II Weyl Semimetal MoTe2

Photodetectors based on Weyl semimetal promise extreme performance in terms of highly sensitive, broadband and self‐powered operation owing to its extraordinary material properties. Layered Type‐II Weyl semimetal that break Lorentz invariance can be further integrated with other two‐dimensional materials to form van der Waals heterostructures and realize multiple functionalities inheriting the advantages of other two‐dimensional materials. Herein, we report the realization of a broadband self‐powered photodetector based on Type‐II Weyl semimetal T_d‐MoTe₂. The prototype metal–MoTe₂–metal photodetector exhibits a responsivity of 0.40 mA W^?1 and specific directivity of 1.07 × 10⁸ Jones with 43 μs response time at 532 nm. Broadband responses from 532 nm to 10.6 μm are experimentally tested with a potential detection range extendable to far‐infrared and terahertz. Furthermore, we identify the response of the detector is polarization angle sensitive due to the anisotropic response of MoTe₂. The anisotropy is found to be wavelength dependent, and the degree of anisotropy increases as the excitation wavelength gets closer to the Weyl nodes. In addition, with power and temperature dependent photoresponse measurements, the photocurrent generation mechanisms are investigated. Our results suggest this emerging class of materials can be harnessed for broadband angle sensitive, self‐powered photodetection with decent responsivities.     

Vacuum‐Drying Processed Micrometer‐Thick Stable CsPbBr3 Perovskite Films with Efficient Blue‐To‐Green Photoconversion

Metal halide perovskite materials have attracted great attention owing to their fascinating optoelectronic characteristics and low cost fabrication via facile solution processing. One of the potential applications of these materials is to employ them as color‐conversion layers (CCLs) for visible blue light to achieve full‐color displays. However, obtaining thick perovskite films to realize complete color conversion is a key challenge. Here, the fabrication of micrometer‐level thick CsPbBr₃ perovskite films is presented through a facile vacuum drying approach. An efficient green photoconversion is realized in a 3.8 µm thick film from blue light @ 463 nm. For a back luminance of 1000 cd m^?2, the brightness of the resulting green emission can reach as high as 200 cd m^?2. Furthermore, only ≈2% of decay in brightness is observed when the films are tested after 18 days of exposure to ambient environment. In addition, a potential design is also proposed for full‐color displays with perovskite materials incorporated as CCLs.     

High‐Performance Inverted Planar Perovskite Solar Cells Enhanced by Thickness Tuning of New Dopant‐Free Hole Transporting Layer

A new hole transporting material (HTM) named DMZ is synthesized and employed as a dopant‐free HTM in inverted planar perovskite solar cells (PSCs). Systematic studies demonstrate that the thickness of the hole transporting layer can effectively enhance the morphology and crystallinity of the perovskite layer, leading to low series resistance and less defects in the crystal. As a result, the champion power conversion efficiency (PCE) of 18.61% with J_SC = 22.62 mA cm^?2, V_OC = 1.02 V, and FF = 81.05% (an average one is 17.62%) is achieved with a thickness of ≈13 nm of DMZ (2 mg mL^?1) under standard global AM 1.5 illumination, which is ≈1.5 times higher than that of devices based on poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT:PSS). More importantly, the devices based on DMZ exhibit a much better stability (90% of maximum PCE retained after more than 556 h in air (relative humidity ≈ 45%–50%) without any encapsulation) than that of devices based on PEDOT:PSS (only 36% of initial PCE retained after 77 h in same conditions). Therefore, the cost‐effective and facile material named DMZ offers an appealing alternative to PEDOT:PSS or polytriarylamine for highly efficient and stable inverted planar PSCs.     

Room‐Temperature Active Modulation of Valley Dynamics in a Monolayer Semiconductor through Chiral Purcell Effects

Spin‐dependent contrasting phenomena at K and K′ valleys in monolayer semiconductors have led to addressable valley degree of freedom, which is the cornerstone for emerging valleytronic applications in information storage and processing. Tunable and active modulation of valley dynamics in a monolayer WSe₂ is demonstrated at room temperature through controllable chiral Purcell effects in plasmonic chiral metamaterials. The strong spin‐dependent modulation on the spontaneous decay of valley excitons leads to tunable handedness and spectral shift of valley‐polarized emission, which is analyzed and predicted by an advanced theoretical model and further confirmed by experimental measurements. Moreover, large active spectral tuning (≈24 nm) and reversible ON/OFF switching of circular polarization of emission are achieved by the solvent‐controllable thickness of the dielectric spacer in the metamaterials. With the on‐demand and active tunability in valley‐polarized emission, chiral Purcell effects can provide new strategies to harness valley excitons for applications in ultrathin valleytronic devices.     

From Nonluminescent to Blue‐Emitting Cs4PbBr6 Nanocrystals: Tailoring the Insulator Bandgap of 0D Perovskite through Sn Cation Doping

All‐inorganic cesium lead halide perovskite nanocrystals (NCs) with different dimensionalities have recently fascinated the research community due to their extraordinary optoelectronic performance such as tunable bandgaps over the entire visible spectral region. However, compared to well‐developed 3D CsPbX₃ perovskites (X = Cl, Br, and I), the bandgap tuning in 0D Cs₄PbX₆ perovskite NCs remains an arduous task. Herein, a simple but valid strategy is proposed to tailor the insulator bandgap (≈3.96 eV) of Cs₄PbBr₆ NCs to the blue spectral region by changing the local coordination environment of isolated [PbBr₆]^4? octahedra in the Cs₄PbBr₆ crystal through Sn cation doping. Benefitting from the unique Pb²⁺‐poor and Br^?‐rich reaction environment, the Sn cation is successfully introduced into the Cs₄PbBr₆ NCs, forming coexisting point defects comprising substitutional Sn_Pb and interstitial Br_i, thereby endowing these theoretically nonluminescent Cs₄PbBr₆ NCs with an ultranarrow blue emission at ≈437 nm (full width at half maximum, ≈12 nm). By combining the experimental results with first‐principles calculations, an unusual electronic dual‐bandgap structure, comprising the newly emerged semiconducting bandgap of ≈2.87 eV and original insulator bandgap of ≈3.96 eV, is found to be the underlying fundamental reason for the ultranarrow blue emission.     

Surface-2D/Bulk-3D Heterophased Perovskite Nanograins for Long-Term-Stable Light-Emitting Diodes

Although metal halide perovskite (MHP) light-emitting diodes (LEDs) have demonstrated great potential in terms of electroluminescence efficiency, the operational stability of MHP LEDs currently remains the biggest bottleneck toward their practical usage. Well-confined excitons/charge carriers in a dielectric/quantum well based on conventional spatial or potential confinement approaches substantially enhance radiative recombination in MHPs, but an increased surface-to-volume ratio and multiphase interfaces likely result in a high degree of surface or interface defect states, which brings about a critical environmentally/operationally vulnerable point on LED stability. Here, an effective solution is suggested to mitigate such drawbacks using strategically designed surface-2D/bulk-3D heterophased MHP nanograins for long-term-stable LEDs. The 2D surface-functionalized MHP renders significantly reduced trap density, environmental stability, and an ion-migration-immune surface in addition to a fast radiative recombination owing to its spatially and potentially confined charge carriers, simultaneously. As a result, heterophased MHP LEDs show substantial improvement in operational lifetime (T₅₀: >200 h) compared to conventional pure 3D or quasi-2D counterparts (T₅₀: < 0.2 h) as well as electroluminescence efficiency (surface-2D/bulk-3D: ≈7.70 ph per el% and pure 3D: ≈0.46 ph per el%).     

Large-scale SnO2 nanowires synthesized by direct sublimation method and their enhanced dielectric responses

In this paper, we developed a direct sublimation method to synthesize large-scale rutile SnO₂ nanowires on 6H–SiC substrate using SnO₂ nanoparticles as starting material. The structural properties of these straight nanowires were investigated in detail. These nanowires grow along [121], and the average diameter and length of these nanowires are 80 nm and 5 μm, respectively. In addition, the dielectric measurement indicates that the dielectric response of the SnO₂ nanowires is significantly enhanced in the low-frequency range. It is suggested that both the rotation direction polarization (RDP) and the space charge polarization (SCP) process should be responsible for the enhancement of ε_r of these SnO₂ nanowires.     

Lead‐Free Halide Rb2CuBr3 as Sensitive X‐Ray Scintillator

Scintillators are widely utilized for radiation detections in many fields, such as nondestructive inspection, medical imaging, and space exploration. Lead halide perovskite scintillators have recently received extensive research attention owing to their tunable emission wavelength, low detection limit, and ease of fabrication. However, the low light yields toward X‐ray irradiation and the lead toxicity of these perovskites severely restricts their practical application. A novel lead‐free halide is presented, namely Rb₂CuBr₃, as a scintillator with exceptionally high light yield. Rb₂CuBr₃ exhibits a 1D crystal structure and enjoys strong carrier confinement and near‐unity photoluminescence quantum yield (98.6%) in violet emission. The high photoluminescence quantum yield combined with negligible self‐absorption from self‐trapped exciton emission and strong X‐ray absorption capability enables a record high light yield of ≈91056 photons per MeV among perovskite and relative scintillators. Overall, Rb₂CuBr₃ provides nontoxicity, high radioluminescence intensity, and good stability, thus laying good foundations for potential application in low‐dose radiography.     

Strongly Coupled Tin‐Halide Perovskites to Modulate Light Emission: Tunable 550–640 nm Light Emission (FWHM 36–80 nm) with a Quantum Yield of up to 6.4%

Colloidal perovskite quantum dots represent one of the most promising materials for applications in solar cells and photoluminescences. These devices require a low density of crystal defects and a high yield of photogenerated carriers, which are difficult to realize in tin‐halide perovskite because of the intrinsic instability of tin during nucleation. Here, an enhancement in the luminescent property of tin‐halide perovskite nanoplates (TPNPs) that are composed of strongly coupled layered structures with the chemical formula of PEA₂SnX₄ (PEA = C₆H₅(CH₂)₂NH₃, X = Br, I) is reported. TPNPs (X = I) show an emission at a wavelength of 640 nm, with high quantum yield of 6.40 ± 0.14% and full width at half maximum (FWHM) as small as 36 nm. The presence of aliphatic carboxylic acid is found to play a key role in reducing the tin perovskite defect density, which significantly improves the emission intensity and stability of TPNPs. Upon mixing iodo‐ and bromo‐ precursors, the emission wavelength is successfully tuned from 640 nm (PEA₂SnI₄) to 550 nm (PEA₂SnBr₄), with a corresponding emission quantum yield and FWHM of 0.16–6.40% and 36–80 nm, respectively. The results demonstrate a major advance for the emission yield and tunability of tin‐halide perovskites.     

MXene‐Derived Ferroelectric Crystals

This study demonstrates the first synthesis of MXene‐derived ferroelectric crystals. Specifically, high‐aspect‐ratio potassium niobate (KNbO₃) ferroelectric crystals is successfully synthesized using 2D Nb₂C, MXene, and potassium hydroxide (KOH) as the niobium and potassium source, respectively. Material analysis confirms that a KNbO₃ orthorhombic phase with Amm2 symmetry is obtained. Additionally, ferroelectricity in KNbO₃ is confirmed using standard ferroelectric, dielectric, and piezoresponse force microscopy measurements. The KNbO₃ crystals exhibit a saturated polarization of ≈21 µC cm^?2, a remnant polarization of ≈17 µC cm^?2, and a coercive field of ≈50 kV cm^?1. This discovery illustrates that the 2D nature of MXenes can be exploited to grow ferroelectric crystals.     

Schottky Barrier‐Controlled Black Phosphorus/Perovskite Phototransistors with Ultrahigh Sensitivity and Fast Response

Phototransistors are recognized as highly sensitive photodetectors owing to their high gain induced by a photogating effect. However, the response speed of a typical phototransistor is rather slow due to the long lifetime of trapped carriers in the channel. Here, a novel Schottky barrier‐controlled phototransistor that shows ultrahigh sensitivity as well as a fast response speed is reported. The device is based on a channel of few‐layer black phosphorous modified with a MAPbI_3?xCl_x perovskite layer, whose channel current is limited by the Schottky barrier at the source electrode. The photoresponse speed of the device can be tuned by changing the drain voltage, which is attributed to a field‐assisted detrapping process of electrons in the perovskite layer close to the Schottky barrier. Under optimal conditions, the device exhibits a high responsivity of 10⁶–10⁸ A W^?1, an ultrahigh specific detectivity up to 9 × 10¹³ Jones, and a response time of ≈10 ms.     

Strong and Tunable Electrical Anisotropy in Type‐II Weyl Semimetal Candidate WP2 with Broken Inversion Symmetry

A transition metal diphosphide, WP₂, is a candidate for type‐II Weyl semimetals (WSMs) in which spatial inversion symmetry is broken and Lorentz invariance is violated. As one of the prerequisites for the presence of the WSM state in WP₂, spatial inversion symmetry breaking in this compound has rarely been investigated. Furthermore, the anisotropy of the WP₂ electrical properties and whether its electrical anisotropy can be tuned remain elusive. Angle‐resolved polarized Raman spectroscopy, electrical transport, optical spectroscopy, and first‐principle studies of WP₂ are reported. The energies of the observed Raman‐active phonons and the angle dependences of the detected phonon intensities are consistent with results obtained by first‐principle calculations and analysis of the proposed crystal symmetry without spatial inversion, showing that spatial inversion symmetry is broken in WP₂. Moreover, the measured ratio (R_c /R_a ) between the crystalline c‐axis and a‐axis electrical resistivities exhibits a weak dependence on temperature (T) in the temperature range from 100 to 250 K, but increases abruptly at T ≤ 100 K, and then reaches the value of ≈8.0 at T = 10 K, which is by far the strongest in‐plane electrical resistivity anisotropy among the reported type‐II WSM candidates with comparable carrier concentrations. Optical spectroscopy study, together with the first‐principle calculations on the electronic band structure, reveals that the abrupt enhancement of the electrical resistivity anisotropy at T ≤ 100 K mainly arises from a sharp increase in the scattering rate anisotropy at low temperatures. More interestingly, the R_c /R_a of WP₂ at T = 10 K can be tuned from 8.0 to 10.6 as the magnetic field increases from 0 to 9 T. The so‐far‐strongest and magnetic‐field‐tunable electrical resistivity anisotropy found in WP₂ can serve as a degree of freedom for tuning the electrical properties of type‐II WSMs, which paves the way for the development of novel electronic applications based on type‐II WSMs.     

Room‐Temperature Ferromagnetic Insulating State in Cation‐Ordered Double‐Perovskite Sr2Fe1+xRe1−xO6Films

Ferromagnetic insulators (FMIs) are one of the most important components in developing dissipationless electronic and spintronic devices. However, FMIs are innately rare to find in nature as ferromagnetism generally accompanies metallicity. Here, novel room‐temperature FMI films that are epitaxially synthesized by deliberate control of the ratio between two B‐site cations in the double perovskite Sr₂Fe_1+xRe_1‐xO₆ (?0.2 ≤ x ≤ 0.2) are reported. In contrast to the known FM metallic phase in stoichiometric Sr₂FeReO₆, an FMI state with a high Curie temperature (T_c ≈ 400 K) and a large saturation magnetization (M_S ≈ 1.8 µ_B f.u.^?1) is found in highly cation‐ordered Fe‐rich phases. The stabilization of the FMI state is attributed to the formation of extra Fe³⁺? Fe³⁺ and Fe³⁺? Re⁶⁺ bonding states, which originate from the relatively excess Fe ions owing to the deficiency in Re ions. The emerging FMI state created by controlling cations in the oxide double perovskites opens the door to developing novel oxide quantum materials and spintronic devices.     

Scalable Design of Two‐Dimensional Oxide Nanosheets for Construction of Ultrathin Multilayer Nanocapacitor

Large size of capacitors is the main hurdle in miniaturization of current electronic devices. Herein, a scalable solution‐based layer‐by‐layer engineering of metallic and high‐κ dielectric nanosheets into multilayer nanosheet capacitors (MNCs) with overall thickness of ≈20 nm is presented. The MNCs are built through neat tiling of 2D metallic Ru_0.95O₂^0.2? and high‐κ dielectric Ca₂NaNb₄O₁₃^? nanosheets via the Langmuir–Blodgett (LB) approach at room temperature which is verified by cross‐sectional high‐resolution transmission electron microscopy (HRTEM). The resultant MNCs demonstrate a high capacitance of 40–52 µF cm^?2 and low leakage currents down to 10^?5–10^?6 A cm^?2. Such MNCs also possess complimentary in situ robust dielectric properties under high‐temperature measurements up to 250 °C. Based on capacitance normalized by the thickness, the developed MNC outperforms state‐of‐the‐art multilayer ceramic capacitors (MLCC, ≈22 µF cm^?2/5 × 10⁴ nm) present in the market. The strategy is effective due to the advantages of facile, economical, and ambient temperature solution assembly.     

Piezoelectricity Across a Strain‐Induced Isosymmetric Ferri‐to‐Ferroelectric Transition

We identify a first‐order, isosymmetric transition between a ferrielectric (FiE) and ferroelectric (FE) state in A‐site ordered LaScO₃/BiScO₃ and LaInO₃/BiInO₃ superlattices. Such a previously unreported ferroic transition is driven by the easy switching of cation displacements without changing the overall polarization direction or crystallographic symmetry. Epitaxial strains less than 2% are predicted to be sufficient to traverse the phase boundary, across which we capture a ≈5× increase in electric polarization. Unlike conventional Pb‐based perovskite ceramics with a morphotropic phase boundary (MPB) that show polarization rotation, we predict an electromechanical response up to 102 pC/N in the vicinity of the FiE‐FE phase boundary due to polarization switching without any change in symmetry. We propose this transition as an alternative ferroic transition to obtain a piezoelectric response, with the additional advantage of occurring in benign chemistries without chemical disorder.     

Enhanced Crystallinity,Dielectric, and Energy Harvesting Performances of Surface‐Treated Barium Titanate Hollow Nanospheres/PVDF Nanocomposites

Enhancement of the energy harvesting performance and dielectric constants of poly(vinylidene fluoride) (PVDF)‐based capacitors is realized by incorporating 16 wt% of surface‐treated BaTiO₃ hollow nanospheres (HNSs) in comparison with the pristine PVDF. The fabricated BaTiO₃ HNSs with particle sizes of ≈20 nm and BET surface area of 297 m² g⁻¹ are treated by three different surface modifiers. The changes in crystallinity of the PVDF containing the surface‐treated BaTiO₃ HNSs are induced by both enlarged surface areas and increased surface functionality of the HNSs. Effects of such surface functionalities on the crystalline, dielectric, and energy harvesting performances of the nanocomposites are systematically investigated to identify the optimal surface modifier to enhance the energy density of the nanocomposites. Consequently, these changes in crystallinity lead to higher dielectric constants (ε′ ≈ 109.6) and energy density (U_e ≈ 21.7 J cm⁻³) with highly retained breakdown strength (E = 3.81 × 10³ kV cm⁻¹) compared to pristine PVDF (ε′ ≈ 11.6 and U_e ≈ 2.16 J cm⁻³ at 3.98 × 10³ kV cm⁻¹), indicating their potential as high energy density capacitors.