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2D van der Waals (vdW) layered semiconductor vertical heterostructures with controllable band alignment are highly desired for nanodevice applications including photodetection and photovoltaics. However, current 2D vdW heterostructures are mainly obtained via mechanical exfoliation and stacking process, intrinsically limiting the yield and reproducibility, hardly achieving large-area with specific orientation. Here, large-area vdW-epitaxial SnSe 2 /SnSe heterostructures are obtained by annealing layered SnSe. These in situ Raman analyses reveal the optimized annealing conditions for the phase transition of SnSe to SnSe 2 . The spherical aberration-corrected transmission electron microscopy investigations demonstrate that layered SnSe 2 epitaxially forms on SnSe surface with atomically sharp interface and specific orientation. Optical characterizations and theoretical calculations reveal valley polarization of the heterostructures that originate from SnSe, suggesting a naturally adjustable band alignment between type-II and type-III, only relying on the polarization angle of incident lights. This work not only offers a unique and accessible approach to obtaining large-area SnSe 2 /SnSe heterostructures with new insight into the formation mechanism of vdW heterostructures, but also opens the intriguing optical applications based on valleytronic nanoheterostructures., (© 2024 Wiley‐VCH GmbH.)

The strategic integration of low-dimensional InAs-based materials and emerging van der Waals systems is advancing in various scientific fields, including electronics, optics, and magnetics. With their unique properties, these InAs-based van der Waals materials and devices promise further miniaturization of semiconductor devices in line with Moore's Law. However, progress in this area lags behind other 2D materials like graphene and boron nitride. Challenges include synthesizing pure crystalline phase InAs nanostructures and single-atomic-layer 2D InAs films, both vital for advanced van der Waals heterostructures. Also, diverse surface state effects on InAs-based van der Waals devices complicate their performance evaluation. This review discusses the experimental advances in the van der Waals epitaxy of InAs-based materials and the working principles of InAs-based van der Waals devices. Theoretical achievements in understanding and guiding the design of InAs-based van der Waals systems are highlighted. Focusing on advancing novel selective area growth and remote epitaxy, exploring multi-functional applications, and incorporating deep learning into first-principles calculations are proposed. These initiatives aim to overcome existing bottlenecks and accelerate transformative advancements in integrating InAs and van der Waals heterostructures., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Cu 2 ZnSn(S,Se) 4 (CZTSSe) has attracted great interest in thin-film solar cells due to its excellent photoelectric performance in past decades, and recently is gradually expanding to the field of photodetectors. Here, the CZTSSe self-powered photodetector is prepared by using traditional photovoltaic device structure. Under zero bias, it exhibits the excellent performance with a maximum responsivity of 0.77 A W -1 , a high detectivity of 8.78 × 10 12 Jones, and a wide linear dynamic range of 103 dB. Very fast response speed with the rise/decay times of 0.576/1.792 µs, and ultra-high switching ratio of 3.54 × 10 5 are obtained. Comprehensive electrical and microstructure characterizations confirm that element diffusion among ITO, CdS, and CZTSSe layers not only optimizes band alignment of CdS/CZTSSe, but also suppresses the formation of interface defects. Such a suppression of interface defects and spike-like band alignment significantly inhibit carrier nonradiative recombination at interface and promote carrier transport capability. The low trap density in CZTSSe and low back contact barrier of CZTSSe/Mo could be responsible for the very fast response time of photodetector. This work definitely provides guidance for designing a high performance self-powered photodetector with high photoresponse, high switching ratio, fast response speed, and broad linear dynamic range., (© 2024 Wiley‐VCH GmbH.)

Light-induced spin currents with the faster response is essential for the more efficient information transmission and processing. Herein, we systematically explore the effect of light illumination energy and direction on the light-induced spin currents in the W/Y 3 Fe 5 O 12 heterojunction. Light-induced spin currents can be clearly categorized into two types. One is excited by the low light intensity, which mainly involves the photo-generated spin current from spin photovoltaic effect. The other is caused by the high light intensity, which is the light-thermally induced spin current and mainly excited by spin Seebeck effect. Under low light-intensity illumination, light-thermally induced temperature gradient is very small so that spin Seebeck effect can be neglected. Furthermore, the mechanism on spin photovoltaic effect is fully elucidated, where the photo-generated spin current in Y 3 Fe 5 O 12 mainly originates from the process of spin precession induced by photons. These findings provide some deep insights into the origin of light-induced spin current., (© 2024. The Author(s).)

Intriguing "slidetronics" has been reported in van der Waals (vdW) layered non-centrosymmetric materials and newly-emerging artificially-tuned twisted moiré superlattices, but correlative experiments that spatially track the interlayer sliding dynamics at atomic-level remain elusive. Here, we address the decisive challenge to in-situ trace the atomic-level interlayer sliding and the induced polarization reversal in vdW-layered yttrium-doped γ-InSe, step by step and atom by atom. We directly observe the real-time interlayer sliding by a 1/3-unit cell along the armchair direction, corresponding to vertical polarization reversal. The sliding driven only by low energetic electron-beam illumination suggests rather low switching barriers. Additionally, we propose a new sliding mechanism that supports the observed reversal pathway, i.e., two bilayer units slide towards each other simultaneously. Our insights into the polarization reversal via the atomic-scale interlayer sliding provide a momentous initial progress for the ongoing and future research on sliding ferroelectrics towards non-volatile storages or ferroelectric field-effect transistors., (© 2024. The Author(s).)

TiCu coatings with controlled copper release and nano-porous structures were fabricated as biocompatible, blood-contacting interfaces through a two-step process. Initially, coatings with 58 % Cu were created using HiPIMS/DC magnetron co-sputtering, followed by immersion in a dilute HF solution for varying durations to achieve dealloying. The presence of Ti elements in the as-deposited TiCu coatings facilitated their dissolution upon exposure to the dilute HF solution, resulting in the formation of nanopores and increased nano-roughness. Dealloying treatment time correlated with higher Cu/(Ti + Cu) values, nanopore size, and nano-roughness in the dealloyed samples. The dealloyed TiCu coatings with 87 % Cu exhibited a controlled release of copper ions and displayed nanopores (approximately 80 nm in length and 31.0 nm in width) and nano-roughness (Ra roughness: 82 nm). These coatings demonstrated inhibited platelet adhesion and suppressed smooth muscle cell behavior, while supporting favorable endothelial cell viability and proliferation, attributed to the controlled release of copper ions and the extent of nanostructures. In contrast, the as-deposited TiCu coatings with 85 % Cu showed high copper ion release, leading to decreased viability and proliferation of endothelial cells and smooth muscle cells, as well as suppressed platelet adhesion. The TiCu coatings met medical safety standards, exhibiting hemolysis rates of <5 %. The technology presented here paves the way for the simple, controllable, and cost-effective fabrication of TiCu coatings, opening new possibilities for surface modification of cardiovascular devices such as vascular stents and inferior vena cava filters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Ferroic compounds Fe 2 O(SeO 3 ) 2 (FSO) and Fe 2 (SeO 3 ) 3 ·3H 2 O (FSOH) prepared by the hydrothermal method are characterized and their optical properties are investigated by combining with first-principles calculations. The results show that (i) FSO is antiferromagnetic below ∼110 K and becomes ferromagnetic at elevated temperatures, while FSOH is antiferromagnetic at low temperatures probably due to a change in the spin state from Fe 3+ ( S = 5/2) to Fe 2+ ( S = 2); (ii) the optical bandgap is determined to be ∼2.83 eV for FSO and ∼2.15 eV for FSOH, consistent with the theoretical calculation; and (iii) the angle-resolved polarized Raman spectroscopy results of both crystals demonstrate the strong anisotropic light absorption and birefringence effects, and the unconventional symmetricity of some Raman modes is observed, which can be interpreted from the variation of Raman scattering elements. This work can provide not only an understanding of the structure and physical properties of iron selenites, but also a strategy for exploring the anomalous Raman behaviors in anisotropic crystals, facilitating the design and engineering of novel functional devices with low-symmetry ferroic materials.

Among today's nonvolatile memories, ferroelectric-based capacitors, tunnel junctions and field-effect transistors (FET) are already industrially integrated and/or intensively investigated to improve their performances. Concurrently, because of the tremendous development of artificial intelligence and big-data issues, there is an urgent need to realize high-density crossbar arrays, a prerequisite for the future of memories and emerging computing algorithms. Here, a two-terminal ferroelectric fin diode (FFD) in which a ferroelectric capacitor and a fin-like semiconductor channel are combined to share both top and bottom electrodes is designed. Such a device not only shows both digital and analog memory functionalities but is also robust and universal as it works using two very different ferroelectric materials. When compared to all current nonvolatile memories, it cumulatively demonstrates an endurance up to 10 10 cycles, an ON/OFF ratio of ~10 2 , a feature size of 30 nm, an operating energy of ~20 fJ and an operation speed of 100 ns. Beyond these superior performances, the simple two-terminal structure and their self-rectifying ratio of ~ 10 4 permit to consider them as new electronic building blocks for designing passive crossbar arrays which are crucial for the future in-memory computing., (© 2024. The Author(s).)

Low-symmetric GeTe semiconductors have attracted wide-ranging attention due to their excellent optical and thermal properties, but only a few research studies are available on their in-plane optical anisotropic nature that is crucial for their applications in optoelectronic and thermoelectric devices. Here, we investigate the optical interactions of anisotropy in GeTe using polarization-resolved Raman spectroscopy and first-principles calculations. After determining both armchair and zigzag directions in GeTe crystals by transmission electron microscopy, we found that the Raman intensity of the two main vibrational modes had a strong in-plane anisotropic nature; the one at ∼88.1 cm -1 can be used to determine the crystal orientation, and the other at ∼124.6 cm -1 can reveal a series of temperature-dependent phase transitions. These results provide a general approach for the investigation of the anisotropy of light-matter interactions in low-symmetric layered materials, benefiting the design and application of optoelectronic, anisotropic thermoelectric, and phase-transition memory devices based on bulk GeTe.

Photodetector based on two-dimensional (2D) materials is an ongoing quest in optoelectronics. 2D photodetectors are generally efficient at low illuminating power but suffer severe recombination processes at high power, which results in the sublinear power-dependent photoresponse and lower optoelectronic efficiency. The desirable superlinear photocurrent is mostly achieved by sophisticated 2D heterostructures or device arrays, while 2D materials rarely show intrinsic superlinear photoresponse. This work reports the giant superlinear power dependence of photocurrent based on multilayer Ta 2 NiS 5 . While the fabricated photodetector exhibits good sensitivity (3.1 mS W -1 per □) and fast photoresponse (31 µs), the bias-, polarization-, and spatial-resolved measurements point to an intrinsic photoconductive mechanism. By increasing the incident power density from 1.5 to 200 µW µm -2 , the photocurrent power dependence varies from sublinear to superlinear. At higher illuminating conditions, prominent superlinearity is observed with a giant power exponent of γ = 1.5. The unusual photoresponse can be explained by a two-recombination-center model where density of states of the recombination centers (RC) effectively closes all recombination channels. The photodetector is integrated into camera for taking photos with enhanced contrast due to superlinearity. This work provides an effective route to enable higher optoelectronic efficiency at extreme conditions., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Analog storage through synaptic weights using conductance in resistive neuromorphic systems and devices inevitably generates harmful heat dissipation. This thermal issue not only limits the energy efficiency but also hampers the very-large-scale and highly complicated hardware integration as in the human brain. Here we demonstrate that the synaptic weights can be simulated by reconfigurable non-volatile capacitances of a ferroelectric-based memcapacitor with ultralow-power consumption. The as-designed metal/ferroelectric/metal/insulator/semiconductor memcapacitor shows distinct 3-bit capacitance states controlled by the ferroelectric domain dynamics. These robust memcapacitive states exhibit uniform maintenance of more than 10 4 s and well endurance of 10 9 cycles. In a wired memcapacitor crossbar network hardware, analog vector-matrix multiplication is successfully implemented to classify 9-pixel images by collecting the sum of displacement currents ( I  =  C  × d V /d t ) in each column, which intrinsically consumes zero energy in memcapacitors themselves. Our work sheds light on an ultralow-power neural hardware based on ferroelectric memcapacitors., Competing Interests: The authors declare no conflicts of interest., (© 2023 The Authors. Exploration published by Henan University and John Wiley & Sons Australia, Ltd.)

Quasi-one-dimensional (Q1D) semiconductor antimony selenide (Sb 2 Se 3 ) shows great potential in the photovoltaic field, but the photoelectric conversion efficiency (PCE) of Sb 2 Se 3 -based solar cells has shown no obvious breakthrough during the past several years, of which the intrinsic reasons are pending experimentally. Here, we prepare high-quality Q1D Sb 2 Se 3 thin films via the vapor transport deposition technique. By investigating the bandedge electronic level structure and carrier relaxation/recombination dynamics, we find that (i) the optimized Se-rich growth conditions can highly improve the crystal quality of the Q1D Sb 2 Se 3 thin films, the carrier lifetime of which is substantially increased up to ∼8.3 μs; (ii) the Se-rich growth conditions have advantages to annihilate the deep selenium vacancies V Se i ( i = 1 and 3 for non-equivalent Se atomic sites) but is not effective for the deep donor V Se 2 , which locates at ∼0.3 eV (300 K) below the conduction band and intrinsically limits the PCE value of devices below ∼7.63%. This work suggests that further optimizing the Se-rich conditions to technically eliminate this kind of deep defect is still essential for preparing high-performance Sb 2 Se 3 film solar cells.

Anisotropy in a crystal structure plays a striking role in determining the optical, electrical and thermal properties of the condensed matter. Here, we investigated in-plane vibrational anisotropy in a two-dimensional (2D) van der Waals (vdW)-layered GeAs narrow-gap semiconductor by combining microstructural characterization and polarization Raman spectroscopy. Interestingly, not only the intensities but also the Raman shifts in all modes evolved periodically with different symmetries as the polarization angle changed continuously, which could be well-analyzed using the Raman tensors and further interpreted from the phonon dispersion relations. More importantly, the temperature-dependent Raman intensities of the Raman modes in the range from 83 K to 823 K gave a thermal-related uniform constant, based on which key parameters, including the thermal expansion coefficient, Grüneisen constant and quasi-particle lifetime, could be directly derived, which were in line with the calculated predictions. This investigation provides a comprehensive understanding of structure-dependent optical anisotropy in 2D vdW-layered GeAs and suggests a new idea for exploring the thermal properties of related materials using temperature-dependent Raman spectroscopy.

Two-dimensional (2D) van-der-Waals (vdW) layered ferroelectric semiconductors are highly desired for in-memory computing and ferroelectric photovoltaics or detectors. Beneficial from the weak interlayer vdW-force, controlling the structure by interlayer twist/translation or doping is an effective strategy to manipulate the fundamental properties of 2D-vdW semiconductors, which has contributed to the newly-emerging sliding ferroelectricity. Here, we report unconventional room-temperature ferroelectricity, both out-of-plane and in-plane, in vdW-layered γ-InSe semiconductor triggered by yttrium-doping (InSe:Y). We determine an effective piezoelectric constant of ∼7.5 pm/V for InSe:Y flakes with thickness of ∼50 nm, about one order of magnitude larger than earlier reports. We directly visualize the enhanced sliding switchable polarization originating from the fantastic microstructure modifications including the stacking-faults elimination and a subtle rhombohedral distortion due to the intralayer compression and continuous interlayer pre-sliding. Our investigations provide new freedom degrees of structure manipulation for intrinsic properties in 2D-vdW-layered semiconductors to expand ferroelectric candidates for next-generation nanoelectronics., (© 2023. The Author(s).)

As a narrow-gap semiconductor, III-VI two-dimensional (2D) van der Waals layered indium selenide (InSe) has attracted a lot of attention due to excellent physical properties. For potential optoelectronic applications, the tunability of the optical property is challenging, e.g., the modulation of optical bandgap commonly by element doping. However, the deep understanding of the influence of element doping on the microstructure and the optical properties lacks of systematic investigation. In this work, by using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, we investigate the influence of Bi doping on controlling of the microstructure and optical properties of InSe single crystal in detail. The results show that Bi doping can introduce additional stacking faults in InSe single crystal, and more importantly, the atomic spacing and lattice constant of Bi-doped InSe are changed a lot as compared to that of the undoped one. Further optical characterizations including photoluminescence and transmission spectra reveal that Bi-doping can broaden the transmission wavelength range of InSe and make its optical bandgap blue-shift, which can also be physically interpreted from the doping-induced structure change. Our work expands new ideas for the optical property modulation of 2D thin-layer materials and brings new possibilities for the development of thin-layer InSe optical devices., (© 2022 IOP Publishing Ltd.)

Searching van der Waals ferroic materials that can work under ambient conditions is of critical importance for developing ferroic devices at the two-dimensional limit. Here we report the experimental discovery of electric-field-induced reversible antiferroelectric (AFE) to ferroelectric (FE) transition at room temperature in van der Waals layered α-GeSe, employing Raman spectroscopy, transmission electron microscopy, second-harmonic generation, and piezoelectric force microscopy consolidated by first-principles calculations. An orientation-dependent AFE-FE transition provides strong evidence that the in-plane (IP) polarization vector aligns along the armchair rather than zigzag direction in α-GeSe. In addition, temperature-dependent Raman spectra showed that the IP polarization could sustain up to higher than 700 K. Our findings suggest that α-GeSe, which is also a potential ferrovalley material, could be a robust building block for creating artificial 2D multiferroics at room temperature.

The phase transition, microscopic morphology and optical and ferroelectric properties are studied in a series of La- and Co-doped KNbO 3 -based ceramics. The results show that the doping induces the transformation from the orthorhombic to the cubic phase of KNbO 3 , significantly reduces the optical bandgap and simultaneously evidently improves the leakage, with a slight weakening of ferroelectric polarization. Further analysis reveals that (i) the Co doping is responsible for the obvious reduction of the bandgap, whereas it is reversed for the La doping; (ii) the slight deterioration of ferroelectricity is due to the doping-induced remarkable extrinsic defect levels and intrinsic oxygen vacancies; and (iii) the La doping can optimize the defect levels and inhibit the leakage. This investigation should both provide novel insight for exploring the bandgap engineering and ferroelectric properties of KNbO 3 , and suggest its potential applications, e.g., photovoltaic and multifunctional materials.

Ti-doped truncated octahedron LiTi x Mn 2- x O 4 nanocomposites were synthesized through a facile hydrothermal treatment and calcination process. By using spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM), the effects of Ti-doping on the structure evolution and stability enhancement of LiMn 2 O 4 are revealed. It is found that truncated octahedrons are easily formed in Ti doping LiMn 2 O 4 material. Structural characterizations reveal that most of the Ti 4+ ions are composed into the spinel to form a more stable spinel LiTi x Mn 2- x O 4 phase framework in bulk. However, a portion of Ti 4+ ions occupy 8a sites around the {001} plane surface to form a new TiMn 2 O 4 -like structure. The combination of LiTi x Mn 2- x O 4 frameworks in bulk and the TiMn 2 O 4 -like structure at the surface may enhance the stability of the spinel LiMn 2 O 4 . Our findings demonstrate the critical role of Ti doping in the surface chemical and structural evolution of LiMn 2 O 4 and may guide the design principle for viable electrode materials.

By comparing optical spectral results of both Sn-rich and Sn-poor Cu 2 ZnSnS 4 (CZTS) with the previously calculated defect levels, we confirm that the band-tail states in CZTS originate from the high concentration of 2Cu Zn + Sn Zn defect clusters, whereas the deep-donor states originate from the high concentration of Sn Zn . In Sn-rich CZTS, the absorption, reflectance, and photocurrent (PC) spectra show band-tail states that shrink the bandgap to only ∼1.34 eV, while photoluminescence (PL) and PC spectra consistently show that abundant Cu Zn + Sn Zn donor states produce a PL peak at ∼1.17 eV and abundant Sn Zn deep-donor states produce a PL peak near 0.85 eV. In contrast, Sn-poor CZTS shows neither bandgap shrinking nor any deep-donor-defect induced PL and PC signals. These results highlight that a Sn-poor composition is critical for the reduction of band-tailing effects and deep-donor defects and thus the overcoming of the severe open-circuit voltage ( V oc ) deficiency problem in CZTS solar cells.

Stainless steel (SUS) capillary tubes were examined as a category of structural tube for establishing a metallic attenuated total reflection (ATR) GeO 2 hollow waveguide. GeO 2 films were grown on the inner wall of SUS tubes by different liquid phase deposition (LPD) cycles. Fourier transform infrared (FTIR) spectra, scanning electronic microscope (SEM) image, and transmission loss for a CO 2 laser were measured to investigate the effects of the LPD cycles on the transmission behavior of the hollow waveguide samples. The film thickness and surface roughness increase with every LPD cycle. The two LPD cycle sample has a film thickness equivalent to the CO 2 laser wavelength, while the surface roughness is acceptable. This sample has the lowest transmission loss (0.27  dB/m) among these samples. The bending loss, output beam profile, and full divergence angle (FDA) were further studied. Higher-order modes are excited by bending the sample, inducing additional loss, decentralized beam profile, and larger FDA.

Silicate- and borosilicate-based PbS:glass material and borosilicate-glass-based fibers are fabricated and analyzed. Optical properties including absorption and emission are characterized and related to growth and annealing conditions. In silicate glasses PbS volume fractions of exceeding 0.4 percent and almost octave-spanning emission spectra with a halfwidth of 940 nm are achieved. Fiber bundles with a core being surrounded by three PbS:Glass fibers are pulled. A confinement factor of Γ = 0.00406 is determined. Emission properties, in particular emission bandwidth, are subsequently tuned and spectrally widened by annealing fibers in a gradient furnace. The results pave the way towards optically pumped broad-bandwidth light emitters based either on 'bulk' PbS:glass or PbS:glass-based fibers.

We report on a new technique of realizing photoreflectance (PR) spectroscopy with a step-scan Fourier-transform infrared spectrometer. The experimental configuration is briefly described and a detailed theoretical analysis is conducted. The results reveal two distinct features of this PR technique that (i) the PR related signal is enhanced by a factor of at least 100 relative to those of the conventional PR techniques and (ii) the unwanted spurious signal introduced by either diffuse reflected pump beam or pump-beam induced material's photoluminescence reaching the photodetector of the PR configuration is eliminated without any special consideration of normalization for deducing the final PR spectrum. Applications are given as examples in the study of GaNAs/GaAs single quantum wells and GaInP/AlGaInP multiple quantum wells, respectively, under different pump-beam excitation energy and/or power. The experimental results approve the theoretically predicted features and illustrate the possibility of investigating weak PR features by using high pump-beam power. A brief comparison of this technique with the conventional PR techniques is given, and the extendibility of this technique to long-wavelength spectral regions is pointed out.