Pressure-Driven Polymorphic Transition, Emergent Insulator-To-Metal Transition, and Photoconductivity Switching in Violet Phosphorus.

Polymorphic phase transition is an essential phenomenon in condensed matter that the physical properties of materials may undergo significant changes due to the structural transformation. Phase transition has thus become an important means and dimension for regulating material properties. Herein, this study demonstrates the pressure-induced multi-transition of both structure and physical properties in violet phosphorus, a novel phosphorus allotrope. Under compression, violet phosphorus undergoes sequential polymorphic phase transitions. Concomitant with the first phase transition, violet phosphorus exhibits emergent insulator-metal transition, superconductivity, and dramatic switching from positive to negative photoconductivity. Remarkably, the resistance of violet phosphorus shows a sudden drop of around 107 along with the phase transition. In addition, piezochromism from translucent red to opaque black and suppression of photoluminescence are observed upon compression. Of particular interest is that the sample irreversibly transforms into black phosphorus with a pronounced discrepancy in physical properties from the pristine violet phosphorus after decompression. The abundant polymorphic transitions and property changes in violet phosphorus have significant implications for designing novel pressure-responsive electronic/optoelectronic devices and exploring concealed polymorphic transition materials.

Optically Controlled Gain Modulation for Microwave Metasurface Antennas.

Over the past decade, metasurfaces (MTSs) have emerged as a highly promising platform for the development of next-generation, miniaturized, planar devices across a wide spectrum of microwave frequencies. Among their various applications, the concept of MTS-based antennas, particularly those that are based on surface wave excitation, represents a groundbreaking advancement with significant implications for communication technologies. However, existing literature primarily focuses on MTS configurations printed on traditional substrates, largely overlooking the potential benefits of employing photosensitive substrates. This paper endeavors to pioneer this novel path. We present a specialized design of a modulated MTS printed on a silicon substrate, which acts as a photosensitive Ka-band surface wave antenna. Remarkably, the gain of this antenna can be time-modulated, achieving a variance of up to 15 dB, under low-power (below 1 W/cm²) optical illumination at a wavelength of 971 nm. This innovative approach positions the antenna as a direct transducer, capable of converting an optically modulated signal into a microwave-modulated radiated signal, thus offering a new dimension in antenna technology and functionality.

Terahertz Photoconductivity in Bilayer Graphene Transistors: Evidence for Tunneling at Gate-Induced Junctions.

Photoconductivity of novel materials is the key property of interest for design of photodetectors, optical modulators, and switches. Despite the photoconductivity of most novel 2d materials having been studied both theoretically and experimentally, the same is not true for 2d p-n junctions that are necessary blocks of most electronic devices. Here, we study the sub-terahertz photocoductivity of gapped bilayer graphene with electrically induced p-n junctions. We find a strong positive contribution from junctions to resistance, temperature resistance coefficient, and photoresistivity at cryogenic temperatures T ∼ 20 K. The contribution to these quantities from junctions exceeds strongly the bulk values at uniform channel doping even at small band gaps of ∼10 meV. We further show that positive junction photoresistance is a hallmark of interband tunneling, and not of intraband thermionic conduction. Our results point to the possibility of creating various interband tunneling devices based on bilayer graphene, including steep-switching transistors and selective sensors.

Long-Range Energy Transfer in Strongly Coupled Donor-Acceptor Phototransistors.

Strong light-matter coupling offers a way to tailor the optoelectronic properties of materials. Energy transfer between strongly coupled donor-acceptor pairs shows remarkable efficiency beyond the Förster distance via coupling through a confined photon. This long-range energy transfer is facilitated through the collective nature of polaritonic states. Here, the cooperative, strong coupling of a donor (MoS2 monolayer) and an acceptor (BRK) generates mixed polaritonic states. The photocurrent spectrum of the MoS2 monolayer is measured in a field effect transistor while coupling the two oscillators to the confined cavity mode. The strongly coupled system shows efficient energy transfer, which is observed through the photoresponsivity even the donor and acceptor are physically separated by 500 Å. These studies are further correlated with the Hopfield coefficients and the overlap integral of the lower polaritonic and uncoupled/dark states. Cavity detuning and distance-dependent studies support the above evidence. These observations open new avenues for using long-range interaction of polaritonic states in optoelectronic devices.

Reversible Photomodulation of Two-Dimensional Electron Gas in LaAlO3/SrTiO3 Heterostructures.

Long-lived photoinduced conductance changes in LaAlO3/SrTiO3 (LAO/STO) heterostructures enable their use in optoelectronic memory applications. However, it remains challenging to quench the persistent photoconductivity (PPC) instantly and reproducibly, which limits the reversible optoelectronic switching. Herein, we demonstrate a reversible photomodulation of two-dimensional electron gas (2DEG) in LAO/STO heterostructures with high reproducibility. By irradiating UV pulses, the 2DEG at the LAO/STO interface is gradually transformed to the PPC state. Notably, the PPC can be completely removed by water treatment when two key requirements are met: (1) the moderate oxygen deficiency in STO and (2) the minimal band edge fluctuation at the interface. Through our X-ray photoelectron spectroscopy and electrical noise analysis, we reveal that the reproducible change in the conductivity of 2DEG is directly attributed to the surface-driven electron relaxation in the STO. Our results provide a stepping-stone toward developing optically tunable memristive devices based on oxide 2DEG systems.

Relevance of alcoholic solvents in the growth of ZnO nanoparticles and ZnO hierarchical nanorod structures on their optical and opto-electrical properties.

We report on the synthesis of ZnO nanoparticles and ZnO hierarchical nanorod structures using four different alcohols i.e. methanol, isopropanol, ethanol, and aqueous ethanol (70% alcohol, 30% water). The syntheses of the nanoparticles were carried out by non-aqueous and hydrothermal routes. In general, absolute alcohol allows a better control of the synthesis reaction and nanoparticles as small as 5 nm were obtained, confirmed by TEM. XPS analysis elucidated the chemical states that were correlated to the synthesis reaction. For the nanorod growth, these four alcohols were used as seeding solvents, followed by hydrothermal ZnO nanorod growth. Here, the seed layer tailored the nanorod diameters and surface defects, which were studied by SEM and photoluminescence spectroscopy. Subsequently, the ZnO nanorods were electrically characterized and exhibited persistent photoconductivity under UV irradiation of 365 nm. The differences in conductivity in dark and under UV irradiation were attributed to the size of the nanorods, defect states, semiconductor band bending and oxygen adsorption-desorption mechanisms. Parameters such as photoresponse and photosensitivity are also calculated in order to evaluate their applicability in UV sensors. This work demonstrates optimization of the physical, chemical, electrical and optical properties of both ZnO nanostructures via the use of alcoholic solvents.

Investigation of efficient photoconduction and enhanced luminescence characteristics of Ce-doped ZnO nanophosphors for UV sensors.

This study involves the single-step, mass-scale productive synthesis, photoconduction, and luminescence characteristics of pure and cerium rare-earth-ion-doped ZnO (CZO) nanophosphors with different Ce concentrations (Ce: 0, 2, 4, 6, and 8 wt.%) synthesized using the solid-state reaction method. The synthesized nanophosphors were characterized for their structural, morphological, optical, and photoconductivity (PC) properties using X-ray diffraction (XRD), field-effect scanning electron microscopy (FE-SEM), energy dispersive spectroscopy, Fourier-transform infrared (FT-IR), photoluminescence (PL), and PC measurements. The sharp diffraction peaks of XRD results exhibit the formation of crystalline hexagonal wurtzite ZnO nanostructures. The decrease in diffraction peak intensities of CZO with an increase in Ce concentrations signifies the deterioration of the ZnO crystal. FE-SEM images exhibit the good crystalline quality of nanophosphors composed of spherical- and elongated-shaped nanoparticles that are distributed consistently on the surface. The energy dispersive X-ray pattern of the 4 wt.% Ce-doped ZnO (CZO4 ) sample confirms the doping of Ce in ZnO. The presence of chemical bonds and functional groups corresponds to transmittance peaks established using FT-IR spectroscopy. Deconvoluted PL spectra show two major emission peaks, one in the UV region, which is near-band-edge, and the other in the visible region ranging from ~456 to 561 nm. In PC studies, current-voltage (I-V) and current-time (I-T) characteristics, that is, rise/decayin current under dark as well as UV light conditions, are also investigated. Efficient photoconduction is observed in CZO samples. The obtained results indicate the suitability to luminescent and photosensor applications.

UV Sensor Based on Surface Acoustic Waves in ZnO/Fused Silica.

Zinc oxide (ZnO) thin films have been grown by radio frequency sputtering technique on fused silica substrates. Optical and morphological characteristics of as-grown ZnO samples were measured by various techniques; an X-ray diffraction spectrum showed that the films exhibited hexagonal wurtzite structure and were c-axis-oriented normal to the substrate surface. Scanning electron microscopy images showed the dense columnar structure of the ZnO layers, and light absorption measurements allowed us to estimate the penetration depth of the optical radiation in the 200 to 480 nm wavelength range and the ZnO band-gap. ZnO layers were used as a basic material for surface acoustic wave (SAW) delay lines consisting of two Al interdigitated transducers (IDTs) photolithographically implemented on the surface of the piezoelectric layer. The Rayleigh wave propagation characteristics were tested in darkness and under incident UV light illumination from the top surface of the ZnO layer and from the fused silica/ZnO interface. The sensor response, i.e., the wave velocity shift due to the acoustoelectric interaction between the photogenerated charge carriers and the electric potential associated with the acoustic wave, was measured for different UV power densities. The reversibility and repeatability of the sensor responses were assessed. The time response of the UV sensor showed a rise time and a recovery time of about 10 and 13 s, respectively, and a sensitivity of about 318 and 341 ppm/(mW/cm2) for top and bottom illumination, respectively. The ZnO/fused silica-based SAW UV sensors can be interrogated across the fused silica substrate thanks to its optical transparency in the UV range. The backlighting interrogation can find applications in harsh environments, as it prevents the sensing photoconductive layer from aggressive environmental effects or from any damage caused by cleaning the surface from dust which could deteriorate the sensor's performance. Moreover, since the SAW sensors, by their operating principle, are suitable for wireless reading via radio signals, the ZnO/fused-silica-based sensors have the potential to be the first choice for UV sensing in harsh environments.

Artificial Vision Adaption Mimicked by an Optoelectrical In2O3 Transistor Array.

Simulation of biological visual perception has gained considerable attention. In this paper, an optoelectrical In2O3 transistor array with a negative photoconductivity behavior is designed using a side-gate structure and a screen-printed ion-gel as the gate insulator. This paper is the first to observe a negative photoconductivity in electrolyte-gated oxide devices. Furthermore, an artificial visual perception system capable of self-adapting to environmental lightness is mimicked using the proposed device array. The transistor device array shows a self-adaptive behavior of light under different levels of light intensity, successfully demonstrating the visual adaption with an adjustable threshold range to the external environment. This study provides a new way to create an environmentally adaptive artificial visual perception system and has far-reaching significance for the future of neuromorphic electronics.

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two-Dimensional Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M-HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time-resolved terahertz spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through-space hole transport mechanism through the interlayer sheet π-π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu-HHTP MOF is found to be 65.5 S m-1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

Synthesis and solar blind photosensitivity of crystalline boron nanowires.

Herein, single crystalline boron nanowires (BNWs) have been synthesized by chemical vapor transport using boron element as boron source, iodine as transport agent, and Au as catalyst. The results demonstrate that BNWs can be all formed at 600 °C-950 °C for 2 h, and possess rhombohedral crystal structure (ß-boron). The NWs have diameters from several to hundreds of nanometers, and lengths from several to hundreds of microns. A single nanowire has been fabricated to field effect transistor (FET) which shows excellent solar blind photosensitivity and selectivity. The photo/dark current ratio and photoresponsitity is 1.14 and 97.6 mA W-1at a bias of 5 V under light illumination of 254 nm with 0.42 mW cm-2, respectively, and both the rising and decay time of the on-off currents are 4.6 s and 10.3 s, respectively. When the FET is used as a personal breath sensor, the ratio of exsufflating and inhaling currents is 2.7, rising and decay time of the breath currents are 0.4 s and 2.2 s, respectively. So the BNWs are important sense materials.

The Effect of Fractionation during the Vacuum Deposition of Stabilized Amorphous Selenium Alloy Photoconductors on the Overall Charge Collection Efficiency.

The general fabrication process for stabilized amorphous selenium (a-Se) detectors is vacuum deposition. The evaporant alloy is typically selenium alloyed with 0.3-0.5%As to stabilize it against crystallization. During the evaporation, fractionation leads to the formation of a deposited film that is rich in As near the surface and rich in Se near the substrate. The As content is invariably not uniform across the film thickness. This paper examines the effect of non-uniform As content on the charge collection efficiency (CE). The model for the actual CE calculation is based on the generalized CE equation under small signals; it involves the integration of the reciprocal range-field product (the schubweg) and the photogeneration profile. The data for the model input were extracted from the literature on the dependence of charge carrier drift mobilities and lifetimes on the As content in a-Se1-xAsx alloys to generate the spatial variation of hole and electron ranges across the photoconductor film. This range variation is then used to calculate the actual CE in the integral equation as a function of the applied field. The carrier ranges corresponding to the average composition in the film are also used in the standard CE equation under uniform ranges to examine whether one can simply use the average As content to calculate the CE. The standard equation is also used with ranges from the spatial average and average inverse. Errors are then compared and quantified from the use of various averages. The particular choice for averaging depends on the polarity of the radiation-receiving electrode and the spatial variation of the carrier ranges.

Enhanced Structural Stability and Pressure-Induced Photoconductivity in Two-Dimensional Hybrid Perovskite (C6 H5 CH2 NH3 )2 CuBr4.

The eco-friendly properties enable two-dimensional (2D) Cu-based perovskites as ideal candidates for next-generation optoelectronics, but practical application is limited by low photoelectric conversion efficiency because of poor carrier transport abilities. Here, we report enhanced structural stability of 2D CuBr4 perovskites under compression up to 30 GPa, without obvious volume collapse or structural amorphization, by inserting organic C6 H5 CH2 NH3 (PMA) groups between layers. The band gap value of (PMA)2 CuBr4 can be effectively tuned from 1.8 to 1.47 eV by employing external pressures, leading to a broadened absorption range of 400-800 nm. Notably, we successfully detected photoconductivity of the photoresponse at pressures from 10 to 40 GPa; the maximum value of 5×10-3  S cm-1 is observed at 28 GPa, indicating potential applications for high performance photovoltaic candidates under extreme conditions.

Experimental and Theoretical Investigation of the Structural and Opto-electronic Properties of Fe-Doped Lead-Free Cs2 AgBiCl6 Double Perovskite.

Lead-free double perovskites have emerged as stable and non-toxic alternatives to Pb-halide perovskites. Herein, the synthesis of Fe-doped Cs2 AgBiCl6 lead-free double perovskites are reported that display blue emission using an antisolvent method. The crystal structure, morphology, optical properties, band structure, and stability of the Fe-doped double perovskites were investigated systematically. Formation of the Fe-doped Cs2 AgBiCl6 double perovskite is confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. XRD and thermo-gravimetric analysis (TGA) shows that the Cs2 AgBiCl6 double perovskite has high structural and thermal stability, respectively. Field emission scanning electron microscopy (FE-SEM) analysis revealed the formation of dipyramidal shape Cs2 AgBiCl6 crystals. Furthermore, energy-dispersive X-ray spectroscopy (EDS) mapping shows the overlapping of Cs, Bi, Ag, Fe, and Cl elements and homogenous incorporation of Fe in Cs2 AgBiCl6 double perovskite. The Fe-doped Cs2 AgBiCl6 double perovskite shows a strong absorption at 380 nm. It extends up to 700 nm, suggesting that sub-band gap states transition may originate from the surface defect of the doped perovskite material. The radiative kinetics of the crystals was studied using the time-correlated single-photon counting (TCSPC) technique. Lattice parameters and band gap value of the Fe-doped Cs2 AgBiCl6 double perovskites predicted by the density functional theory (DFT) calculations are confirmed by XRD and UV/Visible spectroscopy analysis. Time-dependent photo-response characteristics of the Fe-doped Cs2 AgBiCl6 double perovskite show fast response and recovery time of charge carriers. We believe that the successful incorporation of Fe in lead-free, environmentally friendly Cs2 AgBiCl6 double perovskite can open a new class of doped double perovskites with significant potential optoelectronics devices fabrication and photocatalytic applications.

Exciton Transport in Molecular Semiconductor Crystals for Spin-Optoelectronics Paradigm.

Organic semiconductors with long-range exciton diffusion length are highly desirable for optoelectronics but currently remain rare. Here, the estimated diffusion length of singlet excitons (LD ) in 2,6-diphenyl anthracene (DPA) crystals grown by solvent evaporation was shown to be up to approximately 124 nm. These crystals showed a previously unseen parallelogram morphology with layer-by-layer edge-on molecular stacking, isotropic optical waveguiding, radiation rate and non-radiation rate constants of 0.15 and 0.26 ns-1 respectively, as well as good field-effect transistor hole mobility and theoretically computed strong electronic couplings as high as 109 meV. Photoresponse experiments revealed that the photoconductivity of DPA crystals is surprisingly not related to the radiative pathway but associated with rapid exciton diffusion to the crystal surface for charge separation and carrier bimolecular recombination. Taken together, DPA was shown to be a promising semiconducting material for a new organic optoelectronics paradigm.

Plasmon-assisted polarization-sensitive photodetection with tunable polarity for integrated silicon photonic communication systems.

To establish high-bandwidth chip-to-chip interconnects in optoelectronic integrated circuits, requires high-performance photon emitters and signal receiving components. Regarding the photodetector, fast device concepts like Schottky junction devices, large carrier mobility materials and shrinking the channel length will enable higher operation speed. However, integrating photodetectors in highly scaled ICs technologies is challenging due to the efficiency-speed trade-off. Here, we report a scalable and CMOS-compatible approach for an ultra-scaled germanium (Ge) based photodetector with tunable polarity. The photodetector is composed of a Ge Schottky barrier field effect transistor with monolithic aluminum (Al) source/drain contacts, offering plasmon assisted and polarization-resolved photodetection. The ultra-scaled Ge photodetector with a channel length of only 200 nm shows high responsivity of aboutR = 424 A W-1and a maximum polarization sensitivity ratio of TM/TE = 11.

Phase Controlled Growth of Cd3As2 Nanowires and Their Negative Photoconductivity.

The bottom-up synthesis process often allows the growth of metastable phase nanowires instead of the thermodynamically stable phase. Herein, we synthesized Cd3As2 nanowires with a controlled three-dimensional Dirac semimetal phase using a chemical vapor transport method. Three different phases such as the body centered tetragonal (bct), and two metastable primitive tetragonal (P42/nbc and P42/nmc) phases were identified. The conversion between three phases (bct → P42/nbc → P42/nmc) was achieved by increasing the growth temperature. The growth direction is [110] for bct and P42/nbc and [100] for P42/nmc, corresponding to the same crystallographic axis. Field effect transistors and photodetector devices showed the nearly same electrical and photoelectrical properties for three phases. Differential conductance measurement confirms excellent electron mobility (2 × 104 cm2/(V s) at 10 K). Negative photoconductance was first observed, and the photoresponsivity reached 3 × 104 A/W, which is ascribed to the surface defects acting as trap sites for the photogenerated electrons.

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate-Tunable Rubrene/Bi2 Se3 Diodes with Photoinduced Negative Differential Resistance.

Organic single-crystalline semiconductors show great potential in high-performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high-speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi2 Se3 is provided. The rubrene/Bi2 Se3 heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi2 Se3 surface and the strong built-in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54 ms), meanwhile the photoresponsivity can reach 124 A W-1 . To the best of knowledge, this operating speed is among the fastest responses in organic-inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de-trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi2 Se3 heterojunction behaves as a gate-tunable backward-like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi2 Se3 heterojunctions for various emerging optoelectronic applications.

Transient Electrical and Optical Characteristics of Electron and Proton Irradiated SiGe Detectors.

The particle detector degradation mainly appears through decrease of carrier recombination lifetime and manifestation of carrier trapping effects related to introduction of carrier capture and emission centers. In this work, the carrier trap spectroscopy in Si1-xGex structures, containing either 1 or 5% of Ge, has been performed by combining the microwave probed photoconductivity, pulsed barrier capacitance transients and spectra of steady-state photo-ionization. These characteristics were examined in pristine, 5.5 MeV electron and 1.6 MeV proton irradiated Si and SiGe diodes with n+p structure.

Dimension Engineering of High-Quality InAs Nanostructures on a Wafer Scale.

Low-dimensional narrow-band-gap III-V semiconductors are key building blocks for the next generation of high-performance nanoelectronics, nanophotonics, and quantum devices. Realizing these various applications requires an efficient methodology that enables the material dimensional control during the synthesis process and the mass production of these materials with perfect crystallinity, reproducibility, low cost, and outstanding electronic and optoelectronic properties. Although advances in one- and two-dimensional narrow-band-gap III-V semiconductors synthesis, the progress toward reliable methods that can satisfy all of these requirements has been limited. Here, we demonstrate an approach that provides a precise control of the dimension of InAs from one-dimensional nanowires to wafer-scale free-standing two-dimensional nanosheets, which have a high degree of crystallinity and outstanding electrical and optical properties, using molecular-beam epitaxy by controlling catalyst alloy segregation. In our approach, two-dimensional InAs nanosheets can be obtained directly from one-dimensional InAs nanowires by silver-indium alloy segregation, which is much easier than the previously reported methods, such as the traditional buffering technique and select-area epitaxial growth. Detailed transmission electron microscopy investigations provide solid evidence that the catalyst alloy segregation is the origination of the InAs dimensional transformation from one-dimensional nanowires to two-dimensional nanosheets and even to three-dimensional complex crosses. Using this method, we find that the wafer-scale free-standing InAs nanosheets can be grown on various substrates including Si, MgO, sapphire, GaAs, etc. The InAs nanosheets grown at high temperature are pure-phase single crystals and have a high electron mobility and a long time-resolved terahertz kinetics lifetime. Our work will open up a conceptually new and general technology route toward the effective controlling of the dimension of the low-dimensional III-V semiconductors. It may also enable the low-cost fabrication of free-standing nanosheet-based devices on an industrial scale.