The Electrical Behaviors of Grain Boundaries in Polycrystalline Optoelectronic Materials.

Polycrystalline optoelectronic materials are widely used for photoelectric signal conversion and energy harvesting and play an irreplaceable role in the semiconductor field. As an important factor in determining the optoelectronic properties of polycrystalline materials, grain boundaries (GBs) are the focus of research. Particular emphases are placed on the generation and height of GB barriers, how carriers move at GBs, whether GBs act as carrier transport channels or recombination sites, and how to change the device performance by altering the electrical behaviors of GBs. This review introduces the evolution of GB theory and experimental observation history, classifies GB electrical behaviors from the perspective of carrier dynamics, and summarizes carrier transport state under external conditions such as bias and illumination and the related band bending. Then the carrier scattering at GBs and the electrical differences between GBs and twin boundaries are discussed. Last, the review describes how the electrical behaviors of GBs can be influenced and modified by treatments such as passivation or by consciously adjusting the distribution of grain boundary elements. By studying the carrier dynamics and the relevant electrical behaviors of GBs in polycrystalline materials, researchers can develop optoelectronics with higher performance.

Preparation of Mixed Few-Layer GeSe Nanosheets with High Efficiency by the Thermal Sublimation Method.

Two-dimensional (2D) GeSe has been proven promising in fast and broadband optoelectronic applications for its complicated band structure, inert surface property, and excellent stability. The major challenge is the deficiency of the effective technique for controllably prepared large-scale few-to-monolayer GeSe films. For this purpose, a layer-by-layer thinning method by thermal sublimation for manufacturing large-scale mixed few-layer GeSe with direct bandgaps is proposed, and an optimized sublimation temperature of 300 °C in vacuum is evaluated by atomic force microscopy. Scanning electron microscopy, transmission electron microscopy, energy-dispersive spectra, and fluorescence mapping measurements are performed on the thinned GeSe layers, and results are well-indexed to the orthorhombic lattice structure with direct bandgaps with an atomic ratio of Ge/Se ≈ 5:4. Raman and fluorescence spectra show an α-type crystalline structure of the thinned GeSe films, indicating the pure physical process of the sublimation thinning. Both the bulk and few-layer GeSe films demonstrate broadband absorption. Conductivity of the few-layer GeSe device indicates the overall crystalline integrity of the film after thermal thinning. Given the convenience and efficiency, we provide an effective approach for fabrication of large-scale 2D materials that are difficult to be prepared by traditional methods.

Enhanced Photoluminescence and Random Lasing Emission in TiO2-Decorated FAPbBr3 Thin Films.

Herein, titanium-dioxide-decorated organic formamidinium lead bromide perovskite thin films grown by the one-step spin-coating method are studied. TiO2 nanoparticles are widespread in FAPbBr3 thin films, which changes the optical properties of the perovskite thin films effectively. Obvious reductions in the absorption and enhancements in the intensity of the photoluminescence spectra are observed. Over 6 nm, a blueshift of the photoluminescence emission peaks is observed due to 5.0 mg/mL TiO2 nanoparticle decoration in the thin films, which originates from the variation in the grain sizes of the perovskite thin films. Light intensity redistributions in perovskite thin films are measured by using a home-built confocal microscope, and the multiple scattering and weak localization of light are analyzed based on the scattering center of TiO2 nanoparticle clusters. Furthermore, random lasing emission with sharp emission peaks is achieved in the scattering perovskite thin films with a full width at the half maximum of 2.1 nm. The multiple scattering of light, the random reflection and reabsorption of light, and the coherent interaction of light within the TiO2 nanoparticle clusters play important roles in random lasing. This work could be used to improve the efficiency of photoluminescence and random lasing emissions, and it is promising in high-performance optoelectrical devices.

Substantially Enhanced Properties of 2D WS2 by High Concentration of Erbium Doping against Tungsten Vacancy Formation.

Doping in 2D materials is an important method for tuning of band structures. For this purpose, it is important to develop controllable doping techniques. Here, we demonstrate a substitutional doping strategy by erbium (Er) ions in the synthesis of monolayer WS2 by chemical vapor deposition. Substantial enhancements in photoluminescent and photoresponsive properties are achieved, which indicate a tungsten vacancy suppression mechanism by Er filling. Er ion doping in the monolayer WS2 is proved by X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS), fluorescence, absorption, excitation, and Raman spectra. 11.5 at% of the maximum Er concentration is examined by energy dispersive X-ray spectroscopy (EDX). Over 6 times enhancement of intensities with 7.9 nm redshift in peaks are observed from the fluorescent spectra of Er-doped WS2 monolayers compared with their counterparts of the pristine WS2 monolayers, which agrees well with the density functional theory calculations. In addition, over 11 times of dark current, 469 times of photocurrents, photoresponsivity, and external quantum efficiency, and two orders of photoresponse speed are demonstrated from the Er-doped WS2 photodetector compared with those of the pristine WS2 device. Our findings prove rare-earth doping in 2D materials, the exciting and ideal technique for substantially enhanced photoluminescent and photoresponsive properties.

Comprehensive Analysis of Eleutherococcus senticosus (Rupr. & Maxim.) Maxim. Leaves Based on UPLC-MS/MS: Separation and Rapid Qualitative and Quantitative Analysis.

Eleutherococcus senticosus (Rupr. & Maxim.) Maxim. leaves (ESL) have long been people's favorite as a natural edible green vegetable, in which phenols and saponins are the main characteristic and bioactive components. This study was first carried out to comprehensively analyze the phenols and saponins in ESL, including phytochemical, qualitative, quantitative, and bioactivity analysis. The results showed that 30 compounds, including 20 phenolic compounds and 7 saponins, were identified. Twelve of them were isolated from Eleutherococcus Maxim. for the first time. In the qualitative analysis, 30 phenolic compounds and 28 saponins were accurately detected. Their characteristic cleavage processes were described by UPLC-QTOF-MS/MS. Ten representative ingredients were quantitated in 29 different regions via a 4000 QTRAP triple quadrupole tandem mass spectrometer (UPLC-QTRAP-MS/MS), and it was found that S19 (69.89 ± 1.098 mg/g) and S1 (74.28 ± 0.733 mg/g) had the highest contents of total phenols and saponins, respectively. The newly developed analysis method for the quantitative determination was validated for linearity, precision, and limits of detection and quantification, which could be applied to the quality assessment of ESL. In vitro experiment, the α-glucosidase inhibitory effect of the phenolic fraction was higher than others, indicating that the phenolic content may be related to the hypoglycemic activity. It was also suggested that ESL could be developed as a natural potential effective drug or functional food.

Lateral Structured Phototransistor Based on Mesoscopic Graphene/Perovskite Heterojunctions.

Due to their outstanding optical properties and superior charge carrier mobilities, organometal halide perovskites have been widely investigated in photodetection and solar cell areas. In perovskites photodetection devices, their high optical absorption and excellent quantum efficiency contribute to the responsivity, even the specific detectivity. In this work, we developed a lateral phototransistor based on mesoscopic graphene/perovskite heterojunctions. Graphene nanowall shows a porous structure, and the spaces between graphene nanowall are much appropriated for perovskite crystalline to mount in. Hot carriers are excited in perovskite, which is followed by the holes' transfer to the graphene layer through the interfacial efficiently. Therefore, graphene plays the role of holes' collecting material and carriers' transporting channel. This charge transfer process is also verified by the luminescence spectra. We used the hybrid film to build phototransistor, which performed a high responsivity and specific detectivity of 2.0 × 103 A/W and 7.2 × 1010 Jones, respectively. To understand the photoconductive mechanism, the perovskite's passivation and the graphene photogating effect are proposed to contribute to the device's performance. This study provides new routes for the application of perovskite film in photodetection.

Fast and Broadband Photoresponse of a Few-Layer GeSe Field-Effect Transistor with Direct Band Gaps.

Few-to-monolayer germanium selenide, a new IV-VI group layered material recently fabricated by mechanical exfoliation and subsequent laser thinning, is promising in very fast and broadband optoelectronic applications for its excellent stability, complicated band structures, inert surface properties, and being a natural p-type semiconductor. However, large-scale production of such few-layer GeSe devices with superior performance is still in early stages. In this study, field-effect transistors made of few-layer GeSe with direct band gaps are fabricated. Transistor performance with Schottky contact characteristics is measured at room temperature. A field-effect mobility of 4 cm2/(V s) and drain currents modulated both by holes and electrons are measured. Photoresponses as a function of illumination wavelength, power, and frequency are characterized. The few-layer GeSe transistor shows photoresponse to the illumination wavelengths from visible up to 1400 nm and a photoresponse rise (fall) time of 13 µs (19 µs), demonstrating very broadband and fast detection. The ambipolar behavior and the photoresponse characteristics demonstrate great potential of few-layer GeSe for applications in highly stable, very fast, and very broadband optoelectronic devices.

Facile and Controllable Synthesis of Large-Area Monolayer WS2 Flakes Based on WO3 Precursor Drop-Casted Substrates by Chemical Vapor Deposition.

Monolayer WS2 (Tungsten Disulfide) with a direct-energy gap and excellent photoluminescence quantum yield at room temperature shows potential applications in optoelectronics. However, controllable synthesis of large-area monolayer WS2 is still challenging because of the difficulty in controlling the interrelated growth parameters. Herein, we report a facile and controllable method for synthesis of large-area monolayer WS2 flakes by direct sulfurization of powdered WO3 (Tungsten Trioxide) drop-casted on SiO2/Si substrates in a one-end sealed quartz tube. The samples were thoroughly characterized by an optical microscope, atomic force microscope, transmission electron microscope, fluorescence microscope, photoluminescence spectrometer, and Raman spectrometer. The obtained results indicate that large triangular monolayer WS2 flakes with an edge length up to 250 to 370 µm and homogeneous crystallinity were readily synthesized within 5 min of growth. We demonstrate that the as-grown monolayer WS2 flakes show distinctly size-dependent fluorescence emission, which is mainly attributed to the heterogeneous release of intrinsic tensile strain after growth.

Enhancement of photoluminescence efficiency in GeSe ultrathin slab by thermal treatment and annealing: experiment and first-principles molecular dynamics simulations.

The effect of thermal treatment and annealing under different temperatures from 100 °C to 250 °C on the photoluminescence spectroscopy of the GeSe ultrathin slab is reported. After the thermal treatment and annealing under 200 °C, we found that the photoluminescence intensity of A exciton and B exciton in GeSe ultrathin slab is increased to twice as much as that in untreated case, while is increased by ~84% in the photoluminescence intensity of C exciton. Combined by our experimental work and theoretical simulations, our study confirms the significant role of thermal treatments and annealing in reducing surface roughness and removing the Se vacancy to form more compact and smoother regions in GeSe ultrathin slab. Our findings imply that the improved quality of GeSe surface after thermal treatments is an important factor for the photoluminescence enhancement.

Effect of stacking order and in-plane strain on the electronic properties of bilayer GeSe.

Germanium selenide as a new layered material is promising for nanoelectronic applications due to its unique optoelectronic properties and tunable band gap. In this study, based on density functional theory, we systematically investigated the structure, stability, and electronic properties of bilayer germanium selenide with four different stacking orders (namely AA-, AB-, AC- and AD-stacking). The obtained results indicated that the band gap is dependent on the stacking order with an indirect band gap for AA- and AC-stacking and direct band gap for AB- and AD-stacking. In addition, we also found that the band gap of the GeSe bilayer with different stacking orders can be tuned by in-plane strain. The transition between the direct to indirect band gap or semiconductor to metal is tunable. In particular, the direct band gap of the AB-stacking germanium selenide bilayer can be tuned in a wide energy range under applied strain along the armchair direction.

Bandgap modulation of MoS2 monolayer by thermal annealing and quick cooling.

We developed a non-mechanical straining method to simultaneously modulate the bandgap and photoluminescence (PL) quantum efficiency of a synthesized molybdenum disulfide (MoS2) monolayer on SiO2, by vacuum annealing and subsequent quick cooling in ethanol. Influences of the thermal treatments at different temperatures from 100 °C to 600 °C on the PL and Raman spectra of the MoS2 monolayers are reported. A maximum PL peak intensity, twice that of the untreated counterparts under the same measurement conditions, was observed at the treating temperature of 200 °C. At the same time, approximately permanent tensile strains were induced, due to the quick cooling from high temperatures, which led to a red-shift of the direct optical bandgap. Modulation of the bandgap was achieved by changing the treating temperatures; nearly linear PL and Raman frequency shifts of ∼3.82 meV per 100 °C and ∼-0.28 cm-1/100 °C for A exciton photoluminescence and Raman E12g mode frequency were observed, respectively. The proposed thermal modulation promises a wide range of applications in functional 2D nanodevices and semiconductors. To our knowledge, our findings constitute the first demonstration of thermal engineering by combinational manipulation of annealing and quick cooling of the 2D transition-metal dichalcogenides.

Ultrathin fiber-taper coupling with nitrogen vacancy centers in nanodiamonds at cryogenic temperatures.

We demonstrate cooling of ultrathin fiber tapers coupled with nitrogen vacancy (NV) centers in nanodiamonds to cryogenic temperatures. Nanodiamonds containing multiple NV centers are deposited on the subwavelength 480-nm-diameter nanofiber region of fiber tapers. The fiber tapers are successfully cooled to 9 K using our home-built mounting holder and an optimized cooling speed. The fluorescence from the nanodiamond NV centers is efficiently channeled into a single guided mode and shows characteristic sharp zero-phonon lines (ZPLs) of both neutral and negatively charged NV centers. The present nanofiber/nanodiamond hybrid systems at cryogenic temperatures can be used as NV-based quantum information devices and for highly sensitive nanoscale magnetometry in a cryogenic environment.

Observation of 1.2-GHz linewidth of zero-phonon-line in photoluminescence spectra of nitrogen vacancy centers in nanodiamonds using a Fabry-Perot interferometer.

Photoluminescence (PL) spectra of single nitrogen vacancy (NV) centers in 50-nm diamond nanocrystals at the zero-phonon line (ZPL) were directly observed using a Fabry-Perot interferometer at cryogenic temperatures. The narrowest linewidth of ZPL was 1.2 GHz (1.9 ± 0.7 GHz on average), comparable to ZPL linewidths in PL spectra reported for NV centers in pure bulk diamond. This observation is important to the application of NV centers for use in quantum communication and computation devices, and in nano-sensing.

Coupling of ultrathin tapered fibers with high-Q microsphere resonators at cryogenic temperatures and observation of phase-shift transition from undercoupling to overcoupling.

We cooled ultrathin tapered fibers to cryogenic temperatures and controllably coupled them with high-Q microsphere resonators at a wavelength close to the optical transition of diamond nitrogen vacancy centers. The 310-nm-diameter tapered fibers were stably nanopositioned close to the microspheres with a positioning stability of approximately 10 nm over a temperature range of 7-28 K. A cavity-induced phase shift was observed in this temperature range, demonstrating a discrete transition from undercoupling to overcoupling.

Suppression of fluorescence phonon sideband from nitrogen vacancy centers in diamond nanocrystals by substrate effect.

Substrates effect is observed on the suppression of the phonon sideband from nitrogen vacancy (NV) centers in 50nm diamond nanocrystals at cryogenic temperatures. As a quantitative parameter of the population of phonon sidebands, the Debye-Waller factor is estimated from fluorescence spectra on glass, silicon, and silica-on-silicon substrates. Fluorescence spectra of negatively charged NV centers in nanodiamonds on silica-on-silicon substrates have average and maximum Debye-Waller factors of 12.7% (which is about six times greater than that of samples on glass substrates) and 19.3%, respectively. This effect is expected to be very important for future applications of NV centers in quantum information science and nanosensing.

A nanodiamond-tapered fiber system with high single-mode coupling efficiency.

We present a fiber-coupled diamond-based single photon system. Single nanodiamonds containing nitrogen vacancy defect centers are deposited on a tapered fiber of 273 nanometer in diameter providing a record-high number of 689,000 single photons per second from a defect center in a single-mode fiber. The system can be cooled to cryogenic temperatures and coupled evanescently to other nanophotonic structures, such as microresonators. The system is suitable for integrated quantum transmission experiments, two-photon interference, quantum-random-number generation and nano-magnetometry.

Highly efficient coupling of photons from nanoemitters into single-mode optical fibers.

Highly efficient coupling of photons from nanoemitters into single-mode optical fibers is demonstrated using tapered fibers. A percentage (7.4 ± 1.2%) of the total emitted photons from single CdSe/ZnS nanocrystals were coupled into a 300 nm diameter tapered fiber. The dependence of the coupling efficiency on the taper diameter was investigated and the coupling efficiency was found to increase exponentially with decreasing diameter. This method is very promising for nanoparticle sensing and single-photon sources.

A binary-decision-diagram-based two-bit arithmetic logic unit on a GaAs-based regular nanowire network with hexagonal topology.

A two-bit arithmetic logic unit (ALU) was successfully fabricated on a GaAs-based regular nanowire network with hexagonal topology. This fundamental building block of central processing units can be implemented on a regular nanowire network structure with simple circuit architecture based on graphical representation of logic functions using a binary decision diagram and topology control of the graph. The four-instruction ALU was designed by integrating subgraphs representing each instruction, and the circuitry was implemented by transferring the logical graph structure to a GaAs-based nanowire network formed by electron beam lithography and wet chemical etching. A path switching function was implemented in nodes by Schottky wrap gate control of nanowires. The fabricated circuit integrating 32 node devices exhibits the correct output waveforms at room temperature allowing for threshold voltage variation.