Plasma Treatment for Achieving Oxygen Substitution in Layered MoS2 and the Room-Temperature Mid-Infrared (10 µm) Photoresponse.

Highly sensitive photodetectors in the mid-infrared (MIR, 3-15 µm) are highly desired in a growing number of applications. However, only a handful of narrow-band-gap semiconductors are suitable for this purpose, most of which require cryogenic cooling to increase the signal-to-noise ratio. The realization of high-performance MIR photodetectors operating at room temperature remains a challenge. Herein, we report on plasma-treated few-layer MoS2 for room-temperature MIR (10 µm) photodetection. Oxygen plasma treatment, which is a mature microfabrication process, is employed. The ion kinetic energy of oxygen plasma is adjusted to 70-130 eV. A photoresponsivity of 0.042 mA/W and a detectivity of 1.57 × 107 Jones are obtained under MIR light (10 µm) illumination with an average power density of 114.6 mW/cm2. The photoresponse is attributed to the introduction of electronic states in the band gap of MoS2 through oxygen substitution. A graphene/plasma-treated MoS2/graphene device is further demonstrated to shorten the active channel while maintaining the illumination area. The photoresponsivity and detectivity are largely boosted to 1.8 A/W and 2.64 × 109 Jones, respectively. The excellent detective performance of the graphene/plasma-treated MoS2/graphene device is further demonstrated in single-detector MIR (10 µm) scanning imaging. This work offers a facile approach to constructing integrated MoS2-based MIR photodetectors.

High-Performance Planar Field-Emission Photodetector of Monolayer Tungsten Disulfide with Microtips.

Monolayer tungsten disulfide (ML WS2 ) is believed as an ideal photosensitive material due to its small direct bandgap, large exciton/trion binding energy, high carrier mobility, and considerable quantum conversion efficiency. Compared with other photosensitive devices, planar field emission (FE)-type photodetectors with a full-plane structure should simultaneously have rapider switching speed and lower power consumption. In this work, ML WS2 microtips are fabricated by electron beam lithography (EBL) way and used to construct a planar FE-type photodetector. By optimization design, ML WS2 with three microtips can exhibit the maximum current density as high as  52 A cm-2 (@300 V µm-1 ), and the largest photoresponsivity is up to 6.8 × 105 A W-1 under green light irradiation, superior to that of many other ML transition metal dichalcogenide (TMDC) detectors. More interestingly, ML WS2 devices with microtips can effectively solve the contradictory problem between large photoresponsivity and rapid switching speed. The excellent photoresponse performances of ML WS2 with microtips should be attributed to their high carrier mobility, sharp emission edge, ultrahigh quantum yield, and unique planar FE device structure. Our research may shed new light on exploring the fabrication technology and photosensitive mechanism of two dimensional (2D) material-based planar FE photodetectors.

High Responsivity Vacuum Nano-Photodiode Using Single-Crystal CsPbBr3 Micro-Sheet.

Field electron emission vacuum photodiode is promising for converting free-space electromagnetic radiation into electronic signal within an ultrafast timescale due to the ballistic electron transport in its vacuum channel. However, the low photoelectric conversion efficiency still hinders the popularity of vacuum photodiode. Here, we report an on-chip integrated vacuum nano-photodiode constructed from a Si-tip anode and a single-crystal CsPbBr3 cathode with a nano-separation of ~30 nm. Benefiting from the nanoscale vacuum channel and the high surface work function of the CsPbBr3 (4.55 eV), the vacuum nano-photodiode exhibits a low driving voltage of 15 V with an ultra-low dark current (50 pA). The vacuum nano-photodiode demonstrates a high photo responsivity (1.75 AW-1@15 V) under the illumination of a 532-nm laser light. The estimated external quantum efficiency is up to 400%. The electrostatic field simulation indicates that the CsPbBr3 cathode can be totally depleted at an optimal thickness. The large built-in electric field in the depletion region facilitates the dissociation of photoexcited electron-hole pairs, leading to an enhanced photoelectric conversion efficiency. Moreover, the voltage drop in the vacuum channel increases due to the photoconductive effect, which is beneficial to the narrowing of the vacuum barrier for more efficient electron tunneling. This device shows great promise for the development of highly sensitive perovskite-based vacuum opto-electronics.

Highly efficient nonlinear optical emission from a subwavelength crystalline silicon cuboid mediated by supercavity mode.

The low quantum efficiency of silicon (Si) has been a long-standing challenge for scientists. Although improvement of quantum efficiency has been achieved in porous Si or Si quantum dots, highly efficient Si-based light sources prepared by using the current fabrication technooloy of Si chips are still being pursued. Here, we proposed a strategy, which exploits the intrinsic excitation of carriers at high temperatures, to modify the carrier dynamics in Si nanoparticles. We designed a Si/SiO2 cuboid supporting a quasi-bound state in the continuum (quasi-BIC) and demonstrated the injection of dense electron-hole plasma via two-photon-induced absorption by resonantly exciting the quasi-BIC with femtosecond laser pulses. We observed a significant improvement in quantum efficiency by six orders of magnitude to ~13%, which is manifested in the ultra-bright hot electron luminescence emitted from the Si/SiO2 cuboid. We revealed that femtosecond laser light with transverse electric polarization (i.e., the electric field perpendicular to the length of a Si/SiO2 cuboid) is more efficient for generating hot electron luminescence in Si/SiO2 cuboids as compared with that of transverse magnetic polarization (i.e., the magnetic field perpendicular to the length of a Si/SiO2 cuboid). Our findings pave the way for realizing on-chip nanoscale Si light sources for photonic integrated circuits and open a new avenue for manipulating the luminescence properties of semiconductors with indirect bandgaps.

How Materials and Device Factors Determine the Performance: A Unified Solution for Transistors with Nontrivial Gates and Transistor-Diode Hybrid Integration.

Advanced field-effect transistors (FETs) with nontrivial gates (e.g., offset-gates, mid-gates, split-gates, or multi-gates) or hybrid integrations (e.g., with diodes, photodetectors, or field-emitters) have been extensively developed in pursuit for the "More-than-Moore" demand. But understanding their conduction mechanisms and predicting current-voltage relations is rather difficult due to countless combinations of materials and device factors. Here, it is shown that they could be understood within the same physical picture, i.e., charge transport from gated to nongated semiconductors. One proposes an indicator based on material and device factors for characterizing the transport and derives a unified and simplified solution for describing the current-voltage relations, current saturation, channel potentials, and drift field. It is verified by simulations and experiments of different types of devices with varied materials and device factors, employing organic, oxide, nanomaterial semiconductors in transistors or hybrid integrations. The concise and unified solution provides general rules for quick understanding and designing of these complex, innovative devices.

Crystalline Silicon White Light Sources Driven by Optical Resonances.

Silicon (Si) is generally considered as a poor photon emitter, and various scenarios have been proposed to improve the photon emission efficiency of Si. Here, we report the observation of a burst of the hot electron luminescence from Si nanoparticles with diameters of 150-250 nm, which is triggered by the exponential increase of the carrier density at high temperatures. We show that the stable white light emission above the threshold can be realized by resonantly exciting either the mirror-image-induced magnetic dipole resonance of a Si nanoparticle placed on a thin silver film or the surface lattice resonance of a regular array of Si nanopillars with femtosecond laser pulses of only a few picojoules, where significant enhancements in two- and three-photon-induced absorption can be achieved. Our findings indicate the possibility of realizing all-Si-based nanolasers with manipulated emission wavelength, which can be easily incorporated into future integrated optical circuits.

Magnetically Responsive Film Decorated with Microcilia for Robust and Controllable Manipulation of Droplets.

Droplet manipulations are critical for applications ranging from biochemical analysis, medical diagnosis to environmental controls. Even though magnetic actuation has exhibited great potential, the capability of high-speed, precise manipulation, and mixing improvement covering a broad droplet volume has not yet been realized. Herein, we demonstrated that the magnetic actuation could be conveniently achieved via decorating the magnetically responsive film with microcilia. Under magnetic field, the film can quickly response with localized deformation, along with the microcilia to realize the surface superhydrophobicity for droplet manipulation with velocity up to ∼173 mm/s covering a broad volume of 2-100 µL. The robust system further allows us to realize rapid and complete droplet mixing within ∼1.6 s. In addition, the microcilia decorated surface can preserve the robust superhydrophobicity after various stability tests, for example, normal pressing, chemical corrosion, and mechanical abrasion, exhibiting the possibility toward the long-term and real applications. With the multifunctional demonstrations such as obvious mixing improvement, parallel manipulation, and serial dilution, we believe that the methodology can open up a magnetic field-based avenue for future applications in digital microfluidics, and biochemical assays, etc.

High Current Field Emission from Large-Area Indium Doped ZnO Nanowire Field Emitter Arrays for Flat-Panel X-ray Source Application.

Large-area zinc oxide (ZnO) nanowire arrays have important applications in flat-panel X-ray sources and detectors. Doping is an effective way to enhance the emission current by changing the nanowire conductivity and the lattice structure. In this paper, large-area indium-doped ZnO nanowire arrays were prepared on indium-tin-oxide-coated glass substrates by the thermal oxidation method. Doping with indium concentrations up to 1 at% was achieved by directly oxidizing the In-Zn alloy thin film. The growth process was subsequently explained using a self-catalytic vapor-liquid-solid growth mechanism. The field emission measurements show that a high emission current of ~20 mA could be obtained from large-area In-doped sample with a 4.8 × 4.8 cm2 area. This high emission current was attributed to the high crystallinity and conductivity change induced by the indium dopants. Furthermore, the application of these In-doped ZnO nanowire arrays in a flat-panel X-ray source was realized and distinct X-ray imaging was demonstrated.

Microneedles loaded with anti-PD-1-cisplatin nanoparticles for synergistic cancer immuno-chemotherapy.

Programmed cell death protein-1 (PD-1) on T-cells combined with programmed cell death ligand-1 (PD-L1) critically accounts for tumor immune evasion. Anti-PD-1 (aPD-1) blocks the binding of PD-1 to PD-L1, thus allowing T-cell activation for tumor cell eradication. Currently, the major challenges for cancer immunotherapy are how to improve the response rate and overcome drug resistance. Dermal administration turns out to be a promising route for immunotherapy since skin is a highly active immune organ containing a large population of resident antigen-presenting cells. Microneedle arrays can pierce the immune-cell-rich epidermis, leading to a robust T-cell response in the microenvironment of tumor cells. Herein, we successfully developed a microneedle patch loaded with pH-responsive tumor-targeted lipid nanoparticles (NPs), which allows local delivery of aPD-1 and cisplatin (CDDP) precisely to cancer tissues for cancer therapy. For in vivo studies, aPD-1/CDDP@NPs delivered through microneedles effectively boosted the immune response, thereby a remarkable effect on tumor regression was realized. Synergistic anticancer mechanisms were therefore activated through robust microneedle-induced T-cell response, blockage of PD-1 in T-cells by aPD-1, and an increase in direct cytotoxicity of CDDP in tumor cells. Strikingly, transdermal delivery using MNs increased the response rate in the animal model unresponsive to aPD-1 systemic therapy. This exhibited promise in the treatment of immunotherapy-unresponsive cancers. Taken together, microneedle-mediated local delivery of nano-encapsulated chemotherapeutic and immunotherapeutic agents at tumor skin sites provides a novel treatment strategy and insights into cancer therapy.

Study on Pyramidal Molybdenum Nanostructures Cold Cathode with Large-Current Properties Based on Self-Assembly Growth Method.

In order to develop a field emission cold cathode for power vacuum electronic device applications, it is important to realize the properties of large-current and high current density. This requires the design and preparation of cold cathode materials with good crystallization, suitable geometric structure, and good contact interface. In this study, we report a pyramidal molybdenum nanostructure with single crystalline nature, which was self-assembly grown by a thermal evaporation method. We also report the optimization of the nanostructure, successfully sharpening its top end and reducing the thickness of the intermediate layer between the structure and the substrate (from 31.4 to 3.1 nm). By this way, the pyramidal molybdenum nanostructure exhibits high conductivity of about 1.8 × 105 Ω-1 cm-1. The cold cathode composed by these nanostructures shows a large-current field emission performance, with the largest emission current of 47.62 mA as well as the highest current density of 2.38 A cm-2, under a pulsed electric field as high as 28 V µm-1. The proposed pyramidal molybdenum nanostructures provide a candidate for the large-current cold cathode of the power electronic devices.

Raman spectra of MXenes Zr2X(X=C and N).

We investigate a polarized Raman characterization of Zr2X (X = C, N), excited by two commonly used laser lines with wavelenghts of 532 nm and 633 nm, based on first principle calculations. The Raman spectra of Zr2X has two Raman shift peaks which correspond to the degenerate in-plane vibration mode (Eg) and out-of-plane vibration mode (A1g). Furthermore, we study the polarization angle dependent Raman intensity for both Eg and A1g modes in parallel and perpendicular configurations for these two materials. We found that the polarization angle dependent Raman intensity is isotropic when the laser line is perpendicular to the Zr2X plane. There are either only two maxima, or two maxima larger than the other maxima, in the parallel configuration when the laser line is parallel to the Zr2X plane, which might be useful in identifying the orientation of Zr2X in experiment. The results show that the locations of the maxima of the polarization angle dependent Raman intensity rarely depend on the exciting laser line, except that of the Eg mode of Zr2N.

A Universal Method to Weld Individual One-Dimensional Nanostructures with a Tungsten Needle Based on Synergy of the Electron Beam and Electrical Current.

One-dimensional (1D) nanostructures are extensively used in the design of novel electronic devices, sensors, and energy devices. One of the major challenges faced by the electronics industry is the problem of contact between the 1D nanostructure and electrode, which can limit or even jeopardize device operations. Herein, a universal method that can realize good Ohmic and mechanical contact between an individual 1D nanostructure and a tungsten needle at sub-micron or micron scale is investigated and presented in a scanning electron microscope (SEM) chamber with the synergy of an electron beam and electrical current flowing through the welded joint. The linear I‒V curves of five types of individual 1D nanostructures, characterized by in-situ electrical measurements, demonstrate that most of them demonstrate good Ohmic contact with the tungsten needle, and the results of in-situ tensile measurements demonstrate that the welded joints possess excellent mechanical performance. By simulation analysis using the finite element method, it is proved that the local heating effect, which is mainly produced by the electrical current flowing through the welded joints during the welding process, is the key factor in achieving good Ohmic contact.

ß-As Monolayer: Vibrational Properties and Raman Spectra.

Recently, semiconducting and other extraordinary properties of the monolayer of the V-group element have attracted a broad interest and attention. The success of experimentally growing antimonene and black phosphorus makes the arsenic monolayer a reasonable candidate for two-dimensional semiconductors. By using DFT calculation, we investigate the vibrational properties and Raman spectra of the buckled honeycomb monolayer of arsenic (ß-As) for four commonly used laser lines. By calculating Raman tensor of each active modes of the ß-As monolayer, we obtained polarization angle-dependent Raman intensities when the wave vector of incident light is parallel and perpendicular with the plane of the ß-As monolayer. We found that the nonresonant Raman spectra have two peaks at 235 and 305 cm-1 that correspond to the in-plane vibrating mode Eg and out-of-plane vibrating mode A1g, which is similar to germanene, blue phosphorene, and ß-Sb monolayer Raman spectra. There are two (four) minima and two (four) maxima when the polarization direction of scattered light is parallel (perpendicular) to that of the incident light and the wave vector of the incident light is parallel to the ß-As monolayer. The Raman intensities of neither parallel polarization configuration nor perpendicular polarization configuration depend on the polarization direction when the wave vector of incident light is perpendicular to the ß-As monolayer. The relation between shapes of the polar plots and relative values of Raman tensor elements is found. The Raman intensities decrease with increasing wavelength of incident laser lines in most cases. Our results will help experimentalists to identify the existence and the orientation of the ß-As monolayer while they are growing the ß-As monolayer.

Effect of Piezoresistive Behavior on Electron Emission from Individual Silicon Carbide Nanowire.

The excellent properties of silicon carbide (SiC) make it widely applied in high-voltage, high-power, and high-temperature electronic devices. SiC nanowires combine the excellent physical properties of SiC material and the advantages of nanoscale structures, thus attracting significant attention from researchers. Herein, the electron vacuum tunneling emission characteristics of an individual SiC nanowire affected by the piezoresistive effect are investigated using in situ electric measurement in a scanning electron microscope (SEM) chamber. The results demonstrate that the piezoresistive effect caused by the electrostatic force has a significant impact on the electronic transport properties of the nanowire, and the excellent electron emission characteristics can be achieved in the pulse voltage driving mode, including lower turn-on voltage and higher maximum current. Furthermore, a physical model about the piezoresistive effect of SiC nanowire is proposed to explain the transformation of electronic transport under the action of electrostatic force in DC voltage and pulsed voltage driving modes. The findings can provide a way to obtain excellent electron emission characteristics from SiC nanowires.

An in situ characterization technique for electron emission behavior under a photo-electric-common-excitation field: study on the vertical few-layer graphene individuals.

The in situ characterization on the individuals offers an effective way to explore the dynamic behaviors and underlying physics of materials at the nanoscale, and this is of benefit for actual applications. In the field of vacuum micro-nano electronics, the existing in situ techniques can obtain the material information such as structure, morphology and composition in the process of electron emission driven by a single source of excitation. However, the relevant process and mechanism become more complicated when two or more excitation sources are commonly acted on the emitters. In this paper, we present an in situ nano characterization technique to trigger and record the electron emission behavior under the photo-electric-common-excitation multiple physical fields. Specifically, we probed into the in situ electron emission from an individual vertical few-layer graphene (vFLG) emitter under a laser-plus-electrostatic driving field. Electrons were driven out from the vFLG's emission edge, operated in situ under an external electrostatic field coupled with a 785 nm continuous-wave laser-triggered optical field. The incident light has been demonstrated to significantly improve the electron emission properties of graphene, which were recorded as an obvious decrease of the turn-on voltage, a higher emission current by factor of 35, as well as a photo-response on-off ratio as high as 5. More importantly, during their actual electron emission process, a series of in situ characterizations such as SEM observation and Raman spectra were used to study the structure, composition and even real-time Raman frequency changes of the emitters. These information can further reveal the key factors for the electron emission properties, such as field enhancement, work function and real-time surface temperature. Thereafter, the emission mechanism of vFLG in this study has been semi-quantitatively demonstrated to be the two concurrent processes of photon-assisted thermal enhanced field emission and photo field emission.

Non-uniaxial stress-assisted fabrication of nanoconstriction on vertical nanostructured Si.

Vertically aligned Si nanoconstrictions have potential for applications of electronic, photonic and phononic nanodevices. Herein, we report a featured method by utilizing the non-uniaxial tangential tension stress (σ T ) at the Si surface of a vertical hyperbolic Si/SiO2 core-shell nanostructure during thermal oxidation to achieve well defined Si nanoconstrictions. A thermal oxidation model was proposed to describe the correlations between σ T and the structural parameters of the hyperbolic nanostructure, i.e. oxide thickness (t ox ), sidewall curvature radius (R 0) and neck diameter (2r A0). Numerical simulations indicated that the Si surface at the position with the narrowest diameter (neck position) has the highest σ T (∼GPa) and presents a gradient distribution at both ends. By means of stress regulation, an array of well defined Si nanoconstrictions about 10 nm in diameter and about 34 nm in length was obtained. The experimental findings demonstrated that the high σ T would induce a nanofracture and thus a local oxidation to form a nanoconstriction, self-aligned at the neck position. The finding notably extends the capability of stress-assisted 'nanofabrication' of Si via thermal oxidation.

A Plasmon-Mediated Electron Emission Process.

Light-driven electron emission plays an important role in modern optoelectronic devices. However, such a process usually requires a light field with either a high intensity or a high frequency, which is not favorable for its implementations and difficult for its integrations. To solve these issues, we propose to combine plasmonic nanostructures with nanoelectron emitters of low work function. In such a heterostructure, hot electrons generated by plasmon resonances upon light excitation can be directly injected into the adjacent emitter, which can subsequently be emitted into the vacuum. Electron emission of high efficiency can be obtained with light fields of moderate intensities and visible wavelengths, which is a plasmon-mediated electron emission (PMEE) process. We have demonstrated our proposed design using a gold-on-graphene (Au-on-Gr) nanostructure, which can have electron emission with light intensity down to 73 mW·cm-2. It should be noted that the field electron emission is not involved in such a PMEE process. This proposal is of interest for applications including cold-cathode electron sources, advanced photocathodes, and micro- and nanoelectronic devices relying on free electrons.

Defective WO3-x nanowire: possible long lifetime semiconductor nanowire point electron source.

In pursuing high emission current density and high brightness, it is difficult to avoid vacuum breakdown in nanowire cold cathode systems, which will shorten the lifetime of the electron sources. Therefore, investigations on the vacuum breakdown process are important for semiconductor nanowire point electron sources. In this study, non-catastrophic breakdown phenomena that could extend the lifetime of the nanowire electron source were observed in the field emission processes of individual defective WO3-x nanowires. In this non-catastrophic breakdown process, only part of the nanowire emitter was destroyed. After the breakdown, the remaining part of the nanowire could still emit electrons, and due to the shortening of its length, the maximum field emission current density of the remaining nanowire was increased. These results are consistent with the prediction given by theoretical calculations. A defect-related electrical transport induced breakdown mechanism and Nottingham effect induced cooling effect were proposed to be the main causes of this phenomenon. Our work provides an approach for designing long lifetime semiconductor nanowire point electron sources.

Vibrational properties and Raman spectra of pristine and fluorinated blue phosphorene.

Using density functional theory, we investigated the vibrational properties and Raman spectra of pristine blue phosphorene and fluorinated blue phosphorene. The fluorinated blue phosphorene possesses a Dirac cone at the K point (about 310 cm-1). The shape of the Dirac cone remains unchanged under different tensile strains. The Raman tensor and thus angle-dependent Raman intensities of all Raman active modes are calculated for the polarizations of scattered light parallel and perpendicular to that of the incident light. The characteristics of angle-dependent Raman intensities are discussed. Moreover, the polarization direction averaged non-resonant Raman spectra of pristine blue phosphorene and fluorinated blue phosphorene are compared with that of germanene and black phosphorene.

Microneedle-Mediated Delivery of Lipid-Coated Cisplatin Nanoparticles for Efficient and Safe Cancer Therapy.

Cisplatin is the first-line chemotherapeutic agent, but its systemic toxicity and side effects severely limit its clinical use. We report a microneedle technique to mediate the transdermal delivery of lipid-coated cisplatin nanoparticles (LCC-NPs) for efficient and safe cancer therapy. Cisplatin was encapsulated by tumor-targeting pH-responsive lipid nanoparticles with a high loading rate of 80%, and the encapsulation substantially increased the solubility of cisplatin and enhanced its antitumor efficiency in vitro. The LCC-NPs were embedded in dissolvable microneedles, and released from the microneedles after inserting into the skin. This enabled the nanoparticles to pass the stratum corneum for safe local delivery. An in vivo study with a xenograft tumor animal model demonstrated that microneedle arrays loaded with cisplatin nanoparticles significantly increased cytotoxicity and apoptosis in cancer cells with an apoptotic index of 58.6%, resulting in significantly reduced tumor volume and weight. Moreover, serum platinum, pulmonary toxicity, hepatotoxicity, and nephrotoxicity were not detected in vivo, indicating that this technique is biosafe. The cisplatin-nanoparticle microneedle system developed in this study may offer promising opportunities in cancer therapy for enhancing antitumor effects and reducing systemic toxicity and side effects.