基于石墨烯的肖特基结辐射伏特同位素电池

从传统肖特基结辐射伏特同位素电池金属电极存在的对放射源衰变粒子的阻挡及导电性不理想的问题出发,借鉴石墨烯肖特基结太阳电池结构,将石墨烯/硅肖特基结引入辐射伏特同位素电池中,在63Ni放射源的照射下验证石墨烯/硅肖特基结换能单元在辐射伏特同位素电池中应用的可行性.研究结果发现,基于硝酸掺杂,当少层(3?5层)石墨烯经过4...     

Piezo‐Phototronic Effect Modulated Deep UV Photodetector Based on ZnO‐Ga2O3 Heterojuction Microwire

A strain modulated solar‐blinded photodetector (PD) based on ZnO‐Ga₂O₃ core–shell heterojuction microwire is developed. This PD is highly sensitive to deep UV light centered at 261 nm. It performs ultrahigh sensitivity and spectral selectivity, which can response to rare weak deep UV light (≈1.3 µw cm^?2) and almost no response to visible light wavelength ranges. Moreover, by using the piezo‐phototronic effect, the deep UV current response is enhanced to about three times under ?0.042% static strain. This is a three way coupling effect among pizoelectric polarization, simiconductor properties, and optical excitation, which exists in noncentral symmetric wurtzite semiconductors such as ZnO, GaN, and CdS. By modulating the energy band diagrams and charge carriers in the junction area upon straining, the optoelectronic processes are regulated. The strain induced piezopotential modulates carrier transport in the heterostructure, which improves the response of the PD, with potential applications for health monitoring, smart systems, deep space exploration, and security communication.     

Schottky‐Barrier‐Controllable Graphene Electrode to Boost Rectification in Organic Vertical P–N Junction Photodiodes

Monolayer graphene is used as an electrode to develop novel electronic device architectures that exploit the unique, atomically thin structure of the material with a low density of states at its charge neutrality point. For example, a single semiconductor layer stacked onto graphene can provide a semiconductor–electrode junction with a tunable injection barrier, which is the basis for a primitive transistor architecture known as the Schottky barrier field‐effect transistor. This work demonstrates the next level of complexity in a vertical graphene–semiconductor architecture. Specifically, an organic vertical p‐n junction (p‐type pentacene/n‐type N,N′‐dioctyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C₈)) on top of a graphene electrode constituting a novel gate‐tunable photodiode device structure is fabricated. The model device confirms that controlling the Schottky barrier height at the pentacene–graphene junction can (i) suppress the dark current density and (ii) enhance the photocurrent of the device, both of which are critical to improve the performance of a photodiode.     

Fabrication of a Large‐Area Al‐Doped ZnO Nanowire Array Photosensor with Enhanced Photoresponse by Straining

The photosensing properties of flexible large‐area nanowire (NW)‐based photosensors are enhanced via in situ Al doping and substrate straining. A method for efficiently making nanodevices incorporating laterally doped NWs is developed and the strain‐dependent photoresponse is investigated. Photosensors are fabricated by directly growing horizontal single‐crystalline Al‐doped ZnO NW arrays across Au microelectrodes patterned on a flexible SiO₂/steel substrate to enhance the transportation of carriers and the junction between NWs and electrodes. The Raman spectrum of the Al:ZnO NWs, which have an average diameter and maximum length of around 40 nm and 6.8 μm, respectively, shows an Al‐related peak at 651 cm^?1. The device shows excellent photosensing properties with a high ultraviolet/visible rejection ratio, as well as extremely high maximum photoresponsivity and sensitivity at a low bias. Increasing the tensile strain from 0 to 5.6% linearly enhances the photoresponsivity from 1.7 to 3.8 AW^?1 at a bias of 1 V, which is attributed to a decrease in the Schottky barrier height resulting from a piezo‐photonic effect. The high‐performance flexible NW device presented here has applications in coupling measurements of light and strain in a flexible photoelectronic nanodevice and can aid in the development of better flexible and integrated photoelectronic systems.     

Three‐Dimensional Kelvin Probe Microscopy for Characterizing In‐Plane Piezoelectric Potential of Laterally Deflected ZnO Micro‐/Nanowires

Potential characterization of deflected piezoelectric nanowires (NWs) is of great interest for current development of electromechanical nanogenerators that harvest ambient mechanical energy. In this paper, a Kelvin probe microscopy (KPM) technique hybridizing scanning KPM (SKPM) with atomic force microscope (AFM) surface‐approach spectroscopy methods for characterizing in‐plane piezoelectric potential of ZnO microwires (MWs) is presented. This technique decouples the scanning motion of the AFM tip from sample topography, and thus effectively eliminates artifacts induced by high topographical variations along the edges of MWs/NWs which make characterization by conventional SKPM inappropriate or impossible. By virtue of the topography/tip motion decoupling approach, the electrical potential can also be mapped in a three‐dimensional (3D) spatial volume above the sample surface. Therefore, this technique is named 3DKPM. Through 3DKPM mapping, the piezopotential generated by a laterally deflected ZnO MW was determined by extracting the potential asymmetry from opposite sides of the MW. The measurement results agree well with theoretical predictions. Integrating an external bias to the MW sample allowed direct observation of piezopotential and carrier concentration coupling phenomenon in ZnO, opening a door toward quantitative microscopic investigation of the piezotronic effect. With further positioning refinements, 3DKPM could become a powerful technique for the characterization of piezoelectric potential and related effects in micro/nanostructures of high topographical variations, as well as development of MW/NW‐based piezoelectric nanodevices.     

Piezotronic Graphene Artificial Sensory Synapse

The human somatosensory system, consisting of receptors, transmitters, and synapses, functions as the medium for external mechanical stimuli perception and sensing signal delivery/processing. Developing sophisticated artificial sensory synapses with a high performance, uncomplicated fabrication process, and low power consumption is still a great challenge. Here, a piezotronic graphene artificial sensory synapse developed by integrating piezoelectric nanogenerator (PENG) with an ion gel–gated transistor is demonstrated. The piezopotential originating from PENG can efficiently power the synaptic device due to the formation of electrical double layers at the interface of the ion gel/electrode and ion gel/graphene. Meanwhile, the piezopotential coupling is capable of linking the spatiotemporal strain information (strain amplitude and duration) with the postsynaptic current. The synaptic weights can be readily modulated by the strain pulses. Typical properties of a synapse including excitation/inhibition, synaptic plasticity, and paired pulse facilitation are successfully demonstrated. The dynamic modulation of a sensory synapse is also achieved based on dual perceptual presynaptic PENGs coupling to a single postsynaptic transistor. This work provides a new insight into developing piezotronic synaptic devices in neuromorphic computing, which is of great significance in future self‐powered electronic skin with artificial intelligence, a neuromorphic interface for neurorobotics, human–robot interaction, an intelligent piezotronic transistor, etc.     

Comprehensive Pyro‐Phototronic Effect Enhanced Ultraviolet Detector with ZnO/Ag Schottky Junction

As a coupling effect of pyroelectric and photoelectric effect, pyro‐phototronic effect has demonstrated an excellent tuning role for fast response p–n junction photodetectors (PDs). Here, a comprehensive pyro‐phototronic effect is utilized to design and fabricate a self‐powered and flexible ultraviolet PD based on the ZnO/Ag Schottky junction. By using the primary pyroelectric effect, the maximal transient photoresponsivity of the self‐powered PDs can reach up to 1.25 mA W^?1 for 325 nm illumination, which is improved by 1465% relative to that obtained from the steady‐state signal. The relative persistent secondary pyroelectric effect weakens the height of Schottky barrier, leading to a reduction of the steady‐state photocurrent with an increase in the power density. When the power density is large enough, the steady‐state photocurrent turns into a reverse direction. The corresponding tuning mechanisms of the comprehensive pyro‐phototronic effect on transient and steady‐state photocurrent are revealed based on the bandgap diagrams. The results may help us to further clarify the mechanism of the pyro‐phototronic effect on the photocurrent and also provide a potential way to optimize the performance of self‐powered PDs.     

Development of a Seedless Floating Growth Process in Solution for Synthesis of Crystalline ZnO Micro/Nanowire Arrays on Graphene: Towards High‐Performance Nanohybrid Ultraviolet Photodetectors

A seedless solution process is developed for controllable growth of crystalline ZnO micro/nanowire arrays directly on single‐layer graphene sheets made in chemical vapor deposition (CVD). In particular, the alignment of the ZnO micro/nanowires correlates well with the density of the wires, which is determined by both the sample configuration in solution and the graphene surface cleaning. With increasing wire density, the ZnO micro/nanowire array alignment may be varied from horizontal to vertical by increasing the physical confinement. Ultraviolet photodetectors based on the vertically aligned ZnO micro/nanowires on graphene show high responsivity of 1.62 A W^?1 per volt, a 500% improvement over epitxial ZnO sensors, a 300% improvement over ZnO nanoparticle sensors, and a 40% improvement over the previous best results for nanowire/graphene hybrid sensors. This seedless, floating growth process could be scaled up for large scale growth of oriented ZnO micro/nanowires on graphene at low costs.     

Direct Growth of Nanocrystalline Graphene/Graphite Transparent Electrodes on Si/SiO2 for Metal‐Free Schottky Junction Photodetectors

Conventional methods to produce graphene/silicon Schottky junctions inevitably involve graphene transfer and metal deposition, which leads to the techniques being complicated, high‐cost, and environmentally unfriendly. It is possible to directly grow hybrid nanocrystalline graphene/graphite transparent electrodes from photoresist on quartz without any catalyst. Due to the source material being photoresist, nanographene/graphite patterns can easily be made on Si/SiO₂ structures to form nanographene/silicon Schottky junctions via commercial photolithography and silicon techniques. The obtained Schottky junctions exhibit excellent properties with respect to photodetection, with photovoltage responsivity of 300 V W^‐1 at a light power of 0.2 μW and photovoltage response time of less than 0.5 s. The devices also exhibit an excellent reliability with the photovoltage deviating less than 1% when cycled over 200 times.     

Hybrid Solar Cells Using a Zinc Oxide Precursor and a Conjugated Polymer

We describe a new method towards bulk‐heterojunction hybrid polymer solar cells based on composite films of zinc oxide (ZnO) and a conjugated polymer poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV). Spin‐coating diethylzinc as a ZnO precursor and MDMO‐PPV from a common solvent at 40 % humidity and annealing at 110 °C provides films in which crystalline ZnO is found to be intimately mixed with MDMO‐PPV. Photoluminescence and photoinduced spectroscopy demonstrate that photoexcitation of these hybrid composite films results in a fast and long‐lived charge transfer from the polymer as a donor to ZnO as ato be obtained n acceptor. Using the ZnO‐precursor method, hybrid polymer solar cells have been made with an estimated air‐mass of 1.5 (AM 1.5) energy conversion efficiency of 1.1 %. This new method represents a fivefold improved performance compared to similar hybrid polymer solar cells based on amorphous TiO₂.     

Large‐Area Ultrathin Graphene Films by Single‐Step Marangoni Self‐Assembly for Highly Sensitive Strain Sensing Application

Promoted by the demand for wearable devices, graphene has been proved to be a promising material for potential applications in flexible and highly sensitive strain sensors. However, low sensitivity and complex processing of graphene retard the development toward the practical applications. Here, an environment‐friendly and cost‐effective method to fabricate large‐area ultrathin graphene films is proposed for highly sensitive flexible strain sensor. The assembled graphene films are derived rapidly at the liquid/air interface by Marangoni effect and the area can be scaled up. These graphene‐based strain sensors exhibit extremely high sensitivity with gauge factor of 1037 at 2% strain, which represents the highest value for graphene platelets at this small deformation so far. This simple fabrication for strain sensors with highly sensitive performance of strain sensor makes it a novel approach to applications in electronic skin, wearable sensors, and health monitoring platforms.     

Defect Restoration of Low‐Temperature Sol‐Gel‐Derived ZnO via Sulfur Doping for Advancing Polymeric Schottky Photodiodes

This study shows that the deep‐level defect states in sol‐gel‐derived ZnO can be efficiently restored by facile sulfur doping chemistry, wherein the +2 charged oxygen vacancies are filled with the S^2? ions brought by thiocyanate. By fabricating a solution‐processed polymeric Schottky diode with ITO/ZnO as the cathode, the synergetic effects of such defect‐restored ZnO electron selective layers are demonstrated. The decreased chemical defects and thus reduced mid‐gap states enable to not only enlarge the effective built‐in potential, which can expand the width of the depletion region, but also increase the Schottky energy barrier, which can reduce undesired dark‐current injection. As a result, the demonstrated simple‐structure blue‐selective polymeric Schottky photodiode renders near‐ideal diode operation with an ideality factor of 1.18, a noise equivalent power of 1.25 × 10^?14 W Hz^?1/2, and a high peak detectivity of 2.4 × 10¹³ Jones. In addition, the chemical robustness of sulfur‐doped ZnO enables exceptional device stability against air exposure as well as device‐to‐device reproducibility. Therefore, this work opens the possibility of utilizing low‐temperature sol‐gel‐derived ZnO in realizing high‐performance, stable, and reliable organic photodiodes that could be employed in the design of practical image sensors.     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

基于石墨烯/铟砷量子点/砷化镓异质结新型光电探测器

研究了一种石墨烯/铟砷量子点/砷化镓界面形成的异质结探测器的暗电流特性以及光电响应性质.虽然石墨烯具有很高的电子迁移率,但受限于较低的光子吸收率,使其在光电探测领域的应用受到了限制.而半导体量子点具有量子效率高,光吸收能力强等独特优点.于是利用石墨烯-砷化铟量子点-砷化镓异质结结构制备了一种新型光电探测器.并对该探测器的响应率、I-V特性曲线、暗电流特性、探测率、开关比等关键性能进行了研究.其在637 nm入射光情况下的响应率、探测率以及开关比可分别达到为17. 0 m A/W、2. 3×10~(10)cm Hz~(1/2)W~(-1)和1×10~3.而当入射光为近红外波段的940纳米时,响应率进一步增加到了207 m A/W.同时,还证实了该器件的暗电流、肖特基势垒高度和理想因子对温度的都具有较高的依赖性都较强.     

Charge‐Generating Mode Control in High‐Performance Transparent Flexible Piezoelectric Nanogenerators

In this work, we demonstrate the mode transition of charge generation between direct‐current (DC) and alternating‐current (AC) from transparent flexible (TF) piezoelectric nanogenerators (NGs), which is dependent solely on the morphology of zinc oxide (ZnO) nanorods without any use of an AC/DC converter. Tilted ZnO nanorods grown on a relatively low‐density seed layer generate DC‐type piezoelectric charges under a pushing load, whereas vertically aligned ZnO nanorods on a relatively high‐density seed layer create AC‐type charge generation. The mechanism for the geometry‐induced mode transition is proposed and characterized. We also examine the output performance of TF‐NGs which employ an indium zinc tin oxide (IZTO) film as a TF electrode. It is demonstrated that an IZTO film has improved electrical, optical, and mechanical properties, in comparison with an indium tin oxide (ITO) film. Enhanced output charge generation is observed from IZTO‐based TF‐NGs when TF‐NGs composed of only ITO electrodes are compared. This is attributed to the higher Schottky barrier and the lower series resistance of the IZTO‐based TF‐NGs. Thus, by using IZTO, we can expect TF‐NGs with superior mechanical durability and power generating performance.     

Large‐Area Schottky Barrier Transistors Based on Vertically Stacked Graphene–Metal Oxide Heterostructures

The fabrication of all‐transparent flexible vertical Schottky barrier (SB) transistors and logic gates based on graphene–metal oxide–metal heterostructures and ion gel gate dielectrics is demonstrated. The vertical SB transistor structure is formed by (i) vertically sandwiching a solution‐processed indium‐gallium‐zinc‐oxide (IGZO) semiconductor layer between graphene (source) and metallic (drain) electrodes and (ii) employing a separate coplanar gate electrode bridged with a vertical channel through an ion gel. The channel current is modulated by tuning the Schottky barrier height across the graphene–IGZO junction under an applied external gate bias. The ion gel gate dielectric with high specific capacitance enables modulation of the Schottky barrier height at the graphene–IGZO junction over 0.87 eV using a voltage below 2 V. The resulting vertical devices show high current densities (18.9 A cm^?2) and on–off current ratios (>10⁴) at low voltages. The simple structure of the unit transistor enables the successful fabrication of low‐power logic gates based on device assemblies, such as the NOT, NAND, and NOR gates, prepared on a flexible substrate. The facile, large‐area, and room‐temperature deposition of both semiconducting metal oxide and gate insulators integrates with transparent and flexible graphene opens up new opportunities for realizing graphene‐based future electronics.     

Controllable Fabrication of Transparent Macroporous Graphene Thin Films and Versatile Applications as a Conducting Platform

Graphene sheets have been demonstrated to be the building blocks for various assembly structures, which eventually determine the macroscopic properties of graphene materials. As a new assembly structure, transparent macroporous graphene thin films (MGTFs) are not readily prepared due to the restacking tendency of graphene sheets during processing. Here, an ice crystal‐induced phase separation process is proposed for preparation of transparent MGTFs. The ice crystal‐induced phase separation process exhibits several unique features, including efficient prevention of graphene oxide restacking, easy control on the transparency of the MGTFs, and wide applicability to substrates. It is shown that the MGTFs can be used as porous scaffold with high conductivity for electrochemical deposition of various semiconductors and rare metal nanoparticles such as CdSe, ZnO, and Pt, as well as successive deposition of different materials. Notably, the macroporous structures bestow the MGTFs and the nanoparticle‐decorated MGTFs (i.e., Pt@MGTF and CdSe@MGTF) enhanced performance as electrode for oxygen reduction reaction and photoelectrochemical H₂ generation.     

Wide‐Area Strain Sensors based upon Graphene‐Polymer Composite Coatings Probed by Raman Spectroscopy

Functional graphene optical sensors are now viable due to the recent developments in hand‐held Raman spectroscopy and the chemical vapor deposition (CVD) of graphene films. Herein, the strain in graphene/poly (methyl methacrylate) sensor coatings is followed using Raman band shifts. The performance of an “ideal” mechanically‐exfoliated single crystal graphene flake is compared to a scalable CVD graphene film. The dry‐transferred mechanically exfoliated sample has no residual stresses, whereas the CVD sample is in compression following the solvent evaporation during its transfer. The behavior of the sensors under cyclic deformation shows an initial breakdown of the graphene‐polymer interface with the interface then stabilizing after several cycles. The Raman 2D band shift rates per unit strain of the exfoliated graphene are ≈35% higher than CVD graphene making the former more strain sensitive. However, for practical wide‐area applications, CVD graphene coatings are still viable candidates as a Raman system can be used to read the strain in any 5 μm diameter spot in the coating to an absolute accuracy of ≈0.01% strain and resolution of ≈27 microstrains (μs), which compares favorably to commercial photoelastic systems.     

A Multi‐synergistic Platform for Sequential Irradiation‐Activated High‐Performance Apoptotic Cancer Therapy

Artificial hyperthermia is an emerging technique to induce apoptotic cancer cell death. However, achieving effective hyperthermic apoptosis is often difficult, as cells typically acquire resistance to thermal stress. With the aid of sequential irradiation, highly integrated nanoassemblies based on reduced graphene oxide–ZnO nanoparticles–hyaluronic acid (rGo‐ZnO‐HA) can serve as a multi‐synergistic platform for targeted high‐performance apoptotic cancer therapy. The surface engineering of ZnO/graphene hybrid with multifunctional HA biomacromolecules simultaneously confers the system colloidal stability, biocompatibility, and a cancer cell targeting ability. After receptor‐mediated endocytosis, enzyme‐mediated fluorescence activation helps track cellular uptake and provides truly molecular imaging. Furthermore, the reactive oxygen species (ROS) generated by ZnO/rGo under light illumination can effectively sensitize cancer cells to the subsequent NIR laser‐induced apoptotic hyperthermia. In particular, photo modulation of cellular ROS to sensitize cells provides a novel approach to increase the efficacy of hyperthermic apoptosis. These findings suggest that a powerful apoptotic therapeutic platform could be achieved based on the multi‐synergistic platform.