Quasi‐Solid‐State Single‐Atom Transistors

The single‐atom transistor represents a quantum electronic device at room temperature, allowing the switching of an electric current by the controlled and reversible relocation of one single atom within a metallic quantum point contact. So far, the device operates by applying a small voltage to a control electrode or “gate” within the aqueous electrolyte. Here, the operation of the atomic device in the quasi‐solid state is demonstrated. Gelation of pyrogenic silica transforms the electrolyte into the quasi‐solid state, exhibiting the cohesive properties of a solid and the diffusive properties of a liquid, preventing the leakage problem and avoiding the handling of a liquid system. The electrolyte is characterized by cyclic voltammetry, conductivity measurements, and rotation viscometry. Thus, a first demonstration of the single‐atom transistor operating in the quasi‐solid‐state is given. The silver single‐atom and atomic‐scale transistors in the quasi‐solid‐state allow bistable switching between zero and quantized conductance levels, which are integer multiples of the conductance quantum G₀ = 2e²/h. Source–drain currents ranging from 1 to 8 µA are applied in these experiments. Any obvious influence of the gelation of the aqueous electrolyte on the electron transport within the quantum point contact is not observed.     

A single-atom transistor

The ability to control matter at the atomic scale and build devices with atomic precision is central to nanotechnology. The scanning tunnelling microscope can manipulate individual atoms and molecules on surfaces, but the manipulation of silicon to make atomic-scale logic circuits has been hampered by the covalent nature of its bonds. Resist-based strategies have allowed the formation of atomic-scale structures on silicon surfaces, but the fabrication of working devices-such as transistors with extremely short gate lengths, spin-based quantum computers and solitary dopant optoelectronic devices-requires the ability to position individual atoms in a silicon crystal with atomic precision. Here, we use a combination of scanning tunnelling microscopy and hydrogen-resist lithography to demonstrate a single-atom transistor in which an individual phosphorus dopant atom has been deterministically placed within an epitaxial silicon device architecture with a spatial accuracy of one lattice site. The transistor operates at liquid helium temperatures, and millikelvin electron transport measurements confirm the presence of discrete quantum levels in the energy spectrum of the phosphorus atom. We find a charging energy that is close to the bulk value, previously only observed by optical spectroscopy.     

Ultrahigh Photocatalytic Rate at a Single‐Metal‐Atom‐Oxide

Metal oxides, as one of the mostly abundant and widely utilized materials, are extensively investigated and applied in environmental remediation and protection, and in energy conversion and storage. Most of these diverse applications are the result of a large diversity of the electronic states of metal oxides. Noticeably, however, many metal oxides present obstacles for applications in catalysis, mainly due to the lack of efficient active sites with desired electronic states. Here, the fabrication of single‐tungsten‐atom‐oxide (STAO) is demonstrated, in which the metal oxide's volume reaches its minimum as a unit cell. The catalytic mechanism in the STAO is determined by a new single‐site physics mechanism, named as quasi‐atom physics. The photogenerated electron transfer process is enabled by an electron in the spin‐up channel excited from the highest occupied molecular orbital to the lowest unoccupied molecular orbital +1 state, which can only occur in STAO with W⁵⁺. STAO results in a record‐high and stable sunlight photocatalytic degradation rate of 0.24 s^?1, which exceeds the rates of available photocatalysts by two orders of magnitude. The fabrication of STAO and its unique quasi‐atom photocatalytic mechanism lays new ground for achieving novel physical and chemical properties using single‐metal‐atom oxides (SMAO).     

Wafer‐Scale Fabrication of High‐Performance n‐Type Polymer Monolayer Transistors Using a Multi‐Level Self‐Assembly Strategy

Wafer‐scale fabrication of high‐performance uniform organic electronic materials is of great challenge and has rarely been realized before. Previous large‐scale fabrication methods always lead to different layer thickness and thereby poor film and device uniformity. Herein, the first demonstration of 4 in. wafer‐scale, uniform, and high‐performance n‐type polymer monolayer films is reported, enabled by controlling the multi‐level self‐assembly process of conjugated polymers in solution. Since the self‐assembly process happened in solution, the uniform 2D polymer monolayers can be facilely deposited on various substrates, and theoretically without size limitations. Polymer monolayer transistors exhibit high electron mobilities of up to 1.88 cm² V^?1 s^?1, which is among the highest in n‐type monolayer organic transistors. This method allows to easily fabricate n‐type conjugated polymers with wafer‐scale, high uniformity, low contact resistance, and excellent transistor performance (better than the traditional spin‐coating method). This work provides an effective strategy to prepare large‐scale and uniform 2D polymer monolayers, which could enable the application of conjugated polymers for wafer‐scale sophisticated electronics.     

Host–Guest Hybrid Redox Materials Self‐Assembled from Polyoxometalates and Single‐Walled Carbon Nanotubes

The development of next‐generation molecular‐electronic, electrocatalytic, and energy‐storage systems depends on the availability of robust materials in which molecular charge‐storage sites and conductive hosts are in intimate contact. It is shown here that electron transfer from single‐walled carbon nanotubes (SWNTs) to polyoxometalate (POM) clusters results in the spontaneous formation of host–guest POM@SWNT redox‐active hybrid materials. The SWNTs can conduct charge to and from the encapsulated guest molecules, allowing electrical access to >90% of the encapsulated redox species. Furthermore, the SWNT hosts provide a physical barrier, protecting the POMs from chemical degradation during charging/discharging and facilitating efficient electron transfer throughout the composite, even in electrolytes that usually destroy POMs.     

Tunable graphene single electron transistor

We report electronic transport experiments on a graphene single electron transistor. The device consists of a graphene island connected to source and drain electrodes via two narrow graphene constrictions. It is electrostatically tunable by three lateral graphene gates and an additional back gate. The tunneling coupling is a strongly nonmonotonic function of gate voltage indicating the presence of localized states in the barriers. We investigate energy scales for the tunneling gap, the resonances in the constrictions, and for the Coulomb blockade resonances. From Coulomb diamond measurements in different device configurations (i.e., barrier configurations) we extract a charging energy of approximately 3.4 meV and estimate a characteristic energy scale for the constriction resonances of approximately 10 meV.     

A Single‐Electron Transistor Made of a 3D Topological Insulator Nanoplate

Quantum confined devices of 3D topological insulators are proposed to be promising and of great importance for studies of confined topological states and for applications in low‐energy‐dissipative spintronics and quantum information processing. The absence of energy gap on the topological insulator surface limits the experimental realization of a quantum confined system in 3D topological insulators. Here, the successful realization of single‐electron transistor devices in Bi₂Te₃ nanoplates using state‐of‐the‐art nanofabrication techniques is reported. Each device consists of a confined central island, two narrow constrictions that connect the central island to the source and drain, and surrounding gates. Low‐temperature transport measurements demonstrate that the two narrow constrictions function as tunneling junctions and the device shows well‐defined Coulomb current oscillations and Coulomb‐diamond‐shaped charge‐stability diagrams. This work provides a controllable and reproducible way to form quantum confined systems in 3D topological insulators, which should greatly stimulate research toward confined topological states, low‐energy‐dissipative devices, and quantum information processing.     

Mapping Energy Levels for Organic Heterojunctions

An organic semiconductor thin film is a solid‐state matter comprising one or more molecules. For applications in electronics and photonics, several distinct functional organic thin films are stacked together to create a variety of devices such as organic light‐emitting diodes and organic solar cells. The energy levels at these thin‐film junctions dictate various electronic processes such as the charge transport across these junctions, the exciton dissociation rates at donor–acceptor molecular interfaces, and the charge trapping during exciton formation in a host–dopant system. These electronic processes are vital to a device's performance and functionality. To uncover a general scientific principle in governing the interface energy levels, highest occupied molecular orbitals, and vacuum level dipoles, herein a comprehensive experimental research is conducted on several dozens of organic–organic heterojunctions representative of various device applications. It is found that the experimental data map on interface energy levels, after correcting variables such as molecular orientation‐dependent ionization energies, consists of three distinct regions depending on interface fundamental physical parameters such as Fermi energy, work function, highest occupied molecular orbitals, and lowest unoccupied molecular orbitals. This general energy map provides a master guide in selection of new materials for fabricating future generations of organic semiconductor devices.     

Energy Level Alignment at Metal/Solution‐Processed Organic Semiconductor Interfaces

Energy barriers between the metal Fermi energy and the molecular levels of organic semiconductor devoted to charge transport play a fundamental role in the performance of organic electronic devices. Typically, techniques such as electron photoemission spectroscopy, Kelvin probe measurements, and in‐device hot‐electron spectroscopy have been applied to study these interfacial energy barriers. However, so far there has not been any direct method available for the determination of energy barriers at metal interfaces with n‐type polymeric semiconductors. This study measures and compares metal/solution‐processed electron‐transporting polymer interface energy barriers by in‐device hot‐electron spectroscopy and ultraviolet photoemission spectroscopy. It not only demonstrates in‐device hot‐electron spectroscopy as a direct and reliable technique for these studies but also brings it closer to technological applications by working ex situ under ambient conditions. Moreover, this study determines that the contamination layer coming from air exposure does not play any significant role on the energy barrier alignment for charge transport. The theoretical model developed for this work confirms all the experimental observations.     

Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films

Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead‐halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface‐area‐to‐volume ratio, are particularly well‐suited for doping via ground‐state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI₃ nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI₃ nanocrystal films are found to be slightly p‐type with increasing conductivity achieved by incorporating the electron‐accepting dopant 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F₄TCNQ) and decreasing conductivity for the electron‐donating dopant benzyl viologen. Time‐resolved spectroscopic measurements reveal the time scales of Auger‐mediated recombination in the presence of excess electrons or holes. Microwave conductance and field‐effect transistor measurements demonstrate that both the local and long‐range hole mobility are improved by F₄TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p‐type arrays leads to a pronounced enhancement in phototransistors.     

Device Physics of Solution‐Processed Organic Field‐Effect Transistors

Field‐effect transistors based on solution‐processible organic semiconductors have experienced impressive improvements in both performance and reliability in recent years, and printing‐based manufacturing processes for integrated transistor circuits are being developed to realize low‐cost, large‐area electronic products on flexible substrates. This article reviews the materials, charge‐transport, and device physics of solution‐processed organic field‐effect transistors, focusing in particular on the physics of the active semiconductor/dielectric interface. Issues such as the relationship between microstructure and charge transport, the critical role of the gate dielectric, the influence of polaronic relaxation and disorder effects on charge transport, charge‐injection mechanisms, and the current understanding of mechanisms for charge trapping are reviewed. Many interesting questions on how the molecular and electronic structures and the presence of defects at organic/organic heterointerfaces influence the device performance and stability remain to be explored.     

Controllable P‐ and N‐Type Conversion of MoTe2 via Oxide Interfacial Layer for Logic Circuits

To realize basic electronic units such as complementary metal‐oxide‐semiconductor (CMOS) inverters and other logic circuits, the selective and controllable fabrication of p‐ and n‐type transistors with a low Schottky barrier height is highly desirable. Herein, an efficient and nondestructive technique of electron‐charge transfer doping by depositing a thin Al₂O₃ layer on chemical vapor deposition (CVD)‐grown 2H‐MoTe₂ is utilized to tune the doping from p‐ to n‐type. Moreover, a type‐controllable MoTe₂ transistor with a low Schottky barrier height is prepared. The selectively converted n‐type MoTe₂ transistor from the p‐channel exhibits a maximum on‐state current of 10 µA, with a higher electron mobility of 8.9 cm² V^?1 s^?1 at a drain voltage (V_ds) of 1 V with a low Schottky barrier height of 28.4 meV. To validate the aforementioned approach, a prototype homogeneous CMOS inverter is fabricated on a CVD‐grown 2H‐MoTe₂ single crystal. The proposed inverter exhibits a high DC voltage gain of 9.2 with good dynamic behavior up to a modulation frequency of 1 kHz. The proposed approach may have potential for realizing future 2D transition metal dichalcogenide‐based efficient and ultrafast electronic units with high‐density circuit components under a low‐dimensional regime.     

A coupled mechanical‐charge/dipole molecular dynamics finite element method,with multi‐scale applications to the design of graphene nano‐devices

A new Molecular Dynamics Finite Element Method (MDFEM) with a coupled mechanical‐charge/dipole formulation is proposed. The equilibrium equations of Molecular Dynamics (MD) are embedded exactly within the computationally more favourable Finite Element Method (FEM). This MDFEM can readily implement any force field because the constitutive relations are explicitly uncoupled from the corresponding geometric element topologies. This formal uncoupling allows to differentiate between chemical‐constitutive, geometric and mixed‐mode instabilities. Different force fields, including bond‐order reactive and polarisable fluctuating charge–dipole potentials, are implemented exactly in both explicit and implicit dynamic commercial finite element code. The implicit formulation allows for larger length and time scales and more varied eigenvalue‐based solution strategies. The proposed multi‐physics and multi‐scale compatible MDFEM is shown to be equivalent to MD, as demonstrated by examples of fracture in carbon nanotubes (CNT), and electric charge distribution in graphene, but at a considerably reduced computational cost. The proposed MDFEM is shown to scale linearly, with concurrent continuum FEM multi‐scale couplings allowing for further computational savings. Moreover, novel conformational analyses of pillared graphene structures (PGS) are produced. The proposed model finds potential applications in the parametric topology and numerical design studies of nano‐structures for desired electro‐mechanical properties (e.g. stiffness, toughness and electric field induced vibrational/electron‐emission properties). Copyright © 2014 John Wiley & Sons, Ltd.     

Heterogeneous Single‐Atom Catalyst for Visible‐Light‐Driven High‐Turnover CO2 Reduction: The Role of Electron Transfer

Visible‐light‐driven conversion of CO₂ into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single‐atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO₂ conversion, wherein the graphene bridges homogeneous light absorbers with single‐atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min^?1, superior to those obtained with the state‐of‐the‐art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO₂ conversion from the angle of single‐atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts.     

Cross‐Talk Between Ionic and Nanoribbon Current Signals in Graphene Nanoribbon‐Nanopore Sensors for Single‐Molecule Detection

Nanopores are now being used not only as an ionic current sensor but also as a means to localize molecules near alternative sensors with higher sensitivity and/or selectivity. One example is a solid‐state nanopore embedded in a graphene nanoribbon (GNR) transistor. Such a device possesses the high conductivity needed for higher bandwidth measurements and, because of its single‐atomic‐layer thickness, can improve the spatial resolution of the measurement. Here measurements of ionic current through the nanopore are shown during double‐stranded DNA (dsDNA) translocation, along with the simultaneous response of the neighboring GNR due to changes in the surrounding electric potential. Cross‐talk originating from capacitive coupling between the two measurement channels is observed, resulting in a transient response in the GNR during DNA translocation; however, a modulation in device conductivity is not observed via an electric‐field‐effect response during DNA translocation. A field‐effect response would scale with GNR source–drain voltage (V_ds), whereas the capacitive coupling does not scale with V_ds. In order to take advantage of the high bandwidth potential of such sensors, the field‐effect response must be enhanced. Potential field calculations are presented to outline a phase diagram for detection within the device parameter space, charting a roadmap for future optimization of such devices.     

All‐Solid‐State Z‐Scheme Photocatalytic Systems

The current rapid industrial development causes the serious energy and environmental crises. Photocatalyts provide a potential strategy to solve these problems because these materials not only can directly convert solar energy into usable or storable energy resources but also can decompose organic pollutants under solar‐light irradiation. However, the aforementioned applications require photocatalysts with a wide absorption range, long‐term stability, high charge‐separation efficiency and strong redox ability. Unfortunately, it is often difficult for a single‐component photocatalyst to simultaneously fulfill all these requirements. The artificial heterogeneous Z‐scheme photocatalytic systems, mimicking the natural photosynthesis process, overcome the drawbacks of single‐component photocatalysts and satisfy those aforementioned requirements. Such multi‐task systems have been extensively investigated in the past decade. Especially, the all‐solid‐state Z‐scheme photocatalytic systems without redox pair have been widely used in the water splitting, solar cells, degradation of pollutants and CO₂ conversion, which have a huge potential to solve the current energy and environmental crises facing the modern industrial development. Thus, this review gives a concise overview of the all‐solid‐state Z‐scheme photocatalytic systems, including their composition, construction, optimization and applications.     

Stress‐Actuated Spiral Microelectrode for High‐Performance Lithium‐Ion Microbatteries

Miniaturization of batteries lags behind the success of modern electronic devices. Neither the device volume nor the energy density of microbatteries meets the requirement of microscale electronic devices. The main limitation for pushing the energy density of microbatteries arises from the low mass loading of active materials. However, merely pushing the mass loading through increased electrode thickness is accompanied by the long charge transfer pathway and inferior mechanical properties for long‐term operation. Here, a new spiral microelectrode upon stress‐actuation accomplishes high mass loading but short charge transfer pathways. At a small footprint area of around 1 mm², a 21‐fold increase of the mass loading is achieved while featuring fast charge transfer at the nanoscale. The spiral microelectrode delivers a maximum area capacity of 1053 µAh cm^?2 with a retention of 67% over 50 cycles. Moreover, the energy density of the cylinder microbattery using the spiral microelectrode as the anode reaches 12.6 mWh cm^?3 at an ultrasmall volume of 3 mm³. In terms of the device volume and energy density, the cylinder microbattery outperforms most of the current microbattery technologies, and hence provides a new strategy to develop high‐performance microbatteries that can be integrated with miniaturized electronic devices.     

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.     

A Layer‐by‐Layer ZnO Nanoparticle–PbS Quantum Dot Self‐Assembly Platform for Ultrafast Interfacial Electron Injection

Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low‐cost, high‐performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy‐level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer‐by‐layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic‐energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis.     

Dopant‐Free Small‐Molecule Hole‐Transporting Material for Inverted Perovskite Solar Cells with Efficiency Exceeding 21%

Hole‐transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long‐term stability, high‐performance dopant‐free small‐molecule HTMs (SM‐HTMs) are greatly desired. However, such dopant‐free SM‐HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor–acceptor‐type SM‐HTMs (MPA‐BTI and MPA‐BTTI) are devised, which synergistically integrate several design principles for high‐performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant‐free MPA‐BTTI‐based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long‐term stability under illumination, which breaks the long‐time standing bottleneck in the development of dopant‐free SM‐HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well‐aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA‐BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high‐performance dopant‐free SM‐HTMs in PVSCs.