Molecular Electronics: Creating and Bridging Molecular Junctions and Promoting Its Commercialization.

Molecular electronics is driven by the dream of expanding Moore's law to the molecular level for next-generation electronics through incorporating individual or ensemble molecules into electronic circuits. For nearly 50 years, numerous efforts have been made to explore the intrinsic properties of molecules and develop diverse fascinating molecular electronic devices with the desired functionalities. The flourishing of molecular electronics is inseparable from the development of various elegant methodologies for creating nanogap electrodes and bridging the nanogap with molecules. This review first focuses on the techniques for making lateral and vertical nanogap electrodes by breaking, narrowing, and fixed modes, and highlights their capabilities, applications, merits, and shortcomings. After summarizing the approaches of growing single molecules or molecular layers on the electrodes, the methods of constructing a complete molecular circuit are comprehensively grouped into three categories: 1) directly bridging one-molecule-electrode component with another electrode, 2) physically bridging two-molecule-electrode components, and 3) chemically bridging two-molecule-electrode components. Finally, the current state of molecular circuit integration and commercialization is discussed and perspectives are provided, hoping to encourage the community to accelerate the realization of fully scalable molecular electronics for a new era of integrated microsystems and applications.

On-chip integrated process-programmable sub-10 nm thick molecular devices switching between photomultiplication and memristive behaviour.

Molecular devices constructed by sub-10 nm thick molecular layers are promising candidates for a new generation of integratable nanoelectronic applications. Here, we report integrated molecular devices based on ultrathin copper phthalocyanine/fullerene hybrid layers with microtubular soft-contacts, which exhibit process-programmable functionality switching between photomultiplication and memristive behaviour. The local electric field at the interface between the polymer bottom electrode and the enclosed molecular channels modulates the ionic-electronic charge interaction and hence determines the transition of the device function. When ions are not driven into the molecular channels at a low interface electric field, photogenerated holes are trapped as electronic space charges, resulting in photomultiplication with a high external quantum efficiency. Once mobile ions are polarized and accumulated as ionic space charges in the molecular channels at a high interface electric field, the molecular devices show ferroelectric-like memristive switching with remarkable resistive ON/OFF and rectification ratios.

A new dimension for magnetosensitive e-skins: active matrix integrated micro-origami sensor arrays.

Magnetic sensors are widely used in our daily life for assessing the position and orientation of objects. Recently, the magnetic sensing modality has been introduced to electronic skins (e-skins), enabling remote perception of moving objects. However, the integration density of magnetic sensors is limited and the vector properties of the magnetic field cannot be fully explored since the sensors can only perceive field components in one or two dimensions. Here, we report an approach to fabricate high-density integrated active matrix magnetic sensor with three-dimensional (3D) magnetic vector field sensing capability. The 3D magnetic sensor is composed of an array of self-assembled micro-origami cubic architectures with biased anisotropic magnetoresistance (AMR) sensors manufactured in a wafer-scale process. Integrating the 3D magnetic sensors into an e-skin with embedded magnetic hairs enables real-time multidirectional tactile perception. We demonstrate a versatile approach for the fabrication of active matrix integrated 3D sensor arrays using micro-origami and pave the way for new electronic devices relying on the autonomous rearrangement of functional elements in space.

Microbatteries with twin-Swiss-rolls redefine performance limits in the sub-square millimeter range.

To maintain the downscaling of microelectronic devices with footprints less than one square millimeter, next-generation microbatteries should occupy the same area and deliver adequate energy for running a new generation of multi-functional microautonomous systems. However, the current microbattery technology fails in accomplishing this task because the micrometer-sized electrodes are not compatible with on-chip integration protocols and technologies. To tackle this critical challenge, an on-chip Swiss-roll microelectrode architecture is employed that exploits the self-assembly of thin films into ultra-compact device architectures. A twin-Swiss-roll microelectrode on a chip occupies a footprint of 0.045 mm2 and delivers an energy density up to 458 µW h cm-2. After packaging, the footprint of a full cell increases to 0.11 mm2 with a high energy density of 181 µW h cm-2. The volumetric energy density excluding the chip thickness is 16.3 mW h cm-3. These results open opportunities for deploying microbatteries as energy and power sources to drive smart dust microelectronics and microautonomous systems.

Digital Electrochemistry for On-Chip Heterogeneous Material Integration.

Many modern electronic applications rely on functional units arranged in an active-matrix integrated on a single chip. The active-matrix allows numerous identical device pixels to be addressed within a single system. However, next-generation electronics requires heterogeneous integration of dissimilar devices, where sensors, actuators, and display pixels sense and interact with the local environment. Heterogeneous material integration allows the reduction of size, increase of functionality, and enhancement of performance; however, it is challenging since front-end fabrication technologies in microelectronics put extremely high demands on materials, fabrication protocols, and processing environments. To overcome the obstacle in heterogeneous material integration, digital electrochemistry is explored here, which site-selectively carries out electrochemical processes to deposit and address electroactive materials within the pixel array. More specifically, an amorphous indium-gallium-zinc oxide (a-IGZO) thin-film-transistor (TFT) active-matrix is used to address pixels within the matrix and locally control electrochemical reactions for material growth and actuation. The digital electrochemistry procedure is studied in-depth by using polypyrrole (PPy) as a model material. Active-matrix-driven multicolored electrochromic patterns and actuator arrays are fabricated to demonstrate the capabilities of this approach for material integration. The approach can be extended to a broad range of materials and structures, opening up a new path for advanced heterogeneous microsystem integration.

Nano-biosupercapacitors enable autarkic sensor operation in blood.

Today's smallest energy storage devices for in-vivo applications are larger than 3 mm3 and lack the ability to continuously drive the complex functions of smart dust electronic and microrobotic systems. Here, we create a tubular biosupercapacitor occupying a mere volume of 1/1000 mm3 (=1 nanoliter), yet delivering up to 1.6 V in blood. The tubular geometry of this nano-biosupercapacitor provides efficient self-protection against external forces from pulsating blood or muscle contraction. Redox enzymes and living cells, naturally present in blood boost the performance of the device by 40% and help to solve the self-discharging problem persistently encountered by miniaturized supercapacitors. At full capacity, the nano-biosupercapacitors drive a complex integrated sensor system to measure the pH-value in blood. This demonstration opens up opportunities for next generation intravascular implants and microrobotic systems operating in hard-to-reach small spaces deep inside the human body.

Integrated molecular diode as 10 MHz half-wave rectifier based on an organic nanostructure heterojunction.

Considerable efforts have been made to realize nanoscale diodes based on single molecules or molecular ensembles for implementing the concept of molecular electronics. However, so far, functional molecular diodes have only been demonstrated in the very low alternating current frequency regime, which is partially due to their extremely low conductance and the poor degree of device integration. Here, we report about fully integrated rectifiers with microtubular soft-contacts, which are based on a molecularly thin organic heterojunction and are able to convert alternating current with a frequency of up to 10 MHz. The unidirectional current behavior of our devices originates mainly from the intrinsically different surfaces of the bottom planar and top microtubular Au electrodes while the excellent high frequency response benefits from the charge accumulation in the phthalocyanine molecular heterojunction, which not only improves the charge injection but also increases the carrier density.

Stamping Fabrication of Flexible Planar Micro-Supercapacitors Using Porous Graphene Inks.

High performance, flexibility, safety, and robust integration for micro-supercapacitors (MSCs) are of immense interest for the urgent demand for miniaturized, smart energy-storage devices. However, repetitive photolithography processes in the fabrication of on-chip electronic components including various photoresists, masks, and toxic etchants are often not well-suited for industrial production. Here, a cost-effective stamping strategy is developed for scalable and rapid preparation of graphene-based planar MSCs. Combining stamps with desired shapes and highly conductive graphene inks, flexible MSCs with controlled structures are prepared on arbitrary substrates without any metal current collectors, additives, and polymer binders. The interdigitated MSC exhibits high areal capacitance up to 21.7 mF cm-2 at a current of 0.5 mA and a high power density of 6 mW cm-2 at an energy density of 5 µWh cm-2. Moreover, the MSCs show outstanding cycling performance and remarkable flexibility over 10 000 charge-discharge cycles and 300 bending cycles. In addition, the capacitance and output voltage of the MSCs are easily adjustable through interconnection with well-defined arrangements. The efficient, rapid manufacturing of the graphene-based interdigital MSCs with outstanding flexibility, shape diversity, and high areal capacitance shows great potential in wearable and portable electronics.

Self-Assembled Flexible and Integratable 3D Microtubular Asymmetric Supercapacitors.

The rapid development of microelectronics has equally rapidly increased the demand for miniaturized energy storage devices. On-chip microsupercapacitors (MSCs), as promising power candidates, possess great potential to complement or replace electrolytic capacitors and microbatteries in various applications. However, the areal capacities and energy densities of the planar MSCs are commonly limited by the low voltage window, the thin layer of the electrode materials and complex fabrication processes. Here, a new-type three-dimensional (3D) tubular asymmetric MSC with small footprint area, high potential window, ultrahigh areal energy density, and long-term cycling stability is fabricated with shapeable materials and photolithographic technologies, which are compatible with modern microelectronic fabrication procedures widely used in industry. Benefiting from the novel architecture, the 3D asymmetric MSC displays an ultrahigh areal capacitance of 88.6 mF cm-2 and areal energy density of 28.69 mW h cm-2, superior to most reported interdigitated MSCs. Furthermore, the 3D tubular MSCs demonstrate remarkable cycling stability and the capacitance retention is up to 91.8% over 12 000 cycles. It is believed that the efficient fabrication methodology can be used to construct various integratable microscale tubular energy storage devices with small footprint area and high performance for miniaturized electronics.

Self-Assembly of Integrated Tubular Microsupercapacitors with Improved Electrochemical Performance and Self-Protective Function.

Inspired by origami art, we demonstrate a tubular microsupercapacitor (TMSC) by self-assembling two-dimensional (2D) films into a "swiss roll" structure with greatly reduced footprint area. A polymeric framework consisting of swelling hydrogel and polyimide layers ensures excellent ion transport between poly(3,4-ethylenedioxythiophene) (PEDOT)-based electrodes and provides efficient self-protection of the TMSC against external compression up to about 30 MPa. Such TMSCs exhibit an areal capacitance of 82.5 mF cm-2 at 0.3 mA cm-2 with a potential window of 0.8 V, an energy density and power density of 7.73 µWh cm-2 and 17.8 mW cm-2 (0.3 and 45 mA cm-2), and an improved cycling stability with a capacitance retention up to 96.6% over 5000 cycles. Furthermore, as-fabricated TMSC arrays can be detached from their surface and transferred onto target substrates. The connection of devices in parallel/series greatly improves their capacity and voltage output. Overall, our prototype devices and fabrication methodology provide a promising route to create integratable microscale tubular energy storage devices with an efficient self-protection function and high performance for future miniaturized electronics.

Charge transport in organic nanocrystal diodes based on rolled-up robust nanomembrane contacts.

The investigation of charge transport in organic nanocrystals is essential to understand nanoscale physical properties of organic systems and the development of novel organic nanodevices. In this work, we fabricate organic nanocrystal diodes contacted by rolled-up robust nanomembranes. The organic nanocrystals consist of vanadyl phthalocyanine and copper hexadecafluorophthalocyanine heterojunctions. The temperature dependent charge transport through organic nanocrystals was investigated to reveal the transport properties of ohmic and space-charge-limited current under different conditions, for instance, temperature and bias.

Fully Integrated Organic Nanocrystal Diode as High Performance Room Temperature NO2 Sensor.

Organic diodes consisting of molecular nano-pyramid structures sandwiched between metal and strained nano-membrane electrodes are created. The robust and smooth contacts provided by self-curled metal layers render the molecular nano-pyramids efficent channels for detecting nitrogen dioxide airflow.