Organic-based inverters: basic concepts, materials, novel architectures and applications.

While organic materials have demonstrated industry-leading performances in a wide array of electronic applications (including OLEDs and OPVs), their use for integration into electronic circuits has been so far limited, in spite of their potential for portable, flexible, light-weight, low-cost applications. However, recent advances in organic (semi)conductors and novel designs in organic field-effect transistors and hybrid systems have reaffirmed the potential of organic logic circuits. This review article provides an overview of organic-based inverter operation and considers all aspects of such circuits including their active layer, processing methods, hybrid organic/inorganic inverters, novel architectures and potential applications.

Engineering Optically Switchable Transistors with Improved Performance by Controlling Interactions of Diarylethenes in Polymer Matrices.

The integration of photochromic molecules into semiconducting polymer matrices via blending has recently attracted a great deal of attention, as it provides the means to reversibly modulate the output signal of electronic devices by using light as a remote control. However, the structural and electronic interactions between photochromic molecules and semiconducting polymers are far from being fully understood. Here we perform a comparative investigation by combining two photochromic diarylethene moieties possessing similar energy levels yet different propensity to aggregate with five prototypical polymer semiconductors exhibiting different energy levels and structural order, ranging from amorphous to semicrystalline. Our in-depth photochemical, structural, morphological, and electrical characterization reveals that the photoresponsive behavior of thin-film transistors including polymer/diarylethenes blends as the active layer is governed by a complex interplay between the relative position of the energy levels and the polymer matrix microstructure. By matching the energy levels and optimizing the molecular packing, high-performance optically switchable organic thin-film transistors were fabricated. These findings represent a major step forward in the fabrication of light-responsive organic devices.

Current crowding issues on nanoscale planar organic transistors for spintronic applications.

The predominance of interface resistance makes current crowding ubiquitous in short channel organic electronics devices but its impact on spin transport has never been considered. We investigate electrochemically doped nanoscale PBTTT short channel devices and observe the smallest reported values of crowding lengths, found for sub-100 nm electrodes separation. These observed values are nevertheless exceeding the spin diffusion lengths reported in the literature. We discuss here how current crowding can be taken into account in the framework of the Fert-Jaffrès model of spin current propagation in heterostructures, and predict that the anticipated resulting values of magnetoresistance can be significantly reduced. Current crowding therefore impacts spin transport applications and interpretation of the results on spin valve devices.

Supramolecular Self-Assembly in a Sub-micrometer Electrodic Cavity: Fabrication of Heat-Reversible π-Gel Memristor.

The use of biomimetic approaches toward the production of nonsolid yet functional architectures holds potential for the emergence of novel device concepts. Gels, in particular those obtained via self-assembly of π-conjugated molecules, are dynamic materials possessing unique (opto)electronic properties. Their adaptive nature imparts unprecedented responsivity to various stimuli. Hitherto, a viable device platform to electrically probe in situ a sol-gel transition is still lacking. Here we describe the fabrication of a sub-micrometer electrodic cavity, which enables low-voltage electrical operation of π-gels. Thanks to the in situ supramolecular self-assembly of the π-gelator occurring within the cavity, we conceived a novel gel-based memristor whose sol-gel transition is reversible and can be controlled via heating and dc bias. This work opens perspectives toward the fabrication of a novel generation of nonsolid multiresponsive devices.

Charge transport and mobility engineering in two-dimensional transition metal chalcogenide semiconductors.

Two-dimensional (2D) van der Waals semiconductors represent the thinnest, air stable semiconducting materials known. Their unique optical, electronic and mechanical properties hold great potential for harnessing them as key components in novel applications for electronics and optoelectronics. However, the charge transport behavior in 2D semiconductors is more susceptible to external surroundings (e.g. gaseous adsorbates from air and trapped charges in substrates) and their electronic performance is generally lower than corresponding bulk materials due to the fact that the surface and bulk coincide. In this article, we review recent progress on the charge transport properties and carrier mobility engineering of 2D transition metal chalcogenides, with a particular focus on the markedly high dependence of carrier mobility on thickness. We unveil the origin of this unique thickness dependence and elaborate the devised strategies to master it for carrier mobility optimization. Specifically, physical and chemical methods towards the optimization of the major factors influencing the extrinsic transport such as electrode/semiconductor contacts, interfacial Coulomb impurities and atomic defects are discussed. In particular, the use of ad hoc molecules makes it possible to engineer the interface with the dielectric and heal the vacancies in such materials. By casting fresh light on the theoretical and experimental studies, we provide a guide for improving the electronic performance of 2D semiconductors, with the ultimate goal of achieving technologically viable atomically thin (opto)electronics.

Coherent Coupling of WS2 Monolayers with Metallic Photonic Nanostructures at Room Temperature.

Room temperature strong coupling of WS2 monolayer exciton transitions to metallic Fabry-Pérot and plasmonic optical cavities is demonstrated. A Rabi splitting of 101 meV is observed for the Fabry-Pérot cavity. The enhanced magnitude and visibility of WS2 monolayer strong coupling is attributed to the larger absorption coefficient, the narrower line width of the A exciton transition, and greater spin-orbit coupling. For WS2 coupled to plasmonic arrays, the Rabi splitting still reaches 60 meV despite the less favorable coupling conditions, and displays interesting photoluminescence features. The unambiguous signature of WS2 monolayer strong coupling in easily fabricated metallic resonators at room temperature suggests many possibilities for combining light-matter hybridization with spin and valleytronics.

Harnessing the liquid-phase exfoliation of graphene using aliphatic compounds: a supramolecular approach.

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high-quality material and its processing by up-scalable approaches in order to fabricate large-area films with single-layer or a few atomic-layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in N-methyl-2-pyrrolidone (NMP) by using simple molecular modules, which act as dispersion-stabilizing compounds during the liquid-phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE-processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low-cost electrodes and conducting nanocomposite for electronics.

Organic thermoelectric generators: working principles, materials, and fabrication techniques.

Organic thermoelectricity is a blooming field of research that employs organic (semi)conductors to recycle waste heat through its partial conversion to electrical power. Such a conversion occurs by means of organic thermoelectric generator (OTEG) devices. The recent process on the synthesis of novel materials and on the understanding of doping mechanisms to increase conductivity has tremendously narrowed the gap between laboratory research and their application in actual applications. This Feature Article intends to highlight the impressive progress in materials and fabrication techniques for OTEGs made in recent years.

Organic multilevel (opto)electronic memories towards neuromorphic applications.

In the past decades, neuromorphic computing has attracted the interest of the scientific community due to its potential to circumvent the von Neumann bottleneck. Organic materials, owing to their fine tunablility and their ability to be used in multilevel memories, represent a promising class of materials to fabricate neuromorphic devices with the key requirement of operation with synaptic weight. In this review, recent studies of organic multilevel memory are presented. The operating principles and the latest achievements obtained with devices exploiting the main approaches to reach multilevel operation are discussed, with emphasis on organic devices using floating gates, ferroelectric materials, polymer electrets and photochromic molecules. The latest results obtained using organic multilevel memories for neuromorphic circuits are explored and the major advantages and drawbacks of the use of organic materials for neuromorphic applications are discussed.

Multiscale charge injection and transport properties in self-assembled monolayers of biphenyl thiols with varying torsion angles.

This article describes the molecular structure-function relationship for a series of biphenylthiol derivatives with varying torsional degree of freedom in their molecular backbone when self-assembled on gold electrodes. These biphenylthiol molecules chemisorbed on Au exhibit different tilt angles with respect to the surface normal and different packing densities. The charge transport through the biphenylthiol self-assembled monolayers (SAMs) showed a characteristic decay trend with the effective monolayer thickness. Based on parallel pathways model the tunneling decay factor ß was estimated to be 0.27 Å(-1). The hole mobility of poly(3-hexylthiophene)-based thin-film transistors incorporating a biphenylthiol SAM coating the Au source and drain electrodes revealed a dependence on the injection barrier with the highest occupied molecular orbital (HOMO) level of the semiconductor. The possible role of the resistivity of the SAMs on transistor electrodes on the threshold voltage shift is discussed. The control over the chemical structure, electronic properties, and packing order of the SAMs provides a versatile platform to regulate the charge injection in organic electronic devices.

Non-invasive digital etching of van der Waals semiconductors.

The capability to finely tailor material thickness with simultaneous atomic precision and non-invasivity would be useful for constructing quantum platforms and post-Moore microelectronics. However, it remains challenging to attain synchronized controls over tailoring selectivity and precision. Here we report a protocol that allows for non-invasive and atomically digital etching of van der Waals transition-metal dichalcogenides through selective alloying via low-temperature thermal diffusion and subsequent wet etching. The mechanism of selective alloying between sacrifice metal atoms and defective or pristine dichalcogenides is analyzed with high-resolution scanning transmission electron microscopy. Also, the non-invasive nature and atomic level precision of our etching technique are corroborated by consistent spectral, crystallographic, and electrical characterization measurements. The low-temperature charge mobility of as-etched MoS2 reaches up to 1200 cm2 V-1s-1, comparable to that of exfoliated pristine counterparts. The entire protocol represents a highly precise and non-invasive tailoring route for material manipulation.

Graphene transistors via in situ voltage-induced reduction of graphene-oxide under ambient conditions.

Here, we describe a simple approach to fabricate graphene-based field-effect-transistors (FETs), starting from aqueous solutions of graphene-oxide (GO), processed entirely under ambient conditions. The process relies on the site-selective reduction of GO sheets deposited in between or on the surface of micro/nanoelectrodes. The same electrodes are first used for voltage-induced electrochemical GO reduction, and then as the source and drain contacts of FETs, allowing for the straightforward production and characterization of ambipolar graphene devices. With the use of nanoelectrodes, we could reduce different selected areas belonging to one single sheet as well.

Effect of Extrinsic Disorder on the Magnetoresistance Response of Gated Single-Layer Graphene Devices.

Analogous to the case of classical metal oxide semiconductor field-effect transistors, transport properties of graphene-based devices are determined by scattering from adventitious charged impurities that are invariably present. The presence of charged impurities renders experimental graphene samples "extrinsic" in that their electrical performances also depend on the environment in which graphene operates. While the role of such an extrinsic disorder component has been studied for conventional charge transport in graphene, its impact on the magnetotransport remains unexplored. Here, we show that single-layer graphene transistors with a low density of extrinsic disorder feature a larger magnetoresistance (MR) than those with a high density. Importantly, in gated single-layer devices with a low density of charged impurities, we find that MR peaks at gate voltage values far from the charge neutrality point not only at a low temperature but also at room temperature; in particular, MR approaches 800% at room temperature and 1400% at 50 K in such devices. In addition, dynamic measurements of MR on devices with a low degree of extrinsic disorder lead to stable and reliable single-layer graphene magnetosensors endowed with an ultralow power consumption of 2.5 nW. Our work indicates that the initial value of the minimum conductivity σ0 at room temperature along with carrier mobility must be looked at to select the most promising devices for magnetosensing.

Multiresponsive Nonvolatile Memories Based on Optically Switchable Ferroelectric Organic Field-Effect Transistors.

Organic transistors are key elements for flexible, wearable, and biocompatible logic applications. Multiresponsivity is highly sought-after in organic electronics to enable sophisticated operations and functions. Such a challenge can be pursued by integrating more components in a single device, each one responding to a specific external stimulus. Here, the first multiresponsive organic device based on a photochromic-ferroelectric organic field-effect transistor, which is capable of operating as nonvolatile memory with 11 bit memory storage capacity in a single device, is reported. The memory elements can be written and erased independently by means of light or an electric field, with accurate control over the readout signal, excellent repeatability, fast response, and high retention time. Such a proof of concept paves the way toward enhanced functional complexity in optoelectronics via the interfacing of multiple components in a single device, in a fully integrated low-cost technology compatible with flexible substrates.

Analysis of External and Internal Disorder to Understand Band-Like Transport in n-Type Organic Semiconductors.

Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e., related to interactions with the dielectric layer), especially for n-type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (

Local current mapping and patterning of reduced graphene oxide.

Conductive atomic force microscopy (C-AFM) has been used to correlate the detailed structural and electrical characteristics of graphene derived from graphene oxide. Uniform large currents were measured over areas exceeding tens of micrometers in few-layer films, supporting the use of graphene as a transparent electrode material. Moreover, defects such as electrical discontinuities were easily detected. Multilayer films were found to have a higher conductivity per layer than single layers. It is also shown that a local AFM-tip-induced electrochemical reduction process can be used to pattern conductive pathways on otherwise-insulating graphene oxide. Transistors with micrometer-scale tip-reduced graphene channels that featured ambipolar transport and an 8 order of magnitude increase in current density upon reduction were successfully fabricated.

Surface-Confined Macrocyclization via Dynamic Covalent Chemistry.

Surface-confined synthesis is a promising approach to build complex molecular nanostructures including macrocycles. However, despite the recent advances in on-surface macrocyclization under ultrahigh vacuum, selective synthesis of monodisperse and multicomponent macrocycles remains a challenge. Here, we report on an on-surface formation of [6 + 6] Schiff-base macrocycles via dynamic covalent chemistry. The macrocycles form two-dimensional crystalline domains on the micrometer scale, enabled by dynamic conversion of open-chain oligomers into well-defined ∼3.0 nm hexagonal macrocycles. We further show that by tailoring the length of the alkyl substituents, it is possible to control which of three possible products-oligomers, macrocycles, or polymers-will form at the surface. In situ scanning tunneling microscopy imaging combined with density functional theory calculations and molecular dynamics simulations unravel the synergistic effect of surface confinement and solvent in leading to preferential on-surface macrocyclization.

Unconventional Nanofabrication for Supramolecular Electronics.

The scientific effort toward achieving a full control over the correlation between structure and function in organic and polymer electronics has prompted the use of supramolecular interactions to drive the formation of highly ordered functional assemblies, which have been integrated into real devices. In the resulting field of supramolecular electronics, self-assembly of organic semiconducting materials constitutes a powerful tool to generate low-dimensional and crystalline functional architectures. These include 1D nanostructures (nanoribbons, nanotubes, and nanowires) and 2D molecular crystals with tuneable and unique optical, electronic, and mechanical properties. Optimizing the (opto)electronic properties of organic semiconducting materials is imperative to harness such supramolecular structures as active components for supramolecular electronics. However, their integration in real devices currently represents a significant challenge to the advancement of (opto)electronics. Here, an overview of the unconventional nanofabrication techniques and device configurations to enable supramolecular electronics to become a real technology is provided. A particular focus is put on how single and multiple supramolecular fibers and gels as well as supramolecularly engineered 2D materials can be integrated into novel vertical or horizontal junctions to realize flexible and high-density multifunctional transistors, photodetectors, and memristors, exhibiting a set of new properties and excelling in their performances.

Boosting and Balancing Electron and Hole Mobility in Single- and Bilayer WSe2 Devices via Tailored Molecular Functionalization.

WSe2 is a layered ambipolar semiconductor enabling hole and electron transport, which renders it a suitable active component for logic circuitry. However, solid-state devices based on single- and bilayer WSe2 typically exhibit unipolar transport and poor electrical performance when conventional SiO2 dielectric and Au electrodes are used. Here, we show that silane-containing functional molecules form ordered monolayers on the top of the WSe2 surface, thereby boosting its electrical performance in single- and bilayer field-effect transistors. In particular, by employing SiO2 dielectric substrates and top Au electrodes, we measure unipolar mobility as high as µh = 150 cm2 V-1 s-1 and µe = 17.9 cm2 V-1 s-1 in WSe2 single-layer devices when ad hoc molecular monolayers are chosen. Additionally, by asymmetric double-side functionalization with two different molecules, we provide opposite polarity to the top and bottom layer of bilayer WSe2, demonstrating nearly balanced ambipolarity at the bilayer limit. Our results indicate that the controlled functionalization of the two sides of the WSe2 mono- and bilayer flakes with highly ordered molecular monolayers offers the possibility to simultaneously achieve energy level engineering and defect functionalization, representing a path toward deterministic control over charge transport in 2D materials.

Nano-Subsidence-Assisted Precise Integration of Patterned Two-Dimensional Materials for High-Performance Photodetector Arrays.

The spatially precise integration of arrays of micropatterned two-dimensional (2D) crystals onto three-dimensionally structured Si/SiO2 substrates represents an attractive, low-cost system-on-chip strategy toward the realization of extended functions in silicon microelectronics. However, the reliable integration of such atomically thin arrays on planar patterned surfaces has proven challenging due to their poor adhesion to underlying substrates, as ruled by weak van der Waals interactions. Here, we report on an integration method utilizing the flexibility of the atomically thin crystals and their physical subsidence in liquids, which enables the reliable fabrication of the micropatterned 2D materials/Si arrays. Our photodiode devices display peak sensitivity as high as 0.35 A/W and external quantum efficiency (EQE) of ∼90%. The nano-subsidence technique represents a viable path to on-chip integration of 2D crystals onto silicon for advanced microelectronics.