Controlling Molecular Doping in Organic Semiconductors

The field of organic electronics thrives on the hope of enabling low‐cost, solution‐processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution‐processed p‐type doped polymeric semiconductors. Highlighted topics include how solution‐processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication—applications beyond those directly analogous to inorganic doping.     

Organic High Electron Mobility Transistors Realized by 2D Electron Gas

A key breakthrough in inorganic modern electronics is the energy‐band engineering that plays important role to improve device performance or develop novel functional devices. A typical application is high electron mobility transistors (HEMTs), which utilizes 2D electron gas (2DEG) as transport channel and exhibits very high electron mobility over traditional field‐effect transistors (FETs). Recently, organic electronics have made very rapid progress and the band transport model is demonstrated to be more suitable for explaining carrier behavior in high‐mobility crystalline organic materials. Therefore, there emerges a chance for applying energy‐band engineering in organic semiconductors to tailor their optoelectronic properties. Here, the idea of energy‐band engineering is introduced and a novel device configuration is constructed, i.e., using quantum well structures as active layers in organic FETs, to realize organic 2DEG. Under the control of gate voltage, electron carriers are accumulated and confined at quantized energy levels, and show efficient 2D transport. The electron mobility is up to 10 cm² V^?1 s^?1, and the operation mechanisms of organic HEMTs are also argued. Our results demonstrate the validity of tailoring optoelectronic properties of organic semiconductors by energy‐band engineering, offering a promising way for the step forward of organic electronics.     

Solution Adsorption Formation of a π‐Conjugated Polymer/Graphene Composite for High‐Performance Field‐Effect Transistors

Semiconducting polymers with π‐conjugated electronic structures have potential application in the large‐scale printable fabrication of high‐performance electronic and optoelectronic devices. However, owing to their poor environmental stability and high‐cost synthesis, polymer semiconductors possess limited device implementation. Here, an approach for constructing a π‐conjugated polymer/graphene composite material to circumvent these limitations is provided, and then this material is patterned into 1D arrays. Driven by the π–π interaction, several‐layer polymers can be adsorbed onto the graphene planes. The low consumption of the high‐cost semiconductor polymers and the mass production of graphene contribute to the low‐cost fabrication of the π‐conjugated polymer/graphene composite materials. Based on the π‐conjugated system, a reduced π–π stacking distance between graphene and the polymer can be achieved, yielding enhanced charge‐transport properties. Owing to the incorporation of graphene, the composite material shows improved thermal stability. More generally, it is believed that the construction of the π‐conjugated composite shows clear possibility of integrating organic molecules and 2D materials into microstructure arrays for property‐by‐design fabrication of functional devices with large area, low cost, and high efficiency.     

Van der Waals Heterostructures for High-Performance Device Applications: Challenges and Opportunities

The discovery of two-dimensional (2D) materials with unique electronic, superior optoelectronic, or intrinsic magnetic order has triggered worldwide interest in the fields of material science, condensed matter physics, and device physics. Vertically stacking 2D materials with distinct electronic and optical as well as magnetic properties enables the creation of a large variety of van der Waals heterostructures. The diverse properties of the vertical heterostructures open unprecedented opportunities for various kinds of device applications, e.g., vertical field-effect transistors, ultrasensitive infrared photodetectors, spin-filtering devices, and so on, which are inaccessible in conventional material heterostructures. Here, the current status of vertical heterostructure device applications in vertical transistors, infrared photodetectors, and spintronic memory/transistors is reviewed. The relevant challenges for achieving high-performance devices are presented. An outlook into the future development of vertical heterostructure devices with integrated electronic and optoelectronic as well as spintronic functionalities is also provided.     

A Versatile and Simple Approach to Generate Light Emission in Semiconductors Mediated by Electric Double Layers

The light‐emitting device is the primary device for current light sources. In principle, conventional light‐emitting devices need heterostructures and/or intentional carrier doping to form a p–n junction. This junction formation is, however, very difficult to achieve for most emerging semiconductors, and the fabrication of light‐emitting devices is invariably a significant challenge. This study proposes a versatile and simple approach to realize light‐emitting devices. This proposed device requires only a semiconducting film with two electrodes that are covered with an electrolyte. This unique structure achieves light emission at a voltage slightly larger than the bandgap energy of materials. This study applies this concept to emerging direct bandgap semiconductors, such as transition metal dichalcogenide monolayers and zinc oxide single crystals. These devices generate obvious light emission and provide sufficient evidence of the formation of a dynamic p–i–n junction or tunneling junction, presenting a versatile technique to develop optoelectronic devices.     

2D organic single crystals: Synthesis,novel physics,high-performance optoelectronic devices and integration

In the last decade, two-dimensional organic single crystals (2D OSCs), defined as a class of ultrathin crystals with atomic or molecular level thickness and micrometer-scale-lateral dimension, has emerged as a rising star due to ultrathin feature, high crystallinity, low-structure symmetry, larger material library, diverse processing technique and excellent flexibility, etc. Due to these advantages, 2D OSCs offer exciting application prospects for flexible electronics, optoelectronics, sensing, energy harvesting, biology and medicine, etc. However, it is still challenging to synthesize large-area highly crystalline 2D OSCs as well as investigate their intrinsic properties and structure–property relationships. Herein, we first treat the growth techniques of 2D OSCs carefully and then discuss their novel physics and optoelectronic properties at the 2D limit. A significant effort has been made in evaluating the latest advances in high-performance devices applying 2D OSCs and corresponding heterostructures. In terms of practical applications, their integrations and device arrays are discussed. Furthermore, we point out several important research directions of 2D OSCs and corresponding heterostructures. Finally, the state-of-the-art challenges and future opportunities that include the investigation and application of 2D OSCs have been presented, which will provoke more researchers to come into this field.     

Many‐Body Complexes in 2D Semiconductors

2D semiconductors such as transition metal dichalcogenides (TMDs) and black phosphorus (BP) are currently attracting great attention due to their intrinsic bandgaps and strong excitonic emissions, making them potential candidates for novel optoelectronic applications. Optoelectronic devices fabricated from 2D semiconductors exhibit many‐body complexes (exciton, trion, biexciton, etc.) which determine the materials optical and electrical properties. Characterization and manipulation of these complexes have become a reality due to their enhanced binding energies as a direct result from reduced dielectric screening and enhanced Coulomb interactions in the 2D regime. Furthermore, the atomic thickness and extremely large surface‐to‐volume ratio of 2D semiconductors allow the possibility of modulating their inherent optical, electrical, and optoelectronic properties using a variety of different environmental stimuli. To fully realize the potential functionalities of these many‐body complexes in optoelectronics, a comprehensive understanding of their formation mechanism is essential. A topical and concise summary of the recent frontier research progress related to many‐body complexes in 2D semiconductors is provided here. Moreover, detailed discussions covering the aspects of fundamental theory, experimental investigations, modulation of properties, and optoelectronic applications are given. Lastly, personal insights into the current challenges and future outlook of many‐body complexes in 2D semiconducting materials are presented.     

Fully‐Inorganic Trihalide Perovskite Nanocrystals: A New Research Frontier of Optoelectronic Materials

All‐inorganic trihalide perovskite nanocrystals (NCs) are emerging as a new class of superstar semiconductors with excellent optoelectronic properties and great potential for a broad range of applications in lighting, lasing, photon detection, and photovoltaics. This article provides an up‐to‐date review on the developments of fully‐inorganic trihalide perovskite NCs by emphasizing their controllable solution fabrication strategies, structural phase transformation, tunable optoelectronic properties, stability, as well as their photovoltaic and optoelectronic applications. Among the properties to be surveyed, particular focus is on the size‐, shape‐, and composition‐dependent photoluminescence properties. Finally, by identifying new challenges, suggestions are provided for further research and potential development of this area.     

From One‐ to Three‐Dimensional Organic Semiconductors: In Search of the Organic Silicon?

Organic semiconductors based on π‐conjugated systems are the focus of considerable interest in the emerging area of soft or flexible photonics and electronics. Whereas in recent years the performances of devices such as organic light‐emitting diodes (OLEDs), organic field‐effect transistors (OFETs), or solar cells have undergone considerable progress, a number of technical and fundamental problems related to the low dimensionality of organic semiconductors based on linear π‐conjugated systems remain unsatisfactorily resolved. This low dimensionality results in an anisotropy of the optical and charge‐transport properties, which in turn implies a control of the material organization/molecular orientation during or after device fabrication. Such a constraint evidently represents a problem when device fabrication by solution‐based processes, such as printing techniques, is envisioned. The aim of this short Review is to illustrate possible alternative strategies based on the development of organic semiconductors with higher dimensionality, capable to exhibit isotropic electronic properties.     

Ultrathin Semiconductor Superabsorbers from the Visible to the Near‐Infrared

The design of ultrathin semiconducting materials that achieve broadband absorption is a long‐sought‐after goal of crucial importance for optoelectronic applications. To date, attempts to tackle this problem consisted either of the use of strong—but narrowband—or broader—but moderate—light‐trapping mechanisms. Here, a strategy that achieves broadband optimal absorption in arbitrarily thin semiconductor materials for all energies above their bandgap is presented. This stems from the strong interplay between Brewster modes, sustained by judiciously nanostructured thin semiconductors on metal films, and photonic crystal modes. Broadband near‐unity absorption in Ge ultrathin films is demonstrated, which extends from the visible to the Ge bandgap in the near‐infrared and is robust against angle of incidence variation. The strategy follows an easy and scalable fabrication route enabled by soft nanoimprinting lithography, a technique that allows seamless integration in many optoelectronic fabrication procedures.     

Toward negligible charge loss in charge injection memories based on vertically integrated 2D heterostructures

Two-dimensional (2D) crystals have a multitude of forms,including semi-metals,semiconductors,and insulators,which are ideal for assembling isolated 2D atomic materials to create van der Waals (vdW) heterostructures.Recently,artificially-stacked materials have been considered promising candidates for nanoelectronic and optoelectronic applications.In this study,we report the vertical integration of layered structures for the fabrication of prototype non-volatile memory devices.A semiconducting-tungsten-disulfide-channel-based memory device is created by sandwiching high-density-of-states multi-layered graphene as a carrier-confining layer between tunnel barriers of hexagonal boron nitride (hBN) and silicon dioxide.The results reveal that a memory window of up to 20 V is opened,leading to a high current ratio (＞103) between programming and erasing states.The proposed design combination produced layered materials that allow devices to attain perfect retention at 13％ charge loss after 10 years,offering new possibilities for the integration of transparent,flexible electronic systems.     

Lattice Structure and Bandgap Control of 2D GaN Grown on Graphene/Si Heterostructures

2D group‐III nitride materials have shown a great promise for applications in optoelectronic devices thanks to their thickness‐dependent properties. However, the epitaxial growth of 2D group‐III nitrides remains a challenge. In this work, epitaxial growth of 2D GaN with well‐controlled lattice structures and bandgaps is achieved by plasma‐enhanced metal organic chemical vapor deposition via effective regulation of plasma energy and growth temperature. The structure of graphene/2D GaN/Si heterostructures is carefully investigated by high‐resolution transmission electron microscopy. The formation mechanism of the 2D GaN layer is clearly clarified by theoretical calculations. Furthermore, a bandgap for 2D GaN ranging from ≈4.18 to ≈4.65 eV varying with the numbers of layers is theoretically calculated and experimentally confirmed. 2D GaN with well‐controlled lattice structure and bandgap holds great potential for the development of deep ultraviolet light‐emitting diodes, energy conversion devices, etc.     

When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures

van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on‐demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self‐assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design.     

Research Process on Photodetectors based on Group-10 Transition Metal Dichalcogenides

Rapidly evolving group-10 transition metal dichalcogenides (TMDCs) offer remarkable electronic, optical, and mechanical properties, making them promising candidates for advanced optoelectronic applications. Compared to most TMDCs semiconductors, group-10-TMDCs possess unique structures, narrow bandgap, and influential physical properties that motivate the development of broadband photodetectors, specifically infrared photodetectors. This review presents the latest developments in the fabrication of broadband photodetectors based on conventional 2D TMDCs. It mainly focuses on the recent developments in group-10 TMDCs from the perspective of the lattice structure and synthesis techniques. Recent progress in group-10 TMDCs and their heterostructures with different dimensionality of materials-based broadband photodetectors is provided. Moreover, this review accounts for the latest applications of group-10 TMDCs in the fields of nanoelectronics and optoelectronics. Finally, conclusions and outlooks are summarized to provide perspectives for next-generation broadband photodetectors based on group-10 TMDCs.     

2D Organic Materials for Optoelectronic Applications

The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D‐materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self‐assembly monolayers, and covalent organic frameworks. The protocols for 2D‐organic‐crystal‐fabrication and ‐patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.     

Intercalation of Layered Materials from Bulk to 2D

Intercalation in few‐layer (2D) materials is a rapidly growing area of research to develop next‐generation energy‐storage and optoelectronic devices, including batteries, sensors, transistors, and electrically tunable displays. Identifying fundamental differences between intercalation in bulk and 2D materials will play a key role in developing functional devices. Herein, advances in few‐layer intercalation are addressed in the historical context of bulk intercalation. First, synthesis methods and structural properties are discussed, emphasizing electrochemical techniques, the mechanism of intercalation, and the formation of a solid‐electrolyte interphase. To address fundamental differences between bulk and 2D materials, scaling relationships describe how intercalation kinetics, structure, and electronic and optical properties depend on material thickness and lateral dimension. Here, diffusion rates, pseudocapacity, limits of staging, and electronic structure are compared for bulk and 2D materials. Next, the optoelectronic properties are summarized, focusing on charge transfer, conductivity, and electronic structure. For energy devices, opportunities also emerge to design van der Waals heterostructures with high capacities and excellent cycling performance. Initial studies of heterostructured electrodes are compared to state‐of‐the‐art battery materials. Finally, challenges and opportunities are presented for 2D materials in energy and optoelectronic applications, along with promising research directions in synthesis and characterization to engineer 2D materials for superior devices.     

25th Anniversary Article: Carbon Nanotube‐ and Graphene‐Based Transparent Conductive Films for Optoelectronic Devices

Carbon nanotube (CNT)‐ and graphene (G)‐based transparent conductive films (TCFs) are two promising alternatives for commonly‐used indium tin oxide‐based TCFs for future flexible optoelectronic devices. This review comprehensively summarizes recent progress in the fabrication, properties, modification, patterning, and integration of CNT‐ and G‐TCFs into optoelectronic devices. Their potential applications and challenges in optoelectronic devices, such as organic photovoltaic cells, organic light emitting diodes and touch panels, are discussed in detail. More importantly, their key characteristics and advantages for use in these devices are compared. Despite many challenges, CNT‐ and G‐TCFs have demonstrated great potential in various optoelectronic devices and have already been used for some products like touch panels of smartphones. This illustrates the significant opportunities for the industrial use of CNTs and graphene, and hence pushes nanoscience and nanotechnology one step towards practical applications.     

In Situ Fabrication of Vertical Multilayered MoS2/Si Homotype Heterojunction for High‐Speed Visible–Near‐Infrared Photodetectors

c2D transition metal dichalcogenides (TMDCs)‐based heterostructures have been demonstrated to achieve superior light absorption and photovoltaic effects theoretically and experimentally, making them extremely attractive for realizing optoelectronic devices. In this work, a vertical multilayered n‐MoS₂/n‐silicon homotype heterojunction is fabricated, which takes advantage of multilayered MoS₂ grown in situ directly on plane silicon. Electrical characterization reveals that the resultant device exhibits high sensitivity to visible–near‐infrared light with responsivity up to 11.9 A W^–1. Notably, the photodetector shows high‐speed response time of ≈30.5 µs/71.6 µs and capability to work under higher pulsed light irradiation approaching 100 kHz. The high response speed could be attributed to a good quality of the multilayer MoS₂, as well as in situ device fabrication process. These findings suggest that the multilayered MoS₂/Si homotype heterojunction have great potential application in the field of visible–near‐infrared detection and might be used as elements for construction of high‐speed integrated optoelectronic sensor circuitry.     

Engineering Chemically Active Defects in Monolayer MoS2 Transistors via Ion‐Beam Irradiation and Their Healing via Vapor Deposition of Alkanethiols

Irradiation of 2D sheets of transition metal dichalcogenides with ion beams has emerged as an effective approach to engineer chemically active defects in 2D materials. In this context, argon‐ion bombardment has been utilized to introduce sulfur vacancies in monolayer molybdenum disulfide (MoS₂). However, a detailed understanding of the effects of generated defects on the functional properties of 2D MoS₂ is still lacking. In this work, the correlation between critical electronic device parameters and the density of sulfur vacancies is systematically investigated through the fabrication and characterization of back‐gated monolayer MoS₂ field‐effect transistors (FETs) exposed to a variable fluence of low‐energy argon ions. The electrical properties of pristine and ion‐irradiated FETs can be largely improved/recovered by exposing the devices to vapors of short linear thiolated molecules. Such a solvent‐free chemical treatment—carried out strictly under inert atmosphere—rules out secondary healing effects induced by oxygen or oxygen‐containing molecules. The results provide a guideline to design monolayer MoS₂ optoelectronic devices with a controlled density of sulfur vacancies, which can be further exploited to introduce ad hoc molecular functionalities by means of thiol chemistry approaches.     

A “Phase Separation” Molecular Design Strategy Towards Large‐Area 2D Molecular Crystals

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self‐assembly is considered an effective way to grow large‐area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self‐assembly and molecular structure. A “phase separation” molecular design strategy towards 2DMCs is proposed and layer‐by‐layer growth of millimeter‐sized monolayer or few‐layer 2DMCs is realized. High‐performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 10⁷), high responsivity (1.91 × 10⁴ A W^?1), and high detectivity (4.93 × 10¹⁵ Jones). This “phase separation” molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self‐assemble into large‐area 2DMCs for advanced organic (opto)electronics.