High Solid‐State Near Infrared Emissive Organic Fluorophores from Thiadiazole[3,4‐c]Pyridine Derivatives for Efficient Simple Solution‐Processed Nondoped Near Infrared OLEDs

Many efforts have been dedicated to developing near infrared (NIR) fluorescent emitters with strong emission especially in the range of 700–1000 nm due to their potential applications in biomedical and optoelectronic fields. However, high solid state NIR emission fluorophores are still rare for applications. Herein, two efficient donor‐π‐acceptor type NIR emitters, C3HTP and C4HTP , are designed and synthesized by end‐capping two isomeric bis(n‐hexylthienyl)thiadiazole[3,4‐c]pyridines as π‐acceptor with structural bulky, electron rich tercarbazole moiety. They exhibit excellent solid state NIR emission with an emission peak at 725 nm, especially C3HTP , reaching a record high photoluminescence quantum yield (Φ_PL) of 34% for NIR organic fluorescent materials. By taking advantage of their Φ_PL values in the film state (Φ_PL = 10–34%), suitable energy levels (highest occupied molecular orbital (HOMO) level ≈ ?5.3 eV), high hole mobility (5.49 × 10^?8 cm² V^?1 s^?1) as well as good amorphous film forming ability by solution casting, they are used to fabricate a nondoped emissive layer (EML) in simple double‐layer solution processed NIR electroluminescent (EL) devices. The device containing C3HTP as the EML shows a NIR emission peaking at 726 nm and excellent EL performance with a high external quantum efficiency of 1.51%, which is the best solution processed nondoped NIR organic light‐emitting diodes reported to date. Importantly, this represents an advance in near infrared organic fluorescent materials and EL devices that meet the requirements of many applications.     

Molecularly Engineered Near‐Infrared Light‐Emitting Electrochemical Cells

The development of near‐infrared (NIR) luminescent materials has emerged as a promising research field with important applications in solid‐state lighting (SSL), night‐vision‐readable displays, and the telecommunication industry. Over the past two decades, remarkable advances in the development of light‐emitting electrochemical cells (LECs) have stunned the SSL community, which has in turn driven the quest for new classes of stable, more efficient NIR emissive molecules. In this review, an overview of the state of the art in the field of near‐infrared light‐emitting electrochemical cells (NIR‐LEC) is provided based on three families of emissive compounds developed over the past 25 years: i) transition metal complexes, ii) ionic polymers, and iii) host–guest materials. In this context, ionic and conductive emitters are particularly attractive since their emission can be tuned via molecular design, which involves varying the chemical nature and substitution pattern of their ancillary ligands. Herein, the challenges and current limitations of the latter approach are highlighted, particularly with respect to developing NIR‐LECs with high external quantum efficiencies. Finally, useful guidelines for the discovery of new, efficient emitters for tailored NIR‐LEC applications are presented, together with an outlook towards the design of new NIR‐SSL materials.     

Boosting Efficiency of Near‐Infrared Organic Light‐Emitting Diodes with Os(II)‐Based Pyrazinyl Azolate Emitters

Tremendous effort has been devoted to developing novel near‐infrared (NIR) emitters and to improving the performance of NIR organic light‐emitting diodes (OLEDs). Os(II) complexes are known to be an important class of NIR electroluminescent materials. However, the highest external quantum efficiency achieved so far for Os(II)‐based NIR OLEDs with an emission peak wavelength exceeding 700 nm is still lower than 3%. A new series of Os(II) complexes ( 1 – 4 ) based on functional pyrazinyl azolate chelates and dimethyl(phenyl)phosphane ancillaries is presented. The reduced metal‐to‐ligand charge transfer (MLCT) transition energy gap of pyrazinyl units in the excited states results in efficient NIR emission for this class of metal complexes. Consequently, NIR OLEDs based on 1 – 4 show excellent device performance, among which complex 4 with a triazolate fragment gives superior performance with maximum external quantum efficiency of 11.5% at peak wavelength of 710 nm, which represent the best Os(II)‐based NIR‐emitting OLEDs with peak maxima exceeding 700 nm.     

n‐Type Quinoidal Oligothiophene‐Based Semiconductors for Thin‐Film Transistors and Thermoelectrics

Organic electronic devices have gained immense popularity in the last 30 years owing to their increasing performance. Organic thin‐film transistors (OTFTs) are one of the basic organic electronic devices with potential industrial applications. Another class of devices called organic thermoelectric (OTE) materials can directly transform waste heat into usable electrical power without causing any pollution. p‐Type transistors outperform n‐type transistors because the latter requires a lower orbital energy level for efficient electron injection and stable electron transport under ambient conditions. Aromatic building blocks can be utilized in constructing n‐type semiconductors. Quinoidal compounds are another promising platform for optoelectronic applications because of their unique properties. Since their discovery in 1970s, quinoidal oligothiophene‐based n‐type semiconductors have drawn considerable attention as candidates for high‐performance n‐type semiconductors in OTFTs and OTEs. Herein, the development history of quinoidal oligothiophene‐based semiconductors is summarized, with a focus on the molecular design and the influence of structural modification on molecular packing and thus the device performance of the corresponding quinoidal oligothiophene‐based semiconductors. Insights on the potential of quinoidal oligothiophenes for high‐performance n‐type OTFTs and OTEs are also provided.     

Organic Light‐Emitting Diodes Based on Poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2)

A study of the optical properties of poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2) is reported, identifying this polymer as one that possesses a desirable combination of charge transport and light emission properties. The optical and morphological properties of a series of polymer blends with F8T2 dispersed in poly(9,9‐dioctylfluorene) (PFO) are described and almost pure‐green emission from light emitting diodes (LEDs) based thereon is demonstrated. High luminance green electroluminescence from LEDs using only a thin film of F8T2 for emission is also reported. The latter demonstration for a polymer previously primarily of interest for effective charge transport constitutes an important step in the development of emissive materials for applications where a union of efficient light emission and effective charge transport is required.     

Perovskite‐Based Phototransistors and Hybrid Photodetectors

In the past several years, organic–inorganic hybrid perovskites and all inorganic perovskites have attracted enormous research interest in a variety of optoelectronic applications including solar cells, light‐emitting diodes, semiconductor lasers, and photodetectors for their plenty of appealing electrical and optoelectrical properties. Benefiting from the inherent amplification function of transistors and the pronounced photogating effect, perovskite‐based phototransistors and hybrid photodetectors can provide very high photoresponsivity and gain, rendering them highly promising for some specific applications especially ultrasensitive light detection. A review on the recent progress of phototransistors and hybrid photodetectors using perovskites as light‐sensitive materials is presented. The efforts and development in 3D and 2D perovskite‐based phototransistors, and perovskite/functional material (e.g., graphene, 2D semiconductors, organic semiconductors, and other semiconductors) heterojunction‐based hybrid photodetectors are introduced and discussed systematically. Some processing techniques for optimizing device performance are also addressed. In the final section, a conclusion of the research achievements is presented and possible challenges as well as outlook are provided to guide future activity in this research field.     

New Insights into Tunable Volatility of Ionic Materials through Counter‐Ion Control

Recent development in the field of small molecular materials has led to great advances in the performance of vacuum‐evaporated organic light‐emitting diodes. However, as a significant class of phosphorescent emitters, ionic transition metal complexes are seldom sublimable due to the inherent ionic nature and low vapor pressure, restricting their applications in state‐of‐the‐art devices fabricated by vacuum evaporation deposition. Here a facile, feasible and versatile strategy is shown to tune the volatility of ionic transition metal complexes through counter‐ion control. By introducing counter‐ions with large steric hindrance and well‐dispersed charges, a series of evaporable ionic iridium complexes are developed, and efficient vapor‐processed devices with a high brightness, small efficiency roll‐off, and polychromic emission ranging from deep‐blue to red‐orange are achieved. Our findings unlock the utilization of ionic functional materials in vacuum‐evaporated devices, and may open new doors for modern electronic materials technology.     

Systematic Study of Widely Applicable N‐Doping Strategy for High‐Performance Solution‐Processed Field‐Effect Transistors

A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F^? and OH^?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.     

Recent Advances in Structural Design of Efficient Near-Infrared Light-Emitting Organic Small Molecules

Organic light-emitting materials in the near-infrared (NIR) region are important to realize next-generation lightweight and wearable applications in bioimaging, photodynamic therapy, and telecommunications. Inorganic and organometallic light-emitting materials are expensive and toxic; thus, the development of purely organic light-emitting materials is essential. However, the development of highly efficient NIR light-emitting materials made of organic materials is still in its infancy. Therefore, this review outlines molecular design strategies for developing organic small-molecule NIR light-emitting materials with high emission efficiency that can overcome the energy-gap law to be applied to next-generation wearable devices. After briefly reviewing the basic knowledge required for the NIR emission of organic molecules, representative high-efficiency molecules reported over the past 5 years are classified according to their core moieties, and their molecular design, physical properties, and luminescence characteristics are analyzed. Further, the perspective and outlook regarding the development of next-generation high-efficiency NIR organic light-emitting materials are provided.     

Flexible Near‐Infrared Plastic Phototransistors with Conjugated Polymer Gate‐Sensing Layers

Flexible near‐infrared (NIR) light‐sensing detectors are strongly required in the fast‐growing flexible electronics era, because they can serve as a vision system like eyes in various innovative applications including humanoid robots. Recently, keen interest has been paid to organic phototransistors due to their unique signal amplification and active matrix driving features over organic photodiodes. However, conventional NIR‐sensing organic phototransistors suffer from the limited use of organic materials because the channel layers play a dual role in both charge transport and sensing so that organic semiconducting materials with reasonably high charge mobility can be applied only. Here, it is demonstrated that a conjugated polymer, poly[{2,5‐bis‐(2‐ethylhexyl)‐3,6‐bis‐(thien‐2‐yl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐diyl}‐co‐{2,2′‐(2,1,3‐benzothiadiazole)]‐5,5′‐diyl}] (PEHTPPD‐BT), which exhibits no transistor performance as a channel layer, can stably detect a NIR light (up to 1000 nm) as a gate‐sensing layer (GSL) when it is placed between gate‐insulating layers and gate electrodes. The flexible array (10 × 10) detectors with the PEHTPPD‐BT GSLs could effectively sense NIR light without visible light interference by applying visible light cut films.     

Highly Efficient Near‐Infrared Electroluminescence up to 800 nm Using Platinum(II) Phosphors

Near‐infrared organic light‐emitting diodes (NIR OLEDs) enable many unique applications ranging from night‐vision displays and photodynamic therapies. However, the development of efficient NIR OLEDs with a low efficiency roll‐off is still challenging. Here, a series of new heteroleptic Pt(II) complexes ( 1 – 4 ) flanked by both pyridyl pyrimidinate and functional azolate chelates are synthesized. The reduced ππ* energy gap of the pyridyl pyrimidinate chelate, and strong intermolecular interaction and high crystallinity in vacuum‐deposited thin films engender strong intermolecular charge transfer transition including metal–metal‐to‐ligand charge transfer; thereby, exhibiting efficient photoluminescence within 776–832 nm and short radiative lifetimes of 0.52–0.79 µs. Consequently, nondoped NIR‐emitting OLEDs based on these Pt(II) complexes are fabricated, to which Pt(II) complexes 2 and 4 give record high maximum external quantum efficiency of 10.61% at 794 nm and 9.58% at 803 nm, respectively. Moreover, low efficiency roll‐off is also observed, among which the device efficiencies of 2 and 4 are at least four times higher than that of the best NIR‐emitting OLEDs recorded at current density of 100 mA cm^?2.     

Contact Resistance in Organic Field‐Effect Transistors: Conquering the Barrier

Organic semiconductors have sparked interest as flexible, solution processable, and chemically tunable electronic materials. Improvements in charge carrier mobility put organic semiconductors in a competitive position for incorporation in a variety of (opto‐)electronic applications. One example is the organic field‐effect transistor (OFET), which is the fundamental building block of many applications based on organic semiconductors. While the semiconductor performance improvements opened up the possibilities for applying organic materials as active components in fast switching electrical devices, the ability to make good electrical contact hinders further development of deployable electronics. Additionally, inefficient contacts represent serious bottlenecks in identifying new electronic materials by inhibiting access to their intrinsic properties or providing misleading information. Recent work focused on the relationships of contact resistance with device architecture, applied voltage, metal and dielectric interfaces, has led to a steady reduction in contact resistance in OFETs. While impressive progress was made, contact resistance is still above the limits necessary to drive devices at the speed required for many active electronic components. Here, the origins of contact resistance and recent improvement in organic transistors are presented, with emphasis on the electric field and geometric considerations of charge injection in OFETs.     

Copper Iodide Based Hybrid Phosphors for Energy‐Efficient General Lighting Technologies

Solid‐state‐lighting (SSL) is a new lighting technology that is rapidly replacing conventional lighting sources because it is much more energy efficient, longer lasting, and contributes significantly to environmental protection. A main branch of SSL technology is light‐emitting diodes (LEDs), and white‐light LEDs (WLEDs) are in the greatest demand for general lighting and illumination applications. Current WLED devices rely heavily on rare‐earth elements (REEs), which will likely suffer from cost and supply risks and environmental consequences in the near future. Crystalline inorganic–organic hybrid materials based on I–VII binary semiconductors represent a promising material class as REE‐free phosphor alternatives. This article provides a brief overview of recent advancement on this material family, with a focus on the rational design, energy‐efficient and low‐cost synthesis, systematic modification, and optimization of their electronic, optical, and thermal properties. A particular emphasis will be made on our own progress over the past several years in developing four classes of CuI(L) structures with substantially improved performance as energy‐saving lighting phosphors. General strategies for structural design, synthesis, and property optimization of these materials will also be discussed.     

Comparative Study of the N‐Type Doping Efficiency in Solution‐processed Fullerenes and Fullerene Derivatives

Molecular doping of organic semiconductors and devices represents an enabling technology for a range of emerging optoelectronic applications. Although p‐type doping has been demonstrated in a number of organic semiconductors, efficient n‐type doping has proven to be particularly challenging. Here, n‐type doping of solution‐processed C₆₀, C₇₀, [60]PCBM, [70]PCBM and indene‐C₆₀ bis‐adduct by 1H‐benzimidazole (N‐DMBI) is reported. The doping efficiency for each system is assessed using field‐effect measurements performed under inert atmosphere at room temperature in combination with optical absorption spectroscopy and atomic force microscopy. The highest doping efficiency is observed for C₆₀ and C₇₀ and electron mobilities up to ≈2 cm²/Vs are obtained. Unlike in substituted fullerenes‐based transistors where the electron mobility is found to be inversely proportional to N‐DMBI concentration, C₆₀ and C₇₀ devices exhibit a characteristic mobility increase by approximately an order of magnitude with increasing dopant concentration up to 1 mol%. Doping also appears to significantly affect the bias stability of the transistors. The work contributes towards understanding of the molecular doping mechanism in fullerene‐based semiconductors and outlines a simple and highly efficient approach that enables significant improvement in device performance through facile chemical doping.     

Rational Design of Perylenediimide‐Substituted Triphenylethylene to Electron Transporting Aggregation‐Induced Emission Luminogens (AIEgens) with High Mobility and Near‐Infrared Emission

Organic materials with both high electron mobility and strong solid‐state emission are rare although for their importance to advanced organic optoelectronics. In this paper, triphenylethylenes with varying number of perylenediimide (PDI) unit (TriPE‐nPDIs, n = 1?3) are synthesized and their optical and charge‐transporting properties are systematically investigated. All the molecules exhibit strong solid‐stated near infrared (NIR) emission and some of them exhibit aggregation‐enhanced emission characteristics. Organic field‐effect transistors (OFETs) using TriPE‐nPDIs are fabricated. TriPE‐3PDI shows the best performance with maximum quantum yield of ≈30% and optimized electron mobility of over 0.01 cm² V^?1 s^?1, which are the highest values among aggregation‐induced emission luminogens with NIR emissions reported so far. Photophysical property investigation and theoretical calculation indicate that the molecular conformation plays an important role on the optical properties of TriPE‐nPDI, while the result from film microstructure study reveals that the film crystallinity influences greatly their OFET device performance.     

Recent Developments and Novel Applications of Thin Film,Light‐Emitting Transistors

Light‐emitting field‐effect transistors (LEFETs) combine switching and amplification with light emission and thus represent an interesting optoelectronic device. They are not limited anymore to a few examples and specific materials but are nearly universal for a wide range of semiconductors, from organic to inorganic and nanoscale. This review introduces the basic working principles of lateral unipolar and ambipolar LEFETs and discusses recent examples based on various solution‐processed semiconducting materials. Applications beyond simple light emission are presented and possible future directions for light‐emitting transistors with added functionalities are outlined.     

Detection of X‐Rays by Solution‐Processed Cesium‐Containing Mixed Triple Cation Perovskite Thin Films

Materials and technology development for designing innovative and efficient X‐ray radiation detectors is of utmost importance for a wide range of applications ranging from security to medical imaging. Here, highly sensitive direct X‐ray detectors based on novel cesium (Cs)‐based triple cation mixed halide perovskite thin films are reported. Despite being in a thin film form, the devices exhibit a remarkably high X‐ray sensitivity of (3.7 ± 0.1) µC Gy^?1 cm^?2 under short‐circuit conditions. At a small reverse bias of 0.4 V, the sensitivity further increases by orders of magnitude reaching a record value of (97 ± 1) µC Gy^?1 cm^?2 which surpasses state‐of‐the‐art inorganic large‐area detectors (a‐Se and poly‐CZT). Based on detailed structural, electrical, and spectroscopic investigations, the exceptional sensitivity of the triple cation Cs perovskite is attributed to its high ambipolar mobility‐lifetime product as well as to the formation of a pure stable perovskite phase with a low degree of energetic disorder, due to an efficient solution‐based alloying of individual n‐ and p‐type perovskite semiconductors.     

Small Molecules in Light‐Emitting Electrochemical Cells: Promising Light‐Emitting Materials

Light‐emitting electrochemical cells (LECs) are solid‐state lighting devices that convert electric current to light within electroluminescent organic semiconductors, and these devices have recently attracted significant attention. Introduced in 1995, LECs are considered a great breakthrough in the field of light‐emitting devices for their applications in scalable and adaptable fabrication processes aimed at producing cost‐efficient devices. Since then, LECs have evolved through the discovery of new suitable emitters, understanding the working mechanism of devices, and the development of various fabrication methods. LECs are best known for their simple architecture and easy, low‐cost fabrication techniques. The key feature of their fabrication is the use of air stable electrodes and a single active layer consisting of mobile ions that enable efficient charge injection and transport processes within LEC devices. More importantly, LEC devices can be operated at low voltages with high efficiencies, contributing to their widespread interest. This review provides a general overview of the development of LECs and discusses how small molecules can be utilized in LEC applications by overcoming the use of traditional lighting materials like polymers and ionic transition metal complexes. The achievements of each study concerning small molecule LECs are discussed.     

Modulated Thermoelectric Properties of Organic Semiconductors Using Field‐Effect Transistors

Organic thermoelectric materials, which can transform heat flow into electricity, have great potential for flexible, ultra‐low‐cost and large‐area thermoelectric applications. Despite rapid developments of organic thermoelectric materials, exploration and investigation of promising organic thermoelectric semiconductors still remain as a challenge. Here, the thermoelectric properties of several p‐ and n‐type organic semiconductors are investigated and studied, in particular, how the electric field modulations of the Seebeck coefficient in organic field‐effect transistors (OFETs) compare with the Seebeck coefficient in chemically doped films. The extracted relationship between the Seebeck coefficient (S) and electrical conductivity (σ) from the field‐effect transistor (FET) geometry is in good agreement with that of chemically doped films, enabling the investigation of the trade‐off relationship among σ, S, carrier concentration, and charging level. The results make OFETs an effective candidate for the thermoelectric studies of organic semiconductors.     

Plasmon‐Induced Sub‐Bandgap Photodetection with Organic Schottky Diodes

Organic materials for near‐infrared (NIR) photodetection are in the focus for developing organic optical‐sensing devices. The choice of materials for bulk‐type organic photodetectors is limited due to effects like high nonradiative recombination rates for low‐gap materials. Here, an organic Schottky barrier photodetector with an integrated plasmonic nanohole electrode is proposed, enabling structure‐dependent, sub‐bandgap photodetection in the NIR. Photons are detected via internal photoemission (IPE) process over a metal/organic semiconductor Schottky barrier. The efficiency of IPE is improved by exciting localized surface plasmon resonances, which are further enhanced by coupling to an out‐of‐plane Fabry–Pérot cavity within the metal/organic/metal device configuration. The device allows large on/off ratio (>1000) and the selective control of individual pixels by modulating the Schottky barrier height. The concept opens up new design and application possibilities for organic NIR photodetectors.