Showing papers on "Organic semiconductor published in 2018"

Design rules for minimizing voltage losses in high-efficiency organic solar cells.

Abstract: The open-circuit voltage of organic solar cells is usually lower than the values achieved in inorganic or perovskite photovoltaic devices with comparable bandgaps Energy losses during charge separation at the donor–acceptor interface and non-radiative recombination are among the main causes of such voltage losses Here we combine spectroscopic and quantum-chemistry approaches to identify key rules for minimizing voltage losses: (1) a low energy offset between donor and acceptor molecular states and (2) high photoluminescence yield of the low-gap material in the blend Following these rules, we present a range of existing and new donor–acceptor systems that combine efficient photocurrent generation with electroluminescence yield up to 003%, leading to non-radiative voltage losses as small as 021 V This study provides a rationale to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells Key optoelectronic properties for donor and acceptor organic semiconductors are identified to obtain organic solar cells with reduced open-circuit voltage losses and high power conversion efficiencies

Organic semiconductor crystals

Abstract: Organic semiconductors have attracted a lot of attention since the discovery of highly doped conductive polymers, due to the potential application in field-effect transistors (OFETs), light-emitting diodes (OLEDs) and photovoltaic cells (OPVs). Single crystals of organic semiconductors are particularly intriguing because they are free of grain boundaries and have long-range periodic order as well as minimal traps and defects. Hence, organic semiconductor crystals provide a powerful tool for revealing the intrinsic properties, examining the structure–property relationships, demonstrating the important factors for high performance devices and uncovering fundamental physics in organic semiconductors. This review provides a comprehensive overview of the molecular packing, morphology and charge transport features of organic semiconductor crystals, the control of crystallization for achieving high quality crystals and the device physics in the three main applications. We hope that this comprehensive summary can give a clear picture of the state-of-art status and guide future work in this area.

Efficient radical-based light-emitting diodes with doublet emission

Abstract: Organic light-emitting diodes (OLEDs)1–5, quantum-dot-based LEDs6–10, perovskite-based LEDs11–13 and micro-LEDs14,15 have been championed to fabricate lightweight and flexible units for next-generation displays and active lighting. Although there are already some high-end commercial products based on OLEDs, costs must decrease whilst maintaining high operational efficiencies for the technology to realise wider impact. Here we demonstrate efficient action of radical-based OLEDs16, whose emission originates from a spin doublet, rather than a singlet or triplet exciton. While the emission process is still spin-allowed in these OLEDs, the efficiency limitations imposed by triplet excitons are circumvented for doublets. Using a luminescent radical emitter, we demonstrate an OLED with maximum external quantum efficiency of 27 per cent at a wavelength of 710 nanometres—the highest reported value for deep-red and infrared LEDs. For a standard closed-shell organic semiconductor, holes and electrons occupy the highest occupied and lowest unoccupied molecular orbitals (HOMOs and LUMOs), respectively, and recombine to form singlet or triplet excitons. Radical emitters have a singly occupied molecular orbital (SOMO) in the ground state, giving an overall spin-1/2 doublet. If—as expected on energetic grounds—both electrons and holes occupy this SOMO level, recombination returns the system to the ground state, giving no light emission. However, in our very efficient OLEDs, we achieve selective hole injection into the HOMO and electron injection to the SOMO to form the fluorescent doublet excited state with near-unity internal quantum efficiency. Organic light-emitting devices containing radical emitters can achieve an efficiency of 27 per cent at deep-red and infrared wavelengths based on the excitation of spin doublets, rather than singlet or triplet states.

Organic Semiconductor Single Crystals for Electronics and Photonics.

Abstract: Organic semiconducting single crystals (OSSCs) are ideal candidates for the construction of high-performance optoelectronic devices/circuits and a great platform for fundamental research due to their long-range order, absence of grain boundaries, and extremely low defect density. Impressive improvements have recently been made in organic optoelectronics: the charge-carrier mobility is now over 10 cm2 V-1 s-1 and the fluorescence efficiency reaches 90% for many OSSCs. Moreover, high mobility and strong emission can be integrated into a single OSSC, for example, showing a mobility of up to 34 cm2 V-1 s-1 and a photoluminescence yield of 41.2%. These achievements are attributed to the rational design and synthesis of organic semiconductors as well as improvements in preparation technology for crystals, which accelerate the application of OSSCs in devices and circuits, such as organic field-effect transistors, organic photodetectors, organic photovoltaics, organic light-emitting diodes, organic light-emitting transistors, and even electrically pumped organic lasers. In this context, an overview of these fantastic advancements in terms of the fundamental insights into developing high-performance organic semiconductors, efficient strategies for yielding desirable high-quality OSSCs, and their applications in optoelectronic devices and circuits is presented. Finally, an overview of the development of OSSCs along with current challenges and future research directions is provided.

A high dielectric constant non-fullerene acceptor for efficient bulk-heterojunction organic solar cells

Abstract: The majority of organic semiconductors have a low relative dielectric constant (er 6) has attracted a very limited attention. Moreover, high performance OSCs based on high dielectric constant photovoltaic materials are still in their infancy. Herein, we report an oligoethylene oxide side chain-containing non-fullerene acceptor (ITIC-OE) with a high relative dielectric constant of er ≈ 9.4, which is two times larger than that of its alkyl chain-containing counterpart ITIC. Encouragingly, the OSCs based on ITIC-OE show a high power conversion efficiency of 8.5%, which is the highest value for OSCs that employ high dielectric constant materials. Nevertheless, this value is lower than those of ITIC-based control devices. The less phase-separated morphology in blend films due to the reduced crystallinity of ITIC-OE and the too good miscibility between PBDB-T and ITIC-OE are responsible for the lower device performance. This work suggests additional prerequisites to make high dielectric constants play a significant role in OSCs.

Wafer-scale, layer-controlled organic single crystals for high-speed circuit operation.

Abstract: Two-dimensional (2D) layered semiconductors are a novel class of functional materials that are an ideal platform for electronic applications, where the whole electronic states are directly modified by external stimuli adjacent to their electronic channels. Scale-up of the areal coverage while maintaining homogeneous single crystals has been the relevant challenge. We demonstrate that wafer-size single crystals composed of an organic semiconductor bimolecular layer with an excellent mobility of 10 cm2 V-1 s-1 can be successfully formed via a simple one-shot solution process. The well-controlled process to achieve organic single crystals composed of minimum molecular units realizes unprecedented low contact resistance and results in high-speed transistor operation of 20 MHz, which is twice as high as the common frequency used in near-field wireless communication. The capability of the solution process for scale-up coverage of high-mobility organic semiconductors opens up the way for novel 2D nanomaterials to realize products with large-scale integrated circuits on film-based devices.

High-Performance Organic Bulk-Heterojunction Solar Cells Based on Multiple-Donor or Multiple-Acceptor Components.

Abstract: Organic solar cells (OSCs) based on bulk heterojunction structures are promising candidates for next-generation solar cells. However, the narrow absorption bandwidth of organic semiconductors is a critical issue resulting in insufficient usage of the energy from the solar spectrum, and as a result, it hinders performance. Devices based on multiple-donor or multiple-acceptor components with complementary absorption spectra provide a solution to address this issue. OSCs based on multiple-donor or multiple-acceptor systems have achieved power conversion efficiencies over 12%. Moreover, the introduction of an additional component can further facilitate charge transfer and reduce charge recombination through cascade energy structure and optimized morphology. This progress report provides an overview of the recent progress in OSCs based on multiple-donor (polymer/polymer, polymer/dye, and polymer/small molecule) or multiple-acceptor (fullerene/fullerene, fullerene/nonfullerene, and nonfullerene/nonfullerene) components.

Universal strategy for Ohmic hole injection into organic semiconductors with high ionization energies.

Abstract: Barrier-free (Ohmic) contacts are a key requirement for efficient organic optoelectronic devices, such as organic light-emitting diodes, solar cells, and field-effect transistors. Here, we propose a simple and robust way of forming an Ohmic hole contact on organic semiconductors with a high ionization energy (IE). The injected hole current from high-work-function metal-oxide electrodes is improved by more than an order of magnitude by using an interlayer for which the sole requirement is that it has a higher IE than the organic semiconductor. Insertion of the interlayer results in electrostatic decoupling of the electrode from the semiconductor and realignment of the Fermi level with the IE of the organic semiconductor. The Ohmic-contact formation is illustrated for a number of material combinations and solves the problem of hole injection into organic semiconductors with a high IE of up to 6 eV. It is shown that Ohmic contacts for the injection of hole carriers into organic semiconductors with high ionization energy can be formed by adding ultrathin interlayers with higher ionization energy.

(Semi)ladder-Type Bithiophene Imide-Based All-Acceptor Semiconductors: Synthesis, Structure-Property Correlations, and Unipolar n-Type Transistor Performance

Abstract: Development of high-performance unipolar n-type organic semiconductors still remains as a great challenge. In this work, all-acceptor bithiophene imide-based ladder-type small molecules BTIn and semiladder-type homopolymers PBTIn (n = 1–5) were synthesized, and their structure–property correlations were studied in depth. It was found that Pd-catalyzed Stille coupling is superior to Ni-mediated Yamamoto coupling to produce polymers with higher molecular weight and improved polymer quality, thus leading to greatly increased electron mobility (μe). Due to their all-acceptor backbone, these polymers all exhibit unipolar n-type transport in organic thin-film transistors, accompanied by low off-currents (10–10–10–9 A), large on/off current ratios (106), and small threshold voltages (∼15–25 V). The highest μe, up to 3.71 cm2 V–1 s–1, is attained from PBTI1 with the shortest monomer unit. As the monomer size is extended, the μe drops by 2 orders to 0.014 cm2 V–1 s–1 for PBTI5. This monotonic decrease of μe was al...

N-Type 2D Organic Single Crystals for High-Performance Organic Field-Effect Transistors and Near-Infrared Phototransistors.

Abstract: Organic field-effect transistors and near-infrared (NIR) organic phototransistors (OPTs) have attracted world's attention in many fields in the past decades. In general, the sensitivity, distinguishing the signal from noise, is the key parameter to evaluate the performance of NIR OPTs, which is decided by responsivity and dark current. 2D single crystal films of organic semiconductors (2DCOS) are promising functional materials due to their long-range order in spite of only few molecular layers. Herein, for the first time, air-stable 2DCOS of n-type organic semiconductors (a furan-thiophene quinoidal compound, TFT-CN) with strong absorbance around 830 nm, by the facile drop-casting method on the surface of water are successfully prepared. Almost millimeter-sized TFT-CN 2DCOS are obtained and their thickness is below 5 nm. A competitive field-effect electron mobility (1.36 cm2 V-1 s-1 ) and high on/off ratio (up to 108 ) are obtained in air. Impressively, the ultrasensitive NIR phototransistors operating at the off-state exhibit a very low dark current of ≈0.3 pA and an ultrahigh detectivity (D*) exceeding 6 × 1014 Jones because the devices can operate in full depletion at the off-state, superior to the majority of the reported organic-based NIR phototransistors.

Organic 2D Optoelectronic Crystals: Charge Transport, Emerging Functions, and Their Design Perspective

Abstract: 2D organic semiconductor crystals are emerging as a fascinating platform with regard to their applications in organic field-effect transistors (OFETs), attributed to their enhanced charge transport efficiency and their new optoelectronic functions, based on their unique morphological features. Advances in material processing techniques have not only enabled easy fabrication of few-monolayered 2D nanostructures but also facilitated exploration of the interesting properties induced by characteristic 2D morphologies. However, to date, only a limited number of representative organic semiconductors have been utilized in organic 2D optoelectronics. Therefore, in order to further spur this research, an intuitive crystal engineering principle for realizing organic 2D crystals is required. In this regard, here, not only the important implications of applying 2D structures to OFET devices are discussed but also a crystal engineering protocol is provided that first predicts molecular arrangements depending on the molecular factors, which is followed by realizing 2D supramolecular synthon networks for different molecular packing motifs. It is expected that 2D organic semiconductor crystals developed by this approach will pave a promising way toward next-generation organic 2D optoelectronics.

A simple and robust approach to reducing contact resistance in organic transistors

Abstract: Efficient injection of charge carriers from the contacts into the semiconductor layer is crucial for achieving high-performance organic devices. The potential drop necessary to accomplish this process yields a resistance associated with the contacts, namely the contact resistance. A large contact resistance can limit the operation of devices and even lead to inaccuracies in the extraction of the device parameters. Here, we demonstrate a simple and efficient strategy for reducing the contact resistance in organic thin-film transistors by more than an order of magnitude by creating high work function domains at the surface of the injecting electrodes to promote channels of enhanced injection. We find that the method is effective for both organic small molecule and polymer semiconductors, where we achieved a contact resistance as low as 200 Ωcm and device charge carrier mobilities as high as 20 cm2V−1s−1, independent of the applied gate voltage. Minimizing contact effects in organic semiconductor-based devices is a key step toward the development of a low-cost technology for next-generation electronics. Here, the authors reduce contact resistance in organic devices by engineering electrodes with high work function surface domains.

Halogenated Tetraazapentacenes with Electron Mobility as High as 27.8 cm2 V-1 s-1 in Solution-Processed n-Channel Organic Thin-Film Transistors.

Abstract: Molecular engineering of tetraazapentacene with different numbers of fluorine and chlorine substituents fine-tunes the frontier molecular orbitals, molecular vibrations, and π-π stacking for n-type organic semiconductors. Among the six halogenated tetraazapentacenes studied herein, the tetrachloro derivative (4Cl-TAP) in solution-processed thin-film transistors exhibits electron mobility of 14.9 ± 4.9 cm2 V-1 s-1 with a maximum value of 27.8 cm2 V-1 s-1 , which sets a new record for n-channel organic field-effect transistors. Computational studies on the basis of crystal structures shed light on the structure-property relationships for organic semiconductors. First, chlorine substituents slightly decrease the reorganization energy of the tetraazapentacene whereas fluorine substituents increase the reorganization energy as a result of fine-tuning molecular vibrations. Second, the electron transfer integral is very sensitive to subtle changes in the 2D π-stacking with brickwork arrangement. The unprecedentedly high electron mobility of 4Cl-TAP is attributed to the reduced reorganization energy and enhanced electron transfer integral as a result of modification of tetraazapentacene with four chlorine substituents.

Bandgap Engineering of Organic Semiconductors for Highly Efficient Photocatalytic Water Splitting

Abstract: The bandgap engineering of semiconductors, in particular low‐cost organic/polymeric photocatalysts could directly influence their behavior in visible photon harvesting. However, an effective and rational pathway to stepwise change of the bandgap of an organic/polymeric photocatalyst is still very challenging. An efficient strategy is demonstrated to tailor the bandgap from 2.7 eV to 1.9 eV of organic photocatalysts by carefully manipulating the linker/terminal atoms in the chains via innovatively designed polymerization. These polymers work in a stable and efficient manner for both H2 and O2 evolution at ambient conditions (420 nm < λ < 710 nm), exhibiting up to 18 times higher hydrogen evolution rate (HER) than a reference photocatalyst g‐C3N4 and leading to high apparent quantum yields (AQYs) of 8.6%/2.5% at 420/500 nm, respectively. For the oxygen evolution rate (OER), the optimal polymer shows 19 times higher activity compared to g‐C3N4 with excellent AQYs of 4.3%/1.0% at 420/500 nm. Both theoretical modeling and spectroscopic results indicate that such remarkable enhancement is due to the increased light harvesting and improved charge separation. This strategy thus paves a novel avenue to fabricate highly efficient organic/polymeric photocatalysts with precisely tunable operation windows and enhanced charge separation.

Doping: A Key Enabler for Organic Transistors.

Abstract: Organic field-effect transistors (OFETs) are the central building blocks of organic electronics, but still suffer from low performance and manufacturing difficulties. This is due in part to the absence of doping, which is mostly excluded from OFET applications for the concern about uncontrollable dopant diffusion. Doping enabled the modern semiconductor industry to build essential components like Ohmic contacts and P-N junctions, empowering devices to function as designed. Recent breakthroughs in organic semiconductors and doping techniques demonstrated that doping can also be a key enabler for high-performance OFETs. However, the knowledge of organic doping remains limited particularly for OFET use. Therefore, this review addresses OFET doping from a device perspective. The paper overviews doping basics and roles in advanced complementary technologies. These fundamentals help to understand why and how doping provides the desired transistor characteristics. Typical OFETs without doping are discussed, with consideration for operating principle and problems caused by the absence of doping. Achievements for channel, contact, and overall doping are also examined to clarify the corresponding doping roles. Finally, doping mechanisms, techniques, and dopants associated with OFET applications are reviewed. This paper promotes fundamental understanding of OFET doping for the development of high-performance OFETs with doped components.

Semiconducting polymer blends that exhibit stable charge transport at high temperatures

Abstract: Although high-temperature operation (i.e., beyond 150°C) is of great interest for many electronics applications, achieving stable carrier mobilities for organic semiconductors at elevated temperatures is fundamentally challenging. We report a general strategy to make thermally stable high-temperature semiconducting polymer blends, composed of interpenetrating semicrystalline conjugated polymers and high glass-transition temperature insulating matrices. When properly engineered, such polymer blends display a temperature-insensitive charge transport behavior with hole mobility exceeding 2.0 cm2/V·s across a wide temperature range from room temperature up to 220°C in thin-film transistors.

Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)3.

Abstract: Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C6F5)3 in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C6F5)3 is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm2 V-1 s-1, respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C6F5)3 is also shown to increase the maximum hole mobility to 3.7 cm2 V-1 s-1. Analysis of the single and multicomponent materials reveals that B(C6F5)3 plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

Drastic promoting the visible photoreactivity of layered carbon nitride by polymerization of dicyandiamide at high pressure

Abstract: As a typical metal-free layered organic semiconductor photocatalyst, carbon nitride suffers from low light harvesting ability and unsatisfied photocatalytic activity ascribed to insufficient optical absorption and strongly bound exciton. In this paper, we reported the fabrication of a well crystallized carbon nitride with superior visible-light-driven photoreactivity by simply polymerization of dicyandiamide in a closed stainless steel autoclave which is used to afford a high pressure reaction environment. High pressure induced polymerization of dicyandiamide not only prevents the emission of hazardous gas, improving the yield of carbon nitride, but also enhances the crystallization of carbon nitride. The 550 °C calcined sample at high pressure (HP550) extends the interplanar packing distance of layered carbon nitride from 0.676 nm to 0.697 nm while compacts the layered-stacking distance from 0.327 nm to 0.322 nm when compared its counterpart that was synthesized under other identical conditions but at normal pressure (NP550). HP550 exhibits the highest photocatalytic activity towards hydrogen production (772.40 umol−1h−1g−1) under visible light irradiation (λ ≥ 420 nm), which is 7.8 times higher than that of NP550. The drastic improved photocatalytic activity of carbon nitride prepared at high pressure was attributed to the negatively shifted position of conductor band potentials, increased visible-light absorption and efficient separation of charge carriers, benefiting from the reduced π–π layer stacking distance and breaking of intraplanar hydrogen bonds.

Tutorial: Organic field-effect transistors: Materials, structure and operation

Abstract: Chemical versatility and compatibility with a vast array of processing techniques has led to the incorporation of organic semiconductors in various electronic and opto-electronic devices. One such device is the organic field-effect transistor (OFET). In this tutorial, we describe the structure, operation, and characterization of OFETs. Following a short historical perspective, we introduce the architectures possible for OFETs and then describe the device physics and the methods for extracting relevant device parameters. We then provide a brief overview of the myriad organic semiconductors and deposition methods that were adopted for OFETs in the past decades. Non-ideal device characteristics, including contact resistance, are then discussed along with their effects on electrical performance and on the accuracy of extracting device parameters. Finally, we highlight several measurements involving OFETs that allow access to fundamental properties of organic semiconductors and the mechanism of charge transport in these materials.

Closely packed, low reorganization energy π-extended postfullerene acceptors for efficient polymer solar cells

Abstract: New organic semiconductors are essential for developing inexpensive, high-efficiency, solution-processable polymer solar cells (PSCs). PSC photoactive layers are typically fabricated by film-casting a donor polymer and a fullerene acceptor blend, with ensuing solvent evaporation and phase separation creating discrete conduits for photogenerated holes and electrons. Until recently, n-type fullerene acceptors dominated the PSC literature; however, indacenodithienothiophene (IDTT)-based acceptors have recently enabled remarkable PSC performance metrics, for reasons that are not entirely obvious. We report two isomeric IDTT-based acceptors 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz-(5, 6)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]di-thiophene (ITN-C9) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz(6,7)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITzN-C9) that shed light on the exceptional IDTT properties vis-a-vis fullerenes. The neat acceptors and blends with fluoropolymer donor poly{[4,8-bis[5-(2- ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene2,6-diyl]-alt-[2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo4H,8H-benzo[1,2-c:4,5-c′]dithiophene-1,3-diyl]]} (PBDB-TF) are investigated by optical spectroscopy, cyclic voltammetry, thermogravimetric analysis, differential scanning calorimetry, single-crystal X-ray diffraction, photovoltaic response, space-charge-limited current transport, atomic force microscopy, grazing incidence wide-angle X-ray scattering, and density functional theory-level quantum chemical analysis. The data reveal that ITN-C9 and ITzN-C9 organize such that the lowest unoccupied molecular orbital-rich end groups have intermolecular π−π distances as close as 3.31(1) A, with electronic coupling integrals as large as 38 meV, and internal reorganization energies as small as 0.133 eV, comparable to or superior to those in fullerenes. ITN-C9 and ITzN-C9 have broad solar-relevant optical absorption, and, when blended with PBDB-TF, afford devices with power conversion efficiencies near 10%. Performance differences between ITN-C9 and ITzN-C9 are understandable in terms of molecular and electronic structure distinctions via the influences on molecular packing and orientation with respect to the electrode.

Influence of dopant size and electron affinity on the electrical conductivity and thermoelectric properties of a series of conjugated polymers

Abstract: Chemical doping is widely used to manipulate the electrical and thermoelectric properties of organic semiconductors, yet intelligent design of polymer–dopant systems remains elusive. It is challenging to predict the electrical and thermoelectric properties of doped organic semiconductors due to the large number of variables impacting these properties, including film morphology, dopant and polymer energetics, dopant size, and degree of polaron delocalization. Herein, a series of dopants with varying sizes and electron affinities (EAs) are combined with polymers of differing ionization energies (IEs) to investigate how the difference between polymer IE and dopant EA influences the doping efficiency and electrical conductivity, and how the dopant size influences the thermoelectric properties. Our experiments demonstrate that at low doping levels the doping efficiency strongly depends on the difference between the polymer IE and dopant EA; the effectiveness of doping on increasing electrical conductivity drastically decreases at high loadings for the molybdenum dithiolene complexes, while FeCl3 remains effective at high loadings; and the large molybdenum complexes lead to more delocalized polarons as compared to FeCl3. To take advantage of the complementary doping characteristics of the molybdenum complexes and FeCl3, both dopants are employed simultaneously to reach high power factors at relatively low dopant concentrations.

Modification of Side Chains of Conjugated Molecules and Polymers for Charge Mobility Enhancement and Sensing Functionality

Abstract: ConspectusOrganic semiconductors have received increasing attentions in recent years because of their promising applications in various optoelectronic devices. The key performance metric for organic semiconductors is charge carrier mobility, which is governed by the electronic structures of conjugated backbones and intermolecular/interchain π–π interactions and packing in both microscopic and macroscopic levels. For this reason, more efforts have been paid to the design and synthesis of conjugated frameworks for organic semiconductors with high charge mobilities. However, recent studies manifest that appropriate modifications of side chains that are linked to conjugated frameworks can improve the intermolecular/interchain packing order and boost charge mobilities.In this Account, we discuss our research results in context of modification of side chains in organic semiconductors for charge mobility enhancement. These include the following: (i) The lengths of alkyl chains in sulfur-rich thiepin-fused hetero...

Graphene/Organic Semiconductor Heterojunction Phototransistors with Broadband and Bi-directional Photoresponse.

Abstract: A graphene-semiconductor heterojunction is very attractive for realizing highly sensitive phototransistors due to the strong absorption of the semiconductor layer and the fast charge transport in the graphene. However, the photoresponse is usually limited to a narrow spectral range determined by the bandgap of the semiconductor. Here, an organic heterojunction (C60 /pentacene) is incorporated on graphene to realize a broadband (405-1550 nm) phototransistor with a high gain of 5.2 × 105 and a response time down to 275 µs. The visible and near-infrared parts of the photoresponsivity (9127 A W-1 @650 nm and 1800 A W-1 @808 nm) come from the absorption of the organic layer and the graphene, respectively. For the first time, a bi-directional (positive and negative) photoresponse is demonstrated at different wavelengths, due to the opposite charge transfer direction of the photoexcited carriers enforced by the unique band alignment. Such tunability will enable new functionalities such as large-scale real-time optical image and infrared focal plane array detection in the future.

Functional Conjugated Polymers for CO2 Reduction Using Visible Light

Abstract: The reduction of CO2 with visible light is a highly sustainable method for producing valuable chemicals. The function-led design of organic conjugated semiconductors with more chemical variety than that of inorganic semiconductors has emerged as a method for achieving carbon photofixation chemistry. Here, we report the molecular engineering of triazine-based conjugated microporous polymers to capture, activate and reduce CO2 to CO with visible light. The optical band gap of the CMPs is engineered by varying the organic electron-withdrawing (benzothiadiazole) and electron-donating units (thiophene) on the skeleton of the triazine rings while creating organic donor-acceptor junctions to promote the charge separation. This engineering also provides control of the texture, surface functionality and redox potentials of CMPs for achieving the light-induced conversion of CO2 to CO ambient conditions.