Showing papers on "Organic semiconductor published in 2020"

Charge transport in high-mobility conjugated polymers and molecular semiconductors

Abstract: Conjugated polymers and molecular semiconductors are emerging as a viable semiconductor technology in industries such as displays, electronics, renewable energy, sensing and healthcare. A key enabling factor has been significant scientific progress in improving their charge transport properties and carrier mobilities, which has been made possible by a better understanding of the molecular structure–property relationships and the underpinning charge transport physics. Here we aim to present a coherent review of how we understand charge transport in these high-mobility van der Waals bonded semiconductors. Specific questions of interest include estimates for intrinsic limits to the carrier mobilities that might ultimately be achievable; a discussion of the coupling between charge and structural dynamics; the importance of molecular conformations and mesoscale structural features; how the transport physics of conjugated polymers and small molecule semiconductors are related; and how the incorporation of counterions in doped films—as used, for example, in bioelectronics and thermoelectric devices—affects the electronic structure and charge transport properties. Organic semiconductors are making their way into applications ranging from display technology to flexible electronics and biomedical applications. This Review discusses current understanding of charge carrier transport in these materials and strategies to improve their performance.

The role of chemical design in the performance of organic semiconductors

Abstract: Organic semiconductors are solution-processable, lightweight and flexible and are increasingly being used as the active layer in a wide range of new technologies. The versatility of synthetic organic chemistry enables the materials to be tuned such that they can be incorporated into biological sensors, wearable electronics, photovoltaics and flexible displays. These devices can be improved by improving their material components, not only by developing the synthetic chemistry but also by improving the analytical and computational techniques that enable us to understand the factors that govern material properties. Judicious molecular design provides control of the semiconductor frontier molecular orbital energy distribution and guides the hierarchical assembly of organic semiconductors into functional films where we can manipulate the properties and motion of charges and excited states. This Review describes how molecular design plays an integral role in developing organic semiconductors for electronic devices in present and emerging technologies. Many present and emerging electronic devices make use of organic semiconductors in view of their readily tuneable molecular and electronic structures. This Review describes the importance of analytical and computational tools in studying the molecules as well as their hierarchical self-assemblies, in which the motion of charges and excited states govern device properties.

Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles.

Abstract: Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h−1 g−1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux. Photocatalysts formed from a single organic semiconductor can suffer from inefficient charge generation leading to low photocatalytic activities. Incorporating a heterojunction between a donor polymer and non-fullerene acceptor in organic nanoparticles leads to enhanced photocatalytic hydrogen evolution.

Charge carrier traps in organic semiconductors: a review on the underlying physics and impact on electronic devices

Abstract: The weak intermolecular interactions inherent in organic semiconductors make them susceptible to defect formation, resulting in localized states in the band-gap that can trap charge carriers at different timescales. Charge carrier trapping is thus ubiquitous in organic semiconductors and can have a profound impact on their performance when incorporated into optoelectronic devices. This review provides a comprehensive overview on the phenomenon of charge carrier trapping in organic semiconductors, with emphasis on the underlying physical processes and its impact on device operation. We first define the concept of charge carrier trap, then outline and categorize different origins of traps. Next, we discuss their impact on the mechanism of charge transport and the performance of electronic devices. Progress in the filed in terms of characterization and detection of charge carrier traps is reviewed together with insights on future direction of research. Finally, a discussion on the exploitation of traps in memory and sensing applications is provided.

Highly efficient luminescence from space-confined charge-transfer emitters.

Abstract: Charge-transfer (CT) complexes, formed by electron transfer from a donor to an acceptor, play a crucial role in organic semiconductors. Excited-state CT complexes, termed exciplexes, harness both singlet and triplet excitons for light emission, and are thus useful for organic light-emitting diodes (OLEDs). However, present exciplex emitters often suffer from low photoluminescence quantum efficiencies (PLQEs), due to limited control over the relative orientation, electronic coupling and non-radiative recombination channels of the donor and acceptor subunits. Here, we use a rigid linker to control the spacing and relative orientation of the donor and acceptor subunits, as demonstrated with a series of intramolecular exciplex emitters based on 10-phenyl-9,10-dihydroacridine and 2,4,6-triphenyl-1,3,5-triazine. Sky-blue OLEDs employing one of these emitters achieve an external quantum efficiency (EQE) of 27.4% at 67 cd m−2 with only minor efficiency roll-off (EQE = 24.4%) at a higher luminous intensity of 1,000 cd m−2. As a control experiment, devices using chemically and structurally related but less rigid emitters reach substantially lower EQEs. These design rules are transferrable to other donor/acceptor combinations, which will allow further tuning of emission colour and other key optoelectronic properties. The use of rigid linkers to control the relative position and interaction of donor and acceptor units in exciplex emitters leads to the realization of organic light-emitting devices with enhanced external quantum efficiency.

17.1% Efficient Single-Junction Organic Solar Cells Enabled by n-Type Doping of the Bulk-Heterojunction.

Abstract: Molecular doping is often used in organic semiconductors to tune their (opto)electronic properties. Despite its versatility, however, its application in organic photovoltaics (OPVs) remains limited and restricted to p-type dopants. In an effort to control the charge transport within the bulk-heterojunction (BHJ) of OPVs, the n-type dopant benzyl viologen (BV) is incorporated in a BHJ composed of the donor polymer PM6 and the small-molecule acceptor IT-4F. The power conversion efficiency (PCE) of the cells is found to increase from 13.2% to 14.4% upon addition of 0.004 wt% BV. Analysis of the photoactive materials and devices reveals that BV acts simultaneously as n-type dopant and microstructure modifier for the BHJ. Under optimal BV concentrations, these synergistic effects result in balanced hole and electron mobilities, higher absorption coefficients and increased charge-carrier density within the BHJ, while significantly extending the cells' shelf-lifetime. The n-type doping strategy is applied to five additional BHJ systems, for which similarly remarkable performance improvements are obtained. OPVs of particular interest are based on the ternary PM6:Y6:PC71BM:BV(0.004 wt%) blend for which a maximum PCE of 17.1%, is obtained. The effectiveness of the n-doping strategy highlights electron transport in NFA-based OPVs as being a key issue.

Long-range exciton diffusion in molecular non-fullerene acceptors

Abstract: The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors. The short-range diffusion length of organic semiconductors severely limits exciton harvesting and charge generation in organic bulk heterojunction solar cells. Here, the authors report exciton diffusion length in the range of 20 to 47 nm for a wide range of non-fullerene acceptors molecules.

The Emergence of Organic Single-Crystal Electronics.

Abstract: Organic semiconducting single crystals are perfect for both fundamental and application-oriented research due to the advantages of free grain boundaries, few defects, and minimal traps and impurities, as well as their low-temperature processability, high flexibility, and low cost. Carrier mobilities of greater than 10 cm2 V-1 s-1 in some organic single crystals indicate a promising application in electronic devices. The progress made, including the molecular structures and fabrication technologies of organic single crystals, is introduced and organic single-crystal electronic devices, including field-effect transistors, phototransistors, p-n heterojunctions, and circuits, are summarized. Organic two-dimensional single crystals, cocrystals, and large single crystals, together with some potential applications, are introduced. A state-of-the-art overview of organic single-crystal electronics, with their challenges and prospects, is also provided.

The Bulk Heterojunction in Organic Photovoltaic, Photodetector, and Photocatalytic Applications.

Abstract: Organic semiconductors require an energetic offset in order to photogenerate free charge carriers efficiently, owing to their inability to effectively screen charges. This is vitally important in order to achieve high power conversion efficiencies in organic solar cells. Early heterojunction-based solar cells were limited to relatively modest efficiencies (<4%) owing to limitations such as poor exciton dissociation, limited photon harvesting, and high recombination losses. The development of the bulk heterojunction (BHJ) has significantly overcome these issues, resulting in dramatic improvements in organic photovoltaic performance, now exceeding 18% power conversion efficiencies. Here, the design and engineering strategies used to develop the optimal bulk heterojunction for solar-cell, photodetector, and photocatalytic applications are discussed. Additionally, the thermodynamic driving forces in the creation and stability of the bulk heterojunction are presented, along with underlying photophysics in these blends. Finally, new opportunities to apply the knowledge accrued from BHJ solar cells to generate free charges for use in promising new applications are discussed.

Efficient light-emitting diodes from mixed-dimensional perovskites on a fluoride interface

Abstract: Light-emitting diodes based on halide perovskites have recently reached external quantum efficiencies of over 20%. However, the performance of visible perovskite light-emitting diodes has been hindered by non-radiative recombination losses and limited options for charge-transport materials that are compatible with perovskite deposition. Here, we report efficient, green electroluminescence from mixed-dimensional perovskites deposited on a thin (~1 nm) lithium fluoride layer on an organic semiconductor hole-transport layer. The highly polar dielectric interface acts as an effective template for forming high-quality bromide perovskites on otherwise incompatible hydrophobic charge-transport layers. The control of crystallinity and dimensionality of the perovskite layer is achieved by using tetraphenylphosphonium chloride as an additive, leading to external photoluminescence quantum efficiencies of around 65%. With this approach, we obtain light-emitting diodes with external quantum efficiencies of up to 19.1% at high brightness (>1,500 cd m−2). Green perovskite light-emitting diodes with external quantum efficiencies of up to 19.1% at high brightness can be created by depositing an ultrathin layer of strongly polar lithium fluoride between the perovskite and hole-transport layers.

Bioinspired Multifunctional Organic Transistors Based on Natural Chlorophyll/Organic Semiconductors

Abstract: Inspired by the photosynthesis process of natural plants, multifunctional transistors based on natural biomaterial chlorophyll and organic semiconductors (OSCs) are reported. Functions as photodetectors (PDs) and light-stimulated synaptic transistors (LSSTs) can be switched by gate voltage. As PDs, the devices exhibit ultrahigh photoresponsivity up to 2 × 106 A W-1 , detectivity of 6 × 1015 Jones, and Iphoto /Idark ratio of 2.7 × 106 , which make them among the best reported organic PDs. As LSSTs, important synaptic functions similar to biological synapses are demonstrated, together with a dynamic learning and forgetting process and image-processing function. Significantly, benefiting from the ultrahigh photosensitivity of chlorophyll, the lowest operating voltage and energy consumption of the LSSTs can be 10-5 V and 0.25 fJ, respectively. The devices also exhibit high flexibility and long-term air stability. This work provides a new guide for developing organic electronics based on natural biomaterials.

Self-filtering narrowband high performance organic photodetectors enabled by manipulating localized Frenkel exciton dissociation.

Abstract: The high binding energy and low diffusion length of photogenerated Frenkel excitons have long been viewed as major drawbacks of organic semiconductors. Therefore, bulk heterojunction structure has been widely adopted to assist exciton dissociation in organic photon-electron conversion devices. Here, we demonstrate that these intrinsically “poor” properties of Frenkel excitons, in fact, offer great opportunities to achieve self-filtering narrowband organic photodetectors with the help of a hierarchical device structure to intentionally manipulate the dissociation of Frenkel excitons. With this strategy, filter-free narrowband organic photodetector centered at 860 nm with full-width-at-half-maximum of around 50 nm, peak external quantum efficiency around 65% and peak specific detectivity over 1013 Jones are obtained, which is one the best performed no-gain type narrowband organic photodetectors ever reported and comparable to commercialized silicon photodetectors. This novel device structure along with its design concept may help create low cost and reliable narrowband organic photodetectors for practical applications. Narrowband organic photodetectors (OPDs) are attractive for emerging applications. Here, the authors report a simple strategy to produce filter-free narrowband OPDs with outstanding performances by manipulating exciton dissociation with a hierarchical device structure.

Bent-Shaped p-Type Small-Molecule Organic Semiconductors: A Molecular Design Strategy for Next-Generation Practical Applications.

Abstract: Significant progress has been made in both molecular design and fundamental scientific understanding of organic semiconductors (OSCs) in recent years. Suitable charge-carrier mobilities (μ) have be...

A thermally activated and highly miscible dopant for n-type organic thermoelectrics.

Abstract: N-doping plays an irreplaceable role in controlling the electron concentration of organic semiconductors thus to improve performance of organic semiconductor devices However, compared with many mature p-doping methods, n-doping of organic semiconductor is still of challenges In particular, dopant stability/processability, counterion-semiconductor immiscibility and doping induced microstructure non-uniformity have restricted the application of n-doping in high-performance devices Here, we report a computer-assisted screening approach to rationally design of a triaminomethane-type dopant, which exhibit extremely high stability and strong hydride donating property due to its thermally activated doping mechanism This triaminomethane derivative shows excellent counterion-semiconductor miscibility (counter cations stay with the polymer side chains), high doping efficiency and uniformity By using triaminomethane, we realize a record n-type conductivity of up to 21 S cm−1 and power factors as high as 51 μW m−1 K−2 even in films with thicknesses over 10 μm, and we demonstrate the first reported all-polymer thermoelectric generator Realizing efficient n-doping in organic thermoelectrics remains a challenge due to dopant-semiconductor immiscibility, poor dopant stability and low doping efficiency Here, the authors use computer-assisted screening to develop n-dopants for thermoelectric polymers that show record power factors

Solution‐Processed Centimeter‐Scale Highly Aligned Organic Crystalline Arrays for High‐Performance Organic Field‐Effect Transistors

Abstract: Solution-printed organic single-crystalline films hold great potential for achieving low-cost manufacturing of large-area and flexible electronics. For practical applications, organic field-effect transistor arrays must exhibit high performance and small device-to-device variation. However, scalable fabrication of highly aligned organic crystalline arrays is rather difficult due to the lack of control over the crystallographic orientation, crystal uniformity, and thickness. Here, a facile solution-printing method to fabricate centimeter-sized highly aligned organic crystalline arrays with a thickness of a few molecular layers is reported. In this study, the solution shearing technique is used to produce large-area, organic highly crystalline thin films. Water-soluble ink is printed on the hydrophobic surface of organic crystalline films, to selectively protect it, followed by etching. It is shown that the addition of a surfactant dramatically changes the fluid drying dynamics and increases the contact line friction of the aqueous solution to the underlying nonwetting organic crystalline film. As a result, centimeter-scale highly aligned organic crystalline arrays are successfully prepared on different substrates. The devices based on organic crystalline arrays show good performance and uniformity. This study demonstrates that solution printing is close to industrial application and also expands its applicability to various printed flexible electronics.

Ground-state electron transfer in all-polymer donor-acceptor heterojunctions

Abstract: Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor–acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems. Here, we report ground-state electron transfer in all-polymer donor–acceptor heterojunctions. Combining low-ionization-energy polymers with high-electron-affinity counterparts yields conducting interfaces with resistivity values five to six orders of magnitude lower than the separate single-layer polymers. The large decrease in resistivity originates from two parallel quasi-two-dimensional electron and hole distributions reaching a concentration of ∼1013 cm–2. Furthermore, we transfer the concept to three-dimensional bulk heterojunctions, displaying exceptional thermal stability due to the absence of molecular dopants. Our findings hold promise for electro-active composites of potential use in, for example, thermoelectrics and wearable electronics. Doping through spontaneous electron transfer between donor and acceptor polymers is obtained by selecting organic semiconductors with suitable electron affinity and ionization energy, achieving high conductivity in blends and bilayer configuration.

N-type organic thermoelectrics : Demonstration of ZT > 0.3

Abstract: The ‘phonon-glass electron-crystal’ concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly ‘phonon glasses’. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being ‘electron crystals’. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic ‘PGEC’ thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10 S cm −1 and an ultralow thermal conductivity of <0.1 Wm −1K −1, leading to the best figure of merit ZT = 0.34 (at 120 °C) among all reported single-host n-type organic thermoelectric materials. The key factor to achieving the record performance is to use ‘arm-shaped’ double-triethylene-glycol-type side chains, which not only offer excellent doping efficiency (~60%) but also induce a disorder-to-order transition upon thermal annealing. This study illustrates the vast potential of organic semiconductors as thermoelectric materials.

Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications

Abstract: DOI: 10.1002/aenm.202001935 development of sustainable energy sources.[1] Among these, solar energy has the greatest potential, with more solar energy irradiating the surface of the Earth in one hour than human society consumes in one year.[2] However, the intermittency of solar energy limits its utility. In order for solar energy to provide power on a scale commensurate with that currently generated from fossil fuels, it must be stored and supplied to users on demand.[3] On short timescales (seconds to days) this is possible to achieve using batteries, which can store electricity generated from solar photovoltaics.[4,5] However, the expensive materials required and their relatively high rates of self-discharge make batteries unsuitable for seasonal energy storage.[6,7] Storing solar energy in the chemical bonds of a fuel, which can be stored indefinitely at low cost, transported, and converted to electrical or heat energy on demand is therefore highly desirable. Solar fuels such as H2, CH3OH, and CH4 can be generated from abundant and renewable feedstocks such as water and CO2 using semiconductor photocatalysts. The vast majority of research to date has focused on photocatalysts fabricated from wide bandgap semiconductors such as TiO2, SrTiO3, and carbon nitride (CN).[10–14] Photocatalysts based on some of these semiconductors have achieved operational stabilities exceeding 1000 h and maximum external quantum efficiencies (EQEs) of over 50% for overall water splitting.[9,15–18] However, their wide and difficult to tune bandgaps mean that photocatalysts fabricated from these semiconductors are almost exclusively active at UV wavelengths, which carry <5% of solar energy.[19] This fundamentally limits their efficiency below what is required for many practical solar fuels applications. For example, an estimated solar-to-hydrogen efficiency (ηSTH) of 5–10% would be required to photocatalytically produce H2 at a cost that meets the U.S. Department of Energy’s target of $2–4 kg−1, which is difficult or impossible to achieve with the aforementioned wide bandgap semiconductors.[20] This has stimulated interest in developing novel photocatalysts based on semiconductors with narrower bandgaps that are able to absorb a greater proportion of the solar spectrum and can therefore achieve higher maximum theoretical solar energy conversion efficiencies.[18] Among these, non-CN organic semiconductors have recently gained prominence due to the Earth abundance of their constituent elements, and their high extinction coefficients and The photocatalytic synthesis of solar fuels such as hydrogen and methane from water and carbon dioxide is a promising strategy to store abundant solar energy in order to overcome its intermittency. Although this approach has been studied for decades using inorganic semiconductor photocatalysts, organic semiconductors have only recently gained notable attention. The tunable energy levels of organic semiconductors can enable the design of photocatalysts with optimized solar light utilization. However, the solar conversion efficiency of organic semiconductor photocatalysts has so far been limited by their low quantum efficiencies. To address this issue, various photocatalyst design strategies including semiconductor energy level optimization, surface modification, and the fabrication of heterojunctions have been applied, resulting in substantial increases in photocatalytic efficiency. This progress report systematically describes the strategies employed to increase the efficiency of organic semiconductor photocatalysts for the generation of solar fuels from water and carbon dioxide. Particular attention is given to describing strategies to enhance quantum efficiency, and insights are provided on the mechanisms underlying their success to aid the rational design of future organic photocatalysts. Perspectives on the future challenges and promising research directions for the design of efficient organic photocatalysts for the generation of solar fuels are also provided.

Organic Laser Molecule with High Mobility, High Photoluminescence Quantum Yield, and Deep-Blue Lasing Characteristics

Abstract: Here, we design and synthesize an organic laser molecule, 2,7-diphenyl-9H-fluorene (LD-1), which has state-of-the-art integrated optoelectronic properties with a high mobility of 0.25 cm2 V-1 s-1, a high photoluminescence quantum yield of 60.3%, and superior deep-blue laser characteristics (low threshold of Pth = 71 μJ cm-2 and Pth = 53 μJ cm-2 and high quality factor (Q) of ∼3100 and ∼2700 at emission peaks of 390 and 410 nm, respectively). Organic light-emitting transistors based on LD-1 are for the first time demonstrated with obvious electroluminescent emission and gate tunable features. This work opens the door for a new class of organic semiconductor laser molecules and is critical for deep-blue optical and laser applications.

High-performance and stable photoelectrochemical water splitting cell with organic-photoactive-layer-based photoanode.

Abstract: Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials. We achieve a photocurrent density of 15.1 mA cm−2 at 1.23 V vs. reversible hydrogen electrode (RHE) with an onset potential of 0.55 V vs. RHE and a record high half-cell solar-to-hydrogen conversion efficiency of 4.33% under AM 1.5 G solar simulated light. After conducting the stability test at 1.3 V vs. RHE for 10 h, 90% of the initial photocurrent density are retained, whereas the photoactive layer without passivation lost its activity within a few minutes. While organic semiconductors may be useful in photoelectrochemical water-splitting materials, they show low stability in water. Here, the authors report high-performance and stable organic-semiconductor-based photoanodes passivated using nickel foils, GaIn eutectic, and layered double hydroxides.

Structural Engineering of Two-Dimensional Covalent Organic Frameworks for Visible-Light-Driven Organic Transformations

Abstract: Covalent organic frameworks (COFs) emerging as a novel kind of visible light-responsive organic semiconductor have attracted extensive research attention in the field of photocatalytic organic tran...

Organic UV-Sensitive Phototransistors Based on Distriphenylamineethynylpyrene Derivatives with Ultra-High Detectivity Approaching 1018.

Abstract: Organic photodetectors with UV-sensitivity are of great potential for various optoelectronic applications. Integration of high charge carrier mobility, long exciton diffusion length as well as unique UV-sensitivity for active materials is crucial for construction of UV-sensitive devices with high performance, however, very few organic semiconductors can integrate these properties simultaneously. Herein, two novel organic semiconductors containing large steric hindrance triphenylamine groups, 1,6-distriphenylamineethynylpyrene (1,6-DTEP) and 2,7-distriphenylamineethynylpyrene (2,7-DTEP) are designed and synthesized. It demonstrates that the single crystals of both 1,6-DTEP and 2,7-DTEP exhibit superior integrated optoelectronic properties of high charge carrier mobility, unique UV absorption, high photoluminescence quantum yields as well as small exciton binding energies. Organic phototransistors constructed using 1,6-DTEP and 2,7-DTEP single crystals show ultrasensitive performance with ultra-high photoresponsivity of 2.86 × 106 and 1.04 × 105 A W-1 , detectivity (D*) of above 1.49 × 1018 and 5.28 × 1016 Jones under 370 nm light illumination, respectively. It indicates the great potential of 1,6-DTEP and 2,7-DTEP-based phototransistors for organic UV-photodetector applications and also provides a new design strategy to develop series of better performance UV photoelectric organic materials for related research in organic optoelectronics.

High Performance Vertical Organic Transistors

Abstract: Vertical organic thin-film transistors (VOTFTs) are promising devices to overcome the transconductance and cut-off frequency restrictions of horizontal organic thin-film transistors. The basic physical mechanisms of VOTFT operation, however, are not well understood and VOTFTs often require complex patterning techniques using self-assembly processes which impedes a future large-area production. In this contribution, high-performance vertical organic transistors comprising pentacene for p-type operation and C60 for n-type operation are presented. The static current-voltage behavior as well as the fundamental scaling laws of such transistors are studied, disclosing a remarkable transistor operation with a behavior limited by injection of charge carriers. The transistors are manufactured by photolithography, in contrast to other VOTFT concepts using self-assembled source electrodes. Fluorinated photoresist and solvent compounds allow for photolithographical patterning directly and strongly onto the organic materials, simplifying the fabrication protocol and making VOTFTs a prospective candidate for future high-performance applications of organic transistors.

Conductivity and Photoconductivity of a p-Type Organic Semiconductor under Ultrastrong Coupling.

Abstract: During the past decade, it has been shown that light-matter strong coupling of materials can lead to modified and often improved properties which has stimulated considerable interest. While charge transport can be enhanced in n-type organic semiconductors by coupling the electronic transition and thereby splitting the conduction band into polaritonic states, it is not clear whether the same process can also influence carrier transport in the valence band of p-type semiconductors. Here we demonstrate that it is indeed possible to enhance both the conductivity and photoconductivity of a p-type semiconductor rr-P3HT that is ultrastrongly coupled to plasmonic modes. It is due to the hybrid light-matter character of the virtual polaritonic excitations affecting the linear response of the material. Furthermore, in addition to being enhanced, the photoconductivity of rr-P3HT shows a modified spectral response due to the formation of the hybrid polaritonic states. This illustrates the potential of engineering the vacuum electromagnetic environment to improve the optoelectronic properties of organic materials.

Relieving the Photosensitivity of Organic Field-Effect Transistors.

Abstract: It is generally believed that the photoresponse behavior of organic field-effect transistors (OFETs) reflects the intrinsic property of organic semiconductors. However, this photoresponse hinders the application of OFETs in transparent displays as driven circuits due to the current instability resulting from the threshold voltage shift under light illumination. It is necessary to relieve the photosensitivity of OFETs to keep the devices stable. 2,6-diphenyl anthracene thin-film and single-crystal OFETs are fabricated on different substrates, and it is found that the degree of molecular order in the conducting channels and the defects at the dielectric/semiconductor interface play important roles in determining the phototransistor performance. When highly ordered single-crystal OFETs are fabricated on polymeric substrates with low defects, the photosensitivity (P) decreases by more than 105 times and the threshold voltage shift (ΔVT ) is almost eliminated compared with the corresponding thin-film OFETs. This phenomenon is further verified by using another three organic semiconductors for similar characterizations. The decreased P and ΔVT of OFETs ensure a good current stability for OFETs to drive organic light-emitting diodes efficiently, which is essential to the application of OFETs in flexible and transparent displays.

Insight into the structures and dynamics of organic semiconductors through solid-state NMR spectroscopy

Abstract: Organic semiconductors (OSCs) are of fundamental and technological interest, owing to their properties and functions in a range of optoelectronic devices, including organic light-emitting diodes, organic photovoltaics and organic field-effect transistors, as well as emerging technologies, such as bioelectronic devices. The solid-state organization of the subunits in OSC materials, whether molecular or polymeric, determines the properties relevant to device performance. Nevertheless, the systematic relationships between composition, structure and processing conditions are rarely fully understood, owing to the complexity of the organic architectures and the resulting solid-state structures. Characterization over different length scales and timescales is essential, especially for semi-ordered or amorphous regions, for which solid-state NMR (ssNMR) spectroscopy yields nanoscale insight that can be correlated with scattering measurements and macroscopic property analyses. In this Review, we assess recent results, challenges and opportunities in the application of ssNMR to OSCs, highlighting its role in state-of-the-art materials design and characterization. We illustrate how insight is obtained on local order and composition, interfacial structures, dynamics, interactions and how this information can be used to establish structure–property relationships. Finally, we provide our perspective on applying ssNMR to the next generation of OSCs and the development of new ssNMR methods. The structure of organic semiconductor thin films influences their performance in optoelectronic devices. This Review highlights how solid-state NMR techniques can be used to investigate the structure, composition and dynamics of organic semiconductors and, thus, establish structure–property relationships.

Fast-Response, Highly Air-Stable, and Water-Resistant Organic Photodetectors Based on a Single-Crystal Pt Complex

Abstract: Organic semiconductors demonstrate several advantages over conventional inorganic materials for novel electronic and optoelectronic applications, including molecularly tunable properties, flexibility, low-cost, and facile device integration. However, before organic semiconductors can be used for the next-generation devices, such as ultrafast photodetectors (PDs), it is necessary to develop new materials that feature both high mobility and ambient stability. Toward this goal, a highly stable PD based on the organic single crystal [PtBr2 (5,5'-bis(CF3 CH2 OCH2 )-2,2'-bpy)] (or "Pt complex (1o)") is demonstrated as the active semiconductor channel-a material that features a lamellar molecular structure and high-quality, intraligand charge transfer. Benefitting from its unique crystal structure, the Pt-complex (1o) device exhibits a field-effect mobility of ≈0.45 cm2 V-1 s-1 without loss of significant performance under ambient conditions even after 40 days without encapsulation, as well as immersion in distilled water for a period of 24 h. Furthermore, the device features a maximum photoresponsivity of 1 × 103 A W-1 , a detectivity of 1.1 × 1012 cm Hz1/2 W-1 , and a record fast response/recovery time of 80/90 µs, which has never been previously achieved in other organic PDs. These findings strongly support and promote the use of the single-crystal Pt complex (1o) in next-generation organic optoelectronic devices.

Charge-generating mid-gap trap states define the thermodynamic limit of organic photovoltaic devices.

Abstract: Detailed balance is a cornerstone of our understanding of artificial light-harvesting systems. For next generation organic solar cells, this involves intermolecular charge-transfer (CT) states whose energies set the maximum open circuit voltage VOC. We have directly observed sub-gap states significantly lower in energy than the CT states in the external quantum efficiency spectra of a significant number of organic semiconductor blends. Taking these states into account and using the principle of reciprocity between emission and absorption results in non-physical radiative limits for the VOC. We propose and provide compelling evidence for these states being non-equilibrium mid-gap traps which contribute to photocurrent by a non-linear process of optical release, upconverting them to the CT state. This motivates the implementation of a two-diode model which is often used in emissive inorganic semiconductors. The model accurately describes the dark current, VOC and the long-debated ideality factor in organic solar cells. Additionally, the charge-generating mid-gap traps have important consequences for our current understanding of both solar cells and photodiodes – in the latter case defining a detectivity limit several orders of magnitude lower than previously thought. The inability to accurately measure the charge-generating energy states in organic solar cells makes elucidating the photovoltaic effect in these devices difficult. Here, the authors report charge-generating mid-gap trap states in organic solar cells via ultra-sensitive photovoltaic measurements.