High-mobility Organic Semiconductors Research Articles

Band-like transport in solution-processed perylene diimide dianion films with high Hall mobility.

It is crucial to prepare high-mobility organic polycrystalline film through solution processing. However, the delocalized carrier transport of polycrystalline films in organic semiconductors has rarely been investigated through Hall-effect measurement. This study presents a strategy for building strong intermolecular interactions to fabricate solution-crystallized p-type perylene diimide (PDI) dianion films with a closer intermolecular π-π stacking distance of 3.25Å. The highly delocalized carriers enable a competitive Hall mobility of 3cm2V-1s-1, comparable to that of the reported high-mobility organic single crystals. The PDI dianion films exhibit a high electrical conductivity of 17Scm-1 and typical band-like transport, as evidenced by the negative temperature linear coefficient of mobility proportional to T-3/2. This work demonstrates that, as the intermolecular π-π interactions become strong enough, they will display high mobility and conductivity, providing a new approach to developing high-mobility organic semiconductor materials.

Spacer Engineering Enables Fine-Tuned Thin Film Microstructure and Efficient Charge Transport for Ultrasensitive 2D Perovskite-Based Heterojunction Phototransistors and Optoelectronic Synapses.

2D Ruddlesden-Popper phase layered perovskites (RPLPs) hold great promise for optoelectronic applications. In this study, a series of high-performance heterojunction phototransistors (HPTs) based on RPLPs with different organic spacer cations (namely butylammonium (BA+), cyclohexylammonium (CyHA+), phenethylammonium (PEA+), p-fluorophenylethylammonium (p-F-PEA+), and 2-thiophenethylammonium (2-ThEA+)) are fabricated successfully, in which high-mobility organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene is adopted to form type II heterojunction channels with RPLPs. The 2-ThEA+-RPLP-based HPTs show the highest photosensitivity of 3.18 × 107 and the best detectivity of 9.00 × 1018 Jones, while the p-F-PEA+-RPLP-based ones exhibit the highest photoresponsivity of 5.51 × 106 A W-1 and external quantum efficiency of 1.32 × 109%, all of which are among the highest reported values to date. These heterojunction systems also mimicked several optically controllable fundamental characteristics of biological synapses, including excitatory postsynaptic current, paired-pulse facilitation, and the transition from short-term memory to long-term memory states. The device based on 2-ThEA+-RPLP film shows an ultra-high PPF index of 234%. Moreover, spacer engineering brought fine-tuned thin film microstructures and efficient charge transport/transfer, which contributes to the superior photodetection performance and synaptic functions of these RPLP-based HPTs. In-depth structure-property correlations between the organic spacer cations/RPLPs and thin film microstructure/device performance are systematically investigated.

Molecular Engineering of Rylene Diimides via Sila-Annulation Toward High-Mobility Organic Semiconductors.

The continuous innovation of captivating new organic semiconducting materials remains pivotal in the development of high-performance organic electronic devices. Herein, a molecular engineering by combining sila-annulation with the vertical extension of rylene diimides (RDIs) toward high-mobility organic semiconductors is presented. The unilateral and bilateral sila-annulated quaterrylene diimides (Si-QDI and 2Si-QDI) are designed and synthesized. In particular, the symmetrical bilateral 2Si-QDI exhibits a compact, 1D slipped π-π stacking arrangement through the synergistic combination of a sizable π-conjugated core and intercalating alkyl chains. Combining the appreciable elevated HOMO levels and reduced energy gaps, the single-crystalline organic field-effect transistors (SC-OFETs) based on 2Si-QDI demonstrate exceptional ambipolar transport characteristics with an impressive hole mobility of 3.0 cm2 V-1 s-1 and an electron mobility of 0.03 cm2 V-1 s-1, representing the best ampibolar SC-OFETs based on RDIs. Detailed theoretical calculations rationalize that the larger transfer integral along the π-π stacking direction is responsible for the achievement of the superior charge transport. This study showcases the remarkable potential of sila-annulation in optimizing carrier transport performances of polycyclic aromatic hydrocarbons (PAHs).

Compact Model Analysis for Low Voltage OFETs with Electrolytic Gate Dielectrics: Toward a Universal Model for Poly(3-Hexylthiophene) P3HT OFETs

The lightweight with flexibility and low-cost processing engineered the rapid growth of organic field-effect transistors (OFET) in the past three decades. Suitable compact models and parameter extraction methods are being developed to further the use of OFETs in integrated circuits, where stimulations are required to optimize the device performance. To simplify the parameter extraction, metaheuristic approaches are usually made, which otherwise is a cumbersome process. Following these, here investigations are made with the help of such a compact model to extract the operational parameters of P3HT (poly (3-hexylthiophene) based OFETs with electrolytic gate dielectrics using the genetic algorithm (GA) method. The result show that the compact model that was essentially developed in line with the successful models for inorganic material based FETs, can be used as an excellent framework for simulating low voltage OFETs made with both low and high mobility organic semiconductors. Mobility and threshold voltage calculated from the extracted parameters using GA for the two devices having mobility value differences of more than four orders are found to be nicely fitting with the experimental values. These results assume significance to the organic electronic industry as this facilitates the real-time circuit application of OFETs. KEYWORDS: Modeling, Low voltage OFET, Genetic algorithm, Ionic liquid, P3HT

Harvesting Triplet Excitons in High Mobility Emissive Organic Semiconductor for Efficiency Enhancement of Light-Emitting Transistors.

Organic light-emitting transistors (OLETs), a kind of highly integrated and minimized optoelectronic device, demonstrate great potential applications in various fields. The construction of high-performance OLETs requires the integration of high charge carrier mobility, strong emission, and high triplet exciton utilization efficiency in the active layer. However, it remains a significant long-term challenge, especially for single component active layer OLETs. Herein, the successful harvesting of triplet excitons in a high mobility emissive molecule, 2,6-diphenylanthracene (DPA), through the triplet-triplet annihilation process is demonstrated. By incorporating a highly emissive guest into the DPA host system, an obvious increase in photoluminescence efficiency along with exciton utilization efficiency results in an obvious enhancement of external quantum efficiency of 7.2times for OLETs compared to the non-doped devices. Moreover, well-tunable multi-color electroluminescence, especially white emission with Commission Internationale del'Eclairage of (0.31, 0.35), from OLETs is also achieved by modulating the doping concentration with a controlled energy transfer process. This work opens a new avenue for integrating strong emission and efficient exciton utilization in high-mobility organic semiconductors for high-performance OLETs and advancing their related functional device applications.

Efficiently predicting directional carrier mobilities in organic materials with the Boltzmann transport equation.

Describing charge carrier anisotropy in crystalline organic semiconductors with ab initio methods is challenging because of the weak intermolecular interactions that lead to both localized and delocalized charge transport mechanisms. Small polaron hopping models (localized) are generally used to describe materials with small charge carrier mobilities, while periodic band models (delocalized) are used to describe materials with high charge carrier mobilities. Here, we prove the advantage of applying the constant relaxation time approximation of the Boltzmann transport equation (BTE) to efficiently predict the anisotropic hole mobilities of several unsubstituted (anthracene, tetracene, pentacene, and hexacene) and substituted (2,6-diphenylanthracene, rubrene, and TIPS-pentacene) high-mobility n-acene single crystals. Several density functionals are used to optimize the crystals, and the composite density functional PBEsol0-3c/sol-def2-mSVP predicts the most experimentally similar geometries, adequate indirect bandgaps, and the theoretically consistent n-acene charge transport mobility trend. Similarities between BTE and Marcus mobilities are presented for each crystal. BTE and Marcus charge carrier mobilities computed at the same geometry result in similar mobility trends, differing mostly in materials with more substitutions or structurally complex substituents. By using a reduced number of calculations, BTE is able to predict anisotropic carrier mobilities efficiently and effectively for a range of high-mobility organic semiconductors.

Uncovered Effects of thieno[2,3-b]thiophene Substructure in a Tetrathienoacene Backbone: Reorganization Energy and Intermolecular Interaction

Although tetrathienoacene, thieno[2″,3″:4′,5′]thieno[2′,3′-d]thieno[3,2-b]thiophene (4TA), has been used as a representative building block for organic semiconductors and polymers in the last two decades, its structural isomer, thieno[3″,2″:4′,5′]thieno[2′,3′-d]thieno[2,3-b]thiophene (i4TA), is still an unexplored structure. We are interested in the i4TA framework as a potential building block for organic semiconductors because the theoretically calculated reorganization energy (λ) of i4TA (149 meV) is significantly lower than that of 4TA (325 meV). In this study, we performed the synthesis and characterization of parent i4TA and its methylthio derivatives and found that several features of i4TA derivatives differ from those of 4TA. Parent i4TA and its derivatives tend to crystallize into the pitched π-stacking structure, which is a promising crystal structure for high-mobility organic semiconductors. The single-crystal field-effect transistor of β-methylthio-i4TA (β-MT-i4TA) showed typical transistor behaviors including as high as 3.5 cm2 V–1 s–1 hole mobility and band-like transport. This is understood as an outcome of the pitched π-stacking structure and the low λ originating in the i4TA framework. The origins of the low λ and the tendency to adopt the pitched π-stacking structure were investigated by theoretical analyses. The cross-conjugation path resulting from the thieno[2,3-b]thiophene substructure in the i4TA framework plays a pivotal role in reducing λ, meaning that the incorporation of the thieno[2,3-b]thiophene substructure is a potential strategy to reduce λ. On the other hand, the tendency to adopt the pitched π-stacking structure is due to the favorable σ*C–S–π intermolecular interaction of the i4TA framework, and the intermolecular interaction is also regarded as an outcome of the thieno[2,3-b]thiophene substructure. On the basis of these experimental and theoretical results, we conclude that the i4TA framework and the thieno[2,3-b]thiophene substructure are promising but overlooked structures as building blocks for organic semiconductors.

Organic Phase-Change Memory Transistor Based on an Organic Semiconductor with Reversible Molecular Conformation Transition.

Phase-change semiconductor is one of the best candidates for designing nonvolatile memory, but it has never been realized in organic semiconductors until now. Here, a phase-changeable and high-mobility organic semiconductor (3,6-DATT) is first synthesized. Benefiting from the introduction of electrostatic hydrogen bond (S···H), the molecular conformation of 3,6-DATT crystals can be reversibly modulated by the electric field and ultraviolet irradiation. Through experimental and theoretical verification, the tiny difference in molecular conformation leads to crystalline polymorphisms and dramatically distinct charge transport properties, based on which a high-performance organic phase-change memory transistor (OPCMT) is constructed. The OPCMT exhibits a quick programming/erasing rate (about 3 s), long retention time (more than 2h), and large memory window (i.e., large threshold voltage shift over 30V). This work presents a new molecule design concept for organic semiconductors with reversible molecular conformation transition and opens a novel avenue for memory devices and other functional applications.

TCTA:Ir(ppy)3 Green Emissive Blends in Organic Light-Emitting Transistors (OLETs).

Organic light-emitting transistors are photonic devices combining the function of an electrical switch with the capability of generating light under appropriate bias conditions. Achieving high-performance light-emitting transistors requires high-mobility organic semiconductors, optimized device structures, and highly efficient emissive layers. In this work, we studied the optoelectronic response of green blends (TCTA:Ir(ppy)3) with varying doping concentrations in the limit of field-effect within a transistor device configuration. Increasing the dye concentration within the blend leads to a quenching of the photoluminescence signal; however, when implemented in a multilayer stack in a transistor, we observed an approximately 5-fold improvement in the light output for a 10% Ir(ppy)3 doping blend. We analyzed our results in terms of balanced charge transport in the emissive layer, which, in the limit of field-effect (horizontal component), leads to an improved exciton formation and decay process. While the performances of our devices are yet to achieve the state-of-the-art diode counterpart, this work demonstrates that engineering the emissive layer is a promising approach to enhance the light emission in field-effect devices. This opens the way for a broader exploitation of organic light-emitting transistors as alternative photonic devices in several fields, ranging from display technology to flexible and wearable electronics.

Effects of Molecular Encapsulation on the Photophysical and Charge Transport Properties of a Naphthalene Diimide Bithiophene Copolymer.

Engineering the molecular structure of conjugated polymers is key to advancing the field of organic electronics. In this work, we synthesized a molecularly encapsulated version of the naphthalene diimide bithiophene copolymer PNDIT2, which is among the most popular high charge mobility organic semiconductors in n-type field-effect transistors and non-fullerene acceptors in organic photovoltaic blends. The encapsulating macrocycles shield the bithiophene units while leaving the naphthalene diimide units available for intermolecular interactions. With respect to PNDIT2, the encapsulated counterpart displays an increased backbone planarity. Molecular encapsulation prevents preaggregation of the polymer chains in common organic solvents, while it permits π-stacking in the solid state and promotes thin film crystallinity through an intermolecular-lock mechanism. Consequently, n-type semiconducting behavior is retained in field-effect transistors, although charge mobility is lower than in PNDIT2 due to the absence of the fibrillar microstructure that originates from preaggregation in solution. Hence, molecularly encapsulating conjugated polymers represent a promising chemical strategy to tune the molecular interaction in solution and the backbone conformation and to consequently control the nanomorphology of casted films without altering the electronic structure of the core polymer.

Conduction band structure of high-mobility organic semiconductors and partially dressed polaron formation.

The energy band structure provides crucial information on charge transport behaviour in organic semiconductors, such as effective mass, transfer integrals and electron-phonon coupling. Despite the discovery of the valence (the highest occupied molecular orbital (HOMO)) band structure in the 1990s, the conduction band (the lowest unoccupied molecular orbital (LUMO)) has not been experimentally observed. Here we employ angle-resolved low-energy inverse photoelectron spectroscopy to reveal the LUMO band structure of pentacene, a prototypical high-mobility organic semiconductor. The derived transfer integrals and bandwidths from the LUMO are substantially smaller than those predicted by density functional theory calculations. To reproduce this bandwidth reduction, we propose an improved (partially dressed) polaron model that accounts for the electron-intramolecular vibrational interaction with frequency-dependent coupling constants based on Debye relaxation. This model quantitatively reproduces not only the transfer integrals, but also the temperature-dependent HOMO and LUMO bandwidths, and the hole and electron mobilities. The present results demonstrate that electron mobility in high-mobility organic semiconductors is indeed limited by polaron formation.

Molecular doped, color-tunable, high-mobility, emissive, organic semiconductors for light-emitting transistors.

Developing high-mobility emissive organic semiconductors with tunable colors is crucial for organic light-emitting transistors (OLETs), a pivotal component of integrated optoelectronic devices, but remains a great challenge. Here, we demonstrate a series of color-tunable, high-mobility, emissive, organic semiconductors via molecular doping with a high-mobility organic semiconductor, 2,6-diphenylanthracene, as the host. The well-matched molecular structures and sizes with efficient energy transfer between the host and guest enable the intrinsically high charge transport with tunable colors. High mobility with the highest value >2 cm2 V−1 s−1 and strong emission with photoluminescence quantum yield >15.8% are obtained for these molecular-doped organic semiconductors. Last, a large color gamut for constructed OLETs is up to 59% National Television System Committee standard, meanwhile with an extremely high current density approaching 326.4 kA cm−2, showing great potential for full-color smart display, organic electrically pumped lasers and other related logic circuitries.

Band-like transport in non-fullerene acceptor semiconductor Y6

The recently reported non-fullerene acceptor (NFA) Y6 has been extensively investigated for high-performance organic solar cells. However, its charge transport property and physics have not been fully studied. In this work, we acquired a deeper understanding of the charge transport in Y6 by fabricating and characterizing thin-film transistors (TFTs), and found that the electron mobility of Y6 is over 0.3–0.4 cm2/(V⋅s) in top-gate bottom-contact devices, which is at least one order of magnitude higher than that of another well-known NFA ITIC. More importantly, we observed band-like transport in Y6 spin-coated films through temperature-dependent measurements on TFTs. This is particularly amazing since such transport behavior is rarely seen in polycrystalline organic semiconductor films. Further morphology characterization and discussions indicate that the band-like transport originates from the unique molecule packing motif of Y6 and the special phase of the film. As such, this work not only demonstrates the superior charge transport property of Y6, but also suggests the great potential of developing high-mobility n-type organic semiconductors, on the basis of Y6.Graphical

Recent Structural Engineering of Polymer Semiconductors Incorporating Hydrogen Bonds.

Highly planar, extended π-electron organic conjugated polymers have been increasingly attractive for achieving high-mobility organic semiconductors. In addition to the conventional strategy to construct rigid backbone by covalent bonds, hydrogen bond has been employed extensively to increase the planarity and rigidity of polymer via intramolecular noncovalent interactions. This review provides a general summary of high-mobility semiconducting polymers incorporating hydrogen bonds in field-effect transistors over recent years. The structural engineering of the hydrogen bond-containing building blocks and the discussion of theoretical simulation, microstructural characterization, and device performance are covered. Additionally, the effects of the introduction of hydrogen bond on self-healing, stretchability, chemical sensitivity, and mechanical properties are also discussed. The review aims to help and inspire design of new high-mobility conjugated polymers with superiority of mechanical flexibility by incorporation of hydrogen bond for the application in flexible electronics.

BN-Anthracene for High-Mobility Organic Optoelectronic Materials through Periphery Engineering.

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B-N bonds (BN-PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high-mobility organic semiconductors based on existing BN-PAHs through a "periphery engineering" strategy. Tetraphenyl- and diphenyl-substituted BN-anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized. DPBNA exhibits the highest hole mobility of 1.3 cm2 V-1 s-1 in organic field-effect transistors, significantly outperforming TPBNA and all the reported BN-PAHs. Remarkably, this is the first BN-PAH with mobility over 1 cm2 V-1 s-1 , which is a benchmark value for practical applications as compared with amorphous silicon. Furthermore, high-performance phototransistors based on DPBNA are also demonstrated, implying the high potential of BN-PAHs for optoelectronic applications when the "periphery engineering" strategy is implemented.

Highly efficient modulation doping: A path toward superior organic thermoelectric devices.

We investigate the charge and thermoelectric transport in modulation-doped large-area rubrene thin-film crystals with different crystal phases. We show that modulation doping allows achieving superior doping efficiencies even for high doping densities, when conventional bulk doping runs into the reserve regime. Modulation-doped orthorhombic rubrene achieves much improved thermoelectric power factors, exceeding 20 μW m−1 K−2 at 80°C. Theoretical studies give insight into the energy landscape of the heterostructures and its influence on qualitative trends of the Seebeck coefficient. Our results show that modulation doping together with high-mobility crystalline organic semiconductor films is a previosly unexplored strategy for achieving high-performance organic thermoelectrics.

14GHz Schottky Diodes Using a p-Doped Organic Polymer.

The low carrier mobility of organic semiconductors and the high parasitic resistance and capacitance often encountered in conventional organic Schottky diodes hinder their deployment in emerging radio frequency (RF) electronics. Here, these limitations are overcome by combining self-aligned asymmetric nanogap electrodes (≈25nm) produced by adhesion lithography, with a high mobility organic semiconductor, and RF Schottky diodes able to operate in the 5G frequency spectrum are demonstrated. C16 IDT-BT is used, as the high hole mobility polymer, and the impact of p-doping on the diode performance is studied. Pristine C16 IDT-BT-based diodes exhibit maximum intrinsic and extrinsic cutoff frequencies (fC ) of >100and 6GHz, respectively. This extraordinary performance is attributed to the planar nature of the nanogap channel and the diode's small junction capacitance (<2pF). Doping of C16 IDT-BT with the molecular p-dopant C60 F48 improves the diode's performance further by reducing the series resistance resulting to intrinsic and extrinsic fC of >100and ≈14GHz respectively, while the DC output voltage of an RF rectifier circuit increases by a tenfold. Ourwork highlights the importance of the planar nanogap architecture and paves the way for the use of organic Schottky diodes in large-area RF electronics of the future.

Crystal engineering of alkylethynyl fluoroanthradithiophenes

2-Dimensional brickwork packing is desirable for high mobility organic semiconductors. We synthesised acene derivatives that adopt this packing without using heavier group 14 elements to investigate substituent effects on bulk transport properties.

Quasi-Homoepitaxial Junction of Organic Semiconductors: A Structurally Seamless but Electronically Abrupt Interface between Rubrene and Bis(trifluoromethyl)dimethylrubrene

Single-crystalline organic semiconductors exhibiting band transport have opened new possibilities for the utilization of efficient charge carrier conduction in organic electronic devices. The epitaxial growth of molecular materials is a promising route for the realization of well-crystallized organic semiconductor p–n junctions for optoelectronic applications enhanced by the improved charge carrier mobility. In this study, the formation of a high-quality crystalline interface upon “quasi-homoepitaxial” growth of bis(trifluoromethyl)dimethylrubrene (fmRub) on the single-crystal surface of rubrene was revealed by using out-of-plane and grazing-incidence X-ray diffraction techniques. Ultraviolet photoelectron spectroscopy results indicated abrupt electronic energy levels and the occurrence of band bending across this quasi-homoepitaxial interface. This study verifies that the minimization of the lattice mismatch enhances the crystalline qualities at the heterojunctions even for van der Waals molecular condensates, potentially opening an untested route for the realization of high-mobility organic semiconductor optoelectronics.

Solution Processable Pentafluorophenyl End‐Capped Dithienothiophene Organic Semiconductors for Hole‐Transporting Organic Field Effect Transistors

AbstractTwo solution‐processable organic semiconductors, DFPT‐DTTR (1) and DFPbT‐DTTR (2), composed of pentafluorophenyl (FP) end‐capped 3,5‐dialkyl dithienothiophene (DTTR) core with thiophene (T) or bithiophene (bT) as π‐bridged spacers are developed and investigated for their optical, electrochemical, microstructural, and electrical properties. With more conjugated bithiophene units, compound 2 exhibits a red‐shifted UV–vis absorption band and upshifted HOMO/downshifted LUMO energy levels. According to the density functional theory, compound 2 features a more twisted molecular structure due to the intrinsic non‐coplanar blocks in the π‐backbones. Compound 1‐based organic field effect transistors exhibit efficient hole transport with mobility up to 0.48 cm2 V−1 s−1. This is one of the high mobility organic semiconductors exhibiting p‐channel characteristics based on solution‐processable small molecular FP end‐capped fused/oligothiophenes. With large and interconnected crystalline morphologies, decreased π–π stacking distance, and less steric hindrance, compound 1 exhibits two orders of magnitude higher mobility than the more distorted 2, which exhibits lower hole mobility of 1.82 × 10−3 cm2 V−1 s−1.