ε‐Branched Flexible Side Chain Substituted Diketopyrrolopyrrole‐Containing Polymers Designed for High Hole and Electron Mobilities

Based on the integrated consideration and engineering of both conjugated backbones and flexible side chains, solution‐processable polymeric semiconductors consisting of a diketopyrrolopyrrole (DPP) backbone and a finely modulated branching side chain (ε‐branched chain) are reported. The subtle change in the branching point from the backbone alters the π?π stacking and the lamellar distances between polymer backbones, which has a significant influence on the charge‐transport properties and in turn the performances of field‐effect transistors (FETs). In addition to their excellent electron mobilities (up to 2.25 cm² V^?1 s^?1), ultra‐high hole mobilities (up to 12.25 cm² V^?1 s^?1) with an on/off ratio (I_on/I_off) of at least 10⁶ are achieved in the FETs fabricated using the polymers. The developed polymers exhibit extraordinarily high electrical performance with both hole and electron mobilities superior to that of unipolar amorphous silicon.     

Boosting the Charge Transport Property of Indeno[1,2‐b]fluorene‐6,12‐dione though Incorporation of Sulfur‐ or Nitrogen‐Linked Side Chains

Alkyl chains are basic units in the design of organic semiconductors for purposes of enhancing solubility, tuning electronic energy levels, and tailoring molecular packing. This work demonstrates that the carrier mobilities of indeno[1,2‐b ]fluorene‐6,12‐dione ( IFD )‐based semiconductors can be dramatically enhanced by the incorporation of sulfur‐ or nitrogen‐linked side chains. Three IFD derivatives possessing butyl, butylthio, and dibutylamino substituents are synthesized, and their organic field‐effect transistors (OFET) are fabricated and characterized. The IFD possessing butyl substituents exhibits a very poor charge transport property with mobility lower than 10^?7 cm² V^?1 s^?1. In contrast, the hole mobility is dramatically increased to 1.03 cm² V^?1 s^?1 by replacing the butyl units with dibutylamino groups ( DBA‐IFD ), while the butylthio‐modified IFD ( BT‐IFD ) derivative exhibits a high and balanced ambipolar charge transport property with the maximum hole and electron mobilities up to 0.71 and 0.65 cm² V^?1 s^?1, respectively. Moreover, the complementary metal–oxide–semiconductor‐like inverters incorporated with the ambipolar OFETs shows sharp inversions with a maximum gain value up to 173. This work reveals that modification of the aromatic core with heteroatom‐linked side chains, such as alkylthio or dialkylamino, can be an efficient strategy for the design of high‐performance organic semiconductors.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

1,3,6,8‐Tetraphenylpyrene Derivatives: Towards Fluorescent Liquid‐Crystalline Columns?

Tetraphenylpyrene has been selected as a discotic core to promote liquid‐crystalline fluorescent columns in view of its high fluorescence quantum yield in solution and ease of substitution by flexible lateral side chains. The synthesis and characterization of ten new derivatives of pyrene have been carried out; the pyrene core has been substituted at the 1,3,6,8‐positions by phenylene rings bearing alkoxy, ester, thioether, or tris(alkoxy)benzoate groups on the para position; the compounds have been characterized by mass spectrometry and ¹H NMR and UV‐vis spectroscopies. In order to generate liquid‐crystalline phases, the nature, number, and size of the side chains as well as the degree of polarity around the tetraphenylpyrene core have been varied. However, the desired liquid‐crystalline behavior has not been observed. The supramolecular order together with the absorption and emission properties in solution and the solid state are discussed and compared to theoretical predictions. Quantum‐chemical calculations rationalize the high solid‐state fluorescence of a tetraphenylpyrene derivative for which the crystal structure has been determined.     

Ambient‐Stable,Annealing‐Free,and Ambipolar Organic Field‐Effect Transistors Based on Solution‐Processable Poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene) without Long Alkyl Side Chains

An ambipolar conjugated polymer CF₃‐PBTV, poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene), consisting of thienylenevinylene as the donor and trifluoromethyl‐substituted biphenyl as the acceptor has been successfully synthesized. CF₃‐PBTV shows solution‐processability without electrically insulating long alkyl side chains. Grazing incidence X‐ray diffraction results suggest a nearly equal population of flat‐on and end‐on domains in CF₃‐PBTV thin film. The excellent ambipolarity of CF₃‐PBTV is demonstrated by well‐equivalent charge mobilities of 0.065 and 0.078 cm² V^?1 s^?1 for p‐ and n‐channel, respectively. The organic field‐effect transistors (OFET) also shows very high on/off ratio (≈10⁷) which is attributed to the relatively large bandgap and low‐lying highest occupied molecular orbital (HOMO) of CF₃‐PBTV. The OFET performance barely changes after the device is stored in ambient conditions for 90 days. The ambient‐stability is attributed to the enhanced oxidative stability from its low‐lying HOMO and the better moisture resistance from its fluorine contents. The performance of CF₃‐PBTV based OFET is annealing independent. It is noteworthy that the solution‐processable, ambipolar, and thienylenevinylene‐containing conjugated polymer without any long alkyl side chains is reported for the first time. And to the best of our knowledge, it is the first ambient‐stable, annealing‐free OFET with well‐equivalent ambipolarity.     

Self Encapsulated Poly(3‐hexylthiophene)‐poly(fluorinated alkyl methacrylate) Rod‐Coil Block Copolymers with High Field Effect Mobilities on Bare SiO2

Conjugated rod‐coil block copolymers provide an interesting route towards enhancing the properties of the conjugated block due to self‐assembly and the interplay of rod‐rod and rod‐coil interactions. Here, we demonstrate the ability of an attached semi‐fluorinated block to significantly improve upon the charge carrier properties of regioregular poly(3‐hexyl thiophene) (rr‐P3HT) materials on bare SiO₂. The thin film hole mobilities on bare SiO₂ dielectric surfaces of poly (3‐hexyl thiophene)‐block‐polyfluoromethacrylates (P3HT‐b‐PFMAs) can approach up to 0.12 cm² V^?1 s^?1 with only 33 wt% of the P3HT block incorporated in the copolymer, as compared to rr‐P3HT alone which typically has mobilities averaging 0.03 cm² V^?1 s^?1. To our knowledge, this is the highest mobility reported in literature for block copolymers containing a P3HT. More importantly, these high hole mobilities are achieved without multistep OTS treatments, argon protection, or post‐annealing conditions. Grazing incidence wide‐angle x‐ray scattering (GIWAX) data revealed that in the P3HT‐b‐PFMA copolymers, the P3HT rod block self‐assembles into highly ordered lamellar structures, similar to that of the rr‐P3HT homopolymer. Grazing incidence small‐angle x‐ray scattering (GISAXS) data revealed that lamellar structures are only observed in perpendicular direction with short PFMA blocks, while lamellae in both perpendicular and parallel directions are observed in polymers with longer PFMA blocks. AFM, GIWAXS, and contact angle measurements also indicate that PFMA block assembles at the polymer thin film surface and forms an encapsulation layer. The high charge carrier mobilities and the hydrophobic surface of the block copolymer films clearly demonstrates the influence of the coil block segment on device performance by balancing the crystallization and microphase separation in the bulk morphological structure.     

Versatile,Benzimidazole/Amine‐Based Ambipolar Compounds for Electroluminescent Applications: Single‐Layer,Blue, Fluorescent OLEDs,Hosts for Single‐Layer,Phosphorescent OLEDs

A series of compounds containing arylamine and 1,2‐diphenyl‐1H‐benz[d]imidazole moieties are developed as ambipolar, blue‐emitting materials with tunable blue‐emitting wavelengths, tunable ambipolar carrier‐transport properties and tunable triplet energy gaps. These compounds possess several novel properties: (1) they emit in the blue region with high quantum yields; (2) they have high morphological stability and thermal stability; (3) they are capable of ambipolar carrier transport; (4) they possess tunable triplet energy gaps, suitable as hosts for yellow‐orange to green phosphors. The electron and hole mobilities of these compounds lie in the range of 0.68–144 × 10^?6 and 0.34–147 × 10^?6 cm² V^?1 s^?1, respectively. High‐performance, single‐layer, blue‐emitting, fluorescent organic light‐emitting diodes (OLEDs) are achieved with these ambipolar materials. High‐performance, single‐layer, phosphorescent OLEDs with yellow‐orange to green emission are also been demonstrated using these ambipolar materials, which have different triplet energy gaps as the host for yellow‐orange‐emitting to green‐emitting iridium complexes. When these ambipolar, blue‐emitting materials are lightly doped with a yellow‐orange‐emitting iridium complex, white organic light‐emitting diodes (WOLEDs) can be achieved, as well by the use of the incomplete energy transfer between the host and the dopant.     

2,7‐Carbazolenevinylene‐Based Oligomer Thin‐Film Transistors: High Mobility Through Structural Ordering

We have fabricated organic field‐effect transistors based on thin films of 2,7‐carbazole oligomeric semiconductors 1,4‐bis(vinylene‐(N‐hexyl‐2‐carbazole))phenylene (CPC), 1,4‐bis(vinylene‐(N′‐methyl‐7′‐hexyl‐2′‐carbazole))benzene (RCPCR), N‐hexyl‐2,7‐bis(vinylene‐(N‐hexyl‐2‐carbazole))carbazole (CCC), and N‐methyl‐2,7‐bis(vinylene‐(7‐hexyl‐N‐methyl‐2‐carbazole))carbazole (RCCCR). The organic semiconductors are deposited by thermal evaporation on bare and chemically modified silicon dioxide surfaces (SiO₂/Si) held at different temperatures varying from 25 to 200 °C during deposition. The resulting thin films have been characterized using UV‐vis and Fourier‐transform infrared spectroscopies, scanning electron microscopy, and X‐ray diffraction, and the observed top‐contact transistor performances have been correlated with thin‐film properties. We found that these new π‐conjugated oligomers can form highly ordered structures and reach high hole mobilities. Devices using CPC as the active semiconductor have exhibited mobilities as high as 0.3 cm² V^–1 s^–1 with on/off current ratios of up to 10⁷. These features make CPC and 2,7‐carbazolenevinylene‐based oligomers attractive candidates for device applications.     

Alignment of a Perylene‐Based Ionic Self‐Assembly Complex in Thermotropic and Lyotropic Liquid‐Crystalline Phases

The thermotropic and lyotropic liquid‐crystalline (LC) phases of the ionic self‐assembled complex N,N′,‐bis(2‐(trimethylammonium)ethylene)‐perylene‐3,4,9,10‐tetracarboxyldiimide‐bis(2‐ethylhexyl)sulfosuccinate have been studied using polarizing microscopy, differential scanning calorimetry (DSC), and X‐ray scattering techniques. A two‐dimensional (2D) columnar thermotropic LC phase with π–π stacking of the perylene tectonic units and a lyotropic LC phase in dimethyl sulfoxide (DMSO) have been found. Different techniques have been applied to align both systems and included: surface interactions, electric and magnetic fields, shear force, and controlled domain formation at the LC–isotropic phase‐transition front (PTF). Characterization of the alignment in films has been performed using polarized UV‐vis spectroscopy and transmission null‐ellipsometry. The best results have been obtained for alignment of the material in a lyotropic phase by controlled domain formation at the PTF of the LC–isotropic phase transition. In this case, a dichroic ratio of 18 is achieved with packing of columns of perylenediimide tectons perpendicular to the PTF.     

High‐Performance Solution‐Processable Poly(p‐phenylene vinylene)s for Air‐Stable Organic Field‐Effect Transistors

The influence of the substitution pattern (unsymmetrical or symmetrical), the nature of the side chain (linear or branched), and the processing of several solution processable alkoxy‐substituted poly(p‐phenylene vinylene)s (PPVs) on the charge‐carrier mobility in organic field‐effect transistors (OFETs) is investigated. We have found the highest mobilities in a class of symmetrically substituted PPVs with linear alkyl chains (e.g., R¹, R² = n‐C₁₁H₂₃, R³ = n‐C₁₈H₃₇). We have shown that the mobility of these PPVs can be improved significantly up to values of 10^–2 cm² V^–1 s^–1 by annealing at 110 °C. In addition, these devices display an excellent stability in air and dark conditions. No change in the electrical performance is observed, even after storage for thirty days in humid air.     

Synthesis,Characterization, and Field‐Effect Transistor Performance of Thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene Derivatives

The synthesis, characterization, and field‐effect transistor (FET) properties of a new class of thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene derivatives are described. The optical spectra of their films show the presence of stronger interactions between molecules in the solid state. Thermal analyses reveal that the three materials are thermally stable and have no phase transitions at low temperature. The crystal structures are determined, and show π‐stacked structures and intermolecular S···S contacts. These organic materials exhibit p‐type FET behavior with hole mobilities as high as 0.14 cm² V^?1 s^?1 and an on/off current ratio of 10⁶. These results indicate that thieno[3,2‐b]thieno [2′,3′:4,5]thieno[2,3‐d]thiophene, as a linear π‐conjugated system, is an effective building block for developing high‐performance organic semiconductors.     

High‐Mobility Air‐Stable Solution‐Shear‐Processed n‐Channel Organic Transistors Based on Core‐Chlorinated Naphthalene Diimides

High charge carrier mobility solution‐processed n‐channel organic thin‐film transistors (OTFTs) based on core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are demonstrated. These OTFTs were prepared through a solution shearing method. Core‐chlorination of NDIs not only increases the electron mobilities of OTFTs, but also enhances their air stability, since the chlorination in the NDI core lowers the lowest unoccupied molecular orbital (LUMO) levels. The air‐stability of dichlorinated NDI was better than that of the tetrachlorinated NDIs, presumably due to the fact that dichlorinated NDIs have a denser packing of the fluoroalkyl chains and less grain boundaries on the surface, reducing the invasion pathway of ambient oxygen and moisture. The devices of dichlorinated NDIs exhibit good OTFT performance, even after storage in air for one and a half months. Charge transport anisotropy is observed from the dichlorinated NDI. A dichlorinated NDI with ?CH₂C₃F₇ side chains reveals high mobilities of up to 0.22 and 0.57 cm² V^?1 s^?1 in parallel and perpendicular direction, respectively, with regard to the shearing direction. This mobility anisotropy is related to the grain morphology. In addition, we find that the solution‐shearing deposition affects the molecular orientation in the crystalline thin films and lowers the d(001)‐spacing (the out‐of‐plane interlayer spacing), compared to the vapor‐deposited thin films. Core‐chlorinated NDI derivatives are found to be highly suitable for n‐channel active materials in low‐cost solution‐processed organic electronics.     

Transistor Paint: Environmentally Stable N‐alkyldithienopyrrole and Bithiazole‐Based Copolymer Thin‐Film Transistors Show Reproducible High Mobilities without Annealing

New solution processable 4‐(2‐hexyldecan)‐4H‐bisthieno[2,3‐d:3′,2′‐b]pyrrole and 4,4′‐dialkyl‐2,2′‐bithiazole‐based copolymers (PBTzDTPs) are synthesized with excellent FET performance. These novel copolymers have considerable potential in printable electronics as they have high charge carrier mobilities, excellent air stability, good solution processibility, and no requirement for post‐deposition thermal annealing, all requirements for this field of application. The thin film transistors fabricated from PBTzDTPs achieve field effect mobilities as high as 0.14 cm² V^?1 s^?1 with current on/off ratios up to 10⁶ without thermal annealing. In addition, the devices exhibit stable performance in air, showing no significant degradation over 60 days. Moreover, the polymers described here provide an excellent example of the systems in which higher mobility performance does not require higher crystalline, long‐range ordered structures. Such a system appears to be particularly promising for rapid fabrication techniques, where kinetic conditions usually prevent the development of long‐range order.     

High‐Performance Air‐Stable n‐Type Organic Transistors Based on Core‐Chlorinated Naphthalene Tetracarboxylic Diimides

Core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are synthesized and employed for n‐channel organic thin‐film transistors (OTFTs). Structural analyses of the single crystals and thin films are performed and their charge‐transport behavior is investigated in terms of structure–property relationships. NDIs with two chlorine substituents are shown to exhibit a herringbone structure with a very close π‐plane distance (3.3–3.4 Å), a large π‐stack overlap (slipping angle ca. 62°), and high crystal densities (2.046–2.091 g cm^?3). These features result in excellent field‐effect mobilities of up to 1.43 cm² V^?1 s^?1 with minimal hysteresis and high on–off ratios (ca. 10⁷) in air. This is similar to the highest n‐channel mobilities in air reported so far. Despite the repulsive interactions of bulky Cl substituents, tetrachlorinated NDIs adopt a slip‐stacked face‐to‐face packing with an interplanar distance of around 3.4 Å, resulting in a high mobility (up to 0.44 cm² V^?1 s^?1). The air‐stability of dichlorinated NDIs is superior to that of tetrachlorinated NDIs, despite of their higher LUMO levels. This is closely related to the denser packing of the fluorocarbon chains of dichlorinated NDIs, which serves as a kinetic barrier to the diffusion of ambient oxidants. Interestingly, these NDIs show an optimal performance either on bare SiO₂ or on octadecyltrimethoxysilane (OTS)‐treated SiO₂, depending on the carbon number of the fluoroalkyl chains. Their synthetic simplicity and processing versatility combined with their high performance make these semiconductors highly promising for practical applications in flexible electronics.     

Highly Conductive Organosilica Hybrid Films Prepared from a Liquid‐Crystal Perylene Bisimide Precursor

Significant anisotropic electrical conduction in organosilica films is achieved by long‐range orientation of electroactive perylene bisimide (PBI) moieties in the silica scaffold. A new PBI‐based organosilane precursor is designed with lyotropic liquid‐crystalline properties. The PBI precursor with triethoxysilylphenyl groups exhibits a hexagonal columnar phase in the presence of organic solvents. The lyotropic liquid‐crystalline behavior of the precursor enables the preparation of dip‐coated films consisting of uniaxially aligned columnar aggregates of the PBI precursor on the centimeter scale. The oriented structure is successfully fixed by in situ polycondensation, which yields insoluble, thermally stable PBI–silica hybrid films. The oriented organosilica films doped with hydrazine exhibit high electrical conductivities on the order of 10^?2 S cm^?1, which are at the highest level for organosilica materials, and are comparable to those of all‐organic PBI assemblies. Definite anisotropy of conductivities is also found for these films. The present results suggest that the induction of significant electrical properties in organic molecular assemblies is compatible with the structural stabilization by inorganic–organic hybridization.     

Helically π‐Stacked Conjugated Polymers Bearing Photoresponsive and Chiral Moieties in Side Chains: Reversible Photoisomerization‐Enforced Switching Between Emission and Quenching of Circularly Polarized Fluorescence

Novel multifunctional conjugated polymers, [poly(p‐phenylene)s and poly(bithienylene‐phenylene)s with (R)‐ and (S)‐configurations], which have fluorescence, chirality, and photoresponsive properties, have been designed and synthesized. The polymers are composed of π‐conjugated main chains, where poly(p‐phenylene) and poly(bithienylene‐phenylene) are fluorescence moieties, and the side chains of the photochromic dithienylethene moiety are linked with chiral alkyl groups. The polymer films exhibit right‐ or left‐handed circularly polarized fluorescence (CPF) and also show reversible quenching and emitting behaviors as a result of photochemical isomerization of the dithienylethene moiety upon irradiation with ultraviolet and visible light. This is the first report realizing the reversible switching of CPF using chirality and photoresponsive properties.     

Mesomorphic Organization and Thermochromic Luminescence of Dicyanodistyrylbenzene‐Based Phasmidic Molecular Disks: Uniaxially Aligned Hexagonal Columnar Liquid Crystals at Room Temperature with Enhanced Fluorescence Emission and Semiconductivity

A new dicyanodistyrylbenzene‐based phasmidic molecule, (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(3,4,5‐tris(dodecyloxy)phenyl)acrylonitrile), GDCS, is reported, which forms a hexagonal columnar liquid crystal (LC) phase at room temperature (RT). GDCS molecules self‐assemble into supramolecular disks consisting of a pair of molecules in a side‐by‐side disposition assisted by secondary bonding interactions of the lateral polar cyano group, which, in turn, constitute the hexagonal columnar LC structure. GDCS shows very intense green/yellow fluorescence in liquid/solid crystalline states, respectively, in contrast to the total absence of fluorescence emission in the isotropic melt state according to the characteristic aggregation‐induced enhanced emission (AIEE) behavior. The AIEE and two‐color luminescence thermochromism of GDCS are attributed to the peculiar intra‐ and intermolecular interactions of dipolar cyanostilbene units. It was found that the intramolecular planarization and restricted molecular motion associated with a specific stacking situation in the liquid/solid crystalline phases are responsible for the AIEE phenomenon. The origin of the two‐color luminescence was elucidated to be due to the interdisk stacking alteration in a given column driven by the specific local dipole coupling between molecular disks. These stacking changes, in turn, resulted in the different degree of excited‐state dimeric coupling to give different emission colors. To understand the complicated photophysical properties of GDCS, temperature‐dependent steady‐state and time‐resolved PL measurements have been comprehensively carried out. Uniaxially aligned and highly fluorescent LC and crystalline microwires of GDCS are fabricated by using the micromolding in capillaries (MIMIC) method. Significantly enhanced electrical conductivity (0.8 × 10^?5 S?cm^?1/3.9 × 10^?5 S?cm^?1) of the aligned LC/crystal microwires were obtained over that of multi‐domain LC sample, because of the almost perfect shear alignment of the LC material achieved in the MIMIC mold.     

Liquid‐Crystalline Perylene Diester Polymers with Tunable Charge‐Carrier Mobility

New classes of liquid‐crystalline semiconductor polymers based on perylene diester benzimidazole and perylene diester imide mesogens are reported. Two highly soluble side‐chain polymers, poly(perylene diester benzimidazole acrylate) (PPDB) and poly(perylene diester imide acrylate) (PPDI) are synthesized by nitroxide‐mediated radical polymerization (NMRP). PPDB shows n‐type semiconductor performance with electron mobilities of 3.2 × 10^?4 cm² V^?1 s^?1 obtained in a diode configuration by fitting the space‐charge‐limited currents (SCLC) according to the Mott–Gurney equation. Interestingly, PPDI performs preferentially as a p‐type material with a hole mobility of 1.5 × 10^?4 cm² V^?1 s^?1, which is attributed to the less electron‐deficient perylene core of PPDI compared to PPDB. Optical properties are investigated by UV‐vis and fluorescence spectroscopy. The extended π‐conjugation system due to the benzimidazole unit of PPDB leads to a considerably broader absorption in the visible region compared to PPDI. HOMO and LUMO levels of the polymers are also determined by cyclic voltammetry; the resulting energy band‐gaps are 1.86 eV for PPDB and 2.16 eV for PPDI. Thermal behavior and liquid crystallinity are studied by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction measurements. The results indicate liquid‐crystalline order of the polymers over a broad temperature range. These thermal, electrical, and optical properties make the perylene side‐chain polymers attractive materials for organic photovoltaics.     

Poly(diketopyrrolopyrrole‐benzothiadiazole) with Ambipolarity Approaching 100% Equivalency

As a characteristic feature of conventional conjugated polymers, it has been generally agreed that conjugated polymers exhibit either high hole transport property (p‐type) or high electron transport property (n‐type). Although ambipolar properties have been demonstrated from specially designed conjugated polymers, only a few examples have exhibited ambipolar transport properties under limited conditions. Furthermore, there is, as yet, no example with ‘equivalent’ hole and electron transport properties. We describe the realization of an equivalent ambipolar organic field‐effect transistor (FET) by using a single‐component visible–near infrared absorbing diketopyrrolopyrrole (DPP)‐benzothiadiazole (BTZ) copolymer, namely poly[3,6‐dithiene‐2‐yl‐2,5‐di(2‐decyltetradecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐5’,5’’‐diyl‐alt‐benzo‐2,1, 3‐thiadiazol‐4,7‐diyl] ( PDTDPP‐alt‐BTZ ). PDTDPP‐alt‐BTZ shows not only ideally balanced charge carrier mobilities for both electrons (?_e = 0.09 cm²V^?1s^?1) and holes (?_h = 0.1 cm²V^?1s^?1) but also its inverter constructed with the combination of two identical ambipolar FETs exhibits a gain of ～35 that is much higher than usually obtained values for unipolar logic.     

Single Crystal Microwires of p‐DTS(FBTTh2)2 and Their Use in the Fabrication of Field‐Effect Transistors and Photodetectors

Single crystal microwires of a well‐studied organic semiconductor used in organic solar cells, namely p‐DTS(FBTTh₂)₂, are prepared via a self‐assembly method in solution. The high level of intermolecular organization in the single crystals facilitates migration of charges, relative to solution‐processed films, and provides insight into the intrinsic charge transport properties of p‐DTS(FBTTh₂)₂. Field‐effect transistors based on the microwires can achieve hole mobilities on the order of ≈1.8 cm² V^?1 s^?1. Furthermore, these microwires show photoresponsive electrical characteristics and can act as photoswitches, with switch ratios over 1000. These experimental results are interpreted using theoretical simulations using an atomistic density functional theory approach. Based on the lattice organization, intermolecular couplings and reorganization energies are calculated, and hole mobilities for comparison with experimental measurements are further estimated. These results demonstrate a unique example of the optoelectronic applications of p‐DTS(FBTTh₂)₂ microwires.