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The epitaxy of many organic films on inorganic substrates can be classified within the framework of rigid lattices which helps to understand the origin of energy gain driving the epitaxy of the films. Yet, there are adsorbate-substrate combinations with distinct mutual orientations for which this classification fails and epitaxy cannot be explained within a rigid lattice concept. It has been proposed that tiny shifts in atomic positions away from ideal lattice points, so-called static distortion waves (SDWs), are responsible for the observed orientational epitaxy in such cases. Using low-energy electron diffraction and scanning tunneling microscopy, we provide direct experimental evidence for SDWs in organic adsorbate films, namely hexa-peri-hexabenzocoronene on graphite. They manifest as wave-like sub-Ångström molecular displacements away from an ideal adsorbate lattice which is incommensurate with graphite. By means of a density-functional-theory based model, we show that, due to the flexibility in the adsorbate layer, molecule-substrate energy is gained by straining the intermolecular bonds and that the resulting total energy is minimal for the observed domain orientation, constituting the orientational epitaxy. While structural relaxation at an interface is a common assumption, the combination of the precise determination of the incommensurate epitaxial relation, the direct observation of SDWs in real space, and their identification as the sole source of epitaxial energy gain constitutes a comprehensive proof of this effect.

We present scanning tunneling microscopy and spectroscopy (STM/STS) investigations of the electronic structures of different alkyl-substituted oligothiophenes on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes adopted distinct straight and bent conformations. By combining STS maps with STM images, we visualize, in real space, particle-in-a-box-like oligothiophene molecular orbitals. We demonstrate that different planar conformers with significant geometrical distortions of oligothiophene backbones surprisingly exhibit very similar electronic structures, indicating a low degree of conformation-induced electronic disorder. The agreement of these results with gas-phase density functional theory calculations implies that the oligothiophene interaction with the Au(111) surface is generally insensitive to molecular conformation.

A method to produce highly efficient and long-range vertical charge transport is demonstrated in an undoped polythiophene thin film, with average mobilities above 3.1 cm(2) V(-1) s(-1) . These record high mobilities are achieved by controlled orientation of the polymer crystallites enabling the most efficient and fastest charge transport along the chain backbones and across multiple chains. The significant increase in mobility shown here may present a new route to producing faster and more efficient optoelectronic devices based on organic materials., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Charge transport in polymer- and oligomer-based semiconductor materials depends strongly on the structural ordering of the constituent molecules. Variations in molecular conformations influence the electronic structures of polymers and oligomers, and thus impact their charge-transport properties. In this study, we used Scanning Tunneling Microscopy and Spectroscopy (STM/STS) to investigate the electronic structures of different alkyl-substituted oligothiophenes displaying varied torsional conformations on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes self-assemble into chain-like structures, binding to each other via interdigitated alkyl ligands. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations. For each molecule, by using STS mapping, we identify a progression of particle-in-a-box-like states corresponding to the LUMO, LUMO+1 and LUMO+2 orbitals. Analysis of STS data revealed very similar unoccupied molecular orbital energies for different possible molecular conformations. By using density functional theory calculations, we show that the lack of variation in molecular orbital energies among the different oligothiophene conformers implies that the effect of the Au-oligothiophene interaction on molecular orbital energies is nearly identical for all studied torsional conformations. Our results suggest that cis-trans torsional disorder may not be a significant source of electronic disorder and charge carrier trapping in organic semiconductor devices based on oligothiophenes.

With consumer electronics transitioning toward flexible products, there is a growing need for high-performance, mechanically robust, and inexpensive transparent conductors (TCs) for optoelectronic device integration. Herein, we report the scalable fabrication of highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (, Pedot: PSS) thin films via solution shearing. Specific control over deposition conditions allows for tunable phase separation and preferential PEDOT backbone alignment, resulting in record-high electrical conductivities of 4,600 ± 100 S/cm while maintaining high optical transparency. High-performance solution-sheared TC PEDOT:PSS films were used as patterned electrodes in capacitive touch sensors and organic photovoltaics to demonstrate practical viability in optoelectronic applications.

High molecular weight PBTTT-C12 is blended with the pure trimer, BTTT-3, to enhance intergrain connectivity and charge transport. Analysis of the morphology and crystallinity of the blends shows that the polymer and oligomer are well-integrated, leading to high hole mobilities, greater than 0.1 cm(2) V(-1) s(-1), in films that contain as much as 83% oligomer.

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.

Alkyl-substituted quaterthiophenes on Au(111) form dimers linked by their alkyl substituents and, instead of adopting the trans conformation found in bulk oligothiophene crystals, assume cis conformations. Surprisingly, the impact of the conformation is not decisive in determining the lowest unoccupied molecular orbital energy. Scanning tunneling microscopy and spectroscopy of the adsorption geometries and electronic structures of alkyl-substituted quaterthiophenes show that the orbital energies vary substantially because of local variations in the Au(111) surface reactivity. These results demonstrate that interfacial oligothiophene conformations and electronic structures may differ substantially from those expected based on the band structures of bulk oligothiophene crystals.

A series of bulky end-capped [1]benzothieno[3,2-b]benzothiophenes (BTBTs) are developed in order to tune the packing structure via terminal substitution. A coupled theoretical and experimental study allows us to identify 2,7-di-tert-butylBTBT as a new high-performance organic semiconductor with large and well-balanced transfer integrals, as evidenced by quantum-chemical calculations. Single-crystal field-effect transistors show a remarkable average saturation mobility of 7.1 cm(2) V(-1) s(-1) ., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The intergrowth crystal of n -tetracosane/urea presents a misfit parameter, defined by the ratio γ = c h / c g ( c host / c guest ), that is very close to a commensurate value ( γ ≅ 1/3). High-resolution diffraction studies presented here reveal an aperiodic misfit parameter of γ = 0.3369, which is found to be constant at all temperatures studied. A complex sequence of structural phases is reported. The high temperature phase (phase I) exists in the four-dimensional superspace group P 6 1 22(00 γ ). At T c 1 = 179(1) K, a ferroelastic phase transition increases the dimension of the crystallographic superspace. This orthorhombic phase (phase II) is characterized by the five-dimensional (5D) superspace group C 222 1 (00 γ )(10 δ ) with a modulation vector a o * + c m * = a o * + δ · c h * , in which the supplementary misfit parameter is δ = 0.025(1) in host reciprocal units. This corresponds to the appearance of a modulation of very long period (about 440 ± 16 Å). At T c 2 = 163.0(5) K, a 5D to 5D phase transition leads to the crystallographic superspace group P 2 1 2 1 2 1 (00 γ )(00 δ ) with a very similar value of δ . This phase transition reveals a significant hysteresis effect.

Due to the unique crystallinity of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), it is an excellent model polymer to study the structure-property relationship in organic devices, especially those relying on junctions of electron- and hole-transporting materials. Here, we report the synthesis and characterization of a series of monodisperse PBTTT oligothiophenes (n = 1-5) and systematically examine the evolution of crystalline behavior, morphology, and interaction with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the molecular conjugation length increases. We discovered that fullerene intercalation occurs when there is enough free volume between the side chains to accommodate the fullerene molecule. The intercalation of PCBM is observed beyond BTTT-2 and longer oligomers, likely similar to that of PBTTT. Interestingly, both experiments and molecular simulations show that PCBM intercalation also appears to "catalyze" a more efficient packing of the BTTT-2 dimers. Crystal structure analysis revealed that the straight BTTT-2 side chains form one-dimensional (1D) channels that could perfectly host PCBM but, in the pure material, accommodate the interdigitated side chains from adjacent layers. In the blend with PCBM, these channels are maintained and enable the cocrystallization and intercalation of PCBM. This is the first time the actual sublattice cell of PCBM has been determined from the X-ray data, and demonstration the utility of the oligomers as model systems for their polymer counterparts. Among the organic photovoltaic devices (OPVs) made from the BTTT oligomers and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blends, the ones containing the BTTT-2 dimer exhibit the highest performance.

Understanding crystal polymorphism is a long-standing challenge relevant to many fields, such as pharmaceuticals, organic semiconductors, pigments, food, and explosives. Controlling polymorphism of organic semiconductors (OSCs) in thin films is particularly important given that such films form the active layer in most organic electronics devices and that dramatic changes in the electronic properties can be induced even by small changes in the molecular packing. However, there are very few polymorphic OSCs for which the structure-property relationships have been elucidated so far. The major challenges lie in the transient nature of metastable forms and the preparation of phase-pure, highly crystalline thin films for resolving the crystal structures and evaluating the charge transport properties. Here we demonstrate that the nanoconfinement effect combined with the flow-enhanced crystal engineering technique is a powerful and likely material-agnostic method to identify existing polymorphs in OSC materials and to prepare the individual pure forms in thin films at ambient conditions. With this method we prepared high quality crystal polymorphs and resolved crystal structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), including a new polymorph discovered via in situ grazing incidence X-ray diffraction and confirmed by molecular mechanic simulations. We further correlated molecular packing with charge transport properties using quantum chemical calculations and charge carrier mobility measurements. In addition, we applied our methodology to a [1]benzothieno[3,2-b][1]1benzothiophene (BTBT) derivative and successfully stabilized its metastable form.

A novel self-assembled monolayer (SAM) on AlOy /TiOx is terminated with cyclohexyl groups, an unprecedented terminal group for all kinds of SAMs. The SAM-modified AlOy /TiOx functions as a general dielectric, enabling organic thin-film transistors with a field-effect mobility higher than 5 cm(2) V(-1) s(-1) for both holes and electrons, good air stability with low operating voltage, and general applicability to solution-processed and vacuum-deposited n-type and p-type organic semiconductors., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The most efficient architecture for achieving high donor/acceptor interfacial area in organic photovoltaics (OPVs) would employ arrays of vertically interdigitated p- and n- type semiconductor nanopillars (NPs). Such morphology could have an advantage in bulk heterojunction systems; however, precise control of the dimension morphology in a crystalline, interpenetrating architecture has not yet been realized. Here we present a simple, yet facile, crystallization technique for the growth of vertically oriented NPs utilizing a modified thermal evaporation technique that hinges on a fast deposition rate, short substrate-source distance, and ballistic mass transport. A broad range of organic semiconductor materials is beneficial from the technique to generate NP geometries. Moreover, this technique can also be generalized to various substrates, namely, graphene, PEDOT-PSS, ZnO, CuI, MoO3, and MoS2. The advantage of the NP architecture over the conventional thin film counterpart is demonstrated with an increase of power conversion efficiency of 32% in photovoltaics. This technique will advance the knowledge of organic semiconductor crystallization and create opportunities for the fabrication and processing of NPs for applications that include solar cells, charge storage devices, sensors, and vertical transistors.

Oligothiophenes provide a highly controlled and adaptable platform to explore various synthetic, morphologic, and electronic relationships in organic semiconductor systems. These short-chain systems serve as models for establishing valuable structure-property relationships to their polymer analogs. In contrast to their polymer counterparts, oligothiophenes afford high-purity and well-defined materials that can be easily modified with a variety of functional groups. Recent work by a number of research groups has revealed functionalized oligothiophenes to be the up-and-coming generation of advanced materials for organic electronic devices. In this review, we discuss the synthesis and characterization of linear oligothiophenes with a focus on applications in organic field effect transistors and organic photovoltaics. We will highlight key structural parameters, such as crystal packing, intermolecular interactions, polymorphism, and energy levels, which in turn define the device performance.

A crystal's structure has significant impact on its resulting biological, physical, optical and electronic properties. In organic electronics, 6,13(bis-triisopropylsilylethynyl)pentacene (TIPS-pentacene), a small-molecule organic semiconductor, adopts metastable polymorphs possessing significantly faster charge transport than the equilibrium crystal when deposited using the solution-shearing method. Here, we use a combination of high-speed polarized optical microscopy, in situ microbeam grazing incidence wide-angle X-ray-scattering and molecular simulations to understand the mechanism behind formation of metastable TIPS-pentacene polymorphs. We observe that thin-film crystallization occurs first at the air-solution interface, and nanoscale vertical spatial confinement of the solution results in formation of metastable polymorphs, a one-dimensional and large-area analogy to crystallization of polymorphs in nanoporous matrices. We demonstrate that metastable polymorphism can be tuned with unprecedented control and produced over large areas by either varying physical confinement conditions or by tuning energetic conditions during crystallization through use of solvent molecules of various sizes.

Organic semiconductors with higher carrier mobility and better transparency have been actively pursued for numerous applications, such as flat-panel display backplane and sensor arrays. The carrier mobility is an important figure of merit and is sensitively influenced by the crystallinity and the molecular arrangement in a crystal lattice. Here we describe the growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from a blended solution of C8-BTBT and polystyrene by using a novel off-centre spin-coating method. Combined with a vertical phase separation of the blend, the highly aligned, meta-stable C8-BTBT films provide a significantly increased thin film transistor hole mobility up to 43 cm(2) Vs(-1) (25 cm(2) Vs(-1) on average), which is the highest value reported to date for all organic molecules. The resulting transistors show high transparency of >90% over the visible spectrum, indicating their potential for transparent, high-performance organic electronics.

Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5'bis(4-alkylphenyl)-2,2'-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified SiO2 surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd-even effect in the strength of the intermolecular electronic coupling.

Solution coating of organic semiconductors offers great potential for achieving low-cost manufacturing of large-area and flexible electronics. However, the rapid coating speed needed for industrial-scale production poses challenges to the control of thin-film morphology. Here, we report an approach--termed fluid-enhanced crystal engineering (FLUENCE)--that allows for a high degree of morphological control of solution-printed thin films. We designed a micropillar-patterned printing blade to induce recirculation in the ink for enhancing crystal growth, and engineered the curvature of the ink meniscus to control crystal nucleation. Using FLUENCE, we demonstrate the fast coating and patterning of millimetre-wide, centimetre-long, highly aligned single-crystalline organic semiconductor thin films. In particular, we fabricated thin films of 6,13-bis(triisopropylsilylethynyl) pentacene having non-equilibrium single-crystalline domains and an unprecedented average and maximum mobilities of 8.1±1.2 cm(2) V(-1) s(-1) and 11 cm(2) V(-1) s(-1). FLUENCE of organic semiconductors with non-equilibrium single-crystalline domains may find use in the fabrication of high-performance, large-area printed electronics.

Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility. It is found that the side-chain length has a moderate influence on thin-film microstructure but leads to only limited changes in OTFT performance. In contrast, the position of branching point results in subtle, yet critical changes in molecular packing and leads to dramatic differences in electron mobility ranging from ~0.001 to >3.0 cm(2) V(-1) s(-1). Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C(11,6) results in a dense in-plane molecular packing with an unit cell area of 127 Å(2), larger domain sizes of up to 1000 × 3000 nm(2), and an electron mobility of up to 3.50 cm(2) V(-1) s(-1), which is an unprecedented value for ambient stable n-channel solution-processed OTFTs reported to date. These results demonstrate that variation of the alkyl chain branching point is a powerful strategy for tuning of molecular packing to enable high charge transport mobilities.

Monodispersed conjugated oligothiophenes are receiving attention in fundamental and applied science due to their interesting optical, optoelectronic, and charge transport properties. These "low molecular weight" polymers serve as model structures for the corresponding polymer analogues, which are inherently polydispersed. Here we report the synthesis, electronic structure, molecular packing/morphology, and charge transport properties of monodispersed oligothiophenes with up to six didodecylquaterthiophene (DDQT) building block repeat units (i.e., 24 thiophene units). At the point where the effective conjugation length is reached, the electronic structure showed convergence behavior to the corresponding polymer, poly(3,3"-didodecyl-quaterthiophene) (PQT-12). X-ray crystal structure analysis of the dimer (DDQT-2) showed that terminal thiophenes exhibit syn-conformations, similar to the terminal syn-conformations observed in the trimer (DDQT-3). The dimer also exhibits a rare bending of the terminal alkyl side chains in order to prevent steric hindrance with neighboring hydrogens attached to core thiophenes. Grazing incidence X-ray scattering measurements revealed a morphology evolution from small molecule-like packing to polymer-like packing in thin films, with a morphology transition occurring near the effective conjugation length. Charge transport measurements showed a mobility increase with decreasing chain length. We correlated the molecular packing and morphology to charge transport and determined that carrier mobilities are most sensitive to crystallinity and crystal grain misorientation. This indicates that molecular weight is not a decisive factor for improved carrier mobility in the low molecular weight region, but rather the degree in crystallinity and in-plane crystal orientation. These results represent a fundamental advancement in understanding the relationship between conjugation length and carrier mobilities in oligothiophene semiconductors.

We discuss the inhomogeneous stress relaxation of a monolayer of hexahydroxytriphenylene (HHTP) which adopts the rare line-on-line (LOL) coincidence on KCl(001) and forms moiré patterns. The fact that the hexagonal HHTP layer is uniaxially compressed along the LOL makes this system an ideal candidate to discuss the influence of inhomogeneous stress relaxation. Our work is a combination of noncontact atomic force microscopy experiments, density functional theory and potential energy calculations, and a thorough interpretation by means of the Frenkel-Kontorova model. We show that the assumption of a homogeneous molecular layer is not valid for this organic-inorganic heteroepitaxial system since the best calculated energy configuration correlates with the experimental data only if inhomogeneous relaxations of the layer are taken into account.

Circuits based on organic semiconductors are being actively explored for flexible, transparent and low-cost electronic applications. But to realize such applications, the charge carrier mobilities of solution-processed organic semiconductors must be improved. For inorganic semiconductors, a general method of increasing charge carrier mobility is to introduce strain within the crystal lattice. Here we describe a solution-processing technique for organic semiconductors in which lattice strain is used to increase charge carrier mobilities by introducing greater electron orbital overlap between the component molecules. For organic semiconductors, the spacing between cofacially stacked, conjugated backbones (the π-π stacking distance) greatly influences electron orbital overlap and therefore mobility. Using our method to incrementally introduce lattice strain, we alter the π-π stacking distance of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) from 3.33 Å to 3.08 Å. We believe that 3.08 Å is the shortest π-π stacking distance that has been achieved in an organic semiconductor crystal lattice (although a π-π distance of 3.04 Å has been achieved through intramolecular bonding). The positive charge carrier (hole) mobility in TIPS-pentacene transistors increased from 0.8 cm(2) V(-1) s(-1) for unstrained films to a high mobility of 4.6 cm(2) V(-1) s(-1) for a strained film. Using solution processing to modify molecular packing through lattice strain should aid the development of high-performance, low-cost organic semiconducting devices.

For organic semiconductors to find ubiquitous electronics applications, the development of new materials with high mobility and air stability is critical. Despite the versatility of carbon, exploratory chemical synthesis in the vast chemical space can be hindered by synthetic and characterization difficulties. Here we show that in silico screening of novel derivatives of the dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene semiconductor with high hole mobility and air stability can lead to the discovery of a new high-performance semiconductor. On the basis of estimates from the Marcus theory of charge transfer rates, we identified a novel compound expected to demonstrate a theoretic twofold improvement in mobility over the parent molecule. Synthetic and electrical characterization of the compound is reported with single-crystal field-effect transistors, showing a remarkable saturation and linear mobility of 12.3 and 16 cm(2) V(-1) s(-1), respectively. This is one of the very few organic semiconductors with mobility greater than 10 cm(2) V(-1) s(-1) reported to date.

The development of an electronic skin is critical to the realization of artificial intelligence that comes into direct contact with humans, and to biomedical applications such as prosthetic skin. To mimic the tactile sensing properties of natural skin, large arrays of pixel pressure sensors on a flexible and stretchable substrate are required. We demonstrate flexible, capacitive pressure sensors with unprecedented sensitivity and very short response times that can be inexpensively fabricated over large areas by microstructuring of thin films of the biocompatible elastomer polydimethylsiloxane. The pressure sensitivity of the microstructured films far surpassed that exhibited by unstructured elastomeric films of similar thickness, and is tunable by using different microstructures. The microstructured films were integrated into organic field-effect transistors as the dielectric layer, forming a new type of active sensor device with similarly excellent sensitivity and response times.

This article focuses on the growth and transport properties of organic single-crystalline p-n junction nanoribbons. The development of organic nanoelectronics requires the fabrication of organic nanometer-sized p-n junctions for high-performance devices and integrated circuits. Here we demonstrate the formation of single-crystalline p-n junction nanoribbons of organic semiconductors by selective crystallization of copper hexadecafluorophthalocyanine (F(16)CuPc, n-type) on copper phthalocyanine (CuPc, p-type) single-crystalline nanoribbons. The crystallization of F(16)CuPc onto CuPc requires several parameters, including similar molecular structures, similar lattice constants, and pi-stacking along the nanoribbon axis. Ambipolar transport of the p-n junction nanoribbons was observed in field-effect transistors with balanced carrier mobilities of 0.05 and 0.07 cm(2) V(-1) s(-1) for F(16)CuPc and CuPc, respectively. A basic p-n junction nanoribbon photovoltaic device showed current rectification under AM 1.5 simulated light. The discrete p-n junction nanoribbons may serve as ideal systems for understanding basic charge-transport and photovoltaic behaviors at organic-organic interfaces.

Hexacene and larger fused rings remain elusive targets for chemists. Here, we report a hexacene-like molecule containing six linearly fused rings, specifically a pentacene molecule fused with a terminal thiophene ring, pentaceno[2,3-b]thiophene. It can be purified and isolated as a purple-black powder at ambient conditions. This molecule has a low HOMO-LUMO gap of 1.75 eV in o-DCB and an optical band gap of 1.58 eV in thin film. Top contact organic thin film transistors (OTFTs) were made, and atomic force microscopy (AFM) reveals a dendritic thin film growth characteristic of pentacene. An OTFT mobility of 0.574 cm(2)/V s was measured for pentaceno[2,3-b]thiophene under nitrogen.

The development of low-cost, reliable sensors will rely on devices capable of converting an analyte binding event to an easily read electrical signal. Organic thin-film transistors (OTFTs) are ideal for inexpensive, single-use chemical or biological sensors because of their compatibility with flexible, large-area substrates, simple processing, and highly tunable active layer materials. We have fabricated low-operating voltage OTFTs with a cross-linked polymer gate dielectric, which display stable operation under aqueous conditions over >10(4) electrical cycles using the p-channel semiconductor 5,5'-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2'-bithiophene (DDFTTF). OTFT sensors were demonstrated in aqueous solutions with concentrations as low as parts per billion for trinitrobenzene, methylphosphonic acid, cysteine, and glucose. This work demonstrates of reliable OTFT operation in aqueous media, hence opening new possibilities of chemical and biological sensing with OTFTs.

Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on charge carrier mobility are discussed.

Perylenetetracarboxyldiimide (PTCDI) nanowires self-assembled from commercially available materials are demonstrated as the n-channel semiconductor in organic field-effect transistors (OFETs) and as a building block in high-performance complementary inverters. Devices based on a network of PTCDI nanowires have electron mobilities and current on/off ratios on the order of 10(-2) cm2/Vs and 10(4), respectively. Complementary inverters based on n-channel PTCDI nanowire transistors and p-channel hexathiapentacene (HTP) nanowire OFETs achieved gains as high as 8. These results demonstrate the first example of the use of one-dimensional organic semiconductors in complementary inverters.

Two efficient approaches to assembling organic semiconducting single crystals are described. The methods rely on solvent wetting and dewetting on substrates with patterned wettability to selectively direct the deposition or removal of organic crystals. Substrates were functionalized with different self-assembled monolayers (SAMs) to achieve the desired wettabilities. The assembly of different organic crystals over centimeter-squared areas on Au, SiO2, and flexible plastic substrates was demonstrated. By designing line features on the substrate, the alignment of crystals, such as CuPc needles, was also achieved. As a demonstration of the potential application of this assembly approach, arrays of single-crystal organic field-effect transistors were fabricated by patterning organic single crystals directly onto and between transistor source and drain electrodes.

This paper describes a simple, solution-phase route to the synthesis of bulk quantities of hexathiapentacene (HTP) single-crystal nanowires. These nanowires have also been successfully incorporated as the semiconducting material in field-effect transistors (FETs). For devices based on single nanowires, the carrier mobilities and current on/off ratios could be as high as 0.27 cm2/Vs and >103, respectively. For transistors fabricated from a network of nanowires, the mobilities and current on/off ratios could reach 0.057 cm2/Vs and >104, respectively. We have further demonstrated the use of nanowire networks in fabricating transistors on mechanically flexible substrates. Preliminary results show that these devices could withstand mechanical strain and still remain functional. The results from this study demonstrate the potential of utilizing solution-dispersible, nanostructured organic materials for use in low-cost, flexible electronic applications.

Field-effect transistors made of organic single crystals are ideal for studying the charge transport characteristics of organic semiconductor materials. Their outstanding device performance, relative to that of transistors made of organic thin films, makes them also attractive candidates for electronic applications such as active matrix displays and sensor arrays. These applications require minimal cross-talk between neighbouring devices. In the case of thin film systems, simple patterning of the active semiconductor layer minimizes cross-talk. But when using organic single crystals, the only approach currently available for creating arrays of separate devices is manual selection and placing of individual crystals-a process prohibitive for producing devices at high density and with reasonable throughput. In contrast, inorganic crystals have been grown in extended arrays, and efficient and large-area fabrication of silicon crystalline islands with high mobilities for electronic applications has been reported. Here we describe a method for effectively fabricating large arrays of single crystals of a wide range of organic semiconductor materials directly onto transistor source-drain electrodes. We find that film domains of octadecyltriethoxysilane microcontact-printed onto either clean Si/SiO(2) surfaces or flexible plastic provide control over the nucleation of vapour-grown organic single crystals. This allows us to fabricate large arrays of high-performance organic single-crystal field-effect transistors with mobilities as high as 2.4 cm(2) V(-1) s(-1) and on/off ratios greater than 10(7), and devices on flexible substrates that retain their performance after significant bending. These results suggest that our fabrication approach constitutes a promising step that might ultimately allow us to utilize high-performance organic single-crystal field-effect transistors for large-area electronics applications.

We propose a new type of epitaxy, line-on-line coincidence (LOL), which explains the ordering in the organic-organic heterolayer system PTCDA on HBC on graphite. LOL epitaxy is similar to point-on-line coincidence (POL) in the sense that all overlayer molecules lie on parallel, equally spaced lines. The key difference to POL is that these lines are not restricted to primitive lattice lines of the substrate lattice. Potential energy calculations demonstrate that this new type of epitaxy is indeed characterized by a minimum in the overlayer-substrate interaction potential.