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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. [ABSTRACT FROM AUTHOR]

The article discusses recent advancement in experimental techniques for quantitative analysis of organic semiconductor films. It mentions that the techniques are developed by utilization of structural and optoelectronic devices properties of organic semi-conductors. It also highlights importance of utilization of developed techniques through implications of improved materials design that helps in efficient organic semiconductor device performance.

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. [ABSTRACT FROM AUTHOR]

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 (OTFT5) 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 >104 electrical cycles using the p-channel semi-conductor 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. [ABSTRACT FROM AUTHOR]

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 Å, b = 7.71 Å, c= 15.16 Å, a = 97.300, β = 95.630, γ = 90°; there are two molecules per unit cell with herringbone packing (49-59° angle) and tilted about 7° 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. [ABSTRACT FROM AUTHOR]

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/SiO2 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 cm2 V-1 s-1 and on/off ratios greater than 107, 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. [ABSTRACT FROM AUTHOR]

A fine balance between weak molecule-molecule interactions and usually only weakly laterally varying molecule-substrate interactions governs the physical structure of organic-inorganic and organic-organic heteroepitaxial thin films. Therefore, it is important to investigate the energetics of realistically large overlayer domains. So far, Potential calculations for large domains of organic overlayers on crystalline substrates were computationally demanding due to the vast number of atoms to be considered. Here, we present a technique which for the first time enables the calculation of both the molecule-substrate interaction potential and the molecule-molecule interaction potential for large molecular domains (up to several thousands of rather large molecules) by utilizing potential energy grid files. This technique does not only allow the investigation of the substrate influence but also full Monte-Carlo based structural optimizations, if applied to 2D crystalline overlayers. Furthermore, it provides an estimate for the energetic gain combined with the differently aligned overlayer domains. In several examples we will discuss the usefulness of this method. As a general result, we will provide evidence that energetically favorable lattice structures in OMBE systems are not restricted to commensurate unit cells or coincident super cells. [ABSTRACT FROM AUTHOR]

Sol–gel‐based solution‐processed metal oxides have emerged as a key fabrication method for applications in thin film transistors both as a semiconducting and a dielectric layer. Here, a low‐temperature, green solvent‐based, non‐toxic, and cost‐effective solution shearing approach for the fabrication of thin aluminum oxide (AlOx) dielectrics is reported. Optimization of sustainability aspects like energy demand, and selection of chemicals used allows to reduce the environmental impact of the life cycle of the resulting product already in the design phase. Using this approach, ultra‐thin, device‐grade AlOx films of 7 nm are coated—the thinnest films to be reported for any solution‐fabrication method. The metal oxide formation is achieved by both thermal annealing and deep ultra‐violet (UV) light exposure techniques, resulting in capacitances of 750 and 600 nF cm−2, respectively. The structural analysis using microscopy and x‐ray spectroscopy techniques confirmed the formation of smooth, ultra‐thin AlOx films. These thin films are employed in organic field‐effect transistors (OFETs) resulting in stable, low hysteresis devices leading to high mobilities (6.1 ± 0.9 cm2 V−1 s−1), near zero threshold voltage (−0.14 ± 0.07 V) and a low subthreshold swing (96 ± 16 mV dec−1), enabling device operation at only ±0.5 V with a good Ion/Ioff ratio (3.7 × 105). [ABSTRACT FROM AUTHOR]

Organic field-effect transistors containing pentacene or α sexithiophene on random arrays of carbon nanotube bundles were fabricated. The impact of nanotube bundles on the performance of devices with different geometries and surface treatments was studied. Upon incorporation of an appropriate amount of nanotube bundles, we observed an increase in the “effective” field effect mobility as high as 20 times while maintaining the high on/off ratios. Furthermore, our preliminary results show that nanotube bundles might template the growth of organic crystals under certain conditions, resulting in the formation of organic nucleates with preferred orientations. [ABSTRACT FROM AUTHOR]

Vinylene‐linked two‐dimensional polymers (V‐2DPs) and their layer‐stacked covalent organic frameworks (V‐2D COFs) featuring high in‐plane π‐conjugation and robust frameworks have emerged as promising candidates for energy‐related applications. However, current synthetic approaches are restricted to producing V‐2D COF powders that lack processability, impeding their integration into devices, particularly within membrane technologies reliant upon thin films. Herein, we report the novel on‐water surface synthesis of vinylene‐linked cationic 2DPs films (V‐C2DP‐1 and V‐C2DP‐2) via Knoevenagel polycondensation, which serve as the anion‐selective electrode coating for highly‐reversible and durable zinc‐based dual‐ion batteries (ZDIBs). Model reactions and theoretical modeling revealed the enhanced reactivity and reversibility of the Knoevenagel reaction on the water surface. On this basis, we demonstrated the on‐water surface 2D polycondensation towards V‐C2DPs films that show large lateral size, tunable thickness, and high chemical stability. Representatively, V‐C2DP‐1 presents as a fully crystalline and face‐on oriented film with in‐plane lattice parameters of a=b≈43.3 Å. Profiting from its well‐defined cationic sites, oriented 1D channels, and stable frameworks, V‐C2DP‐1 film possesses superior bis(trifluoromethanesulfonyl)imide anion (TFSI−)‐transport selectivity (transference, t_=0.85) for graphite cathode in high‐voltage ZDIBs, thus triggering additional TFSI−‐intercalation stage and promoting its specific capacity (from ~83 to 124 mAh g−1) and cycling life (>1000 cycles, 95 % capacity retention). [ABSTRACT FROM AUTHOR]

This article explores the synthesis and properties of Vinylen-bridged cationic 2DP films (V-C2DPs) for use in anion-selective electrodes and high-voltage zinc-ion batteries. The films are highly crystalline and possess oriented one-dimensional channels, which enhance anion-selective transport. The authors conducted experiments and calculations to understand the reactivity and structure of the films, finding that synthesis on the water surface had advantages over aqueous solution synthesis. The films exhibited a well-ordered hexagonal lattice structure and showed improved electrochemical performance when used as coatings for graphite cathodes in zinc-ion batteries. The study highlights the potential of V-C2DP films for next-generation energy devices. The research was supported by various funding sources and the data is available upon request from the authors. [Extracted from the article]

Conjugated polymers often show efficient charge carrier transport along their backbone which is a primary factor in the electrical behavior of Organic Field Effect Transistor (OFETs) devices fabricated from these materials. Herein, a solution shearing procedure is reported to fabricate micro/nano wires from a diketopyrrolopyrrole (DPP)‐based polymer. Millimeter to nanometer long polymer wires orientated in the coating direction are developed after a thorough analysis of the deposition conditions. It shows several morphological regimes—film, transition, and wires and experimentally derive a phase diagram for the parameters coating speed and surface energy of the substrate. The as‐fabricated wires are isolated, which is confirmed by optical, atomic force, and scanning electron microscopy. Beside the macroscopic alignment of wires, cross‐polarized optical microscopy images show strong birefringence suggesting a high degree of molecular orientation. This is further substantiated by polarized UV‐Vis‐NIR spectroscopy, selected area electron diffraction transmission electron microscopy, and grazing‐incidence wide‐angle X‐ray scattering. Finally, an enhanced electrical performance of single wire OFETs is observed with a 15‐fold increase in effective charge carrier mobility to 1.57 cm2 V−1 s−1 over devices using films (0.1 cm2 V−1 s−1) with similar values for on/off current ratio and threshold voltage. [ABSTRACT FROM AUTHOR]

Synthetic insecticides are widely used against plant pest insects to protect the crops. However, many insecticides have poor selectivity and are toxic also to beneficial insects, animals, and humans. In addition, insecticide residues can remain on fruits for many days, jeopardizing food safety. For these reasons, a reusable, low‐cost electronic trap that can attract, detect, and identify, but attack only the pest while leaving beneficial insects unharmed could provide a sustainable, nature‐friendly replacement. Here, for the first time, research results are presented suggesting the great potential and compatibility of organic electronic devices and technologies with pest management. Electrical characterizations confirm that an insect's body has relatively high dielectric permittivity. Adaptive memcapacitor circuits can track the impedance change for insect detection. Other experiments show that printed polymer piezoelectric transducers on a plastic substrate can collect information about the weight and activity of insects for identification. The breakdown voltage of most insects´ integument is measured to be <200 V. Long channel organic transistors easily work at such high voltages while being safe to touch for humans thanks to their inherent low current. This feasibility study paves the way for the future development of organic electronics for physical pest control and biodiversity protection. [ABSTRACT FROM AUTHOR]

The water surface provides a highly effective platform for the synthesis of two-dimensional polymers (2DP). In this study, we present an efficient on-water surface synthesis of crystalline monolayer 2D polyimide (2DPI) through the imidization reaction between tetra (4-aminophenyl) porphyrin (M1) and perylenetracarboxylic dianhydride (M2), resulting in excellent stability and coverage over a large area (tens of cm2). We further fabricate innovative organic-inorganic hybrid van der Waals heterostructures (vdWHs) by combining with exfoliated few-layer molybdenum sulfide (MoS2). High-resolution transmission electron microscopy (HRTEM) reveals face-to-face stacking between MoS2 and 2DPI within the vdWH. This stacking configuration facilitates remarkable charge transfer and noticeable n-type doping effects from monolayer 2DPI to MoS2, as corroborated by Raman spectroscopy, photoluminescence measurements, and field-effect transistor (FET) characterizations. Notably, the 2DPI-MoS2 vdWH exhibits an impressive electron mobility of 50 cm2/V·s, signifying a substantial improvement over pristine MoS2 (8 cm2/V·s). This study unveils the immense potential of integrating 2D polymers to enhance semiconductor device functionality through tailored vdWHs, thereby opening up exciting new avenues for exploring unique interfacial physical phenomena. The water surface has recently proven to be an effective platform for the synthesis of large-area two-dimensional polymers with high crystallinity. Here, the authors report the on-water synthesis of a crystalline monolayer 2D polyimide, as well as its incorporation into organic–inorganic hybrid van der Waals heterostructures that display significant charge transfer and high electron mobility. [ABSTRACT FROM AUTHOR]

The article presents the description of Harald Ade and colleagues of a resonant scattering of polarized soft X-rays (P-SoXS) X-ray scattering technique that has the potential to remedy the performance of organic electronic materials. It says that Ade and colleagues demonstrates P-SoXS utility for three organic systems such as polycrystalline films and polymer dielectric. It adds that the P-SoXS uses a polarized X-ray beam passing through a thin sample.

The article discusses the use of pentaceno thiophene as a hexacene analogue for organic thin film transistors. Acenes with five or more fused aromatic rings are useful in the field of organic electronics and especially pentacene, is the largest member of the unsubstituted linearly fused carbocyclic series that has been isolated and purified, with a thin film transistor mobility similar to amorphous silicon.

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy‐efficient and nature‐inspired next‐generation computing devices. Here, we disclose the generalized concept for bias‐direction‐adjustable n‐ and p‐CAPodes based on selective ion sieving. Controllable‐unidirectional ion flux is realized by blocking electrolyte ions from entering sub‐nanometer pores. The resulting CAPodes exhibit charge‐storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations ('OR', 'AND'). This work demonstrates CAPodes as a generalized concept to achieve p‐n and n‐p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion‐based diodes in ionologic architectures. [ABSTRACT FROM AUTHOR]

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy‐efficient and nature‐inspired next‐generation computing devices. Here, we disclose the generalized concept for bias‐direction‐adjustable n‐ and p‐CAPodes based on selective ion sieving. Controllable‐unidirectional ion flux is realized by blocking electrolyte ions from entering sub‐nanometer pores. The resulting CAPodes exhibit charge‐storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations ('OR', 'AND'). This work demonstrates CAPodes as a generalized concept to achieve p‐n and n‐p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion‐based diodes in ionologic architectures. [ABSTRACT FROM AUTHOR]

Organic phototransistors can enable many important applications such as nonvolatile memory, artificial synapses, and photodetectors in next‐generation optical communication and wearable electronics. However, it is still a challenge to achieve a big memory window (threshold voltage response ∆Vth) for phototransistors. Here, a nanographene‐based heterojunction phototransistor memory with large ∆Vth responses is reported. Exposure to low intensity light (25.7 µW cm−2) for 1 s yields a memory window of 35 V, and the threshold voltage shift is found to be larger than 140 V under continuous light illumination. The device exhibits both good photosensitivity (3.6 × 105) and memory properties including long retention time (>1.5 × 105 s), large hysteresis (45.35 V), and high endurance for voltage‐erasing and light‐programming. These findings demonstrate the high application potential of nanographenes in the field of optoelectronics. In addition, the working principle of these hybrid nanographene‐organic structured heterojunction phototransistor memory devices is described which provides new insight into the design of high‐performance organic phototransistor devices. [ABSTRACT FROM AUTHOR]

Metal oxide (MO) semiconductors are widely used in electronic devices due to their high optical transmittance and promising electrical performance. This work describes the advancement toward an eco‐friendly, streamlined method for preparing thin‐film transistors (TFTs) via a pure water‐solution blade‐coating process with focus on a low thermal budget. Low temperature and rapid annealing of triple‐coated indium oxide thin‐film transistors (3C‐TFTs) and indium oxide/zinc oxide/indium oxide thin‐film transistors (IZI‐TFTs) on a 300 nm SiO2 gate dielectric at 300 °C for only 60 s yields devices with an average field effect mobility of 10.7 and 13.8 cm2 V−1 s−1, respectively. The devices show an excellent on/off ratio (>106), and a threshold voltage close to 0 V when measured in air. Flexible MO‐TFTs on polyimide substrates with AlOx dielectrics fabricated by rapid annealing treatment can achieve a remarkable mobility of over 10 cm2 V−1 s−1 at low operating voltage. When using a longer post‐coating annealing period of 20 min, high‐performance 3C‐TFTs (over 18 cm2 V−1 s−1) and IZI‐TFTs (over 38 cm2 V−1 s−1) using MO semiconductor layers annealed at 300 °C are achieved. [ABSTRACT FROM AUTHOR]

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 ?-? stacking distance) greatly influences electron orbital overlap and therefore mobility. Using our method to incrementally introduce lattice strain, we alter the ?-? 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 ?-? stacking distance that has been achieved in an organic semiconductor crystal lattice (although a ?-? 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?cm2?V?1?s?1 for unstrained films to a high mobility of 4.6?cm2?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. [ABSTRACT FROM AUTHOR]

This work highlights recent literature dealing with the fabrication of field-effect transistors from the vacuum deposition of organic semiconductors. We pay special attention to recent advances in molecular design and specific ways that synthesis has been used to tune crystal packing, and thus charge transport, in organic semiconductors. This work also looks into the fundamental processes of nucleation and growth of organic semiconductors that are deposited by vacuum deposition. The parameters that affect the morphology of the corresponding films are discussed in detail. We also provide specific examples from a family of fluorene-thiophene containing oligomers that correlate the molecular structure to device performance. [ABSTRACT FROM AUTHOR]

This work highlights recent literature dealing with the fabrication of field‐effect transistors from the vacuum deposition of organic semiconductors. We pay special attention to recent advances in molecular design and specific ways that synthesis has been used to tune crystal packing, and thus charge transport, in organic semiconductors. This work also looks into the fundamental processes of nucleation and growth of organic semiconductors that are deposited by vacuum deposition. The parameters that affect the morphology of the corresponding films are discussed in detail. We also provide specific examples from a family of fluorene‐thiophene containing oligomers that correlate the molecular structure to device performance. [ABSTRACT FROM PUBLISHER]

We explore the charge transport properties of phytic acid (PA) doped polyaniline thin films prepared by the surfactant monolayer‐assisted interfacial synthesis (SMAIS). Structural and elemental analysis confirms the inclusion of PA in the thin films and reveals a progressive loss of crystallinity with the increase of PA doping content. Charge transport properties are interrogated by time‐resolved terahertz (THz) spectroscopy. Notably, independently of doping content and hence crystallinity, the frequency‐resolved complex conductivity spectra in the THz region can be properly described by the Drude model, demonstrating band‐like charge transport in the samples and state‐of‐the‐art charge carrier mobilities of ≈1 cm2V−1s−1. A temperature‐dependent analysis for the conductivity further supports band‐like charge transport and suggest that charge carrier mobility is primarily limited by impurity scattering. This work highlights the potential of PA doped polyaniline for organic electronics. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

2D conjugated metal–organic frameworks (2D c‐MOFs) are emerging as electroactive materials for chemiresistive sensors, but selective sensing with fast response/recovery is a challenge. Phthalocyanine‐based Ni2[MPc(NH)8] 2D c‐MOF films are presented as active layers for polarity‐selective chemiresisitors toward water and volatile organic compounds (VOCs). Surface‐hydrophobic modification by grafting aliphatic alkyl chains on 2D c‐MOF films decreases diffused analytes into the MOF backbone, resulting in a considerably accelerated recovery progress (from ca. 50 to ca. 10 s) during humidity sensing. Toward VOCs, the sensors deliver a polarity‐selective response among alcohols but no signal for low‐polarity aprotic hydrocarbons. The octadecyltrimethoxysilane‐modified Ni2[MPc(NH)8] based sensor displays high‐performance methanol sensing with fast response (36 s)/recovery (13 s) and a detection limit as low as 10 ppm, surpassing reported room‐temperature chemiresistors. [ABSTRACT FROM AUTHOR]

2D conjugated metal–organic frameworks (2D c‐MOFs) are emerging as electroactive materials for chemiresistive sensors, but selective sensing with fast response/recovery is a challenge. Phthalocyanine‐based Ni2[MPc(NH)8] 2D c‐MOF films are presented as active layers for polarity‐selective chemiresisitors toward water and volatile organic compounds (VOCs). Surface‐hydrophobic modification by grafting aliphatic alkyl chains on 2D c‐MOF films decreases diffused analytes into the MOF backbone, resulting in a considerably accelerated recovery progress (from ca. 50 to ca. 10 s) during humidity sensing. Toward VOCs, the sensors deliver a polarity‐selective response among alcohols but no signal for low‐polarity aprotic hydrocarbons. The octadecyltrimethoxysilane‐modified Ni2[MPc(NH)8] based sensor displays high‐performance methanol sensing with fast response (36 s)/recovery (13 s) and a detection limit as low as 10 ppm, surpassing reported room‐temperature chemiresistors. [ABSTRACT FROM AUTHOR]

Organic light‐emitting materials exhibiting thermally activated delayed fluorescence (TADF) show great promise for improving display applications. Recently, intermolecular effects between emitting molecules have been given more attention, revealing strong solid‐state solvation or aggregation induced changes of sample performance. Implications of this on device performance are not yet fully covered. In this work, a thorough investigation of a novel TADF emitter, methyl 2,3,4,5,6‐penta(carbazol‐9‐yl)benzoate (5CzCO2Me), is provided. Steady‐state emission spectra reveal a luminescence redshift with increasing emitter concentration in a small molecule host. In all investigated concentrations, the emission profile remains the same; thus, the redshift is attributed to the solid‐state solvation effect. The highest photoluminescence quantum yield (PLQY) is achieved in the 20 wt% sample, reaching 66%. The best organic light‐emitting diode (OLED) in terms of current–voltage–luminance and external quantum efficiency (EQE) parameters is the device with 60 wt% emitter concentration, reaching maximal EQE values of 7.5%. It is shown that the emitter transports holes and that charge‐carrier recombination does not take place on the bandgap of the host, but rather, a mixed host–guest concentration‐dependent recombination is seen. The hole‐transporting properties of 5CzCO2Me allow for a new dimension in tuning the device performance by controlling the emitter concentration. [ABSTRACT FROM AUTHOR]

Two‐dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on‐water surface synthesis of large‐area (cm2), monolayer 2D polyimide (2DPI) with 3.1‐nm lattice. Such 2DPI comprises metal‐free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI‐graphene (2DPI‐G) vdWHs via a face‐to‐face co‐assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra‐fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI‐G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene. [ABSTRACT FROM AUTHOR]

Two‐dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on‐water surface synthesis of large‐area (cm2), monolayer 2D polyimide (2DPI) with 3.1‐nm lattice. Such 2DPI comprises metal‐free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI‐graphene (2DPI‐G) vdWHs via a face‐to‐face co‐assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra‐fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI‐G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene. [ABSTRACT FROM AUTHOR]

The article discusses a solution-coating technique developed by Mannsfeld et al. to produce aligned polymer micro/nano wires of a diketopyrrolopyrrole-based polymer, resulting in a significant enhancement in charge carrier mobility in organic field effect transistor devices.

The article explores the near–atomic-scale observation of grain boundaries in a layer-stacked two-dimensional (2D) polymer. It presents a direct observation of the grain boundaries in a layer-stacked two-dimensional polyimine. It mentions that opportunity for future investigations on defect-property correlations in 2D polymers.

Dopants, i.e., electronically active impurities, are added to organic semiconductor materials to control the material's Fermi level and conductivity, to improve injection at the device contacts, or to fill trap states in the active device layers and interfaces. In contrast to bulk doping as achieved by blending or co-deposition of dopant and semiconductor, surface doping has a lower propensity to introduce additional traps or scattering centers or to even alter the layer morphology relative to the undoped active material layers. In this study, the electrical effects of a very simple, post-device-fabrication surface doping process involving various amine group-containing alkoxysilanes on the performance of organic field-effect transistors (OFETs) made from the well-known n-type materials PTCDI-C8 and N2200 are researched. It is demonstrated that OFETs doped in such a way generally show enhanced characteristics (up to 10 times mobility increase and a significant reduction in threshold voltage) without any adverse effects on the devices' on/off ratio. It is also shown that the efficiency of the doping process is linked to the number of amine groups. [ABSTRACT FROM AUTHOR]

The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. A materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor is presented. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate. [ABSTRACT FROM AUTHOR]

In this work, the detailed morphology studies of polymer poly(3-hexylthiophene-2,5-diyl) (P3HT):fullerene(PCBM) and polymer(P3HT):polymer naphthalene diimide thiophene (PNDIT) solar cell are presented to understand the challenge for getting high performance all-polymer solar cells. The in situ X-ray scattering and optical interferometry and ex situ hard and soft X-ray scattering and imaging techniques are used to characterize the bulk heterojunction (BHJ) ink during drying and in dried state. The crystallization of P3HT polymers in P3HT:PCBM bulk heterojunction shows very different behavior compared to that of P3HT:PNDIT BHJ due to different mobilities of P3HT in the donor:acceptor glass. Supplemented by the ex situ grazing incidence X-ray diffraction and soft X-ray scattering, PNDIT has a lower tendency to form a mixed phase with P3HT than PCBM, which may be the key to inhibit the donor polymer crystallization process, thus creating preferred small phase separation between the donor and acceptor polymer. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A general impact of solution shearing on molecular orientation correlation is observed in polymer:fullerene organic solar cells in which one of the components forms fibrils or aggregates. Further investigation with polarized soft X-ray scattering reveals that solution shearing induces more face-to-face orientation relative to the interface of two components compared to spin-coating. This impact is shearing speed dependent, that is, slow shearing speed can induce more face-to-face orientation than a fast shearing speed. These results demonstrate that solution shearing is an effective method to control the relative molecular orientation. Solution shearing can also modify the domain size and average composition variations. [ABSTRACT FROM AUTHOR]

The intergrowth crystal of n-tetracosane/urea presents a misfit parameter, defined by the ratio γ=ch/cg(chost/cguest), 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 P6122(00γ). At Tc1=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 C2221(00γ)(10δ) with a modulation vector αo*+cm*=ao*+δ·ch*, 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±16Å). At Tc2=163.0(5)K, a 5D to 5D phase transition leads to the crystallographic superspace group P212121(00γ)(00δ) with a very similar value of δ. This phase transition reveals a significant hysteresis effect. [ABSTRACT FROM AUTHOR]

Side-chain engineering is increasingly being utilized as a technique to impact the structural order and enhance the electronic properties of semiconducting polymers. However, the correlations drawn between structural changes and the resulting charge transport properties are typically indirect and qualitative in nature. In the present work, a combination of grazing incidence X-ray diffraction and crystallographic refinement calculations is used to determine the precise molecular packing structure of two thiophene-based semiconducting polymers to study the impact of side-chain modifications. The optimized structures provide high-quality fits to the experimental data and demonstrate that in addition to a large difference in interchain spacing between the two materials, there exists a significant disparity in backbone orientation as well. The calculated structures are utilized in density functional theory calculations to determine the band structure of the two materials and are shown to exhibit a dramatic disparity in interchain dispersion which accounts for the large observed difference in charge carrier mobility. The techniques presented here are meant to be general and are therefore applicable to many other highly diffracting semicrystalline polymers. [ABSTRACT FROM AUTHOR]

The crystallization and electrical characterization of the semiconducting polymer poly(3-hexylthiophene) (P3HT) on a single layer graphene sheet is reported. Grazing incidence X-ray diffraction revealed that P3HT crystallizes with a mixture of face-on and edge-on lamellar orientations on graphene compared to mainly edge-on on a silicon substrate. Moreover, whereas ultrathin (10 nm) P3HT films form well oriented face-on and edge-on lamellae, thicker (50 nm) films form a mosaic of lamellae oriented at different angles from the graphene substrate. This mosaic of crystallites with π-π stacking oriented homogeneously at various angles inside the film favors the creation of a continuous pathway of interconnected crystallites, and results in a strong enhancement in vertical charge transport and charge carrier mobility in the thicker P3HT film. These results provide a better understanding of polythiophene crystallization on graphene, and should help the design of more efficient graphene based organic devices by control of the crystallinity of the semiconducting film. [ABSTRACT FROM AUTHOR]

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 (ID) 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Using non-chlorinated solvents for polymer device fabrication is highly desirable to avoid the negative environmental and health effects of chlorinated solvents. Here, a non-chlorinated mixed solvent system, composed by a mixture of tetrahydronaphthalene and p­-xylene, is described for processing a high mobility donor-acceptor fused thiophene-diketopyrrolopyrrole copolymer (PTDPPTFT4) in thin film transistors. The effects of the use of a mixed solvent system on the device performance, e.g., charge transport, morphology, and molecular packing, are investigated. p-Xylene is chosen to promote polymer aggregation in solution, while a higher boiling point solvent, tetrahydronaphthalene, is used to allow a longer evaporation time and better solubility, which further facilitates morphological tuning. By optimizing the ratio of the two solvents, the charge transport characteristics of the polymer semiconductor device are observed to significantly improve for polymer devices deposited by spin coating and solution shearing. Average charge carrier mobilities of 3.13 cm2 V−1 s−1 and a maximum value as high as 3.94 cm2 V−1 s−1 are obtained by solution shearing. The combination of non-chlorinated mixed solvents and the solution shearing film deposition provide a practical and environmentally-friendly approach to achieve high performance polymer transistor devices. [ABSTRACT FROM AUTHOR]

The research leading to the results published in this manuscript was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. This corrigendum corrects an omission from the Acknowledgement section. Corrigendum: Surface-Modified Phthalocyanine-Based Two-Dimensional Conjugated Metal-Organic Framework Films for Polarity-Selective Chemiresistive Sensing. [Extracted from the article]

Berichtigung: Surface-Modified Phthalocyanine-Based Two-Dimensional Conjugated Metal-Organic Framework Films for Polarity-Selective Chemiresistive Sensing This corrigendum corrects an omission from the Acknowledgement section. The research leading to the results published in this manuscript was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. [Extracted from the article]

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 cm2 V−1 s−1 and 11 cm2 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. [ABSTRACT FROM AUTHOR]

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 cm2 V-1 s-1. Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C11,6 results in a dense in-plane molecular packing with an unit cell area of 127 Å2, larger domain sizes of up to 1000 x 3000 nm2, and an electron mobility of up to 3.50 cm2 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We report the cooperative self-assembly of functionalizedfullerenesand all conjugated block copolymers (BCPs) containing polythiophenederivatives in both segments to yield solar cells with well-definednanostructures and enhanced morphological stability. Favorable hydrogenbonding interactions between the COOH-functionalized fullerene, bis-[6,6]-phenyl C61-butyric acid (bis-PCBA), and the tetraethyleneglycolside chains of poly(3-hexylthiophene)-block-poly[3-(2,5,8,11-tetraoxadodecane)thiophene](P3HT-b-P3TODT) allows for high loading of bis-PCBA(up to 40 wt % to the blend) within the P3TODT domains, while preservingthe lamellar morphology. Characterization by grazing incidence small-angleX-ray scattering, electron microscopy, and atomic force microscopyindicates that the periods of the structures range between 24 and29 nm depending on the bis-PCBA loading. The hydrogen bond interactionsbetween bis-PCBA and P3TODT segments further suppress crystallizationand macrophase separation of the fullerenes, even under harsh annealingconditions (150 °C for 12 h). Bulk heterojunction solar cellsprepared using P3HT-b-P3TODT/bis-PCBA exhibit a photoconversionefficiency of 2.04%, which is greater than that of a reference system,P3HT-b-P3TODT/bis-PCBM. Accelerated aging experimentsreveal enhanced thermal stability as a result of the limited translationalmobility of COOH-functionalized fullerene in P3HT-b-P3TODT relative to devices prepared using bis-PCBM in P3HT-b-P3TODT or P3HT. We believe that cooperative assembly usingstrong noncovalent interactions is a general approach that can beused to improve the processing, morphological stability, and agingof organic and hybrid photovoltaic devices. [ABSTRACT FROM AUTHOR]

Shear coating is a promising deposition method for upscaling device fabrication and enabling high throughput, and is furthermore suitable for translating to roll-to-roll processing. Although common polymer semiconductors (PSCs) are solution processible, they are still prone to mechanical failure upon stretching, limiting applications in e.g., electronic skin and health monitoring. Progress made towards mechanically compliant PSCs, e.g., the incorporation of soft segments into the polymer backbone, could not only allow such applications, but also benefit advanced fabrication methods, like roll-to-roll printing on flexible substrates, to produce the targeted devices. Tri-block copolymers (TBCs), consisting of an inner rigid semiconducting poly-diketo-pyrrolopyrrole-thienothiophene (PDPP-TT) block flanked by two soft elastomeric poly(dimethylsiloxane) (PDMS) chains, maintain good charge transport properties, while being mechanically soft and flexible. Potentially aiming at the fabrication of TBC-based wearable electronics by means of cost-efficient and scalable deposition methods (e.g., blade-coating), a tolerance of the electrical performance of the TBCs to the shear speed was investigated. Herein, we demonstrate that such TBCs can be deposited at high shear speeds (film formation up to a speed of 10 mm s−1). While such high speeds result in increased film thickness, no degradation of the electrical performance was observed, as was frequently reported for polymer−based OFETs. Instead, high shear speeds even led to a small improvement in the electrical performance: mobility increased from 0.06 cm2 V−1 s−1 at 0.5 mm s−1 to 0.16 cm2 V−1 s−1 at 7 mm s−1 for the TBC with 24 wt% PDMS, and for the TBC containing 37 wt% PDMS from 0.05 cm2 V−1 s−1 at 0.5 mm s−1 to 0.13 cm2 V−1 s−1 at 7 mm s−1. Interestingly, the improvement of mobility is not accompanied by any significant changes in morphology. [ABSTRACT FROM AUTHOR]