Mass-Synthesized Solution-Processable Polyimide Gate Dielectrics for Electrically Stable Operating OFETs and Integrated Circuits.

Polyimides (PIs) are widely utilized polymeric materials for high-temperature plastics, adhesives, dielectrics, nonlinear optical materials, flexible hard-coating films, and substrates for flexible electronics. PIs can be facilely mass-produced through factory methods, so the industrial application value is limitless. Herein, we synthesized a typical poly(amic acid) (PAA) precursor-based solution through an industrialized reactor for mass production and applied the prepared solution to form thin films of PI using thermal imidization. The deposited PI thin films were successfully applied as gate dielectrics for organic field-effect transistors (OFETs). The PI layers showed suitable characteristics for dielectrics, such as a smooth surface, low leakage current density, uniform dielectric constant (k) values regardless of frequency, and compatibility with organic semiconductors. Utilizing this PI layer, we were able to fabricate electrically stable operated OFETs, which exhibited a threshold voltage shift lower than 1 V under bias-stress conditions and a field-effect mobility of 4.29 cm2 V-1 s-1. Moreover, integrated logic gates were manufactured using these well-operated OFETs and displayed suitable operation behavior.

Electrohydrodynamic-Jet-Printed Cinnamate-Fluorinated Cross-Linked Polymeric Dielectrics for Flexible and Electrically Stable Operating Organic Thin-Film Transistors and Integrated Devices.

Herein, printable polymer series containing different portions of cinnamate and perfluorinated phenyl functionalities, namely, polyperfluorostyrene-co-poly(vinylbenzyl cinnamates) (PFS-co-PVBCi (x:y)) copolymers, were synthesized and applied as gate dielectrics for organic thin-film transistors (OTFTs). The polymeric dielectrics were successfully printed via electrostatic force-assisted dispensing mode of electrohydrodynamic jet printing. The dielectric characteristics of the printed polymers, such as surface energy, dielectric constant, leakage current, atomic depth profiles, and deposited semiconducting layer characteristics, were clearly identified. In particular, the difference in driving stability of OTFTs according to the type of polymer was analyzed in detail and a possible mechanism was proposed. Results suggested that PFS-co-PVBCi (3:7) led to optimized consequences, yielding an almost negligible Vth shift under continuous bias stress. Through this, we successfully implemented flexible OTFT and logic devices using printed PFS-co-PVBCi (3:7) dielectrics with stable operation properties. Therefore, we believe that this study will facilitate the printing and synthesis of polymer dielectrics to produce printed and flexible OTFTs.

Strategy for Selective Printing of Gate Insulators Customized for Practical Application in Organic Integrated Devices.

Direct drawing techniques have contributed to the ease of patterning soft electronic materials, which are the building blocks of analog and digital integrated circuits. In parallel with the printing of semiconductors and electrodes, selective deposition of gate insulators (GI) is an equally important factor in simplifying the fabrication of integrated devices, such as NAND and NOR gates, and memory devices. This study demonstrates the fabrication of six types of printed GI layers (high/low-k polymer and organic-inorganic hybrid material), which are utilized as GIs in organic field-effect transistors (OFETs), using the electrostatic-force-assisted dispensing printing technique. The selective printing of GIs on the gate electrodes enables us to develop practical integrated devices that go beyond unit OFET devices, exhibiting robust switching performances, non-destructive operations, and high gain values. Moreover, the flexible integrated devices fabricated using this technique exhibit excellent operational behavior. Therefore, this facile fabrication technique can pave a new path for the production of practical integrated device arrays for next-generation devices.

Direct Printing of Asymmetric Electrodes for Improving Charge Injection/Extraction in Organic Electronics.

Engineering the energy levels of organic conducting materials can be useful for developing high-performance organic field-effect transistors (OFETs), whose electrodes must be well controlled to facilitate easy charge carrier transport from the source to drain through an active channel. However, symmetric source and drain electrodes that have the same energy levels are inevitably unfavorable for either charge injection or charge extraction. In this study, asymmetric source and drain electrodes are simply prepared using the electrohydrodynamic (EHD)-jet printing technique after the careful work function engineering of organic conducting material composites. Two types of additives effectively tune the energy levels of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-based composites. These solutions are alternately patterned using the EHD-jet printing process, where the use of an electric field makes fine jet control that enables to directly print asymmetric electrodes. The asymmetric combination of EHD-printed electrodes helps in obtaining advanced charge transport properties in p-type and n-type OFETs, as well as their organic complementary inverters. This strategy is believed to provide useful guidelines for the facile patterning of asymmetric electrodes, enabling the desirable properties of charge injection and extraction to be achieved in organic electronic devices.

Side chain engineering in DTBDT-based small molecules for efficient organic photovoltaics.

A new small-molecule donor with a dithieno[2,3-d:2',3'-d']-benzo[1,2-b:4,5-b']-dithiophene (DTBDT) core and both alkyl and alkylthio substituents is designed and synthesized to improve the miscibility between DTBDT-based small molecules and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). The alkyl substituent on the 4-position and the alkylthio substituent on the 5-position of the substituted thiophene are expected to improve intermolecular interactions and prevent severe aggregation of the small molecules. The new small molecule, DTBDT-S-C8-TTR, exhibits a homogenous blend morphology with small domains and edge-on-oriented crystalline structures in blends with PC71BM, and give a maximum power conversion efficiency (PCE) of 8.43%. To recover the crystallinity of the DTBDT-S-C8-TTR small molecules weakened after being blended with PC71BM, a solvent vapor annealing (SVA) treatment is performed. The SVA-treated blend films reveal well-developed crystalline domains with interconnected fibrillar structures. This blend morphology allows efficient charge carrier transport in blends and leads to increased PCEs. The maximum PCE of 9.18% achieved using DTBDT-S-C8-TTR suggests that substituting both alkylthio and alkyl groups into DTBDT can yield small-molecule-based organic photovoltaics (OPVs) displaying improved photovoltaic performances.

Acene-Modified Small-Molecule Donors for Organic Photovoltaics.

A series of acene-modified small molecules have been designed and synthesized, and their photovoltaic characteristics were studied by using the small molecules in organic photovoltaics (OPVs). Different cores were introduced to modulate the conjugation lengths of the small molecules and the bulk heterojunction (BHJ) morphologies. Three small-molecule donors were prepared, namely Ph-TTR, Na-TTR, and An-TTR, which have phenyl, naphthalene, and anthracene moieties, respectively, as conjugated cores. These donors were synthesized in a few steps and exhibited favorable BHJ morphologies, thereby giving promising power conversion efficiencies (PCEs). The donors showed excellent miscibility with the acceptor PC71 BM, and the use of the additive 1,8-diiodooctane (DIO) led to a remarkable increase in crystallinity, thereby increasing the PCEs of their OPVs. Of the three donors, Na-TTR showed the most efficient charge carrier generation and favorable molecular packing structures; hence, of the three types of devices tested, the Na-TTR:PC71 BM devices exhibited the highest PCE, specifically 6.27 %, without pre- or post-treatments. The promising PCEs achieved from these easily synthesized acene-modified small molecules suggested that acene-modified small molecules can be useful materials in OPVs.

Facile and Microcontrolled Blade Coating of Organic Semiconductor Blends for Uniaxial Crystal Alignment and Reliable Flexible Organic Field-Effect Transistors.

The ability to fabricate uniform and high-quality patterns of organic semiconductors using a simple method is necessary to realize high-performance and reliable organic field-effect transistors (OFETs) for practical applications. Here, we report the facile fabrication of chemically patterned substrates in order to provide solvent wetting/dewetting regions and grow patterned crystals during blade coating of a small-molecule semiconductor/insulating polymer blend solution. Polyurethane acrylate is selected as the solvent dewetting material, not only because of its hydrophobicity but also because its patterns are easily produced by selective UV irradiation onto precursor films. 6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) crystal patterns are grown on the line-shaped wetting regions of the patterned film, and the crystallinity of TIPS-PEN and alignment of molecules are found using various crystal analysis tools depending on the pattern widths. The smallest width of 5 µm yielded an OFET showing the highest field-effect mobility value of 1.63 cm2/(V·s), which is much higher than the value of the OFET based on the unpatterned TIPS-PEN crystal. Notably, we demonstrate flexible and low-voltage-operating OFETs for practical use of the patterned crystals, and the OFETs show highly stable operation under sustained gate bias stress thanks to the patterned crystals.

Morphology Driven by Molecular Structure of Thiazole-Based Polymers for Use in Field-Effect Transistors and Solar Cells.

The effects of the molecular structure of thiazole-based polymers on the active layer morphologies and performances of electronic and photovoltaic devices were studied. Thus, thiazole-based conjugated polymers with a novel thiazole-vinylene-thiazole (TzVTz) structure were designed and synthesized. The TzVTz structure was introduced to extend the π conjugation and coplanarity of the polymer chains. By combining alkylthienyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) or dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) electron-donating units and a TzVTz electron-accepting unit, enhanced intermolecular interactions and charge transport were obtained in the novel polymers BDT-TzVTz and DTBDT-TzVTz. With a view to using the polymers in transistor and photovoltaic applications, the molecular self-assembly in and their nanoscale morphologies of the active layers were controlled by thermal annealing to enhance the molecular packing and by introducing a diphenyl ether solvent additive to improve the miscibility between polymer donors and [6,6]phenyl-C71-butyric acid methyl ester (PC71 BM) acceptors, respectively. The morphological characterization of the photoactive layers showed that a higher degree of π-electron delocalization and more favorable molecular packing in DTBDT-TzVTz compared with in BDT-TzVTz leads to distinctly higher performances in transistor and photovoltaic devices. The superior performance of a photovoltaic device incorporating DTBDT-TzVTz was achieved through the superior miscibility of DTBDT-TzVTz with PC71 BM and the improved crystallinity of DTBDT-TzVTz in the nanofibrillar structure.

Enhanced chemical and physical properties of PEDOT doped with anionic polyelectrolytes prepared from acrylic derivatives and application to nanogenerators.

Acrylic monomers, 4-hydroxybutyl acrylate (HBA) and 2-carboxyethyl acrylate (CEA), were each co-polymerized with styrene sulfonate in 10 mol% ratio to synthesize two types of anionic polyelectrolytes, P(SS-co-HBA) and P(SS-co-CEA), respectively. Through oxidative polymerization, two types of PEDOT composites (PEDOT:P(SS-co-HBA) and PEDOT:P(SS-co-CEA)) were synthesized, to which the anionic templates were applied as dopants. The composites were similar to PEDOT:PSS; however, crosslinking occurred with an increase in annealing temperature after film casting, which increased the electrical conductivity and hydrophobicity. The composites were applied as electrodes to PVDF-based piezoelectric nanogenerators (PNGs) having an electrode/PVDF/electrode structure. The output voltage, current, and maximum output power of PNG-2D(60) (PEDOT:P(SS-co-HBA)) annealed at a mild temperature (60 °C) were 4.12 V, 817.3 nA, and 847.5 nW, respectively, while those of PNG-3D(60) (PEDOT:P(SS-co-CEA)) annealed at 60 °C were 3.75 V, 756.5 nA, and 716.9 nW, respectively. Thus, the composites showed 13.4% and 11.3% improvements in the maximum output power compared with that of PNG-2D & 3D(RT) dried at room temperature, respectively. These results indicated 27.4% and 7.8% improvements, respectively, compared with PNG-1D(60) in which PEDOT:PSS without any crosslinking effect was applied. The PNGs demonstrated high potential as power sources owing to their sensitivity and excellent charging voltage performance for a 1 µF capacitor.

Understanding Structure-Property Relationships in All-Small-Molecule Solar Cells Incorporating a Fullerene or Nonfullerene Acceptor.

To investigate the influence of donor molecule crystallinity on photovoltaic performance in all-small-molecule solar cells, two dithieno[2,3- d:2',3'- d']-benzo[1,2- b:4,5- b']dithiophene (DTBDT)-based small molecules, denoted as DTBDT-Rho and DTBDT-S-Rho and incorporating different side chains, are synthesized and characterized. The photovoltaic properties of solar cells made of these DTBDT-based donor molecules are systemically studied with the [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) fullerene acceptor and the O-IDTBR nonfullerene acceptor to study the aggregation behavior and crystallinity of the donor molecules in both blends. Morphological analyses and a charge carrier dynamics study are carried out simultaneously to derive structure-property relationships and address the requirements of all-small-molecule solar cells. This study reveals exciton decay loss driven by large-scale phase separation of the DTBDT molecules to be a crucial factor limiting photocurrent generation in the all-small-molecule solar cells incorporating O-IDTBR. In the all-small-molecule blends, DTBDT domains with dimensions greater than 100 nm limit the exciton migration to the donor-acceptor interface, whereas blends with PC71BM exhibit homogeneous phase separation with smaller domains than in the O-IDTBR blends. The significant energy losses in nonfullerene-based devices lead to decreased Jsc and fill factor values and unusual decrease in Voc values. These results indicate the modulation of phase separation to be important for improving the photovoltaic performances of all-small-molecule blends. In addition, the enhanced molecular aggregation of DTBDT-S-Rho with the alkylthio side chain leads to higher degrees of phase separation and unfavorable charge transfer, which are mainly responsible for the relatively low photocurrent when using DTBDT-S-Rho compared with that when using DTBDT-Rho. On the other hand, this enhanced molecular aggregation improves the crystallinity of DTBDT-S-Rho and results in its increased hole mobility.

Surface Modification of CdSe Quantum-Dot Floating Gates for Advancing Light-Erasable Organic Field-Effect Transistor Memories.

Photoresponsive transistor memories that can be erased using light-only bias are of significant interest owing to their convenient elimination of stored data for information delivery. Herein, we suggest a strategy to improve light-erasable organic transistor memories, which enables fast "photoinduced recovery" under low-intensity light. CdSe quantum dots (QDs) whose surfaces are covered with three different organic molecules are introduced as photoactive floating-gate interlayers in organic transistor memories. We determine that CdSe QDs capped or surface-modified with small molecular ligands lead to efficient hole diffusion from the QDs to the conducting channel during "photoinduced recovery", resulting in faster erasing times. In particular, the memories with QDs surface-modified with fluorinated molecules function as normally-ON type transistor memories with nondestructive operation. These memories exhibit high memory ratios over 105 between OFF and ON bistable current states for over 10 000 s and good dynamic switching behavior with voltage-driven programming processes and light-assisted erasing processes within 1 s. Our study provides a useful guideline for designing photoactive floating-gate materials to achieve desirable properties of light-erasable organic transistor memories.

Three-Dimensional Observation of a Light-Soaked Photoreactant Layer in BTR:PCBM Solar Cells Treated with/without Solvent Vapor Annealing.

A key challenge to the commercialization of solution-processed solar cells is a proper understanding of the morphological variations during long periods, particularly under light-soaking conditions. Many research groups have competitively reported solvent vapor annealing (SVA)-treated small-molecule devices with efficiency rates exceeding 11%; however, their light-soaking effects have been rarely studied. Here, we investigate the morphological changes in the light-soaked devices with/without SVA treatments depending on the illumination time via three-dimensional observations. From the results, we found that the trends of morphological variations differ in the surface and bulk parts of the active film and that the difference is closely related to the device performance capabilities. Therefore, our research will enhance the underlying knowledge of the light-soaking effect on active morphologies over long term.

All-Small-Molecule Solar Cells Incorporating NDI-Based Acceptors: Synthesis and Full Characterization.

A series of naphthalene diimide (NDI)-based small molecules were synthesized as nonfullerene acceptors and incorporated in all-small-molecule solar cells. Three NDI-based small molecules, NDICN-T, NDICN-BT, and NDICN-TVT, were designed with different linkers between two NDI units to induce the different conjugation length and modulate the geometric structures of the NDI dimers. The small NDI-based dimer electron acceptors with slip-stacked structures that facilitate π-π stacking interactions and/or hinder excessive aggregation exhibited different morphological behaviors, such as miscibility or crystallinity in bulk heterojunction blends with 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (DTS-F) electron donors. The photovoltaic devices prepared with NDICN-TVT gave the highest power conversion efficiency (PCE) of 3.01%, with an open-circuit voltage (Voc) of 0.75 V, a short-circuit current density (Jsc) of 7.10 mA cm-2, and a fill factor of 56.2%, whereas the DTS-F:NDICN-T and DTS-F:NDICN-BT devices provided PCEs of 1.81 and 0.13%, respectively. Studies of the charge-generation properties, charge-transfer dynamics, and charge-transport properties for understanding the structure-property relations revealed that DTS-F:NDICN-TVT blend films with well-developed domains and well-ordered crystalline structures performed well, whereas an excessive miscibility between DTS-F and NDICN-BT disrupted the crystallinity of the material and yielded a poor device performance.

Directionally Aligned Amorphous Polymer Chains via Electrohydrodynamic-Jet Printing: Analysis of Morphology and Polymer Field-Effect Transistor Characteristics.

Electrohydrodynamic-jet (EHD-jet) printing provides an opportunity to directly assembled amorphous polymer chains in the printed pattern. Herein, an EHD-jet printed amorphous polymer was employed as the active layer for fabrication of organic field-effect transistors (OFETs). Under optimized conditions, the field-effect mobility (µFET) of the EHD-jet printed OFETs was 5 times higher than the highest µFET observed in the spin-coated OFETs, and this improvement was achieved without the use of complex surface templating or additional pre- or post-deposition processing. As the chain alignment can be affected by the surface energy of the dielectric layer in EHD-jet printed OFETs, dielectric layers with varying wettability were examined. Near-edge X-ray absorption fine structure measurements were performed to compare the amorphous chain alignment in OFET active layers prepared by EHD-jet printing and spin coating.

Direct Writing and Aligning of Small-Molecule Organic Semiconductor Crystals via "Dragging Mode" Electrohydrodynamic Jet Printing for Flexible Organic Field-Effect Transistor Arrays.

Patterning and aligning of organic small-molecule semiconductor crystals over large areas is an important issue for their commercialization and practical device applications. This Letter reports "dragging mode" electrohydrodynamic jet printing that can simultaneously achieve direct writing and aligning of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) crystals. Dragging mode provides favorable conditions for crystal growth with efficient controls over supply voltages and nozzle-to-substrate distances. Optimal printing speed produces millimeter-long TIPS-PEN crystals with unidirectional alignment along the printing direction. These crystals are highly crystalline with a uniform packing structure that favors lateral charge transport. Organic field-effect transistors (OFETs) based on the optimally printed TIPS-PEN crystals exhibit high field-effect mobilities up to 1.65 cm2/(V·s). We also demonstrate the feasibility of controlling pattern shapes of the crystals as well as the fabrication of printed flexible OFET arrays.

Markedly different molecular formation in DPP-based small-molecule solar cells probed by grazing-incidence wide-angle X-ray scattering.

This study comprehensively explores the nanostructural properties of two diketopyrrolo[3,4-c]pyrrole-1,4-dione (DPP)-based small molecules with different alkyl side groups and their blends with the fullerene derivative PC71BM, using grazing-incidence wide-angle X-ray scattering synchrotron techniques. Preferentially relative face-on orientation within the larger and more ordered stacking phase of SM1 with its shorter side group (ethylhexyl) was observed in the majority of both pristine and blend thin films, whereas SM2 crystals showed strictly perpendicular orientation. These contrasting crystalline characteristics led to significant differences in the results, from which crystalline structure-performance property correlations are proposed. Thus, the results not only demonstrate important scientific insights into the relationship between molecular structure and crystalline formation but also provide molecular design directions that will facilitate further improvement to the morphology and performance of DPP-based small-molecule solar cells.

Anomalous Ambipolar Transport of Organic Semiconducting Crystals via Control of Molecular Packing Structures.

Organic crystals deposited on 2-dimensional (2D) van der Waals substrates have been widely investigated due to their unprecedented crystal structures and electrical properties. van der Waals interaction between organic molecules and the substrate induces epitaxial growth of high quality organic crystals and their anomalous crystal morphologies. Here, we report on unique ambipolar charge transport of a "lying-down" pentacene crystal grown on a 2D hexagonal boron nitride van der Waals substrate. From in-depth analysis on crystal growth behavior and ultraviolet photoemission spectroscopy measurement, it is revealed that the pentacene crystal at the initial growth stage have a lattice-strained packing structure and unique energy band structure with a deep highest occupied molecular orbital level compared to conventional "standing-up" crystals. The lattice-strained pentacene few layers enable ambipolar charge transport in field-effect transistors with balanced hole and electron field-effect mobilities. Complementary logic circuits composed of the two identical transistors show clear inverting functionality with a high gain up to 15. The interesting crystal morphology of organic crystals on van der Waals substrates is expected to attract broad attentions on organic/2D interfaces for their electronic applications.

Photoinduced Recovery of Organic Transistor Memories with Photoactive Floating-Gate Interlayers.

Optical memories based on photoresponsive organic field-effect transistors (OFETs) are of great interest due to their unique applications, such as multibit storage memories and flexible imaging circuits. Most studies of OFET-type memories have focused on the photoresponsive active channels, but more useful functions can be additionally given to the devices by using floating gates that can absorb light. In this case, effects of photoirradiation on photoactive floating-gate layers need to be fully understood. Herein, we studied the photoinduced erasing effects of floating-gate interlayers on the electrical responses of OFET-type memories and considered the possible mechanisms. Polymer/C60 composites were inserted between pentacene and SiO2 to form photoresponsive floating-gate interlayers in transistor memory. When exposed to light, C60 generated excitons, and these photoexcited carriers contributed to the elimination of trapped charge carriers, which resulted in the recovery of OFET performance. Such memory devices exhibited bistable current states controlled with voltage-driven programming and light-driven erasure. Furthermore, these devices maintained their charge-storing properties over 10 000 s. This proof-of-concept study is expected to open up new avenues in information technology for the development of organic memories that exhibit photoinduced recovery over a wide range of wavelengths of light when combined with appropriate photoactive floating-gate materials.

Dithienobenzodithiophene-Based Small Molecule Organic Solar Cells with over 7% Efficiency via Additive- and Thermal-Annealing-Free Processing.

Here we introduce a novel small molecule based on dithienobenzodithiophene and rhodanine, DTBDT-Rho, developed to study the effect of the rhodanine substitutuent on small molecule bulk heterojunction (BHJ) solar cells. DTBDT-Rho possesses distinct crystalline characteristics, sufficient solubility in chlorinated solvents, and broad absorption properties. Therefore, solution-processed BHJ photovoltaic cells made with DTBDT-Rho:PC71BM blends showed an extremely high power conversion efficiency (PCE; 7.10%); notably, this PCE value was obtained without the use of additives or thermal treatments. To our knowledge, the PCE over 7% is a significantly powerful value among rhodanine-based small molecule BHJ solar cells without additives or thermal treatments.