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When designing organic semiconductors, side-chain engineering is as important as modifying the conjugated backbone, which has a significant impact on molecular ordering, morphology, and thus electronic device performance. We have developed three dicyanovinyl-end-capped donor-acceptor diketopyrrolopyrrole-based n-type small molecules (C2C9CN, SiC4CN, and EH4PCN) bearing an identical length of alkyl spacer yet different end-functionalized side chains (i.e., alkyl-, siloxane-, and phosphonate-end pendants). The effects of the end-functionalized side chains on the intrinsic molecular properties, microstructure, and charge transport of the small-molecule series were investigated. In comparison with the alkyl-end side chains, incorporating siloxane-end side chains into the backbone facilitates 2D edge-on oriented high intergrain connectivity/crystallinity and compatibility with the substrate surface, whereas the phosphonate-end analogues have an adverse effect on the film-forming quality due to high polarity. Thereby, an organic field-effect transistor fabricated by SiC4CN shows the best electron mobility up to 1.59 × 10-1 cm2 V-1 s-1 along with a high current on/off ratio >105. This study contributes to our understanding of the role of the end-functionalized side chains (e.g., the effects of polarity and bulkiness of the end groups) for the development of high-performance semiconductors.

One-dimensional (1D) organic chiral supramolecules have received a great deal of attention for their promising applications in chiral recognition systems, chemical sensors, catalysts, and optoelectronics. Compared to modifications at the imide position of a perylene diimide (PDI), few studies have explored bay substitution of chiral PDIs and their self-assemblies into 1D nanomaterials. Herein, we describe the synthesis of three bay-substituted PDIs and explore the effects of bay substitution on supramolecular chirality by examining circular dichroism spectra and the optoelectronic performance of chiral PDI nanomaterials in phototransistors. Among the three fabricated self-assemblies, nanomaterials based on (R)-CN-CPDI-Ph exhibited the highest electron mobility of 0.17 cm2 V-1 s-1, a low threshold voltage of -1 V, and enhanced optoelectronic performance. For example, the photoresponsivity and external quantum efficiency of (R)-CN-CPDI-Ph assemblies were 4-fold higher than those of (R)-2Br-CPDI-Ph and (R)-2F-CPDI-Ph. All three nanomaterials exhibited fast switching speeds compared with previously reported N-substituted PDIs, suggesting that bay substitution can be an effective means of achieving rapid photoswitching. A comprehensive study using density functional theory calculations and crystal analyses revealed that the enhanced optoelectronic performance of (R)-CN-CPDI-Ph nanomaterials is related to the substitution of CN at the bay position of PDI. This minor change provides simultaneous improvements in electron injectability and structural order. Our findings demonstrate that bay substitution can significantly impact the self-assembly, supramolecular chirality, and optoelectronic properties of PDI nanomaterials.

Organic phototransistors (OPTs) have been widely used in biomedical sensing, optical communications, and imaging. Charge-trapping effect has been utilized as an effective strategy for enhancing their photoresponsivity by effectively decreasing the dark current. The combination of organic semiconductors (OSCs), especially chiral OSCs, with insulating polymers has rarely been carried out for optoelectronic applications. Here, we fabricated OPTs containing both enantiopure and racemic air-stable n-type perylene diimide derivatives, CPDI-CN2-C6, and insulating biopolymer polylactide (PLA) and evaluated their photoresponsive properties. The PLA-blended systems exhibited greatly enhanced optoelectronic performances owing to the intense charge-trapping effect. Interestingly, the racemic system showed 3 times higher electron mobility and 12 times higher specific detectivity (1.3 × 1013 jones) compared with the enantiopure systems due to the more aggregated morphologies and larger grains, indicating that chiral composition can be used as a tuning parameter in optoelectronic devices. Our systematic study provides a feasible and effective method for producing high-performance n-type OPTs under ambient conditions.

Chiral organic optoelectronics using circularly polarized light (CPL) as the key element in the photonic signal has recently emerged as a next-generation photonic technology. However, it remains challenging to simultaneously achieve high polarization selectivity and superior optoelectronic performance. Supramolecular two-dimensional (2D) chiral organic single crystals may be good candidates for this purpose due to their defect-free nature, molecular diversity, and morphologies. Here, quasi-2D single crystals of chiral perylene diimides with parallelogram and triangle/hexagon morphologies have been selectively fabricated

Multifunctional hydrogels with properties including transparency, flexibility, self-healing, and high electrical conductivity have attracted great attention for their potential application to soft electronic devices. The presence of an ionic species can make hydrogels conductive in nature. However, the conductivity of hydrogels is often influenced by temperature, due to the change of the internal nano/microscopic structure when temperature reaches the sol-gel phase transition temperature. In this regard, by introducing a novel surface-capacitive sensor device based on polymers with lower critical solution temperature (LCST) behavior, near-perfect stimulus discriminability of touch and temperature may be realized. Here, we demonstrate a multimodal sensor that can monitor the location of touch points and temperature simultaneously, using poly(N-isopropylacrylamide) (PNIPAAm) in hybrid poly(vinyl alcohol) (PVA) and sodium tetraborate decahydrate cross-linked hydrogels doped with poly(sodium acrylate) (SA) [w/w/w = 5:2.7:1-3]. This multimodal sensor exhibits a response time of 0.3 s and a temperature coefficient of resistance of -0.58% K-1 from 20 to 40 °C. In addition, the LCST behavior of PNIPAAm-incorporated PVA/SA gels is investigated. Incorporation of LCST polymers into high-end hydrogel systems may contribute to the development of temperature-dependent soft electronics that can be applied in smart windows.

Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal-organic frameworks for micro/nanooptoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital level of the ligands provide charge carriers that can undergo "through-space" transport between π-π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro/nanooptoelectronic applications.

Bioelectronics for healthcare that monitor the health information on users in real time have stepped into the limelight as crucial electronic devices for the future due to the increased demand for "point-of-care" testing, which is defined as medical diagnostic testing at the time and place of patient care. In contrast to traditional diagnostic testing, which is generally conducted at medical institutions with diagnostic instruments and requires a long time for specimen analysis, point-of-care testing can be accomplished personally at the bedside, and health information on users can be monitored in real time. Advances in materials science and device technology have enabled next-generation electronics, including flexible, stretchable, and biocompatible electronic devices, bringing the commercialization of personalized healthcare devices increasingly within reach, e.g., wearable bioelectronics attached to the body that monitor the health information on users in real time. Additionally, the monitoring of harmful factors in the environment surrounding the user, such as air pollutants, chemicals, and ultraviolet light, is also important for health maintenance because such factors can have short- and long-term detrimental effects on the human body. The precise detection of chemical species from both the human body and the surrounding environment is crucial for personal health care because of the abundant information that such factors can provide when determining a person's health condition. In this respect, sensor applications based on an organic-transistor platform have various advantages, including signal amplification, molecular design capability, low cost, and mechanical robustness (e.g., flexibility and stretchability). This Account covers recent progress in organic transistor-based chemical sensors that detect various chemical species in the human body or the surrounding environment, which will be the core elements of wearable electronic devices. There has been considerable effort to develop high-performance chemical sensors based on organic-transistor platforms through material design and device engineering. Various experimental approaches have been adopted to develop chemical sensors with high sensitivity, selectivity, and stability, including the synthesis of new materials, structural engineering, surface functionalization, and device engineering. In this Account, we first provide a brief introduction to the operating principles of transistor-based chemical sensors. Then we summarize the progress in the fabrication of transistor-based chemical sensors that detect chemical species from the human body (e.g., molecules in sweat, saliva, urine, tears, etc.). We then highlight examples of chemical sensors for detecting harmful chemicals in the environment surrounding the user (e.g., nitrogen oxides, sulfur dioxide, volatile organic compounds, liquid-phase organic solvents, and heavy metal ions). Finally, we conclude this Account with a perspective on the wearable bioelectronics, especially focusing on organic electronic materials and devices.

Improving the charge-carrier mobility of conjugated polymers is important for developing high-performance, solution-processed optoelectronic devices. Although [1]benzothieno[3,2-b]benzothiophene (BTBT) has been frequently used as a high-performance p-type small molecular semiconductor and employed a few times as a building block for p-type conjugated polymers, it has never been explored as a donor moiety for high-performance n-type conjugated polymers. Here, BTBT has been conjugated with either n-type perylene diimide (PDI) or naphthalene diimide (NDI) units to generate a donor–acceptor copolymer backbone, for the first time. Charge-transport measurements of organic field-effect transistors show n-type dominant behaviors, with the electron mobility reaching ∼0.11 cm2 V–1 s–1 for PDI–BTBT and ∼0.050 cm2 V–1 s–1 for NDI–BTBT. The PDI–BTBT mobility value is one of the highest among the PDI-containing polymers. The high π–π stacking propensity of BTBT significantly improves the charge-carrier mobility in thes...

By changing the rate of evaporation, two kinds of crystalline films composed of redox-active porous coordination networks (1 and 2) were selectively prepared on a gold-patterned substrate using a DMF solution of 2,5,8-tri(4-pyridyl)1,3-diazaphenalene and Cd(NO3)2. We found the highly sensitive humidity sensing ability of film 1. Single crystal structures and infrared spectroscopic analyses before and after hydration of a single crystal of 1 revealed the sensing mechanism: exchange of nitrate ions with water on Cd atoms occurred in hydrated conditions to generate a conductive cationic network.

We report eco- and human-friendly fabrication of organic field-effect transistors (OFETs) and polymer solar cells (PSCs) using only ethanol as a processing solvent at ambient condition, in stark contrast to that involving the use of halogenated and/or aromatic solvents. New ethanol-processable electroactive materials, p-type polymer (PPDT2FBT-A) and n-type bis-adduct fullerene acceptor (Bis-C60-A) are designed rationally by incorporation of oligoethylene glycol (OEG) side-chains. By ethanol processing, PPDT2FBT-A shows a broad light absorption in the range of 300–700 nm and highly crystalline interchain ordering with out-of-plane interlamellar scattering up to (400) with strong π–π stacking. As a result, the ethanol-processed PPDT2FBT-A OFETs yield high charge-carrier mobilities up to 1.0 × 10–2 cm2 V–1 s–1, which is the highest value reported to date from alcohol-processed devices. Importantly, the ethanol-processed PPDT2FBT-A OFET outperformed that processed using typical processing solvent, chlorobenze...

The π-extended (E)-2-(2-(thiophen-2-yl)-vinyl)thiophene (TVT)-based polymers are an interesting class of semiconducting polymers because of their excellent mobilities and unique film microstructures. Despite these properties, the effect of the side-chain regiochemistry of TVT skeletons on the intrinsic properties of these polymers remains unclear. To investigate this, in this study, hexyl-substituted TVT subunits with a “tail in (TI)” or “tail out (TO)” regiosymmetrical arrangement were first introduced into diketopyrrolopyrrole (DPP)-based copolymer main chains to afford “isomeric” polymers PI and PO, respectively. By combining optical spectroscopy, atomic force microscopy (AFM), and grazing incidence X-ray diffraction (GIXD) data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of both polymer films, which were then correlated to the charge-carrier mobilities. The PI film exhibited a bimodal packing motif comprising a mixture of edge-on and face-on orientations...

To achieve extremely high planarity and processability simultaneously, we have newly designed and synthesized copolymers composed of donor units of 2,2'-(2,5-dialkoxy-1,4-phenylene)dithieno[3,2-b]thiophene (TT-P-TT) and acceptor units of diketopyrrolopyrrole (DPP). These copolymers consist of a highly planar backbone due to intramolecular interactions. We have systematically investigated the effects of intermolecular interactions by controlling the side chain bulkiness on the polymer thin-film morphologies, packing structures, and charge transport. The thin-film microstructures of the copolymers are found to be critically dependent upon subtle changes in the intermolecular interactions, and charge transport dynamics of the copolymer based field-effect transistors (FETs) has been investigated by in-depth structure-property relationship study. Although the size of the fibrillar structures increases as the bulkiness of the side chains in the copolymer increases, the copolymer with the smallest side chain shows remarkably high charge carrier mobility. Our findings reveal the requirement for forming efficient 3-D charge transport pathway and highlight the importance of the molecular packing and interdomain connectivity, rather than the crystalline domain size. The results obtained herein demonstrate the importance of tailoring the side chain bulkiness and provide new insights into the molecular design for high-performance polymer semiconductors.

To systematically address the intriguing question of how siloxane termini of the side chains relative to alkyl-terminal groups affect the various inherent properties of conjugated polymers—including optical, electrical, and morphological characteristics—we have synthesized model polymers (PDPPTT-RTG and PDPPTT-SiTG, together with an accompanying reference PDPPTT-ref) containing an identical backbone yet possessing different terminal groups. In order to fairly compare the end functionalities by eliminating molecular weight (Mn) and polydispersity index (PDI) variations that may act as complicating factors, the polymers used in this study have been controlled to have similar Mn and PDI by carefully optimizing the catalyst system and reaction conditions. Although the molecular packing and orientation behaviors of PDPPTT-RTG and PDPPTT-SiTG are very different from each other, both polymers exhibit very high mobility exceeding 4.5 cm2 V–1 s–1. More meaningfully, organic field-effect transistors (OFETs) based o...

Phototransistors based on organic photoactive materials combine tunable light absorption in the spectral region from ultraviolet to near-infrared with low-temperature processability over large areas on flexible substrates. However, they often exhibit low photoresponsivity because of low molar extinction coefficient of photoactive components. We report a simple, yet highly efficient solution method for enhancing the performance of organic phototransistors using ruthenium complex 1 (Ru-complex 1). An air-stable n-type organic semiconductor, N,N'-bis(2-phenylethyl)-perylene-3,4:9,10-tetracarboxylic diimide (BPE-PTCDI), has been deposited on a silicon wafer and a transparent polyimide (PI) substrate via thermal evaporation under vacuum. The BPE-PTCDI phototransistors functionalized with Ru-complex 1 exhibit ∼5000 times higher external quantum efficiency (EQE) than that of pristine BPE-PTCDI phototransistors, owing to the metal-ligand charge transfer (MLCT) from Ru-complex 1 to the active component of the device. In addition, a large 10 × 10 phototransistor array (2.5 × 2.5 cm(2)) has been prepared on a transparent PI substrate, showing distinct light mapping. The fabricated phototransistor array is highly flexible and twistable and works well under tensile and compressive strains. We believe that our simple method will pave a viable way for improvements in the photoresponsivity of organic semiconductors for applications in wearable organic optoelectronic devices.

We report a systematic investigation of the correlations between the electron mobility of polymer acceptors and the photovoltaic performances of all-polymer solar cells (all-PSCs) by using a series of naphthalene diimide (NDI)-based polymer acceptors. Polymer acceptors typically have much lower electron mobility than fullerenes, which is one of the main factors in limiting the performance of all-PSCs. In addition, the anisotropic charge transport properties of the polymers require careful control of their packing structure and orientation suitable for their use in all-PSCs. To control the planarity of the polymer backbone and enhance electron mobility, we introduce three different electron-rich units (i.e., thiophene (T), bithiophene (T2), and thienylene–vinylene–thienylene (TVT)) into the NDI-based polymers. Particularly, P(NDI2OD–TVT) polymers exhibit the highest electron mobility (2.31 cm2 V–1 s–1) in organic field-effect transistors owing to various factors including enhanced degree of coplanarity, st...

Systematic side-chain engineering has been performed for diketopyrrolopyrrole-selenophene vinylene selenophene (DPP-SVS) polymers to determine the optimal side-chain geometries for the most efficient charge transport, and the structure–property relationship has been thoroughly investigated using a range of analyses. A series of DPP-SVS polymers, ranging from 25-DPP-SVS to 32-DPP-SVS, with branched alkyl groups containing linear spacer groups from C2 to C9 has been synthesized, and the electrical performance of these polymers is significantly dependent on both the length of the spacer group and its odd–even characteristics. Spacer groups with even numbers of carbon atoms exhibit charge-carrier mobilities that are 1 order of magnitude higher than those with odd numbers of carbon atoms. The optimized charge transport has been obtained from 29-DPP-SVS with a C6 spacer, showing the maximum mobility of 13.9 cm2 V–1 s–1 (VGS, VDS = −100 V) and 17.8 cm2 V–1 s–1 (VGS, VDS = −150 V). Longer spacer groups deviate fr...

A new series of conjugated random terpolymers (PDPP2T-Se-Th) was synthesized from an electron-deficient diketopyrrolopyrrole (DPP)-based unit in conjugation with two electron-rich selenophene (Se) and thiophene (Th) species, with a view to inducing different crystalline behaviors of the polymers. The crystallinity of the polymers can be systematically controlled by tuning the ratio between Se and Th; an increase in Se content induced a remarkable increase in the melting and crystallization temperatures as well as the crystallinity of the PDPP2T-Se-Th terpolymers. These changes in the crystalline properties of polymers had a dramatic effect on the performances of organic field-effect transistors (OFETs) and polymer solar cells (PSCs). However, their effect on each type of devices was very different. The charge carrier mobilities of the PDPP2T-Se-Th terpolymers in OFET devices increased remarkably as the Se content increased in the polymers, showing that PDPP2T-Se100 with Se/Th ratio = 100/0 had very high h...

Over the past few years, one of the most remarkable advances in the field of polymer solar cells (PSCs) has been the development of fluorinated 2,1,3-benzothiadiazole (BT)-based polymers that lack the solid working principles of previous designs, but boost the power conversion efficiency. To assess a rich data set for the influence of the fluorinated BT units on the charge-transport characteristics in organic field-effect transistors (OFETs), we synthesized two new polymers (PDPP-FBT and PDPP-2FBT) incorporating diketopyrrolopyrrole (DPP) and either single- or double-fluorinated BT and thoroughly investigated them via a range of techniques. Unlike the small differences in the absorption properties of PDPP-FBT and its nonfluorinated analogue (PDPP-BT), the introduction of doubly fluorinated BT into the polymer backbone induces a noticeable change in its optical profiles and energy levels, which results in a slightly wider bandgap and deeper HOMO for PDPP-2FBT, relative to the others. Grazing incidence X-ray diffraction (GIXD) analysis reveals that both fluorinated polymer films have long-range orders along the out-of-plane direction, and π-π stacking in the in-plane direction, implying semicrystalline lamellar structures with edge-on orientations in the solid state. Thanks to the strong intermolecular interactions and highly electron-deficient π-systems driven by the inclusion of F atoms, the polymers exhibit electron mobilities of up to 0.42 and 0.30 cm2 V(-1) s(-1) for PDPP-FBT and PDPP-2FBT, respectively, while maintaining hole mobilities higher than 0.1 cm2 V(-1) s(-1). Our results highlight that the use of fluorinated BT blocks in the polymers is a promising molecular design strategy for improving electron transporting performance without sacrificing their original hole mobility values.

Recognizing the importance of molecular coplanarity and with the aim of developing new, ideal strong acceptor-building units in semiconducting polymers for high-performance organic electronics, herein we present a simplified single-step synthesis of novel vinylene- and acetylene-linked bis-benzothiadiazole (VBBT and ABBT) monomers with enlarged planarity relative to a conventionally used acceptor, benzothiadiazole (BT). Along these lines, four polymers (PDPP-VBBT, PDPP-ABBT, PIID-VBBT, and PIID-ABBT) incorporating either VBBT or ABBT moieties are synthesized by copolymerizing with centro-symmetric ketopyrrole cores, such as diketopyrrolopyrrole (DPP) and isoindigo (IID), and their electronic, physical, and transistor properties are studied. These polymers show relatively balanced ambipolar transport, and PDPP-VBBT yields hole and electron mobilities as high as 0.32 and 0.13 cm2 V–1 s–1, respectively. Interestingly, the acetylenic linkages lead to enhanced electron transportation in ketopyrrole-based polym...

A family of naphthalene diimide (NDI)-based donor (D)-acceptor (A) copolymers with various acene- (benzene (Bz), naphthalene (Np), and pyrene (Py)) and heteroacene-type (selenophene (Se) and thiophene (Th)) donor rings has been designed and synthesized as a means to systematically understand structure–property relationships on the subject of the structural factor and electron-donating capability of the donor portions for applications in organic field-effect transistors (OFETs) based on NDIs. Alongside of two categories dealing with the lack or existence of the heteroatoms in the donor framework, the resulting copolymers can also be classified into ‘thiophene-free’ D–A copolymers (PNDI-Bz, PNDI-Np, PNDI-Py, and PNDI-Se) and thiophene-containing copolymer (PNDI-Th). The results from optical and electronic properties lead to the determination that the empirical electron-donating strength of donor co-units is in the order of Bz < Np < Py < Th < Se. In contrast with the similarity of the LUMO levels (−3.73∼−3....

The development of a versatile method for nitrogen-doping of graphitic structure is an important challenge for many applications, such as energy conversions and storages and electronic devices. Here, we report a simple but efficient method for preparing nitrogen-doped graphene nanoplatelets via wet-chemical reactions. The reaction between monoketone (C═O) in graphene oxide (GO) and monoamine-containing compound produces imine (Shiff base) functionalized GO (iGO). The reaction between α-diketone in GO and 1,2-diamine (ortho-diamine)-containing compound gives stable pyrazine ring functionalized GO (pGO). Subsequent heat-treatments of iGO and pGO result in high-quality, nitrogen-doped graphene nanoplatelets to be designated as hiGO and hpGO, respectively. Of particular interest, hpGO was found to display the n-type field-effect transistor behavior with a charge neutral point (Dirac point) located at around -16 V. Furthermore, hpGO showed hole and electron mobilities as high as 11.5 and 12.4 cm(2)V(-1)s(-1), respectively.

We investigated electrical charge transport through individual strands of single-crystalline dipentyl perylene tetracarboxylic diimide (PTCDI-C5) and dioctyl perylene tetracarboxylic diimide (PTCDI...

A novel highly π-extended heteroacene with four symmetrically fused thiophene-ring units and solubilizing substituents at the terminal β-positions on the central ring, dithieno[2,3-d;2′,3′-d′]benzo[1,2-b;4,5-b′]dithiophene (DTBDT) was synthesized via intramolecular electrophilic coupling reaction. The α-positions availability in the DTBDT motif enables the preparation of solution-processable DTBDT-based polymers such as PDTBDT, PDTBDT-BT, PDTBDT-DTBT, and PDTBDT-DTDPP. Even with its highly extended acene-like π-framework, all polymers show fairly good environmental stability of their highest occupied molecular orbitals (HOMOs) from −5.21 to −5.59 eV. In the course of our study to assess a profile of semiconductor properties, field-effect transistor performance of the four DTBDT-containing copolymers via solution-process is characterized, and PDTBDT-DTDPP exhibits the best electrical performance with a hole mobility of 1.70 × 10–2 cm2 V–1 s–1. PDTBDT-DTDPP has a relatively smaller charge injection barrier ...

Conjugated polymers, in general, are unstable when exposed to air, solvent, or thermal treatment, and these challenges limit their practical applications. Therefore, it is of great importance to develop new materials or methodologies that can enable organic electronics with air stability, solvent resistance, and thermal stability. Herein, we have developed a simple but powerful approach to achieve solvent-resistant and thermally stable organic electronic devices with a remarkably improved air stability, by introducing an azide cross-linkable group into a conjugated polymer. To demonstrate this concept, we have synthesized polythiophene with azide groups attached to end of the alkyl chain (P3HT-azide). Photo-cross-linking of P3HT-azide copolymers dramatically improves the solvent resistance of the active layer without disrupting the molecular ordering and charge transport. This is the first demonstration of solvent-resistant organic transistors. Furthermore, the bulk-heterojunction organic photovoltaics (B...

5-Perfluorophenyl-11-phenyltetracene (FPPT) having both aryl (Ar) and perfluoroaryl (FAr) groups has been designed and synthesized to obtain well-defined π−π stacking structure of the tetracene core. Single-crystal X-ray analyses as well as photoconductivity and hole mobility measurements revealed that this strategy is promising for enhancement of the charge carrier properties.

A scalable synthesis of swallow-tailed quaterrylene diimides (STQDIs) and a method for the solution processing of sparingly soluble quaterrylene diimide (QDI) thin films are described. The pressure-assisted thermal cleavage of swallow tails yields crystalline QDI layers with electron mobility up to 0.088 cm(2) V(-1) s(-1). The developed method opens up a new route toward the solution processing of higher rylene diimides with poor solubility.

The effects of the interplay between energetic and kinetic factors on the air stability of n-channel organic thin-film transistors (OTFTs) were studied using two perylene diimide (PDI) compounds with distinctly different lowest unoccupied molecular orbital (LUMO) levels. On the basis of the empirical energy level windows, one compound (N,N′-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-3,4:9,10-tetracarboxylic acid diimide (PDI-F): −3.84 eV) is at the onset region for air stability, whereas the other (N,N′-bis(cyclohexyl)-1,7-dicyano-perylene-3,4:9,10-tetracarboxylic acid diimide (PDI-CN2): −4.33 eV) is in the air-stable region. Charge-transport behaviors under an inert atmosphere and in air were investigated as a function of active layer thickness. Charge transport in air was greatly affected by the active layer thickness for both compounds, an effect that has been overlooked so far. The ambient stability of the air-unstable PDI-F TFTs increased significantly for thicknesses over ∼10 monolayers (ML). Surprisin...

Poly(acrylonitrile) (PAN) nanotubes with tunable wall thickness were successfully fabricated using a modified vapor deposition polymerization technique. To enhance the uniformity, heptane was employed as a nonreactive solvent. It is revealed that the heptane vapor in the reaction vessel plays an important role for producing nanotubes with tunable and uniform wall thickness. In addition, photoluminescence dyes such as pyrene for blue emission and rhodamine B for red emission were employed as host materials. These dyes were loaded into the inner surface of the PAN nanotubes and effectively encapsulated with a supplemental PAN layer. Confocal laser scanning microscopy images confirmed the successful fabrication of PAN−dye−PAN nanotubes without phase separation of the organic dyes. The photoluminescent analysis demonstrated the effective confinement of pyrene as well as rhodamine B in the PAN layer with a varying concentration of pyrene and rhodamine B as a multi-emission polymer nanotube.

Evaporation-induced self-assemblies (EISAs) with various morphologies were selectively fabricated by drying a solution containing polypyrrole nanoparticles. The morphogenesis of EISAs was strongly dependent upon the solvent evaporation rate and the nanoparticle concentration. In the case of fast evaporation, 2-D dendrites or pseudo 1-D dendrites were observed. When the liquid medium evaporated slowly, ring and spherulitic assemblies took place. Multiple rings could be created on a substrate surface under one single drop.

The effects of terminal groups and composition of hyperbranched polymers (HBPs) on the crystallization behavior of poly(ethylene terephthalate) (PET) in HBP/PET blends were investigated using in situ FT-IR spectroscopy and differential scanning calorimetry. Hyperbranched aliphatic polyester was synthesized from an AB2 type monomer and a B3 type core. The hydroxyl terminal groups of the HBP were transformed into acetate and benzoate groups by organic synthetic methods. The effects of the HBPs were compared with those of linear polyester (LPE) synthesized from an AB type monomer and a B2 type core. A small amount of HBP with hydroxyl groups could greatly reduce the relative crystallinity of PET through hydrogen bonds. HBP with acetate groups showed effects similar to those of LPE. As the composition of LPE was increased, the relative crystallinity of PET was slightly decreased. On the contrary, HBP with benzoate groups played the role of nucleating agent in the blends with PET. The crystallization rate of PET was highest in the blend with 12 wt % HBP. Dynamic viscosity measurements were performed to investigate the role of the HBPs as processing aids.