Gi Xue

Solution coating of large-area organic semiconductor thin films with aligned single-crystalline domains

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

Highly stretchable polymer semiconductor films through the nanoconfinement effect

Trapping polymers to improve flexibility Polymer molecules at a free surface or trapped in thin layers or tubes will show different properties from those of the bulk. Confinement can prevent crystallization and oddly can sometimes give the chains more scope for motion. Xu et al. found that a conducting polymer confined inside an elastomer—a highly stretchable, rubber-like polymer—retained its conductive properties even when subjected to large deformations (see the Perspective by Napolitano). Science, this issue p. 59; see also p. 24 A high-performance conjugated polymer is combined with an elastomer to produce a fully stretchable transistor. Soft and conformable wearable electronics require stretchable semiconductors, but existing ones typically sacrifice charge transport mobility to achieve stretchability. We explore a concept based on the nanoconfinement of polymers to substantially improve the stretchability of polymer semiconductors, without affecting charge transport mobility. The increased polymer chain dynamics under nanoconfinement significantly reduces the modulus of the conjugated polymer and largely delays the onset of crack formation under strain. As a result, our fabricated semiconducting film can be stretched up to 100% strain without affecting mobility, retaining values comparable to that of amorphous silicon. The fully stretchable transistors exhibit high biaxial stretchability with minimal change in on current even when poked with a sharp object. We demonstrate a skinlike finger-wearable driver for a light-emitting diode.

Understanding Polymorphism in Organic Semiconductor Thin Films through Nanoconfinement

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.

The electrochemical copolymerization of pyrrole and furan in a novel binary solvent system

Electrochemical copolymerization of furan and pyrrole was performed potentiostatically in a binary solvent system consisting of boron trifluoride ethyl ether and additional ethyl ether. The influence of applied polymerization potential and the monomer feed ratio of furan and pyrrole on the synthesis of copolymer was investigated. The higher potential favored the incorporation of furan units into the copolymer, while the amount of pyrrole units incorporated into the film increased with the increasing concentration of pyrrole in the solution. The film obtained was characterized by cyclic voltammetry, infrared and Raman spectroscopies.

The formation of an effective anti-corrosion film on copper surfaces from 2-mercaptobenzimidazole solution

Abstract The formation of an effective anti-corrosion film on copper surfaces has been achieved by immersion of a chemically cleaned copper plate into a solution of 2-mercaptobenzimidazole in ethanol. This film is extremely stable as compared with the anti-corrosion layer formed on an oxidized surface. The formation mechanism and the structure of the inert film have been investigated by the use of infrared and X-ray photoelectron spectroscopy. Its anti-corrosion characteristics in several media were investigated by the use of cyclic voltammetry.

Synthesis and characterization of electrically conducting polyaniline in water–oil microemulsion

Nanoscopic polyaniline particles were successfully synthesized in a stable water–oil microemulsion. FT-IR spectra showed that sodium dodecylbenzenesulfonate (SDBA) acted both as surfactant and dopant in the acidic reaction media. Wide-angle X-ray diffraction, UV–visible spectra and thermal analysis suggested that the crystallinity of PANI synthesized in the microemulsion system was increased dramatically while the chain-transfer reactions of co-surfactants decreased the π-conjugation length along the polymer chain.

Preparation of electrically conducting polypyrrole in oil/water microemulsion

Nanoscopic conducting polypyrrole powder was prepared in an oil/water microemulsion with FeCl3 as a dopant. Compared with solution and conventional emulsion polymerizations, a microemulsion polymerization system increases the yield of the resultant polypyrrole. The results of FTIR spectra and thermal analysis studies indicate that the microemulsion polymerization system increased the extent of the π-conjugation length along the polymer backbone and ordered the arrangement of the macromolecule chains. These two effects bring about enhanced conductivity as well as higher thermal stability of polypyrrole.

Glass transition of nano-sized single chain globules

Abstract Nano-sized polymer globules were prepared by atomization spraying and drying of a dilute polymer solution. Transmission electron microscope measurements indicated that the particle of the globules matched with that of polymer single chains. Thermal analysis showed that the nano-sized particles exhibit a significantly higher glass transition temperature (Tg) than does the corresponding bulk polymer. This discovery cannot be explained by kinetic theories. Entropy analysis does indicate that polymer chains in the globular state should have a higher Tg.

Facile and controlled fabrication of functional gold nanoparticle-coated polystyrene composite particle.

Gold nanoparticles-coated polystyrene (AuNPs-coated PS) composite particles with raspberry-like morphology are successfully prepared with the aid of a unique thermodynamically driving effect. It is of considerable interest that the AuNPs generate and self-assemble with raw, ordinary PS microspheres that preexist in the oxidation-reduction systems. The synthesized AuNPs-coated PS composite particles have been extensively characterized using scanning electron microscope, transmission electron microscope, and UV-Vis-NIR spectroscopy. The results indicate that the morphology of the resultant composite particles is governed by simply changing the amount and type of reductants and the concentration of PS microspheres. The AuNPs-coated PS composite particles also exhibit the good surface-enhanced Raman scattering and catalytic performances.

Surface segregation of fluorinated moieties on random copolymer films controlled by random-coil conformation of polymer chains in solution.

The relationship between solution properties, film-forming methods, and the solid surface structures of random copolymers composed of butyl methacrylate and dodecafluorheptyl methylacrylate (DFHMA) was investigated by contact angle measurements, X-ray photoelectron spectroscopy, sum frequency generation vibrational spectroscopy, and surface tension measurements. The results, based on thermodynamic considerations, demonstrated that the random copolymer chain conformation at the solution/air interface greatly affected the surface structure of the resulting film, thereby determining the surface segregation of fluorinated moieties on films obtained by various film-forming techniques. When the fluorinated monomer content of the copolymer solution was low, entropic forces dominated the interfacial structure, with the perfluoroalkyl groups unable to migrate to the solution/air interface and thus becoming buried in a random-coil chain conformation. When employing this copolymer solution for film preparation by spin-coating, the copolymer chains in solution were likely extended due to centrifugal forces, thereby weakening the entropy effect of the polymer chains. Consequently, this resulted in the segregation of the fluorinated moieties on the film surface. For the films prepared by casting, the perfluoroalkyl groups were, similar to those in solution, incapable of segregating at the film surface and were thus buried in the random-coil chains. When the copolymers contained a high content of DFHMA, the migration of perfluoroalkyl groups at the solution/air interface was controlled by enthalpic forces, and the perfluoroalkyl groups segregated at the surface of the film regardless of the film-forming technique. The aim of the present work was to obtain an enhanced understanding of the formation mechanism of the chemical structure on the surface of the polymer film, while demonstrating that film-forming methods may be used in practice to promote the segregation of fluorinated moieties on film surfaces.