A highly durable, stretchable, transparent and conductive carbon nanotube-polymeric acid hybrid film.

We demonstrate a highly durable and stretchable carbon nanotube (CNT)-polymer transparent conductive film by utilizing polyacrylic acid wrapping to simultaneously disperse and dope CNTs. This novel strategy not only enables an easy and industrially scalable process where neither removal of dispersant nor further doping is necessary, but also results in a boost in the conductivity and durability, and correspondingly it provides infinite versatility for various applications. A significant improvement in conductivity being comparable to acid doping is achieved through a hybrid structure in which a polyacrylic acid monolayer helically and partially wraps the CNT surface. The optimum films show sheet resistances of 150 and 60 Ω per square at 91% and 84% optical transmittances, respectively. Notably, the sheet resistances of hybrid films remain almost constant after aging tests under conditions of 85 °C and 85% relative humidity for more than 3000 h, and bending and stretching tests of more than 1 million cycles, suggesting outstanding long-term stability and record-high flexibility and stretchability. Therefore, the highly transparent conductive film, combined with excellent long-term and mechanical durability, and surprisingly easy processability, opens new routes for next-generation wearable electronics and bioelectronics.

Light-induced mechanical response in crosslinked liquid-crystalline polymers with photoswitchable glass transition temperatures.

Energy conversion of light into mechanical work is of fundamental interest in applications. In particular, diligent molecular design on nanoscale, in order to achieve efficient photomechanical effects on macroscopic scale, has become one of the most interesting study topics. Here, by incorporating a "photomelting" azobenzene monomer crosslinked into liquid crystalline (LC) networks, we generate photoresponsive polymer films that exhibit reversible photoswitchable glass transition temperatures (Tg) at room temperature (~20 °C) and photomechanical actuations under the stimulus of UV/visible light. The trans-to-cis isomerization of azo chromophores results in a change in Tg of the crosslinked LC polymers. The Tg of the polymer network is higher than room temperature in the trans-form and lower than room temperature in the cis-form. We demonstrate the photoswitchable Tg contribute to the photomechanical bending and a new mechanism for photomechanical bending that attributes the process to an inhomogeneous change in Tg of the film is proposed.

Carbon nanotube based transparent conductive films: progress, challenges, and perspectives.

Developments in the manufacturing technology of low-cost, high-quality carbon nanotubes (CNTs) are leading to increased industrial applications for this remarkable material. One of the most promising applications, CNT based transparent conductive films (TCFs), are an alternative technology in future electronics to replace traditional TCFs, which use indium tin oxide. Despite significant price competition among various TCFs, CNT-based TCFs have good potential for use in emerging flexible, stretchable and wearable optoelectronics. In this review, we summarize the recent progress in the fabrication, properties, stability and applications of CNT-based TCFs. The challenges of current CNT-based TCFs for industrial use, in comparison with other TCFs, are considered. We also discuss the potential of CNT-based TCFs, and give some possible strategies to reduce the production cost and improve their conductivity and transparency.

Light-induced crawling of crystals on a glass surface.

Motion is an essential process for many living organisms and for artificial robots and machines. To date, creating self-propelled motion in nano-to-macroscopic-sized objects has been a challenging issue for scientists. Herein, we report the directional and continuous motion of crystals on a glass surface when irradiated simultaneously with two different wavelengths, using simple azobenzenes as a photoresponsive organic compound. The direction of the motion can be controlled by the position of the light sources, and the crystals can even climb vertical surfaces. The motion is driven by crystallization and melting at the front and rear edges of the crystal, respectively, via photochemical conversion between the crystal and liquid phases induced by the trans-cis isomerization of azobenzenes. This finding could lead to remote-controlled micrometre-sized vehicles and valves on solid substrates.

Understanding device-structure-induced variations in open-circuit voltage for organic photovoltaics.

We investigate the structural influences on the device performance, especially on open-circuit voltage (V(OC)) in squaraine (SQ)/fullerene (C60) bilayer cells. Simply changing the SQ thickness could lead to 40% variation in V(OC) from 0.62 to 0.86 V. The ionization potential (IP) of SQ films and recombination at the anode surface as well as donor/acceptor (D/A) interface sensitively vary with film thicknesses, which account for the shifts in V(OC). The anode recombination can be effectively suppressed by preventing direct contact between C60 and the anode with a buffer layer, delivering an elevated V(OC). Through polarized infrared-multiple-angle incidence resolution spectroscopy measurement, the molecular structure of SQ films is found to gradually evolve from lying-down on indium-tin oxide substrates with noncentrosymmetric orientation at low thicknesses to random structure at high thicknesses. The different molecular orientation may yield different strengths of electronic coupling, which affects the charge-carrier recombination and thus V(OC). Moreover, the oriented SQ films would spontaneously compose aligned dipole moments at the D/A interface because of the strong dipolar effects in SQ molecules identified by density functional theory calculations, whereas no aligned interfacial dipole moment exists in the random structure. The resulting interfacial dipole moments would form an electric field at the D/A interface, leading to variations in the IP and thus impacting V(OC). Our findings demonstrate that V(OC) in organic photovoltaic cells is critically associated with the molecular orientation that affects the charge-carrier recombination and interfacial dipole alignment, which should be seriously taken into consideration for the design of organic molecules and optimization of the cell efficiency.

Photoinduced crystal-to-liquid phase transitions of azobenzene derivatives and their application in photolithography processes through a solid-liquid patterning.

The direct and reversible transformation of matter between the solid and liquid phases by light at constant temperature is of great interest because of its potential applications in various manufacturing settings. We report a simple molecular design strategy for the phase transitions: azobenzenes having para-dialkoxy groups with a methyl group at the meta-position. The photolithography processes were demonstrated using the azobenzene as a photoresist in a single process combining development and etching of a copper substrate.

Crystal melting by light: X-ray crystal structure analysis of an azo crystal showing photoinduced crystal-melt transition.

Trans-cis photoisomerization in an azo compound containing azobenzene chromophores and long alkyl chains leads to a photoinduced crystal-melt transition (PCMT). X-ray structure analysis of this crystal clarifies the characteristic coexistence of the structurally ordered chromophores through their π···π interactions and disordered alkyl chains around room temperature. These structural features reveal that the PCMT starts near the surface of the crystal and propagates into the depth, sacrificing the π···π interactions. A temporal change of the powder X-ray diffraction pattern under light irradiation and a two-component phase diagram allow qualitative analysis of the PCMT and the following reconstructive crystallization of the cis isomer as a function of product accumulation. This is the first structural characterization of a compound showing the PCMT, overcoming the low periodicity that makes X-ray crystal structure analysis difficult.

Photochemically reversible liquefaction and solidification of multiazobenzene sugar-alcohol derivatives and application to reworkable adhesives.

Multiazobenzene compounds, hexakis-O-[4-(phenylazo)phenoxyalkylcarboxyl]-D-mannitols and hexakis-O-[4-(4-hexylphenylazo)phenoxyalkylcarboxyl]-D-mannitols, exhibit photochemically reversible liquefaction and solidification at room temperature. Their photochemical and thermal phase transitions were investigated in detail through thermal analysis, absorption spectroscopy, and dynamic viscoelasticity measurements, and were compared with those of other sugar-alcohol derivatives. Tensile shear strength tests were performed to determine the adhesions of the compounds sandwiched between two glass slides to determine whether the compounds were suitable for application as adhesives. The adhesions were varied by alternately irradiating the compounds with ultraviolet and visible light to photoinduce phase transitions. The azobenzene hexyl tails, lengths of the methylene spacers, and differences in the sugar-alcohol structures affected the photoresponsive properties of the compounds.

Control of the orientation and photoinduced phase transitions of macrocyclic azobenzene.

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups (1) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal-isotropic phase-crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be -0.84. Heating enhances the thermal cis-to-trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.

Simple push coating of polymer thin-film transistors.

Solution processibility is a unique advantage of organic semiconductors, permitting the low-cost production of flexible electronics under ambient conditions. However, the solution affinity to substrate surfaces remains a serious dilemma; liquid manipulation is more difficult on highly hydrophobic surfaces, but the use of such surfaces is indispensable for improving device characteristics. Here we demonstrate a simple technique, which we call 'push coating', to produce uniform large-area semiconducting polymer films over a hydrophobic surface with eliminating material loss. We utilize a poly(dimethylsiloxane)-based trilayer stamp whose conformal contact with the substrate enables capillarity-induced wetting of the surface. Films are formed through solvent sorption and retention in the stamp, allowing the stamp to be peeled perfectly from the film. The planar film formation on hydrophobic surfaces also enables subsequent fine film patterning. The technique improves the crystallinity and field-effect mobility of stamped semiconductor films, constituting a major step towards flexible electronics production.

"Click"-modification of a functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) soluble in organic solvents.

A PEDOT-based conductive copolymer soluble in organic solvents was synthesized electrochemically using dihexyl-EDOT and azidomethyl-EDOT as monomers and was successfully post-functionalized by "click"-cycloaddition reaction with a functionalized terminal alkyne under mild heterogeneous conditions.

Effect of subphase temperature on the phase-separated structures of mixed Langmuir and Langmuir-Blodgett films of fatty acids and hybrid carboxylic acids.

We examined the phase-separated structures of the mixed Langmuir-Blodgett (LB) films of C(k)H(2k+1)COOH (HkA: k=17, 21) and C(m)F(2m+1)C(10)H(20)COOH (FmH10A: m=6, 8) fabricated isothermally or after isobaric thermal treatments. Under isothermal fabrication conditions, disks and wire-type domains formed in the H17A/F6H10A LB films at high and low fabrication temperatures, respectively, because the line tension and dipole-dipole interaction were comparable with each other. The thermodynamically stable phases of H21A/F6H10A LB films at high and low fabrication temperatures were disks and polygonal domains, respectively. Isobaric thermal treatments of the Langmuir films affected the domain size and not the domain shape when the transfer temperature was the same. Isobaric thermal treatments were effective in controlling the domain size. The thermodynamically stable phases of both H17A/F8H10A LB films and H21A/F8H10A LB films were nanowires in the range of the fabrication temperatures studied. Isobaric thermal treatments of the Langmuir films did not affect the domain shape significantly and affected the domain size in both the LB films studied. The change in the value m of FmH10A was more effective in controlling the phase-separated structures of the mixed LB films than the value of k of HkA.

Soluble fullerene-based n-channel organic thin-film transistors printed by using a polydimethylsiloxane stamp.

A polydimethylsiloxane stamp was applied for the first time to the fabrication of n-channel thin-film transistors based on soluble small molecule organic semiconducting materials. The stamping method was found to facilitate film transfer onto a gate insulator surface irrespective of its surface free energy. We used [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) and C(60)-fused N-methylpyrrolidine-meta-dodecyl phenyl (C60MC12) as n-channel materials. The stamped thin-film transistors of C60MC12 achieved a high electron mobility of 0.39 cm(2)/(V s) and a current on-off ratio of 1 × 10(7). The mobility of the stamped C60MC12 thin-film transistors did not depend much on the surface free energy of the SiO(2) gate insulator with and without surface treatment using a silane-coupling reagent. In particular, the stamped C60MC12 thin-film transistor exhibited a relatively high mobility of 0.1 cm(2)/(V s) on a high energy surface of untreated SiO(2). In addition, a complementary inverter composed of an n-channel and a p-channel stamped thin-film transistor was demonstrated for the first time, which exhibits a maximum gain of 63 at a supply voltage of 50 V.

Patterning of J-aggregated dyes using directed self-assembly on micro- and nanopatterned templates fabricated from phase-separated mixed Langmuir-Blodgett films.

We report a useful technique for the deposition of dyes in the form of J-aggregates using directed self-assembly on the micro- and nanopatterned templates fabricated from the phase-separated mixed Langmuir-Blodgett (LB) films. The patterns of the mixed LB films can be tuned by adjusting the intermolecular interactions between the film-forming molecules. We used the mixed LB films containing silane coupling agent for the fabrication of micro- and nanopatterned templates, taking advantage of the difference between the surface free energy of the patterned regions and that of the self-assembled monolayers of the silane coupling agent. Atomic force microscopy showed that dyes were deposited by casting, spin-coating and the LB technique in accordance with the patterns of the original mixed LB films. Emission spectroscopy revealed that J-aggregates were formed in the patterned films. We succeeded in obtaining nanopatterns of a cyanine dye in the form of J-aggregates on the templates.

Multi-layered oriented polyfluorene films.

Multilayered oriented polyfluorene (PF) films were obtained by applying thermal treatment procedure to a multilayered PF film constructed with fluorene derivatives layer formed on top of a highly oriented friction-transferred crystalline poly(9,9-dioctylfluorene) (PF8) film. The orientations in the multilayered PF films were investigated by polarized photoluminescence (PL) spectroscopy and grazing incident X-ray diffraction (GIXD) analysis. The results of the multilayered PF film constructed with spin-coated PF8 on friction-transferred PF8 indicate that the rearrangement of the upper PF8 layer is induced from the orientation of lower PF8 layer by thermal treatment at the nematic phase temperature. Polarized green emission from the multilayered oriented PF film was demonstrated using the blend of PF8 and poly(9,9-dioctylfluorene-co-benzothiadiazol) (F8BT) as green light emitter for upper layer. By this method, the polarized emission color can be tuned using polymer blends for upper layer similar to the liquid-crystalline polymer arrangement without using different materials as an underlying layer such as the rubbed polyimide.

Phase-separated structures of mixed Langmuir-Blodgett films of fatty acid and hybrid carboxylic acid.

Phase separation often occurs in mixed Langmuir-Blodgett (LB) films. Usually circular domains at the micrometer length scale form in the LB films. The size and shape of the domains are governed by a compromise between two competing interactions of line tension and dipole-dipole interaction. An attempt was made to control the line tension by varying systematically the hydrophobic moieties of the film-forming molecules. Phase-separated structures of two-component mixed LB films of fatty acid [C(k)H(2k+1)COOH (HkA)] and hybrid carboxylic acid [C(m)F(2m+1)C(n)H(2n)COOH (FmHnA)] were investigated. IR spectra of the mixed LB films of H17A and F8H10A revealed that the alkyl chains were in an all-trans conformation and that the molecular orientation remained unchanged when the two components were mixed. Nanowires formed in the mixed LB films of HkA and F8H10A. The width of the nanowires increased with an increase in k. Domain size and shape in the mixed LB films of H17A and FmHnA depended strongly on the values of m and n. Circular domains at the micrometer length scale formed in the region m + n < 16. In contrast, domains at the nanometer length scale formed in the region m + n > or = 16 except for F6H10A. These results were explained by using a lattice model that considers the effect of the hydrophobic moieties of fatty acid and hybrid carboxylic acid on the line tension.

Micro- and nanopatterned copper structures using directed self-assembly on templates fabricated from phase-separated mixed Langmuir-Blodgett films.

We report a versatile method to confine metal thin films in micro- and nanopatterns using directed self-assembly on the templates fabricated from phase-separated mixed Langmuir-Blodgett (LB) films. The pattern of the mixed LB films can be tuned by adjusting intermolecular interaction between the film-forming molecules in the LB films and by varying the fabrication conditions of the films such as the mixing ratio, subphase temperature, and surface pressure. We use the patterned LB films for templates to confine metal in patterned regions, taking advantage of the difference between the surface free energy of the patterned regions and that of the self-assembled monolayer of the silane coupling agent. Au nanoparticles are confined onto the patterned films as a catalyst for the succeeding Cu electroless deposition. The atomic force microscopic images, Auger electron spectra, and scanning Auger electron maps of a Cu-deposited film show that Cu is selectively deposited on the patterns of phase separation of the original mixed LB films.

Crystal structure of friction-transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene).

Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat.

Monolayers assembled from a glycolipid biosurfactant from Pseudozyma (Candida) antarctica serve as a high-affinity ligand system for immunoglobulin G and M.

A carbohydrate ligand system has been developed which is composed of self-assembled monolayers (SAMs) of mannosylerythritol lipid-A (MEL-A) from Pseudozyma antarctica, serving for human immunoglobulin G and M (HIgG and HIgM). The estimated binding constants from surface plasmon resonance (SPR) measurement were Ka = 9.4 x 10(6) M(-1) for HIgG and 5.4 x 10(6) M(-1) for HIgM, respectively. The binding site was not in the Fc region of immunoglobulin but in the Fab region. Large amounts of HIgG and HIgM bound to MEL-A SAMs were directly observed by atomic force microscopy.

Correlation of the number of thiophene units with structural order and carrier mobility in unsubstituted even- and odd-numbered alpha-oligothiophene films.

We investigate the correlation of the number of thiophene units with the structural order and carrier mobility of the films through studies on thin-film transistors (TFTs) based on alpha-quinquethiophene (5T), alpha-sexithiophene (6T), and alpha-septithiophene (7T). The X-ray diffraction (XRD) data of the nT films deposited at low substrate temperatures present obviously different structural orders depending on the parity of the number of thiophene units. Although even-numbered nT films present well-ordered structures and large carrier mobilities, odd-numbered nT films present two different crystalline polymorphs and vastly low carrier mobilities reflecting the coexistence of two crystalline polymorphs. However, the XRD data of both even- and odd-numbered nT films deposited at high substrate temperatures indicate that the nT molecules form single well-ordered structures. Those ordered TFTs exhibit large carrier mobilities accompanying an increase in the number of thiophene units, 0.05, 0.08, and 0.13 cm2 V(-1) s(-1) for 5T, 6T, and 7T, respectively. The parity of the number of thiophene units affects the structural order intrinsically in grown thin films, and affects carrier mobilities extrinsically in their TFTs.