Flexible biomimetic block copolymer composite for temperature and long-wave infrared sensing.

Biological compounds often provide clues to advance material designs. Replicating their molecular structure and functional motifs in artificial materials offers a blueprint for unprecedented functionalities. Here, we report a flexible biomimetic thermal sensing (BTS) polymer that is designed to emulate the ion transport dynamics of a plant cell wall component, pectin. Using a simple yet versatile synthetic procedure, we engineer the physicochemical properties of the polymer by inserting elastic fragments in a block copolymer architecture, making it flexible and stretchable. The thermal response of our flexible polymer outperforms current state-of-the-art temperature sensing materials, including vanadium oxide, by up to two orders of magnitude. Thermal sensors fabricated from these composites exhibit a sensitivity that exceeds 10 mK and operate stably between 15° and 55°C, even under repeated mechanical deformations. We demonstrate the use of our flexible BTS polymer in two-dimensional arrays for spatiotemporal temperature mapping and broadband infrared photodetection.

Green-light-selective organic photodiodes for full-color imaging.

In this work, organic photodiodes (OPDs) based on two newly synthesized p-type dipolar small molecules are reported for application to green-light-selective OPDs. In order to reduce the blue-color absorption induced by the use of C60 as the n-type material in a bulk heterojunction (BHJ), the electron donor:electron acceptor composition ratio is tuned in the BHJ. With this light manipulation approach, the blue-wavelength external quantum efficiency (EQE) is minimized to 18% after reducing the C60 concentration in the center part of the BHJ. The two p-type molecules get a cyanine-like character with intense and sharp absorption in the green color by adjusting the strength of their donating and accepting parts and by choosing a selenophene unit as a π-linker. When combined to C60, the green-wavelength EQE reaches 70% in a complete device composed of two transparent electrodes. Finally, the optical simulation shows the good color-balance performance of hybrid full-color image sensor without an additional filter by using the developed green OPD as the top-layer in stacked device architecture.

Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates.

Benzothieno[60]fullerenes were synthesized using fullerenyl cations as key intermediates. The reaction proceeded through a nucleophilic attack of the sulfur atom as a weak nucleophile to the fullerenyl cation electrophile. A monoarylated fullerene, (2-methylthiophenyl)hydro[60]fullerene, C60ArH (Ar = C6H4-SMe-2 and so on; four derivatives) was subjected to deprotonation with KO tBu to form a fullerenyl anion ArC60-, followed by oxidation using I2 to generate a fullerenyl cation ArC60+, leading to intramolecular demethylative cyclization via fullerene cation-S interaction to the product. Electrochemical and computational studies revealed slightly narrower band gap of this compound than usual fullerene derivatives because of the relatively high-lying HOMO of the fused thieno moiety.

Printable organometallic perovskite enables large-area, low-dose X-ray imaging.

Medical X-ray imaging procedures require digital flat detectors operating at low doses to reduce radiation health risks. Solution-processed organic-inorganic hybrid perovskites have characteristics that make them good candidates for the photoconductive layer of such sensitive detectors. However, such detectors have not yet been built on thin-film transistor arrays because it has been difficult to prepare thick perovskite films (more than a few hundred micrometres) over large areas (a detector is typically 50 centimetres by 50 centimetres). We report here an all-solution-based (in contrast to conventional vacuum processing) synthetic route to producing printable polycrystalline perovskites with sharply faceted large grains having morphologies and optoelectronic properties comparable to those of single crystals. High sensitivities of up to 11 microcoulombs per air KERMA of milligray per square centimetre (µC mGyair-1 cm-2) are achieved under irradiation with a 100-kilovolt bremsstrahlung source, which are at least one order of magnitude higher than the sensitivities achieved with currently used amorphous selenium or thallium-doped cesium iodide detectors. We demonstrate X-ray imaging in a conventional thin-film transistor substrate by embedding an 830-micrometre-thick perovskite film and an additional two interlayers of polymer/perovskite composites to provide conformal interfaces between perovskite films and electrodes that control dark currents and temporal charge carrier transportation. Such an all-solution-based perovskite detector could enable low-dose X-ray imaging, and could also be used in photoconductive devices for radiation imaging, sensing and energy harvesting.

Enhanced performance and stability of polymer BHJ photovoltaic devices from dry transfer of PEDOT:PSS.

Polymer solar cells with enhanced initial cell performances and long-term stability were fabricated by performing a simple dry transfer of a hole extraction layer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)] onto an indium tin oxide (ITO) substrate. Due to the very flat surface of the polyurethane acrylate/polycarbonate (PUA/PC) film, which was used as a mold and resembled the surface of the original substrate (silicon wafer), the transferred layer had a very smooth surface morphology, resulting in enhancement of the interfacial characteristics. The work function of the PEDOT:PSS layer and the morphology of bulk hetero junction (BHJ) layer were tuned by controlling the position of PSS enrichment in the PEDOT:PSS layer using the dry transfer. The power conversion efficiency of PTB7:PC71 BM BHJ device prepared by the dry transfer was 8.06%, which was significantly higher than that of the spin-cast device (7.32%). By avoiding direct contact between the ITO substrate and the PEDOT:PSS solution in the dry transfer system, etching and diffusion of indium in the ITO substrate were greatly reduced, thereby improving the stability.

Polymer bulk heterojunction solar cells with PEDOT:PSS bilayer structure as hole extraction layer.

A high current density obtained in a limited, nanometer-thick region is important for high efficiency polymer solar cells (PSCs). The conversion of incident photons to charge carriers only occurs in confined active layers; therefore, charge-carrier extraction from the active layer within the device by using solar light has an important impact on the current density and the related to power conversion efficiency. In this study, we observed a surprising result, that is, extracting the charge carrier generated in the active layer of a PSC device, with a thickness-controlled PEDOT:PSS bilayer that acted as a hole extraction layer (HEL), yielded a dramatically improved power conversion efficiency in two different model systems (P3HT:PC60BM and PCDTBT:PC70BM). To understand this phenomenon, we conducted optical strength simulation, photocurrent-voltage measurements, incident photon to charge carrier efficiency measurements, ultraviolet photoelectron spectroscopy, and AFM studies. The results revealed that approximately 60 nm was the optimum PEDOT:PSS bilayer HEL thickness in PSCs for producing the maximum power conversion efficiency.

Controlled nanomorphology of PCDTBT-fullerene blends via polymer end-group functionalization for high efficiency organic solar cells.

We propose a novel method for the control of nanoscale morphologies of the photoactive layers of organic solar cells by using end group functionalization of p-type polymers. The devices based on the end-fluorinated PCDTBT exhibit a remarkably enhanced efficiency as high as 6.0% without applying any post-treatments, additives or optical spacers.

Energy transfer in ionic-liquid-functionalized inorganic nanorods for highly efficient photocatalytic applications.

Energy transfer in self-assembled ionic liquids (ILs) and iron oxyhydroxide nanocrystals and the controlled surface chemistry of functionalized nanomaterials for photocatalytic applications are reported. Self-assembled ILs play the role of multifunctional materials in terms of constructing a well-designed nanostructure, controlling the surface chemistry, and triggering the energy transfer of functionalized materials. IL-functionalized beta-FeOOH nanorods show approximately 10-fold higher performances than those of commercial materials due to the synergistic effect of well-defined nanomaterials in diffusion-controlled reactions, specific interactions with target pollutants, and energy transfers in hybrid materials. In particular, the energy transfer in C(4)MimCl-functionalized beta-FeOOH nanorods enhances photocatalytic activity due to the generation of Fe(2+). The strategy described herein provides new insight into the rational design of functionalized inorganic nanomaterials for applications in emerging technologies.

Green one-pot assembly of iron-based nanomaterials for the rational design of structure.

Green one-pot solution chemistry described herein could delicately manipulate the size and shape of iron oxyhydroxide nanocrystals, even in the aqueous phase, and easily derive a family of iron-based nanomaterials.

Intermolecular interaction-induced hierarchical transformation in 1D nanohybrids: analysis of conformational changes by 2D correlation spectroscopy.

We have examined both self-assembly and confinement effect in room-temperature ionic liquid (RTIL)-aluminum hydroxide hybrids (RAHs) to attain a fundamental understanding of special phenomena in nanoscale spaces as well as to design functional nanomaterials for practical applications. Phase-controlled one-dimensional (1D) RAHs were synthesized through a simple ionothermal process. The RAHs were hierarchically transformed in terms of the molecular structures, morphologies, and phases of the materials during the ionothermal process with respect to the concentration of RTIL. In addition to the hierarchical transformation, the RTIL/aluminum hydroxide nanohybrids revealed unexpected physical behaviors, including thermal transition variation of the RTIL in confined environments and a phase transition from nanosolid to nanoliquid affected by changes of the melting points. More importantly, intermolecular interaction induced-self-assembly and confinement effect of RTILs inside an integrated hybrid system, which have not been clearly explained to date, were analyzed by 2D infrared correlation spectroscopy (2D IR COS); dynamic behaviors of RTILs, i.e., sequentially spatial reorientation and kinetically conformational changes, were attributed to the interactions between RTILs and aluminum hydroxides. 2D IR COS offers a new way to interpret highly complex, veiled systems such as the formation mechanism of nanoparticles, biomineralization, self/supramolecular assembly, and nanoconfinement.

Macroporous polymer thin film prepared from temporarily stabilized water-in-oil emulsion.

We report a simple and convenient method for fabricating ordered porous structure in a polymeric thin film. A temporarily stabilized water-in-oil emulsion, where aqueous droplets were dispersed in the medium of polymer-organic solvent solution, was utilized for the preparation of porous structure. The water-in-oil emulsion was simply prepared by sonicating the mixture of water and polymer-organic solvent solution without any colloid stabilizer. The growth of aqueous droplets was profoundly retarded by dissolving a small amount of sucrose, selectively soluble in the dispersed phase. The prepared emulsion was recovered onto a substrate through dip-coating and subsequently air-dried to get a well-ordered porous polymer film. The polymer content in the polymer solution phase and the compositional ratio of the aqueous phase to the polymer solution phase was optimized to fabricate well-ordered structures.

An explanation of dispersion states of single-walled carbon nanotubes in solvents and aqueous surfactant solutions using solubility parameters.

Dispersions of single-walled carbon nanotubes in various solvents and aqueous surfactant emulsions were investigated to correlate the degree of dispersion state with Hansen solubility parameters (deltat2=deltad2+deltap2+deltah2). It was found that the nanotubes were dispersed or suspended very well in the solvents with certain dispersive component (deltad) values. They were precipitated in the solvents with high polar component (deltap) values or hydrogen-bonding component (deltah) values. The solvents in the dispersed group occupied a certain region in a 3-dimensional space of three components. The surfactants with a lipophilic group equal to and longer than decyl, containing 9 methylene groups and 1 methyl group, contributed to the dispersion of nanotubes in water. The surfactants in the dispersed group had a lower limit in the dispersive component (deltad) of the Hansen parameter.