Mechanism of high photoluminescence quantum yield of melem.

To produce high-efficiency organic light-emitting diodes, materials that exhibit thermally activated delayed fluorescence (TADF) are attracting attention as alternatives to phosphorescent materials containing heavy metallic elements. Melem, a small molecule with a heptazine backbone composed only of nitrogen, carbon, and hydrogen, is known to emit light in the near-ultraviolet region and exhibit high photoluminescence (PL) quantum yield and delayed fluorescence. However, the mechanism underlying the high PL quantum yield remains unclear. This study aimed to elucidate the mechanism of the high PL quantum yield of melem by examining its optical properties in detail. When the amount of dissolved oxygen in the melem solution was increased by bubbling oxygen through it, the PL quantum yield and emission lifetime decreased significantly, indicating that the triplet state was involved in the light-emission mechanism. Furthermore, the temperature dependence of the PL intensity of melem was investigated; the PL intensity decreased with decreasing temperature, indicating that it increases thermally. The experimental results show that melem is a TADF material that produces an extremely high PL quantum yield by upconversion from the triplet to the singlet excited state.

Growth and characterization of melem hydrate crystals with a hydrogen-bonded heptazine framework.

In carbon nitride (CN) compounds, hydrogen bonds play a major role in cohesion, in addition to dispersion forces. The crystal structures of CN compounds produced via thermal polymerization are complex, but they possess unique and attractive features. Melem is a well-known building unit of CN compounds such as melon and g-C3N4, which have recently attracted attention as photocatalysts. Melem hydrate (Mh) forms hexagonal prismatic crystals that are sufficiently porous to accommodate small molecules. In this study, we grew and characterized single crystals of Mh and investigated their optical properties and hygroscopicity. By precisely adjusting the hydration conditions, we succeeded in growing a well-formed hexagonal prismatic single crystal of Mh (Mhr) with a length measuring several tens of micrometers. Furthermore, we discovered a parallelogram-shaped Mh single crystal (Mhp), which possessed a different crystal structure and optical properties from those of Mh and melem crystals. Although the crystal structure of Mh was greatly disrupted by dehydration, it exhibited hygroscopicity and could absorb moisture even in air, restoring the crystal structure of Mh. In addition, Mh demonstrated a high photoluminescence quantum yield and long lifetime delayed fluorescence, similar to melem crystal. The high quantum yield of Mh can be attributed to the effect of the strong anchoring of the melem molecule by several hydrogen bonds in the Mh crystal, since the strongly anchored molecule is less likely to undergo radiation-free deactivation due to the small displacement of atomic positions in the excited state after light absorption. The findings obtained in this study shed light not only on the application of CN compounds as photocatalysts, but also on a wider range of applications based on their optoelectronic functions.

Precise and rapid solvent-assisted geometric protein self-patterning with submicron spatial resolution for scalable fabrication of microelectronic biosensors.

Precise and high-resolution coupling of functional proteins with micro-transducers is critical for the manufacture of miniaturized bioelectronic devices. Moreover, electrochemistry on microelectrodes has had a major impact on electrochemical analysis and sensor technologies, since the small size of microelectrode affects the radial diffusion flux of the analyte to deliver enhanced mass transport and electrode kinetics. However, a large technology gap has existed between the process technology associated with such microelectronics and the conventional bio-conjugation techniques that are generally used. Here, we report on a high-resolution and rapid geometric protein self-patterning (GPS) method using solvent-assisted protein-micelle adsorption printing to couple biomolecules onto microelectrodes with a minimum feature size of 5 µm and a printing time of about a minute. The GPS method is versatile for micropatterning various biomolecules including enzymes, antibodies and avidin-biotinylated proteins, delivering good geometric alignment and preserving biological functionality. We further demonstrated that enzyme-coupled microelectrodes for glucose detection exhibited good electrochemical performance which benefited from the GPS method to maximize effective signal transduction at the bio-interface. These microelectrode arrays maintained fast convergent analyte diffusion displaying typical steady-state I-V characteristics, fast response times, good linear sensitivity (0.103 nA mm-2 mM-1, R2 = 0.995) and an ultra-wide linear dynamic range (2-100 mM). Our findings provide a new technical solution for the precise and accurate coupling of biomolecules to a microelectronic array with important implications for the scaleup and manufacture of diagnostics, biofuel cells and bioelectronic devices that could not be realized economically by other existing techniques.

Nanoparticle chemisorption printing technique for conductive silver patterning with submicron resolution.

Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of weakly encapsulated silver nanoparticles on a photoactivated surface. The process includes masked irradiation of vacuum ultraviolet light on an amorphous perfluorinated polymer layer to photoactivate the surface with pendant carboxylate groups, and subsequent coating of alkylamine-encapsulated silver nanocolloids, which causes amine-carboxylate conversion to trigger the spontaneous formation of a self-fused solid silver layer. The technique can produce silver patterns of submicron fineness adhered strongly to substrates, thus enabling manufacture of flexible transparent conductive sheets. This printing technique could replace conventional vacuum- and photolithography-based device processing.

Polymorphism in the 1:1 Charge-Transfer Complex DBTTF-TCNQ and Its Effects on Optical and Electronic Properties.

The organic charge-transfer (CT) complex dibenzotetrathiafulvalene - 7,7,8,8-tetracyanoquinodimethane (DBTTF-TCNQ) is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the ß-polymorph. Structural and elemental analysis via selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor:acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in our experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the ß-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the ß-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor-acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for charge-transfer complexes.

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.

Inkjet printing of single-crystal films.

The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. 'Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C(8)-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm(2) V(-1) s(-1). This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.

Competition between charge-transfer exciton dissociation and direct photocarrier generation in molecular donor-acceptor compounds.

The interfacial charge-separation and photovoltaic characteristics of a molecular donor-acceptor charge-transfer compound were examined. Measurements of laser beam-induced currents on the single crystals allowed selective detection of hole and electron photocurrents through the metal-semiconductor interfaces. This method also reveals the exceptionally long diffusion length of 20 µm in the crystal. The transition from charge-transfer exciton dissociation to direct photocarrier generation is discussed on the basis of the photon-energy-dependent diffusion length and photon-to-current conversion spectrum.

An accurate calculation of electronic contribution to static permittivity tensor for organic molecular crystals on the basis of the charge response kernel theory.

We have developed a new method to calculate the static permittivity tensors of organic molecular crystals by applying the charge response kernel theory (Morita, A.; Kato, S. J. Am. Chem. Soc. 1997, 119, 4021) in which all the parameters were obtained with the density functional theory. The accuracy together with the requirements of the computation was discussed in terms of positions of the charge response sites and choice of a basis set. The calculated permittivities of typical organic compounds turned out to agree with the experimentally obtained values in the deviation of about 7% when a reasonable computational cost was maintained.