Stabilization of Interfacial Polarization and Induction of Polarization Hysteresis in Organic MISIM Devices.

Molecule-based ferroelectrics has attracted much attention because of its advantages, such as flexibility, light weight, and low environmental load. In the present work, we examined an organic metal|insulator|semiconductor|insulator|metal (MISIM) device structure to stabilize the interfacial polarization in the S layer and to induce polarization hysteresis even without bulk ferroelectrics. The MISIM devices with I = parylene C and S = TMB (=3,3',5,5'-tetramethylbenzidine)-TCNQ (=tetracyanoquinodimethane) exhibited hysteresis loops in the polarization-voltage (P-V) curves not only at room temperature but also over a wide temperature range down to 80 K. The presence of polarization hysteresis for MISIM devices was theoretically confirmed by an electrostatic model, which also explained the observed thickness dependence of the I layers on the P-V curves. Polarization hysteresis curves were also obtained in MISIM devices using typical organic semiconductors (ZnPc, C60, and TCNQ) as the S layer, demonstrating the versatility of the interfacial polarization mechanism.

Chemical potentials of electric double layers at metal-electrolyte interfaces: dependence on electrolyte concentration and electrode materials, and application to field-effect transistors.

When a metal is soaked in an electrolyte solution, the metal and solution affect each other through the formation of electric double layers (EDLs) at their interfaces. The EDLs at metal-electrolyte interfaces can realize high-density charge-carrier injections and accumulations, and thus have recently attracted attention for their potential application to energy storage, and electronic and electrochemical devices. In such EDL-based devices, including field-effect transistors (FETs), the potential energy of surface electrons in the metal electrodes (EM) governs the transistor device performance. This is in clear contrast to redox-driven electrochemical devices such as dye-sensitized solar cells and electrochromic devices, whose performance is primarily governed by the potentials of the redox-active species. However, there has been no systematic research to bridge the distance between metal electrons and electrolyte ions. In the present study, we carefully examined the dependence of EM of ITO, Au and Pt electrodes on the concentration of the PEG solutions of LiCl and MgCl2, because it has been well established that the chemical potential of electrolyte solutions is dependent on the solution concentrations. Our results showed that, at the same electrolyte concentration, the values of EM increased in the order of ITO, Au and Pt; moreover, on the same electrode, EM showed linear decreases as a function of the logarithm of the electrolyte concentrations. To understand these behaviors, we developed a theoretical treatment of the EDLs based on the simple Gouy-Chapman model, and obtained the theoretical expressions of EM in terms of the concentration of electrolyte and the work function of the metal electrode (ΦM), which were found to successfully explain the dependences of EM on the electrolyte concentration and the electrode materials. We also examined the EDL-FETs of platinum phthalocyanine (PtPc), with various LiCl-PEG solutions of different concentrations as gate electrolytes. The threshold voltage eVT and EM exhibited a linear relation, which was well explained by the relation between EM and the valence band energy EVB of PtPc. The transfer characteristics at various gate voltage VG were found to be well normalized by a function of eVG + EM.

Ionic liquid thin layer-induced memory effects in organic field-effect transistors.

We examined the morphologies and structures of pentacene and C60 thin films grown on thin layers of an ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI), and found that the characteristics of the films depended significantly on the thickness of DEME-TFSI. In addition, we fabricated organic field-effect transistors (OFETs) of pentacene and C60 in which a thin layer of DEME-TFSI was inserted between the organic semiconductor (pentacene or C60) and the gate insulating layer, and measured their performance in situ. We found that 1.5-2 ML (ML: monolayer) DEME-TFSI produced a large hysteresis loop in the transfer characteristics in these OFETs, but 5 ML DEME-TFSI resulted in the formation of normally-on states with far smaller memory effects. The curvatures of the hysteresis loops were caused by the formation of trap states induced by the DEME-TFSI layers. This novel technique provides a simple tool for creating hysteresis behavior and could potentially be applied to transistor memory devices.

Rate-determining process in MISIM photocells for optoelectronic conversion using photo-induced pure polarization current without carrier transfer across interfaces.

Recently, we proposed a [metal|insulator|semiconductor|insulator|metal] (MISIM) photocell, as a novel architecture for high-speed organic photodetectors. The electric polarization in the S layer, induced by modulated light illumination, propagates into the outside circuit as a polarization current through the I layers, without any carrier transfer across the interfaces. In the present work, we examined the MISIM photocells consisting of zinc-phthalocyanine(ZnPc)-C60 bilayers for the S layer and Parylene C for the two I layers, to understand the fundamental aspects of the MISIM photocells, such as current polarity and modulation-frequency dependence. It was found that, in such devices, the current polarity was primarily determined by the polarization in the S layer, which was induced by the donor-acceptor charge-transfer upon illumination. Furthermore, the ON and OFF current, which appeared in the periods of illumination-on and -off, respectively, exhibited significantly different dependence on the modulation frequency. This was well-explained by an imbalance between a quick polarization in the S layer during illumination and its slow relaxation in the dark.

Electron Highways into Nanochannels of Covalent Organic Frameworks for High Electrical Conductivity and Energy Storage.

To enhance the electron transfer within the covalent organic frameworks (COFs), we obtained a nanocomposite of conductive poly(3,4-ethylenedioxythiophene) (PEDOT) and redox-active AQ-COF by performing a facile in situ solid-state polymerization inside the nanochannels of COFs. The PEDOT chains functioned like electron highways within the nanochannels, resulting in a PEDOT@AQ-COF nanocomposite with an excellent electrical conductivity of 1.1 S cm-1 and a remarkably improved performance in faradaic energy storage. The all-organic PEDOT@AQ-COF electrode showed specific capacitance as high as 1663 F g-1 (at 1 A g-1), ultrafast charge/discharge rate performance (998 F g-1 at 500 A g-1), and excellent stability for 10 000 cycles. This research demonstrates a promising strategy for increasing the conductivity of COF-based materials and broadening their applications.

Multifunctional Dithiadiazolyl Radicals: Fluorescence, Electroluminescence, and Photoconducting Behavior in Pyren-1'-yl-dithiadiazolyl.

The pyren-1'-yl-functionalized dithiadiazolyl (DTDA) radical, C16H9CNSSN (1), is monomeric in solution and exhibits fluorescence in the deep-blue region of the visible spectrum (440 nm) upon excitation at 241 nm. The salt [1][GaCl4] exhibits similar emission, reflecting the largely spectator nature of the radical in the fluorescence process, although the presence of the radical leads to a modest quenching of emission (ΦF = 98% for 1+ and 50% for 1) through enhancement of non-radiative decay processes. Time-dependent density functional theory studies on 1 coupled with the similar emission profiles of both 1+ and 1 are consistent with the initial excitation being of predominantly pyrene π-π* character. Spectroscopic studies indicate stabilization of the excited state in polar media, with the fluorescence lifetime for 1 (τ = 5 ns) indicative of a short-lived excited state. Comparative studies between the energies of the frontier orbitals of pyren-1'-yl nitronyl nitroxide (2, which is not fluorescent) and 1 reveal that the energy mismatch and poor spatial overlap between the DTDA radical SOMO and the pyrene π manifold in 1 efficiently inhibit the non-radiative electron-electron exchange relaxation pathway previously described for 2. Solid-state films of both 1 and [1][GaCl4] exhibit broad emission bands at 509 and 545 nm, respectively. Incorporation of 1 within a host matrix for OLED fabrication revealed electroluminescence, with CIE coordinates of (0.205, 0.280) corresponding to a sky-blue emission. The brightness of the device reached 1934 cd/m2 at an applied voltage of 16 V. The crystal structure of 1 reveals a distorted π-stacked motif with almost regular distances between the pyrene rings but alternating long-short contacts between DTDA radicals. Solid state measurements on a thin film of 1 reveal emission occurs at shorter wavelengths (375 nm) whereas conductivity measurements on a single crystal of 1 show a photoconducting response at longer wavelength excitation (455 nm).

Giant negative magnetoresistance in Ni(quinoline-8-selenoate)2.

The magnetic, structural, conductivity and magnetoresistance properties of [Ni(quinoline-8-selenoate)2] ([Ni(qs)2]) have been studied. Despite the insolubility of the material necessitating its study as a powdered sample, a remarkably high conductivity has been measured. The conductivity is an order of magnitude greater than the thin-film processable thiol analogue previously reported and has been interpreted through the same space-charge limited conduction mechanism with charges injected from the electrodes. The introduction of selenium, results in a material with conductivity approaching metallic due to the enhanced interaction between adjacent molecules. Additionally, under an applied magnetic field, the material displays a negative magnetoresistance effect above 35% at 2 K. The effect can still be observed at 200 K and is interpreted in terms of a double-exchange mechanism.

3D Spin-Liquid State in an Organic Hyperkagome Lattice of Mott Dimers.

We report the first 3D spin liquid state of isotropic organic spins. Structural analysis, and magnetic and heat-capacity measurements were carried out for a chiral organic radical salt, (TBA)_{1.5}[(-)-NDI-Δ] (TBA denotes tetrabutylammonium and NDI denotes naphthalene diimide), in which (-)-NDI-Δ forms a K_{4} structure due to its triangular molecular structure and an intermolecular π-π overlap between the NDI moieties. This lattice was identical to the hyperkagome lattice of S=1/2 Mott dimers, and should exhibit 3D spin frustration. In fact, even though the high-temperature magnetic susceptibility followed the Curie-Weiss law with a negative Weiss constant of θ=-15 K, the low-temperature magnetic measurements revealed no long-range magnetic ordering down to 70 mK, and suggested the presence of a spin liquid state with a large residual paramagnetism χ_{0} of 8.5×10^{-6} emu g^{-1} at the absolute zero temperature. This was supported by the ^{14}N NMR measurements down to 0.38 K. Further, the low-temperature heat capacities c_{p} down to 68 mK clearly indicated the presence of c_{p} for the spin liquid state, which can be fitted to the power law of T^{0.62} in the wide temperature range 0.07-4.5 K.

Molecular and thin film properties of cobalt half-sandwich compounds for optoelectronic application.

The structure and electronic properties of a novel cobalt half sandwich complex of cyclopentadiene (Cp) and diaminonaphthalene (DAnap) [CpCo(DAnap)] are described and compared to the previously reported diaminobenzene derivative [CpCo(DAbnz)] in view of their potential for (opto)electronic device application. Both complexes show stable redox processes, tunable through the diaminoacene ligand, and show strong absorption in the visible region, with additional transitions stretching into the near infrared (NIR). CpCo(DAnap) crystallises with a particularly large unit cell (9301 Å3), comprising 32 molecules, with a gradual rotation over 8 molecules along the long c-axis. In the solid state the balance of the optical transitions in both complexes is reversed, with a suppression of the visible band and an enhancement of the NIR band, attributed to extensive intermolecular electronic interaction. In the case of CpCo(DAnap), highly crystalline thin films could be formed under physical vapor deposition, which show a photocurrent response stretching into the NIR, and p-type semiconductor behavior in field effect transistors with mobility values of the order 1 × 10-4 cm2 V-1 s-1. The device performance is understood through investigation of the morphology of the grown films.

Transport Characteristics of the Organic Field-Effect Transistors Based on Charge Transfer Complex as Semiconductors.

The n-type organic field-effect transistors are fabricated with using four kinds of charge transfer (CT) complexes with PXX (peri-xanthenoxanthene) as a donor component. The CT complexes with four kinds of acceptors form mixed-stack type one-dimentional columns with different PXX-acceptor overlaps. Comparison of the field-effect properties reveals the correlation between the device performance and intermolecular interaction in the semiconducting CT complexes.

Electrochemical deposition of highly-conducting metal dithiolene films.

Electrochemical deposition has been used to prepare a thin film of neutral 4',4-(3-alkyl)-thiophene-5',5-hydogen-nickel and copper dithiolenes (Ni-C2, Cu-C2). The application of molecular electrodeposition provides a means to solution process molecular semiconductors of poor solubility, which results from the strong intermolecular interaction required for charge transport. Both Ni-C2 and Cu-C2 form continuous thin films that show intense NIR absorptions, extending to 1800 nm and 2000 nm respectively giving evidence for the strong intermolecular interactions in the solid state. Both films are highly conducting and temperature dependence of resistance gave an activation energy of 0.42 eV and 0.072 eV respectively, with the near-metallic behaviour of Cu-C2 attributed to the additional presence of an unpaired electron.

Discovery of the K4 Structure Formed by a Triangular π Radical Anion.

The K4 structure was theoretically predicted for trivalent chemical species, such as sp(2) carbon. However, since attempts to synthesize the K4 carbon have not succeeded, this allotrope has been regarded as a crystal form that might not exist in nature. In the present work, we carried out electrochemical crystallization of the radical anion salts of a triangular molecule, naphthalene diimide (NDI)-Δ, using various electrolytes. X-ray crystal analysis of the obtained crystals revealed the K4 structure, which was formed by the unique intermolecular π overlap directed toward three directions from the triangular-shape NDI-Δ radical anions. Electron paramagnetic resonance and static magnetic measurements confirmed the radical anion state of NDI-Δ and indicated an antiferromagnetic intermolecular interaction with the Weiss constant of θ = -10 K. The band structure calculation suggested characteristic features of the present material, such as a metallic ground state, Dirac cones, and flat bands.

Factors affecting the stability and performance of ionic liquid-based planar transient photodetectors.

A novel planar architecture has been developed for the study of photodetectors utilizing the transient photocurrent response induced by a metal/insulator/semiconductor/metal (MISM) structured device, where the insulator is an ionic liquid (IL-MISM). Using vanadyl 2,3-naphthalocyanine, which absorbs in the communications-relevant near-infrared wavelength region (λ(max,film) ≈ 850 nm), in conjunction with C60 as a bulk heterojunction, the high capacitance of the formed electric double layers at the ionic liquid interfaces yields high charge separation efficiency within the semiconductor layer, and the minimal potential drop in the bulk ionic liquid allows the electrodes to be offset by distances of over 7 mm. Furthermore, the decrease in operational speed with increased electrode separation is beneficial for a clear modeling of the waveform of the photocurrent signal, free from the influence of measurement circuitry. Despite the use of a molecular semiconductor as the active layer in conjunction with a liquid insulating layer, devices with a stability of several days could be achieved, and the operational stability of such devices was shown to be dependent solely on the solubility of the active layer in the ionic liquid, even under atmospheric conditions. Furthermore, the greatly simplified device construction process, which does not rely on transparent electrode materials or direct electrode deposition, provides a highly reproducible platform for the study of the electronic processes within IL-MISM detectors that is largely free from architectural constraints.

Photocurrent generation in organic photodetectors with tailor-made active layers fabricated by layer-by-layer deposition.

Photodetectors supply an electric response when illuminated. The detectors in this study consist of an active layer and a polyvinylidene fluoride (PVDF) blocking layer, which are sandwiched by an aluminum and an indium tin oxide (ITO) electrode. The active layer was prepared of Zn porphyrins and assembled by covalent layer-by-layer (LbL) deposition. Layer growth was monitored by UV-vis absorbance, ellipsometry, and X-ray photoelectron spectroscopy. Upon exposure to chopped light, the detectors show an alternating transient photocurrent, which is limited by the accumulation of space charges at the blocking layer/active layer interface. We could show that the number of photoactive layers has a significant impact on device performance. The fastest response was achieved with fewer layers. The highest photocurrents were measured for detectors with an intermediate number of layers, beyond which, more layers did not lead to an increase in the photocurrent despite containing more active material.

Chemical control of the monovalent-divalent electron-transfer phase transition in biferrocenium-TCNQ salts.

An ionic molecular crystal of (1',1'''-dineopentylbiferrocene)(F1TCNQ)3 exhibits a first-order phase transition from a monovalent state (D(+)A3(-)) to a divalent state (D(2+)A3(2-)) at around 120 K. The transition was successfully controlled by modulation of the redox potentials using FnTCNQ (n = 0-2) and by chemical-pressure effects.

Storage of an electric field for photocurrent generation in ferroelectric-functionalized organic devices.

Organic optoelectronic devices are usually driven by the electric field generated from an electrode potential difference or bias voltage. Although poled ferroelectric domains may produce oriented stray fields, few efforts have been made to utilize them for photocurrent generation in organic devices. Here we show that large net fields caused by incomplete screening during ferroelectric polarization, and which can be 'restored' by short voltage pulses, can facilitate exciton dissociation in organic semiconductors. The oriented fields, comparable with that produced by an electrode potential difference (1~10 MV m(-1)), here are found to be responsible for the photocurrent in our devices. A prototype for an organic photodetector driven by such stray fields is demonstrated. The photoresponsivity, without any optimization, can achieve ~0.1 mA W(-1). This study provides a different operation principle for the generation of photocurrent in organic optoelectronic devices. Furthermore, the polarity-tunable photoresponse may lead to new photoresponsive memory devices.

Thiadiazole dioxide-fused picene: acceptor ability, anion radical formation, and n-type charge transport characteristics.

Picene, which is an organic p-channel semiconductor and a component of superconductors, was derivatized with a thiadiazole-dioxide moiety to afford a novel acceptor molecule (PTDAO2). PTDAO2 can form stable anion radical species in solution and as a crystal, and its neutral crystalline thin film exhibits n-type transistor characteristics.

Utilizing photocurrent transients for dithiolene-based photodetection: stepwise improvements at communications relevant wavelengths.

Photodetection based on bis-(4-dimethylaminodithiobenzil)-Ni(II) (BDN), a representative and well-studied metal dithiolene that shows strong absorption in the near-infrared region of the electromagnetic spectrum, has been investigated. By adopting a metal/insulator/semiconductor/metal (MISM) structure, the peak photocurrent response to an oscillating light chain is increased by up to 50 times, compared to devices without an insulating layer. The transient form of the MISM photoresponse, while unsuitable for steady-state photodetection, can be used to detect periodic light signals of frequencies up to 1 MHz, and is thus applicable for optical communication. Further improvements have been realized by nanostructuring carbon black into the dithiolene layer, improving charge collection, and yielding detectivity of up to 1.6 × 10(11) Jones at wavelengths beyond the scope of silicon photodiodes. Such an architecture may allow the favorable absorption properties of other such metal dithiolenes to be harnessed, where their low charge carrier mobilities and short excitation lifetimes have previously limited their applicability to this field.

Crystal structure, spin polarization, solid-state electrochemistry, and high n-type carrier mobility of a paramagnetic semiconductor: vanadyl tetrakis(thiadiazole)porphyrazine.

We report the synthesis, crystal structure, and magnetic, electrochemical, and carrier-transport properties of vanadyl tetrakis(thiadiazole)porphyrazine (abbreviated as VOTTDPz) with S = ½. X-ray crystal analysis reveals two polymorphs, the α and ß forms; the former consists of a 1D regular π stacking, while the latter forms a 2D π network. Molecular orbital calculations suggest a V(4+)(d(1)) ground state and a characteristic spin polarization on the whole molecular skeleton. The temperature dependence of the paramagnetic susceptibility of the α form clearly indicates a ferromagnetic interaction with a positive Weiss constant of θ = 2.4 K, which is well-explained by McConnell's type I mechanism. VOTTDPz forms amorphous thin films with a flat and smooth surface, and their cyclic voltammogram curves indicate a one-electron reduction process, which is highly electrochromic, because of a reduction of the porphyrazine π ring. Thin-film field-effect transistors of VOTTDPz with ionic-liquid gate dielectrics exhibit n-type performance, with a high mobility of µ = 2.8 × 10(-2) cm(2) V(-1) s(-1) and an on/off ratio of 10(4), even though the thin films are amorphous.

Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni.

Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.