Kei Noda

Remanent polarization of evaporated films of vinylidene fluoride oligomers

A remanent polarization of 130±3 mC/m2, large among the values reported for organic materials, and rectangular D–E hysteresis curves were realized in synthesized vinylidene fluoride (VDF) oligomer [CF3(CH2CF2)17I] film evaporated onto a platinum surface around liquid nitrogen temperature. The results suggested that the VDF oligomer film has an extremely high crystallinity, and the electric dipoles arrange almost perfectly perpendicular to the film surface, and that a Lorentz local field factor of ferroelectric VDF oligomer crystals is nearly zero. Moreover, the obtained value of the coercive field, which was larger than those of ferroelectric polymers, might be attributed to the steric hindrance arising from the existence of iodine atoms at the VDF oligomer chains.

Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin–Chemically Converted Graphene Composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl-functionalized CCG and porphyrin boronic ester. The covalently linked CCG-porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady-state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin-linked CCG revealed a short-lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO(2) electrode coated with the porphyrin-linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π-conjugated systems in the excited and ground states.

Structures of vinylidene fluoride oligomer thin films on alkali halide substrate

Structures and crystal transformation of the newly synthesized vinylidene fluoride (VDF) oligomer with large electric dipoles evaporated on KCl (001) at various substrate temperatures have been investigated by an energy dispersive–grazing incidence x-ray diffraction system, Fourier transform infrared spectroscopy, and atomic force microscope (AFM). It was revealed that the molecules grow epitaxially and are influenced greatly by forces of the crystal surface field in terms of van der Waals or electrostatic potentials, and found that the phase transformation from form II (α phase) to form I (β phase) is induced by raising the temperature of the substrate from 50 to 80 °C, accompanying the alternation in the crystal axes on the substrate from the a axis of form II to the polar b axis of the form I crystal. This fact suggests that the molecular chain of VDF oligomers aligns their c axes along the 〈110〉 row of K+ or Cl− with the aid of electrostatic interaction under enough thermal movement. Moreover, in the ...

Alkyl and Alkoxyl Monolayers Directly Attached to Silicon: Chemical Durability in Aqueous Solutions

For practical application of self-assembled monolayers (SAMs), knowledge of their chemical durability in acidic or basic solutions is important. In the present work, a series of SAMs directly immobilized on a silicon (111) surface through Si-C or Si-O-C covalent bonds without a native oxide layer were prepared by thermally activated chemical reactions of a hydrogen-terminated Si(111) substrate with linear molecules, i.e., 1-hexadecene, 1-hexadecanol, 1-dodecanol, and n-dodecanal, to investigate the durability of the SAMs to HF and Na2CO3 solutions. While grazing incidence X-ray reflectivity measurements showed that all the as-prepared SAMs had almost the same film density and molecular coverage, keeping the original step and terrace structure of Si(111) as is observed by atomic force microscopy, they gave different degradation behaviors, i.e., pitting and concomitant surface roughening in both solutions. 1-hexadecene SAM was stable against immersion in both solutions, while the other SAMs were damaged within 60 min, most likely due to the difference in chemical bonding modes at the SAM/Si interface, i.e., Si-C and Si-O-C.

Molecular Ferroelectricity of Vinylidene Fluoride Oligomer Investigated by Atomic Force Microscopy

Nanometer-scale electrical properties of local ferroelectric domains formed in thin films of newly synthesized vinylidene fluoride (VDF) oligomer were investigated by atomic force microscopy (AFM). Local poling and observation of the piezoelectric response revealed that the polarized domains were reversibly formed and erased in a nanometer-thick film by applying dc or pulse voltages between the electrically conductive AFM tip and the bottom electrode. The formed domain size depends on the pulse poling conditions and increases when the magnitude and the duration of a pulse voltage are increased. A local domain with a diameter of 65 nm was successfully created. The results in this work are comparable to those of previous studies performed on ferroelectric polymer thin films, suggesting that this material is one of the promising candidates for ferroelectric applications such as high-density data storages, and for molecular controls of ferroelectric properties.

Structures and Ferroelectric Natures of Epitaxially Grown Vinylidene Fluoride Oligomer Thin Films

Structural and electrical properties of newly synthesized vinylidene fluoride (VDF) oligomer thin film have been investigated. The FTIR spectrum showed that the epitaxially grown film on KBr(001) substrate consists of form I (β phase) crystals and their c axes (molecular axes) and b axes (polar axes) are arranged parallel to the KBr substrate. To make electrical measurements possible, this film was transferred onto a gold bottom electrode without causing any changes in the crystalline structures. By using a modified atomic force microscope, we succeeded in the formation of local polarized domains as well as the clear observation of piezoresponse hysteresis curves in this sample. The coercive field and piezoelectric coefficient (d33) for the 37-nm-thick film were about 200 MV/m and -3 pm/V, respectively. It was suggested that the b axis in the as-grown film rotated from the parallel to the perpendicular direction to the film surface during the poling process. This study reveals the ferroelectric characteristics in the VDF oligomer thin films for the first time.

Molecular doping effect in bottom-gate, bottom-contact pentacene thin-film transistors

A bottom-gate, bottom-contact (BGBC) organic thin-film transistor (OTFT) with carrier-doped regions over source-drain electrodes was investigated. Device simulation with our originally developed device simulator demonstrates that heavily doped layers (p+ layers) on top of the source-drain contact region can compensate the deficiency of charge carriers at the source-channel interface during transistor operation, leading to the increase of the drain current and the apparent field-effect mobility. The phenomena expected with the device simulation were experimentally confirmed in typical BGBC pentacene thin-film transistors. The 5-nm-thick p+ layers, located 10 nm (or 20 nm) over the source-drain electrodes, were prepared by coevaporation of pentacene and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane as an acceptor dopant. Since the molecular doping in this study can increase the drain current without positive shift of threshold voltage, p+ layers were formed precisely on top of the source-drain region...

Investigation of electrical transport in anodized single TiO2 nanotubes

Electrical transport in anodized single titania nanotube (TNT) free from any structural effects of titania nanotube array (TNA) was investigated. An anodized TNA was disassembled into single TNTs with two-step anodization technique. Then, single TNT bridges between gold electrodes with a gap of 500 nm were prepared by dielectrophoretic alignment. Quantitative assessment of electron mobility inside single anatase and rutile TNT was carried out by 2-probe current-voltage measurement and analysis based on a metal-semiconductor-metal circuit model with Schottky barriers. Our approach to intrinsic electrical transport of single nanotube is quite effective for understanding the electronic and optical properties of TNA.

Pyroelectricity of Ferroelectric Vinylidene Fluoride-Oligomer-Evaporated Thin Films

The pyroelectricity of ferroelectric vinylidene fluoride (VDF)-oligomer [CF3(CH2CF2)17I]-evaporated film was investigated utilizing a low-frequency sinusoidal heat source. A current profile appeared as the summation of a fundamental sine wave with a frequency of the temperature change and its harmonic responses. The pyroelectric coefficient (p) of the 600-nm-thick VDF oligomer film was estimated to be -68 µC/m2K at 37°C, whose absolute value is larger than those reported for ferroelectric polymers. Various characteristics such as a large |p|, a small dielectric constant and suitability for preparation of thinner films suggest that the VDF oligomer is a promising material for application in pyroelectric thin-film infrared detectors.

Numerical investigation of organic thin-film transistors using a thermionic field emission model

Charge injection barriers at the electrode/semiconductor interface were considered for numerical investigation of electrical characteristics in realistic organic thin-film transistors (OTFTs). A new thermionic field emission (TFE) model, which addresses tunneling of thermally excited electrons, was used as the carrier injection model of OTFTs in this study. Device simulation for an n-channel OTFT with a bottom-gate, bottom-contact configuration was performed with a thin-film organic transistor advanced simulator (TOTAS). Typical electrical characteristics of realistic OTFTs such as severe nonlinearity in output characteristics were reproduced by this simulation using the TFE model. The effects of contact-area-limited doping for n-channel OTFTs were also examined from the simulation results, suggesting that highly doped semiconducting layers prepared over contact electrodes can neutralize the effect of a Schottky energy barrier. Both the simulation technique with the TFE model and the contact-area-limited doping are promising in designing and developing high-performance OTFTs.