Youichi Sakamoto

Highly efficient phosphorescence from organic light-emitting devices with an exciton-block layer

One of the keys to highly efficient phosphorescent emission in organic light-emitting devices is to confine triplet excitons generated within the emitting layer. We employ “starburst” perfluorinated phenylenes (C60F42) as a both hole- and exciton-block layer, and a hole-transport material 4,4′,4″-tri(N-carbazolyl) triphenylamine as a host for the phosphorescent dopant dye in the emitting layer. A maximum external quantum efficiency reaches to 19.2%, and keeps over 15% even at high current densities of 10–20 mA/cm2, providing several times the brightness of fluorescent tubes for lighting. The onset voltage of the electroluminescence is as low as 2.4 V and the peak power efficiency is 70–72 lm/W, promising for low-power display devices.

Impact of Perfluorination on the Charge-Transport Parameters of Oligoacene Crystals

The charge-transport parameters of the perfluoropentacene and perfluorotetracene crystals are studied with a joint experimental and theoretical approach that combines gas-phase ultraviolet photoelectron spectroscopy and density functional theory. To gain a better understanding of the role of perfluorination, the results for perfluoropentacene and perfluorotetracene are compared to those for their parent oligoacenes, that is, pentacene and tetracene. Perfluorination is calculated to increase the ionization potentials and electron affinities by approximately 1 eV, which is expected to reduce significantly the injection barrier for electrons in organic electronics devices. Perfluorination also leads to significant changes in the crystalline packing, which greatly affects the electronic properties of the crystals and their charge-transport characteristics. The calculations predict large conduction and valence bandwidths and low hole and electron effective masses in the perfluoroacene crystals, with the largest mobilities expected along the pi-stacks. Perfluorination impacts as well both local and nonlocal vibrational couplings, whose strengths increase by a factor of about 2 with respect to the parent compounds.

Organic Thin-Film Transistors with High Electron Mobility Based on Perfluoropentacene

We report on n-channel organic thin-film transistors (OTFTs) based on the novel n-type organic semiconductor, perfluoropentacene. The transistor exhibits excellent electrical characteristics, with a high electron mobility of 0.22 cm2/(V s) and a good current on/off ratio of 105. The electron mobility is comparable to the hole mobility of a pentacene OTFT. By combining the n-type perfluoropentacene and the p-type pentacene, we have fabricated ambipolar OTFTs and complementary inverter circuits. The OTFTs with heterostructures of the p- and n-type organic semiconductors can operate as an ambipolar device with high electron and hole mobilities of 0.042 and 0.041 cm2/(V s). The complementary inverter using an n-channel perfluoropentacene OTFT and a p-channel pentacene OTFT exhibits excellent transfer characteristics with a voltage gain of 45. A complementary inverter using the ambipolar OTFTs is also demonstrated.

Tetrabenzo[8]circulene: Aromatic Saddles from Negatively Curved Graphene

An aromatic saddle was designed from the hypothetical three-dimensional graphene with the negative Gaussian curvature (Schwarzite P192). Two aromatic saddles, tetrabenzo[8]circulene (TB8C) and its octamethyl derivative OM-TB8C, were synthesized by the Scholl reaction of cyclic octaphenylene precursors. The structure of TB8C greatly deviates from planarity, and the deep saddle shape was confirmed by single-crystal X-ray crystallography. There are two conformers with the S4 symmetry, which are twisted compared to the DFT structure (D2d). The theoretical studies propose that the interconversion of TB8C via the planar transition state (125 kcal mol(-1)) is not possible. However, the pseudorotation leads to a low-energy tub-to-tub inversion via the nonplanar transition state (7.3 kcal mol(-1)). The ground-state structure of TB8C in solution is quite different from the X-ray structure because of the crystal-packing force and low-energy pseudorotation. OM-TB8C is a good electron donor and works as the p-type semiconductor.

Optical properties of pentacene and perfluoropentacene thin films.

The optical properties of pentacene (PEN) and perfluoropentacene (PFP) thin films on various SiO(2) substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using x-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A strong optical anisotropy was observed, and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorption spectra of the monomers in solution shows significant changes due to the crystalline environment. Relative to the monomer spectrum, the highest occupied molecular orbital to lowest unoccupied molecular orbital transition observed in PEN (PFP) thin film is reduced by 210 meV (280 meV). A second absorption band in the PFP thin film shows a slight blueshift (40 meV) compared to the spectrum of the monomer with its transition dipole perpendicular to that of the first absorption band.

Structural Order in Perfluoropentacene Thin Films and Heterostructures with Pentacene

Synchrotron x-ray diffraction reciprocal space mapping was performed on perfluoropentacene (PFP) thin films on SiO2 in order to determine the crystal structure of a novel, substrate-induced thin film phase to be monoclinic with unit cell parameters of a = 15.76 +/- 0.02 A, b = 4.51 +/- 0.02 A, c = 11.48 +/- 0.02 A, and beta = 90.4 +/- 0.1 degrees . Moreover, layered and co-deposited heterostructures of PFP and pentacene (P) were investigated by specular and grazing-incidence x-ray diffraction, atomic force microscopy, and Fourier-transform infrared spectroscopy. For a ca. three-monolayers-thick PFP film grown on a P underlayer, slightly increased lattice spacing was found. In contrast, co-deposited P/PFP films form a new mixed-crystal structure with no detectable degree of phase separation. These results highlight the structural complexity of these technically relevant molecular heterojunctions for use in organic electronics.

Perfluoropentacene and Perfluorotetracene: Syntheses, Crystal Structures, and FET Characteristics

The syntheses and FET characteristics of perfluoropentacene and perfluorotetracene are described. Both acenes are planar and crystalline materials that adopt π-stack structures with the short interpalnar distances of 3.27 Å in perfluorotetracene and 3.21 Å in perfluoropentacene. The oxidation and reduction peak potentials of the perfluorinated acenes shift positively compared with those of the corresponding acenes, suggesting that the HOMO and LUMO energies are diminished by fluorine substituents. Organic field-effect transistors (OFETs) with perfluoropentacene exhibit n-type semiconducting properties with high electron mobility of 0.22 cm2/V s.

Optical properties of fully and partially fluorinated rubrene in films and solution

We present the optical properties of fully (C42F28, PF-RUB) and half-fluorinated (C42F14H14, F14-RUB) rubrene, both in thin films and as monomers in solution and compare them to hydrogenated rubrene (C42H28, RUB). All three compounds show similar optical absorption bands and photoluminescence line shapes. The results are interpreted with density functional calculations of the orbital energies and time-dependent density functional theory for the HOMO-LUMO transition. Red shifts induced by the surrounding solvent or organic thin films remain much smaller than for polyacenes, in keeping with previous observations for rubrene and existing models for the solvatochromic shifts.

Formation and structural features of novel cage compounds with a pentacyclo[6.4.0.03,7.04,11.05,10]dodecane skeleton via photolysis of [33](1,3,5)cyclophane

The photolysis of [3 3 ](1,3,5)cyclophane 8 in MeOH:2N HCl (17:1 v/v) afforded new polycyclic caged dimethoxy and methoxy–hydroxy compounds 12 and 13 with a novel pentacyclo[6.4.0.0 3,7 .0 4,11 .0 5,10 ]dodecane skeleton 7 , in addition to methyl ether 9c with the previously reported skeleton 6 . The unique structural features of 12 and 13 were elucidated by X-ray structural analysis.

Crystal structural properties of a pinwheel compound: [36](1,2,3,4,5,6)cyclophane

In the crystal structures of [3 6 ](1,2,3,4,5,6)cyclophane 1 and the 1 :TCNQ (1:1) complex, the cyclophane moiety is observed as the D 6 h structure because of the disorder of the molecules with C 6 h symmetry. In contrast, the C 6 h structure is observed in the crystals of the 1 :TCNQ-F 4 (1:1) complex, and the complex shows an alternating donor–acceptor stacking with partial donor–acceptor overlap.