Atomic layer deposition for rutile structure TiO2thin films using a SnO2seed layer and low temperature heat treatment.

We study the rutile-TiO2film deposition with a high-kvalue using a SnO2seed layer and a low temperature heat treatment. Generally, heat treatment over 600 °C is required to obtain the rutile-TiO2film. However, By using a SnO2seed layer, we obtained rutile-TiO2films with heat treatments as low as 400 °C. The XPS analysis confirms that the SnO2and TiO2film were deposited. The XRD analysis showed that a heat treatment at 400 °C after depositing the SnO2and TiO2films was effective in obtaining the rutile-TiO2film when the SnO2film was thicker than 10 nm. The TEM/EDX analysis show that no diffusion in the thin film between TiO2and SnO2. The dielectric constant of the TiO2film deposited on the SnO2film (20 nm) was 67, which was more than twice as high as anatase TiO2dielectric constant (Anatase TiO2dielectric constant : 15-40). The current density was 10-4A cm-2at 0.7 V and this value confirmed that the leakage current was not affected by the SnO2seed layer.

Fabrication and ink-jet patterning of copper nanoparticles with improved dispersion stability.

Copper (Cu) nanoparticles as the metal nanoparticles in the conductive ink were synthesized using electrochemical reaction. This method is characterized as the synthesis process without any metal salts and the post-treatment of washing and drying. It means that it does not need to consider about oxidized and agglomerated metal nanoparticles during the extra treatments. The Cu nanoparticles were synthesized in the various conditions of electrolyte to investigate the mechanism of the synthesis reaction of Cu nanoparticles. And also, the synthesized Cu nanoparticles were controlled the dispersion stability with the addition of dispersion agent such as PVP and Dextran. Finally, it was achieved the ink-jet printed Cu patterns using the synthesized Cu nanoparticles, and examined the morphology of the patterns.

Study on a set of bis-cyclometalated Ir(III) complexes with a common ancillary ligand.

Bis-cyclometalated iridium(III) complexes [Ir(F2ppy)2ZN] (FZN), [Ir(F2CNppy)2ZN] (FCZN), [Ir(DMAF2ppy)2ZN] (FDZN) and [Ir(MeOF2ppy)2ZN] (MeOFZN) (F2ppy = 4',6'-difluoro-2-phenylpyridinate, F2CNppy = 5-cyano-4',6'-difluoro-2-phenylpyridinate, DMAF2ppy = 4',6'-difluoro-4-dimethylamino-2-phenylpyridinate, MeOF2ppy = 4',6'-difluoro-4-methyl-2-phenylpyridinate and ZN = 3,5-dimethylpyrazole-N-carboxamide) emitting in the sky blue region were synthesized. We studied the effect of the ancillary ligand ZN and the substituents on the cyclometalating ligands on the crystal structures, photophysical and electrochemical properties and the frontier orbitals. Density functional theory (DFT) calculation results indicate that in FCZN and FDZN the cyclometalating ligands show negligible participation in the HOMO, the ancillary ligand ZN being the main participant along with the Ir(III) d-orbitals. MeOFZN exhibits the maximum photoluminescence quantum efficiency and radiative emission rates along with the dominant low frequency metal-ligand vibrations and maximum reorganization energy in the excited state. All the substituted complexes show more polar characteristics than FZN, FCZN possessing the highest dipole moment among the complexes. The performances of the solution-synthesised organic light emitting devices (OLEDs) of FZN, FCZN and FDZN doped in a blend of mCP (m-bis(N-carbazolylbenzene)) and polystyrene are studied.

Solution-processed high-efficiency organic phosphorescent devices utilizing a blue Ir(III) complex.

We report high-efficiency blue phosphorescence organic light-emitting devices by solution process utilizing a blue Ir(III) complex [(F2ppy)2Ir(ph-imz)CN] (F2ppy = 2',6' -difluoro-2-phenyl pyridine and ph-imz = N-phenyl imidazole) blended with the host mCP (N, N'-dicarbazolyl-3,5-benzene), and the inert polymers polystyrene (PS) and polymethylmethacrylate (PMMA). The effects of the dopant confinement in the PS and PMMA matrix on the device performance are studied by field emission transmission electron microscopy (FE-TEM) and atomic force microscopy (AFM). The complex shows photoluminescence peaked at 458 nm with CIE color coordinates (0.14, 0.21) in solution and (0.14, 0.18) in doped PMMA film. The PS based device showed better device performance than the PMMA based device with a maximum luminous efficiency of (etaL) 5.11 cd/A with CIE color coordinates (0.17, 0.29) (at 10 mA/cm2) and a maximum luminance of 9765 cd/m2.

Substituent effect on the luminescent properties of a series of deep blue emitting mixed ligand Ir(III) complexes.

The syntheses of the bright deep blue emitting mixed ligand Ir(III) complexes comprising two cyclometalating, one phosphine and one cyano, ligands are reported. In this study, a firm connection between the nature of the excited states and the physicochemical behavior of the complexes with different ligand systems is elucidated by correlating the observed crystal structures, spectroscopic properties, and electrochemical properties with the theoretical results obtained by the density functional theory (DFT) methods. The cyclometalating ligands used here are the anions of 2-(4',6'-difluorophenyl)-pyridine (F2ppy), 2-(4',6'-difluorophenyl)-4-methyl pyridine (F2ppyM), and 4-amino-2-(4',6'-difluorophenyl)-pyridine (DMAF2ppy). The phosphine ligands are PhP(O-(CH2CH2O)3-CH3)2 and Ph2P(O-(CH2CH2O)n-CH3), where Ph = phenyl and n = 1 (P1), 3 (P3), or 8 (P350). The thermal stabilities of the complexes were enhanced upon increasing the "n" value. The crystal structures of the complexes, [(DMAF2ppy)2Ir(P1)CN], (P1)DMA, and [(F2ppyM)2Ir(P3)CN], (P3)F2M, show the cyano and phosphine groups being in a cis configuration to each other and in a trans configuration to the coordinating Cring atoms. The long Ir-Cring bond lengths are ascribed to the trans effect of the strong phosphine and cyano ligands. DFT calculations indicate that the highest occupied molecular orbital (HOMO) is mainly contributed from the d-orbitals of the iridium atom and the pi-orbitals of cyclometalating and cyano ligands, whereas the lowest unoccupied molecular orbital (LUMO) spreads over only one of the cyclometalating ligands, with no contribution from phosphine ligands to both frontier orbitals. Dimethylamino substitution increases the energy of the emitting state that has more metal-to-ligand-charge-transfer (MLCT) character evidenced by the smaller vibronic progressions, smaller difference in the 1MLCT and 3MLCT absorption wavelengths, and higher extinction coefficients (epsilon) than the F2ppy and F2ppyM complexes. However, the increase in the basicity of the dimethylamino group in the DMAF2ppy complexes in the excited states leads to distortions and consequent nonradiative depopulation of the excited states, decreasing their lower photoluminescence (PL) efficiency. The effect of the substituents in the phosphine ligand is more pronounced in the electroluminescence (EL) than in the PL properties. Multilayer organic light emitting devices (OLEDs) are fabricated by doping the Ir(III) complexes in a blend of mCP (m-bis(N-carbazolyl benzene)) and polystyrene, and their device characteristics are studied. The (P3)F2M complex shows a maximum external quantum efficiency (etaex) of 2%, a maximum luminance efficiency (etaL) of 4.13 cd/A at 0.04 mA/cm2, and a maximum brightness of 7200 cd/m2 with a shift of the Commission Internationale de L'Eclairage (CIE) coordinates from (0.14, 0.15) in film PL to (0.19, 0.34) in EL.

Mono- and Dinuclear d(10) Metal Complexes of Hexakis(3,5-dimethylpyrazolyl)cyclotriphosphazene. Synthesis, Structures, and Unusual Solution Dynamic Behavior.

Synthesis, structures, and unusual solution dynamic processes of d(10) metal complexes of hexakis(3,5-dimethylpyrazolyl)cyclotriphosphazene (L) are reported. Reaction systems with three MX(n):L mole ratios (MX(n) = d(10) metal halide) in CH(2)Cl(2) have resulted in the formation of [ICu(&mgr;,eta(3),eta(3)-L)CuI] (1), [Cl(2)Zn(&mgr;,eta(2),eta(3)-L)ZnCl(2)] (2), [Cl(2)Cd(&mgr;,eta(3),eta(3)-L)CdCl(2)] (3), and [(eta(3)-L)HgCl(2)] (4). These compounds were characterized by single crystal X-ray diffraction studies, and crystallographic data are given in the order of compound: crystal system; space group; unit cell parameters; Z; unique data (I > 2sigma(I)); R(1). 1.0.5CH(2)Cl(2): monoclinic; P2(1)/c; a = 8.268(4) Å; b = 22.365(5) Å; c = 23.325(8) Å, beta = 93.06(1) degrees; 4; 5736; 4.82. 2.CH(3)CN: monoclinic; P2(1)/c; a = 17.021(3) Å; b = 12.161(2) Å; c = 23.608(5) Å; beta = 107.72(1) degrees; 4; 5469; 3.16. 3.CH(2)Cl(2): monoclinic; P2(1)/n; a = 18.585(5) Å; b = 17.585(4) Å; c = 14.404(3) Å; beta = 102.71(2) degrees; 4; 3814; 3.65. The structure of 4 was attempted but resulted in data of low precision. Reaction of L with CuI and ZnCl(2) in an equimolar ratio afforded [ICu(&mgr;,eta(3),eta(3)-L)ZnCl(2)] (5) which crystallizes in monoclinic space group P2(1)/n with a = 22.876(5) Å, b = 21.594(4) Å, c = 9.177(2) Å, beta = 93.54(2) degrees, Z = 4, and R(1) = 7.00 for 3806 (I > 2sigma(I)) data. In all cases, metal halide centers except the Td zinc site in 2 are coordinated by L via a kappa(3)N binding core consisting of two nongeminal pyrazolyl nitrogen atoms and one phosphazene ring nitrogen atom. The eta(2)-N(2) coordination in 2 involves two geminal pyrazolyl nitrogen atoms. Factors which govern the nuclearity of the complex were partially demonstrated. The intermetallic distances in dinuclear metallophosphazenes range from 6.790 to 7.195 Å. The solution behavior of five compounds was studied by variable temperature (31)P{(1)H}, (1)H, and (113)Cd FT NMR spectroscopy. Compounds 1 and 4 are associated with fluxional motions involving A(2)B low-temperature limit spectrum while compounds 2 and 5 show solvent-dependent dynamic processes with ABX and A(2)B low-temperature limit spectral patterns. Compounds 3 constitutes a fluxional system involving three A(2)B species. Accounts of solution NMR spectra were attempted by using PANIC, by assuming the formation of new solution metallophosphazene species and by considering several types of dynamic processes such as a ring-around type hopping motion for the kappa(3)N metal site, a Td conformational change for the geminal pyrazolyl kappa(2)N metal site, and a wigwag motion for the nongeminal pyrazolyl kappa(2)N metal unit.