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We theoretically investigate microscopic origins of vibronic coupling (VC) contributing to singlet fission (SF) dynamics in pentacene and its halogenated derivatives. The features of VCs related to diabatic exciton states and interstate electronic couplings (Holstein and Peierls couplings, respectively) are interpreted by the VC density (VCD) analysis, which allows one to clarify the relationship between the chemical structure and VC as spatial contribution. It is found for the pentacene dimer face-to-edge configuration in a herringbone crystal that characteristic intermolecular vibrations with low frequencies exhibit strong Holstein couplings for the intermediate charge-transfer (CT) exciton states as well as Peierls couplings. From VCD analysis, the comprising density of the intermolecular CT and that of the intermolecular vibration are found to be constructively mixed in the intermolecular space, leading to the enhancement of VC. Moreover, in order to assess the chemical modification manner for controlling VC, we design several halogenated pentacene derivatives with slip-stack configurations. Our strategy to enhance VCD by halogenation is found to be rational, whereas the peaks of VC spectra for the CT states in the slip-stack packings are observed in high frequency regions. We compare their SF dynamics based on the quantum master equation explicitly including the exciton state-dependent VCs. From the analysis on relative relaxation factors between the adiabatic exciton states, their difference in the SF rate is highlighted by exciton configurations in addition to VCs. The present study is expected to be a first step toward efficient SF based on the design of VC in terms of both the chemical structure and intermolecular packing. [ABSTRACT FROM AUTHOR]

Theoretical molecular design of efficient nonlinear optical (NLO) systems using singlet fission (SF) is performed for butterfly-shaped acenes with/without nitrogen and sulfur substitutions using quantum chemical calculations, exciton dynamics simulations, and Marcus theory. It is found that these large systems meet the energy level matching conditions of efficient SF and exhibit superior third-order NLO properties (second hyperpolarizability γ at the molecular scale) to a typical SF molecule, pentacene. In addition, we investigate SF rates and γ in the correlated triplet pair [1(TT)] state generated by SF for various slip-stacked dimer models of these systems. For molecular packing with relatively large 1(TT) yields, a significant increase in γ/monomer in the 1(TT) state is observed, which is in good agreement with the electronic-coupling-based design guidelines obtained from our previous study. In particular, the butterfly-shaped acenes involving heteroatoms are found to exhibit a significant increase in γ/monomer as compared to the other systems. By analyzing the excitation properties in the 1(TT) state and intermolecular orbital interactions, we clarify the origin of such γ enhancement. The obtained results contribute to the construction of design guidelines for efficient SF-induced-NLO materials and demonstrate that butterfly-shaped acenes have the potential to surpass conventional NLO systems. [ABSTRACT FROM AUTHOR]

Degradation mechanism of stacked high-k gate dielectrics has been studied with metal-oxide-semiconductor capacitors having HfAlOX/SiO2 films of various thickness combinations. A large leakage current with a peaked shape, named as the low-voltage peak current (LVPC), has been observed in the low-voltage region even in the initial current–voltage characteristics. It has been shown that a main part of LVPC is the transient current component controlled by the process of hole injection to traps in the vicinity of the HfAlOX/SiO2 interface through the interfacial SiO2 layer. By the electrical stress, both the transient and the steady-state current components monotonically increase with time having different rates. Steady-state component has significantly larger rate than the transient component, and the same rate with the stress-induced leakage current (SILC) observed in the high-voltage region, indicating that the steady-state component of LVPC should be regarded as the SILC in the higher-voltage region extending down to the lower gate voltage region where the LVPC is observed. [ABSTRACT FROM AUTHOR]

The preparation of transparent conducting impurity-doped ZnO thin films by both pulsed laser deposition (PLD) and magnetron sputtering deposition (MSD) using impurity-doped ZnO targets sintered with a newly developed energy saving millimeter-wave (28 GHz) heating technique is described. Al-doped ZnO (AZO) and V-co-doped AZO (AZO:V) targets were prepared by sintering with various impurity contents for 30 min at a temperature of approximately 1250 °C in an air or Ar gas atmosphere using the millimeter-wave heating technique. The resulting resistivity and its thickness dependence obtainable in thin films prepared by PLD using millimeter-wave-sintered AZO targets were comparable to those obtained in thin films prepared by PLD using conventional furnace-sintered AZO targets; a low resistivity on the order of 3×10-4 Ω cm was obtained in AZO thin films prepared with an Al content [Al/(Al+Zn) atomic ratio] of 3.2 at. % and a thickness of 100 nm. In addition, the resulting resistivity and its spatial distribution on the substrate surface obtainable in thin films prepared by rf-MSD using a millimeter-wave-sintered AZO target were almost the same as those obtained in thin films prepared by rf-MSD using a conventional powder AZO target. Thin films prepared by PLD using millimeter-wave-sintered AZO:V targets exhibited an improved resistivity stability in a high humidity environment. Thin films deposited with a thickness of approximately 100 nm using an AZO:V target codoped with an Al content of 4 at. % and a V content [V/(V+Zn) atomic ratio] of 0.2 at. % were sufficiently stable when long-term tested in air at 90% relative humidity and 60 °C. [ABSTRACT FROM AUTHOR]

Degradation behavior of oxide–nitride–oxide (ONO) stacked gate dielectrics used in metal–oxide–nitride–oxide–silicon (MONOS)-based flash memories has been studied. Occurrence of the soft breakdown (SBD), which is well known in single-layer ultrathin silicon dioxides, has been revealed even in these thick and stacked dielectrics. The SBD of ONO dielectrics shows similar characteristics with that of silicon dioxides in locality, current/voltage fluctuation, and the dependencies of the ratio of SBD on the gate area and stress condition. These findings require the countermeasure for SBD even in MONOS-based flash memories and also give useful information on the reliability of high-k stacked gate dielectrics. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Investigates the electrical stress-induced variable range hopping conduction in ultrathin silicon dioxides. Proposal of a model for the conduction mechanism of the B-mode stress-induced leakage current (B-SILC); Function of B-SILC; Discussion on the empirical expression for the current-voltage characteristics of the B-SILC.