The effect of dendritic substituents on a nonlinear optical chromophore for optical power limiting (OPL) has been investigated. Synthesis and characterization of bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II) with dendritic end groups are described. Polyester dendrimers up to the fourth generation were grown divergently using the anhydride of 2,2-bis(methylol)propionic acid (bis-MPA). The introduction of the dendritic moieties onto the NLO chromophore enables further processing of the materials using polymeric and related techniques. OPL measurements performed at 532, 580, and 630 nm show that the OPL properties improve with increasing size of the dendritic substituent. It is also shown that the addition of the dendrons increase the OPL as compared to the nondecorated bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II). By use of femtosecond z-scan measurements carried out at different pulse-repetition frequencies, it is shown that the two-photon absorption cross section is ∼10 GM. Using pulse repetition frequencies (100 kHz-4.75 MHz) so that the time between the pulses is comparable with the triplet excited lifetime, the z-scans become dominated by excited-state absorption of excited triplet states.

A model equation governing the amplitude of the electric field in an array of coupled optical waveguides embedded in a material with Kerr nonlinearities is derived and explored. The equation is an extended discrete nonlinear Schrödinger equation with intersite nonlinearities. Attention is turned towards localized solutions and investigations are made from the viewpoint of the theory of discrete breathers (DBs). Stability analysis reveals an inversion of stability between stationary one-site and symmetric or antisymmetric two-site solutions connected to bifurcations with a pair of asymmetric intermediate DBs. The stability inversion leads to the existence of high-intensity narrow mobile solutions, which can propagate essentially radiationless. The direction and transverse velocity of the mobile solutions can be controlled by appropriate perturbations. Such solutions may have an important application for multiport switching, allowing unambiguous selection of output channel. The derived equation also supports compact DBs, which in some sense yield the best possible solutions for switching purposes.

Optical power limiting and luminescence properties of two Pt(II) complexes with thiophenyl and phenyl groups in the ligands, trans-Pt(P(n-Bu)3)2(C[triple bond]C-Ar)2, where Ar = -C4H2S-C[triple bond]C-p-C6H4-n-C5H11 (1) and -p-C6H4-C[triple bond]C-C4H3S (2), have been investigated. The fluorescence lifetimes were found to be on the sub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing from the excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of a Pt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in the ground state, the 13C NMR chemical shift of the carbon directly bonded to Pt, the coupling constants 1JPtC, 2JPtC, and 1JPtP, and IR nuC[triple bond]C wavenumbers were obtained for 1, 2, and three other trans-diarylalkynyl Pt(II) complexes. X-ray diffraction data of 1 and 2 and density functional theory calculated geometries of models of 1, 2, and trans-Pt(P(n-Bu)3)2(C[triple bond]C-p-C6H4-C[triple bond]C-C6H5)2 (3) show that 1 preferably exists in a different conformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalized by differences in geometry and pi-backbonding from Pt to the alkynyl ligand.

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DC arc plasma from Ti, Al, and Ti 1-x Al x (x ¼ 0.16, 0.25, 0.50, and 0.70) compound cathodes was characterized with respect to plasma chemistry and charge-state-resolved ion energy. Scanning electron microscopy, X-ray diffraction, and Energy-dispersive X-ray spectroscopy of the deposited films and the cathode surfaces were used for exploring the correlation between cathode-, plasma-, and film composition. Experimental work was performed at a base pressure of 10 À6 Torr, to exclude plasma-gas interaction. The plasma ion composition showed a reduction of Al of approximately 5 at. % compared to the cathode composition, while deposited films were in accordance with the cathode stoichiometry. This may be explained by presence of neutrals in the plasma/vapour phase. The average ion charge states (Ti ¼ 2.2, Al ¼ 1.65) were consistent with reference data for elemental cathodes, and approximately independent on the cathode composition. On the contrary, the width of the ion energy distributions (IEDs) were drastically reduced when comparing the elemental Ti and Al cathodes with Ti 0.5 Al 0.5 , going from $150 and $175 eV to $100 and $75 eV for Ti and Al ions, respectively. This may be explained by a reduction in electron temperature, commonly associated with the high energy tail of the IED. The average Ti and Al ion energies ranged between $50 and $61 eV, and $30 and $50 eV, respectively, for different cathode compositions. The attained energy trends were explained by the velocity rule for compound cathodes, which states that the most likely velocities of ions of different mass are equal. Hence, compared to elemental cathodes, the faster Al ions will be decelerated, and the slower Ti ions will be accelerated when originating from compound cathodes. The intensity of the macroparticle generation and thickness of the deposited films were also found to be dependent on the cathode composition. The presented results may be of importance for choice of cathodes for thin film depositions involving compound cathodes. V C 2014 AIP Publishing LLC.

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This paper presents the physical mechanism behind the phenomenon of self-layering in thin films made by industrial scale cathodic arc deposition systems using compound Ti-Si-C cathodes and rotating substrate fixture. For the as-deposited films, electron microscopy and energy dispersive X-ray spectrometry reveals a trapezoid modulation in Si content in the substrate normal direction, with a period of 4 to 23 nm dependent on cathode configuration. This is caused by preferential resputtering of Si by the energetic deposition flux incident at high incidence angles, when the substrates are facing away from the cathodes. The Ti-rich sub-layers exhibit TiC grains with sizes up to 5 nm, while layers with high Si-content are less crystalline. The nanoindentation hardness of the films increases with decreasing layer thickness.

Arc plasma from Ti-C, Ti-Al, and Ti-Si cathodes was characterized with respect to charge-stateresolved ion energy. The evaluated peak velocities of different ion species in plasma generated from a compound cathode were found to be equal and independent on ion mass. Therefore, measured difference in kinetic energies can be inferred from the difference in ion mass, with no dependence on ion charge state. The latter is consistent with previous work. These findings can be explained by plasma quasineutrality, ion acceleration by pressure gradients, and electron-ion coupling. Increasing the C concentration in Ti-C cathodes resulted in increasing average and peak ion energies for all ion species. This effect can be explained by the "cohesive energy rule," where material and phases of higher cohesive energy generally result in increasing energies (velocities). This is also consistent with the here obtained peak velocities around 1.37, 1.42, and 1.55 (10 4