Untersuchungen zur Spin-Trapping-Kinetik in Systemen von Radikalen unterschiedlicher Reaktivität. Die Photolyse von α-Phenylbenzoin in Gegenwart von Benzyliden-tert.-butylamin-N-oxid

Investigations on Spin-Trapping Kineties in Radical Systems with Different Reactivity. Photolyses of α-Phenylbenzoine in the Presence of Benzylideneter. -butylamine N-oxide As a model system to study the spin-trapping kinetics of systems forming two radicals of different reactivity α-phenylbenzoine (PhB) was chosen. The photolysis of PhB forms benzoyl (B·) and diphenylketylradikals (K·), respectively, which can be trapped by benzylidene-tert-butyl-amine N-oxide (PBN), as a spin trap. The rate constants of radical addition to PBN and their reactions with the spin adducts were determined by means of flash photolysis and kinetic calculations of the PBN concentration dependence. For B· and K· addtion rate constants to PBN of k₁ = 8,1 × 10⁵ M⁻¹s⁻¹, and k₂ = 5,8 · 10⁴ M⁻¹s⁻¹, respectively, were found. The rate constants for the reactions of B· and K· with the spin adducts are in the order of 10⁹…10¹⁰ M⁻¹s⁻¹.     

Lichtinitiierte Polymer- und Polymerisationsreaktionen. 14. Radikalische Photopolymerisation mit Kaliumtrisoxalatocobaltat-Aryloniumsalz-Systemen

Light Induced Polymer and Polymerization Reactions. 14. Radical Photopolymerization by Potassium Trisoxalato Cobaltate Arylonium Salts Systems. The photopolymerization of acrylamide (AA) by trisoxalato cobaltate ([Co(ox)₃]³⊖) is inefficient because the produced nucleophilic ·CO₂⊖-radicals are oxidized or they terminate with polymer radicals. If onium compounds are added to this system the initiation efficiency is increased as follows : p-CH₃OC₆H₄N₂⊕>Ph₂I⊕>PhCOCH₂S(CH₃)₂⊕>Ph₃S⊕. By means of quantum yield measurements a mechanism was proposed including the electron transfer from ·CO₂⊖ to onium compounds. The produced radicals also initiate the polymerization of AA. The exponent m of the polymerization rate (v_p ≈︁ [AA]^m) is decreased from 1.4 to 1.1 in the presence of Ph₂I⊕, deciding the decrease of termination reaction between ·CO₂⊖ and polymer radicals. In comparison with K₃[Fx(ox)₃] the corresponding cobalt complex possesses higher polymerization quantum yields for AA.     

The TRAPS Apparatus: Enhancing Target Density of Nanoparticle Beams in Vacuum for X-ray and Optical Spectroscopy

We present an experimental setup that allows the injection of charged nanoparticles in a diameter range of 3–15 nm into a vacuum chamber and their storage there in an electrodynamic cage. The nanoparticle density in the trap is limited by space charge and can be several orders of magnitude higher than in a free nanoparticle beam. The setup provides for the first time a tool for the application of advanced techniques of spectroscopy to free nanoparticles in this size range. It consists of a combination of (1) a plasma discharge nanoparticle source that generates a high density of nanoparticles of various composition suspended in helium carrier gas at a pressure of about 10–150 mbar, (2) an aerodynamic lens optimized for small particles (diameter 3–15 nm) that forms a well-collimated beam of charged nanoparticles and focuses it into (3) an octopole ion trap operated at low frequencies and filled with helium buffer gas at 10^?2 mbar in order to moderate and store the nanoparticles at densities of more than 10⁷ cm^?3.     

Polaron recombination in pristine and annealed bulk heterojunction solar cells

The major loss mechanism of photogenerated polarons was investigated in P3HT:PCBM solar cells by the photo-CELIV technique. For pristine and annealed devices, we find that the experimental data can be explained by a bimolecular recombination rate reduced by a factor of about 10 (pristine) and 25 (annealed) as compared to Langevin theory. Aided by a macroscopic device model, we discuss the implications of the lowered loss rate on the characteristics of polymer:fullerene solar cells.     

Properties of single-walled carbon nanotube-based aerogels as a function of nanotube loading

Here, we present the synthesis and characterization of low-density single-walled carbon nanotube-based aerogels (SWNT-CA). Aerogels with varying nanotube loading (0–55 wt.%) and density (20–350 mg cm^?3) were fabricated and characterized by four-probe method, electron microscopy, Raman spectroscopy and nitrogen porosimetry. Several properties of the SWNT-CAs were highly dependent upon nanotube loading. At nanotube loadings of 55 wt.%, shrinkage of the aerogel monoliths during carbonization and drying was almost completely eliminated. Electrical conductivities are improved by an order of magnitude for the SWNT-CA (55 wt.% nanotubes) compared to those of foams without nanotubes. Surface areas as high as 184 m² g^?1 were achieved for SWNT-CAs with greater than 20 wt.% nanotube loading.     

Science and Technology of High Dielectric Constant Thin Films and Materials Integration for Application to High Frequency Devices

Thin films of Ba_1?x Sr _x Ti_1+y O_3+z (BST), were fabricated using both by RF-magnetron sputtering and MOCVD to demonstrate application to high frequency devices. Precise control of composition and microstructure is critical for the production of (Ba _x Sr_1?x )Ti_1+y O_3+z (BST) dielectric thin films with the large dependence of permittivity on electric field, low losses, and high electrical breakdown fields that are required for successful integration of BST into tunable high frequency devices. Here we review results on composition-microstructure-electrical property relationships of polycrystalline BST films produced by magnetron sputter deposition that are appropriate for microwave devices such as phase shifters. BST films with a multilayer structure were also developed with different Ti-elemental ratio in each layer to minimize losses and leakage current. Interfacial contamination from C and H species was studied and implications on electrical properties are highlighted. Finally, York's group at the University of California-Santa Barbara successfully integrated our BST films onto phase shifter arrays. The results show potential of BST films in such applications. Results from initial work on the integration of Cu-electrodes with BST films are also presented.