Flexible Stamp for Nanoimprint Lithography

The design, fabrication and performance of a flexible silicon stamp for homogenous large area nanoimprint lithography (NIL) are presented. The flexible stamp is fabricated by bulk semiconductor micro machining of a 4-inch silicon wafer and consists of thick anchor like imprint areas connected by membranes. The bending stiffness difference between the imprint areas and the membranes ensures that the deformation of the stamp during the imprint process mainly takes place in the membranes, leaving the imprint structures unaffected. By this design the strong demand to the parallelism between stamp and substrate in the imprint situation is decoupled from the pressing tool and the wafer quality. The stamp consist of 1562 imprint areas (1 mm × 1 mm) containing the patterns to be replicated. The imprinted patterns are characterized with respect to the imprint depth and the polymer residual layer thickness. It is found that within a 50 mm diameter the polymer residual layer thickness is 18.8 nm with a standard deviation of 6.6 nm

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn_(3)MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

The oxygen-evolving complex (OEC) of photosystem II contains a Mn_(4)CaO_n catalytic site, in which reactivity of bridging oxidos is fundamental to OEC function. We synthesized structurally relevant cuboidal Mn_(3)MO_n complexes (M = Mn, Ca, Sc; n = 3,4) to enable mechanistic studies of reactivity and incorporation of μ_(3)-oxido moieties. We found that Mn^(IV)_(3)CaO_4 and Mn^(IV)_(3)ScO_4 were unreactive toward trimethylphosphine (PMe_3). In contrast, our Mn^(III)_(2)Mn^(IV)_(2)O_4 cubane reacts with this phosphine within minutes to generate a novel Mn^(III)_(4)O_3 partial cubane plus Me_(3)PO. We used quantum mechanics to investigate the reaction paths for oxygen atom transfer to phosphine from Mn^(III)_(2)Mn^(IV)_(2)O_4 and Mn^(IV)_(3)CaO_4. We found that the most favorable reaction path leads to partial detachment of the CH_(3)COO^– ligand, which is energetically feasible only when Mn(III) is present. Experimentally, the lability of metal-bound acetates is greatest for Mn^(III)_(2)Mn^(IV)_(2)O_4. These results indicate that even with a strong oxygen atom acceptor, such as PMe_3, the oxygen atom transfer chemistry from Mn_(3)MO_4 cubanes is controlled by ligand lability, with the Mn^(IV)_(3)CaO_4 OEC model being unreactive. The oxidative oxide incorporation into the partial cubane, Mn^(III)_(4)O_3, was observed experimentally upon treatment with water, base, and oxidizing equivalents. ^(18)O-labeling experiments provided mechanistic insight into the position of incorporation in the partial cubane structure, consistent with mechanisms involving migration of oxide moieties within the cluster but not consistent with selective incorporation at the site available in the starting species. These results support recent proposals for the mechanism of the OEC, involving oxido migration between distinct positions within the cluster

Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn_3CaO_4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal

Synthetic model compounds have been targeted to benchmark and better understand the electronic structure, geometry, spectroscopy, and reactivity of the oxygen-evolving complex (OEC) of photosystem II, a low-symmetry Mn_4CaO_n cluster. Herein, low-symmetry Mn^(IV)_3GdO_4 and Mn^(IV_)3CaO_4 cubanes are synthesized in a rational, stepwise fashion through desymmetrization by ligand substitution, causing significant cubane distortions. As a result of increased electron richness and desymmetrization, a specific μ_3-oxo moiety of the Mn_3CaO_4 unit becomes more basic allowing for selective protonation. Coordination of a fifth metal ion, Ag+, to the same site gives a Mn_3CaAgO_4 cluster that models the topology of the OEC by displaying both a cubane motif and a “dangler” transition metal. The present synthetic strategy provides a rational roadmap for accessing more accurate models of the biological catalyst

A Modular Design for the 56 Variants of the Short Straight Section in the Arcs of the Large Hadron Collider (LHC)

The 360 Short Straight Sections (SSS) necessary for the eight arcs of the LHC machine have to fulfil different requirements. Their main function is to house the lattice two-in-one superconducting quadrupole and various correction magnets, all operating at 1.9 K in a superfluid helium bath. The magnetic and powering schemes of the arcs and the fact that the two proton beams alternate between the inner and outer magnet channels impose 24 different combinations of magnet assemblies, all housed in an identical helium enclosure. The cryogenic architecture of the LHC machine is based on cryogenic loops spanning over one half-cell (53 m) for the 4.6-20 K circuit, over a full cell (107 m) for the 1.9 K circuits, up to the full arc (about 2.3 km) for the shield cooling line. This cryogenic layout, when superimposed to the magnetic scheme, further complicated by the cryostat insulation vacuum sectorisation every 2 cells, creates additional assembly variants, up to a total number of 56. The required flexibility in the manufacture and assembly, as well as economic considerations, have led to a modular design for the different SSS components and sub-assemblies. This modularity allows to "specialise" the SSS at the latest possible assembly step of the "just in time" production line. This paper presents the conceptual design considerations to achieve this modularity, the SSS design retained for the series manufacture, and the assembly procedures recently validated on a prototype program at CERN