Using self-assembled monolayers for controlled electrodeposition of copper into submicrometer size surface features/decrements

This work presents the application of alkanethiols for selectively masking the main surface of copper-seed-layer-covered silicon wafer, as used for the microprocessor production. The target of the investigation was to deposit copper only in the trenches and vias (channels of various shape) of micrometer size and not over the entire surface as in the presently used methods. The procedure developed starts with filling the trenches and vias with water, which is followed by dipping the wafers in a hexane solution containing dissolved dodekanetiol. Alkanetiol adsorbs and self-organizes on copper not protected with water and blocks the electroreduction of copper ions from the bath. The trenches and vias are free from adsorbed alkanetiols due to their very limited solubility in water. The surface-blocking process works very well and may effectively simplify the copper electrodeposition for microelectronic applications. The selective electrodeposition of copper accomplished by the proposed method significantly reduces the problems associated with the removal of excess of copper from the processed circuit elements.     

Appearance of topological phases in superconducting nanocircuits

We construct non-Abelian geometric transformations in superconducting nanocircuits, which resemble in properties the Aharonov-Bohm phase for an electron transported around a magnetic flux line. The effective magnetic fields can be strongly localized, and the path is traversed in the region where the energy separation between the states involved is at maximum, so that the adiabaticity condition is weakened. In particular, we present a scheme of topological charge pumping.     

Isotope selective ionization by optimal control using shaped femtosecond laser pulses

We report on selective optimization of different isotopes in an ionization process by means of spectrally broad shaped fs-laser pulses. This is demonstrated for (39,39)K2 and (39,41)K2 by applying evolution strategies in a feedback loop, whereby a surprisingly high enhancement of one isotope versus the other and vice versa is achieved (total factor approximately 140). Information about the dynamics on the involved vibrational states is extracted from the optimal pulse shapes, which provides a new spectroscopical approach of yielding distinct frequency pattern on fs-time scales. The method should, in principle, be feasible for all molecules.     

Pattern replication in blends of semiconducting and insulating polymers casted by horizontal dipping

Pattern replication in solution‐deposited thin films of insulating and conjugated polymer mixtures might provide an alternative to spatially resolved printing techniques for the fabrication of polymer‐based circuitries. Though it has been previously shown that phase separation in the course of spin‐casting leads to the formation of domain structures resembling the chemical patterns pre‐set on the film substrate, finding optimal casting conditions is a tedious process, which requires multiple sample preparations. Here, we have demonstrated pattern replication in a mixture of poly(3,3′′′‐didodecyl quarter thiophene) (PQT‐12) and deuterated poly(styrene‐co?4‐bromostyrene) (dPBrS) deposited by horizontal‐dipping on substrates, patterned with self‐assembling molecules by micro‐contact printing. Moreover, we show that casting conditions for accomplishing pattern replication can be efficiently screened by preparing thickness gradient samples. We have optimized the reconstruction of the substrate pattern in the PQT‐12:dPBrS film. Our results prove that desired structures of semiconducting and insulating polymers can be produced in a simple, high‐throughput technological process. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1419–1426     

Novel 1,2,3-Triazole Derivatives as Mimics of Steroidal System—Synthesis,Crystal Structures Determination,Hirshfeld Surfaces Analysis and Molecular Docking

Herein, we present the synthesis and crystal structures determination of five 4-(1-phenyl-1H-1,2,3-triazol-4-yl)phenol derivatives containing halogen atoms, 6a–e, which may be used as an excellent mimic of steroids in the drug development process. Good quality crystals obtained for all of the synthesized compounds allowed the analysis of their molecular structures. Subsequently, the determined crystal structures were used to calculate the Hirshfeld surfaces for each of the synthesized compounds. Furthermore, results of our docking studies indicated that synthesized derivatives are able to bind effectively to the active sites of selected enzymes and receptors involved in the hormone biosynthesis and signaling pathways, analogously to the native steroids.     

Large breathing effect induced by water sorption in a remarkably stable nonporous cyanide-bridged coordination polymer

While metal–organic frameworks (MOFs) are at the forefront of cutting-edge porous materials, extraordinary sorption properties can also be observed in Prussian Blue Analogs (PBAs) and related materials comprising extremely short bridging ligands. Herein, we present a bimetallic nonporous cyanide-bridged coordination polymer (CP) {[Mn(imH)]₂[Mo(CN)₈]}_n (1Mn; imH = imidazole) that can efficiently and reversibly capture and release water molecules over tens of cycles without any fatigue despite being based on one of the shortest bridging ligands known – the cyanide. The sorption performance of {[Mn(imH)]₂[Mo(CN)₈]}_n matches or even outperforms MOFs that are typically selected for water harvesting applications with perfect sorption reversibility and very low desorption temperatures. Water sorption in 1Mn is possible due to the breathing effect (accompanied by a dramatic cyanide-framework transformation) occurring in three well-defined steps between four different crystal phases studied structurally by X-ray diffraction structural analysis. Moreover, the capture of H₂O by 1Mn switches the EPR signal intensity of the Mn^II centres, which has been demonstrated by in situ EPR measurements and enables monitoring of the hydration level of 1Mn by EPR. The sorption of water in 1Mn controls also its photomagnetic behavior at the cryogenic regime, thanks to the presence of the [Mo^IV(CN)₈]⁴⁻ photomagnetic chromophore in the structure. These observations demonstrate the extraordinary sorption potential of cyanide-bridged CPs and the possibility to merge it with the unique physical properties of this class of compounds arising from their bimetallic character (e.g. photomagnetism and long-range magnetic ordering).

A cyanide-bridged coordination polymer {[Mn(imH)]₂[Mo(CN)₈]}_n shows exceptional water sorption properties, very large breathing effect and outstanding stability – properties that are unique for this class of compounds – Prussian blue analogs.     

Controlled synthesis of tuned bandgap nanodimensional alloys of PbS(x)Se(1-x)

Truly alloyed PbS(x)Se(1-x) (x = 0-1) nanocrystals (～5 nm in size) have been prepared, and their resulting optical properties are red-shifted systematically as the sulfur content of the materials increases. Their optical properties are discussed using a modified Vegard's approach and the bowing parameter for these nanoalloys is reported for the first time. The alloyed structure of the nanocrystals is supported by the energy-filtered transmission electron microscope images of the samples, which show a homogeneous distribution of sulfur and selenium within the nanocrystals. X-ray photoelectron spectroscopy studies on ligand-exchanged nanocrystals confirmed the expected stoichiometry and various oxidized species.     

Efficient electron transfer in β-substituted porphyrin-C60 dyads connected through a p-phenylenevinylene dimer

Two new porphyrin-C₆₀ dyads have been synthesized in which the electroactive moieties have been connected through a p-phenylenevinylene dimer. The electrochemical study confirms the amphoteric redox behavior of these dyads. Irradiation of these compounds gives rise to the corresponding radical pair confirming that substitution on the β-position of the porphyrin facilitates the electronic communication between the porphyrin and C₆₀.