1,8-Bis[3-(triethoxy­silyl)prop­yl]-1,8-diazo­niatricyclo­[9.3.1.14,8]hexa­decane diiodide

The organic mol­ecule of title compound, C30H66N4O6Si2 2+·2I−, is located around a centre of symmetry. The structure exhibits disorder of the trieth­oxy groups with the ratios 0.78 (1)/0.22 (1), 0.67 (1)/0.33 (1) and 0.58 (1)/0.42 (1)

Mesoporous Silica-Based Materials for Electronics-Oriented Applications

International audienceElectronics, and nanoelectronics in particular, represent one of the most promising branches of technology. The search for novel and more efficient materials seems to be natural here. Thus far, silicon-based devices have been monopolizing this domain. Indeed, it is justified since it allows for significant miniaturization of electronic elements by their densification in integrated circuits. Nevertheless, silicon has some restrictions. Since this material is applied in the bulk form, the miniaturization limit seems to be already reached. Moreover, smaller silicon-based elements (mainly processors) need much more energy and generate significantly more heat than their larger counterparts. In our opinion, the future belongs to nanostructured materials where a proper structure is obtained by means of bottom-up nanotechnology. A great example of a material utilizing nanostructuring is mesoporous silica, which, due to its outstanding properties, can find numerous applications in electronic devices. This focused review is devoted to the application of porous silica-based materials in electronics. We guide the reader through the development and most crucial findings of porous silica from its first synthesis in 1992 to the present. The article describes constant struggle of researchers to find better solutions to supercapacitors, lower the k value or redox-active hybrids while maintaining robust mechanical properties. Finally, the last section refers to ultra-modern applications of silica such as molecular artificial neural networks or super-dense magnetic memory storage

An imidazolium ionic liquid as effective structure-directing agent for the fabrication of silica thin films with vertically aligned nanochannels

In parallel to the increasing variety of ionic liquids that show different kinds of nanometer-scale structuration in their pure and solved forms, there is a raising interest in exploring the possibility of using ionic liquids as soft-templates for the synthesis of mesoporous materials. We report the case of 1-hexadecyl-3-methylimidazolium chloride (C16MIMCl), a surface active ionic liquid (SAIL), here used as an excellent soft-template for the formation of vertically aligned, uniform mesochannels, with a well defined pore width of 2.5 nm in silica thin films deposited with the electrochemically assisted self-assembly (EASA) method. The obtained mesochannels run through the entire thickness of the films and after removal of the ionic liquid the emptied mesochannels ensure a thorough mass transport to the substrate, here monitored by the redox-active electrochemical probe Ru(II)/Ru(III) during cyclic voltammetry (CV). Moreover, the mechanism of pore formation is explained; unlike the mechanisms reported for short chain imidazolium ionic liquid silica templates, in the case of C16MIMCl the dominating so-called cooperative interaction is the electrostatic attraction between the C16MIM+ and the network-forming negatively charged silicate oligomers. Therefore, this study provides a better understanding of the templating behavior of long chain imidazolium ionic liquids and motivates further research on the synthesis of ionic liquid-based functional hybrid materials

Cu nanodendrite foams on integrated band array electrodes for the nonenzymatic detection of glucose

We demonstrate the successful electrodeposition of Cu nanodendrite foams (CuFoams) onto a series of lithographically formed gold band array electrodes at negative overpotentials in an acidic environment. The nanodendrite foams were deposited onto two different integrated microelectrode arrays fabricated using standard lithographic techniques. Each electrode consisted of 17 gold band electrodes deposited onto a silicon wafer substrate, labeled BA5 (with a width of 5 μm and a length of 250 μm) and BA10 (with a width of 10 μm and a length of 500 μm). Prior to Cu deposition the gold electrodes were characterized by scanning electron microscopy (SEM) in order to evaluate the morphology of each design and by cyclic voltammetry (CV) in order to investigate their diffusion profiles. After Cu deposition the resulting 3D foam structures were studied using SEM, XPS, and EDX. The CuFoam/Au microelectrodes were then used for the electrocatalytic detection of glucose via oxidation at a potential of +0.45 V vs Ag/AgCl in an alkaline medium. It was found that both types of electrode arrays used showed excellent analytical performance in terms of sensitivity, reproducibility, and stability in comparison with the best performances reported in the literature. In particular, the BA5-CuFoam electrode exhibited an outstanding sensitivity of 10,630 μA mM–1 cm–2 toward glucose with a wide linear range up to 22.55 mM, while the BA10-CuFoam electrode showed a sensitivity of 4,437 μA mM–1 cm–2. The performance of the proposed electrochemical sensor is attributed to a combination of the use of the very high surface area Cu nanodendrite foam and the enhanced radial distribution profile associated with the use of the smaller band microfabricated electrodes. Additionally, both sensors also showed a strong resistance to the poisoning effects of chlorine ions and excellent stability over a period of three months

Bimodal mesoporous titanium dioxide anatase films templated by a block polymer and an ionic liquid: influence of the porosity on the permeability

In the present paper, we report the synthesis of bimodal mesoporous anatase TiO2 films by the EISA (Evaporation-Induced Self-Assembly) method using sol-gel chemistry combining two porogen agents, a low molecular weight ionic template and a neutral block copolymer. The surfactant template (C(16)mimCl) generates non-oriented worm-like pores (8 to 10 nm) which connect the regularly packed ellipsoidal mesopores (15 to 20 nm diameter) formed by an amphiphilic block copolymer of the type poly(isobutylene)-b-poly(ethylene oxide) (PIB-PEO). The surfactant template can also significantly influence the size and packing of the ellipsoidal mesopores. The mesostructural organization and mesoporosity of the films are studied by Environmental Ellipsometry-Porosimetry (EEP), Grazing-Incidence Small-Angle X-ray Scattering (GISAXS) and electron microscopy techniques. Electrochemical characterization is performed to study the permeability of the films to liquid solutions, using two types of probe moieties (K3FeIII(CN)(6) and Ru(bpy)(3)(2+)) by the wall-jet technique. An optimum ratio of C(16)mimCl/PIB-PEO provides anatase films with a continuous bimodal mesopore structure, possessing a permeability up to two times higher than that of the mesoporous films templated by PIB-PEO only (with partially isolated mesopores). When C(16)mimCl is used in large quantities, up to 20% weight vs. PIB-PEO, large overall porous volume and surface area are obtained, but the mesostructure is increasingly disrupted, leading to a severe loss of permeability of the bimodal films. A dye-sensitized solar cell set-up is used with anatase films as the photoelectrode. The photosensitizer loading and the total energy conversion efficiency of the solar cells using the mesoporous films templated by an optimal ratio of the two porogen agents C(16)mimCl and PIB-PEO can be substantially increased in comparison with the solar cells using mesoporous films templated by PIB-PEO only.DFG/SM 199/6-1DFG/OE 420/5-1BMBF/SOHyb/03X3525

Positronium reemission yield from mesostructured silica films

The reemission yield of ortho-positronium (o-Ps) into vacuum outside mesoporous silica films on glass is measured in reflection mode with a specially designed lifetime (LT) spectrometer. Values as high as 40% are found. The intensity of the 142 ns vacuum LT is recorded as a function of reemission depth. The LT depth profiling is correlated to the 2gamma and 3gamma energy ones to determine the annihilation characteristics inside the films. Positron lifetime in capped films is used to determine the pore size. For the first time, a set of consistent fingerprints for Ps annihilation, o-Ps reemission into vacuum, and pore size, is directly determined in CTACl-TEOS films

Visualization of Diffusion within Nanoarrays

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems

Electrochemical Applications of Silica-Based Organic−Inorganic Hybrid Materials

International audienceThe attractive properties of both class I and class II silicica-based organic−inorganic hybrid materials have been successfully exploited in electrochemistry. This is exemplified in this review by means of several application examples