Spectromicroscopy Studies of Silicon Nanowires Array Covered by Tin Oxide Layers

The composition and atomic and electronic structure of a silicon nanowire (SiNW) array coated with tin oxide are studied at the spectromicroscopic level. SiNWs are covered from top to down with a wide bandgap tin oxide layer using a metal–organic chemical vapor deposition technique. Results obtained via scanning electron microscopy and X-ray diffraction showed that tin-oxide nanocrystals, 20 nm in size, form a continuous and highly developed surface with a complex phase composition responsible for the observed electronic structure transformation. The “one spot” combination, containing a chemically sensitive morphology and spectroscopic data, is examined via photoemission electron microscopy in the X-ray absorption near-edge structure spectroscopy (XANES) mode. The observed spectromicroscopy results showed that the entire SiNW surface is covered with a tin(IV) oxide layer and traces of tin(II) oxide and metallic tin phases. The deviation from stoichiometric SnO2 leads to the formation of the density of states sub-band in the atop tin oxide layer bandgap close to the bottom of the SnO2 conduction band. These observations open up the possibility of the precise surface electronic structures estimation using photo-electron microscopy in XANES mode

Localization of the E. coli Dps protein molecules in a silicon wires under removal of residual salt

The work is related to the removal of residual salts in hybrid structures formed as a result of silicon wires arrays combining with a nanomaterial of natural origin – bacterial ferritin-like protein Dps. The study of the morphology and composition of the surface and the bulk part of the hybrid structure as a result of combination and subsequent washing in water was carried out. The method of metal-assisted wet chemical etching was used to obtain silicon wires arrays. To obtain recombinant protein, Escherichia coli BL21*(DE3) cells with chromatographic purification were used as producers. The combination of silicon wires with protein molecules was carried out by layering them in laboratory conditions, followed by drying. The residual salt found earlier in the hybrid material was removed by washing in water. The resulting hybrid material was studied by scanning electron microscopy and X-ray photoelectron spectroscopy. A well-proven complementary combination of scanning electron microscopy and X-ray photoelectron spectroscopy together with ion etching was used to study the morphology of the hybrid material “silicon wires – bacterial protein Dps” and the composition with physico-chemical state respectively. In arrays of silicon wires with a wire diameter of about 100 nm and a distance between them from submicron to nanometer sizes, protein was found as a result of layering and after treatment in water. At the same time, the amount of residual NaCl salt is minimized on the surface of the hybrid structure and in its volume. The obtained data can be used in the development of coating technology for the silicon wires developed surface available for functionalization with controlled delivery of biohybrid materia

X-ray photoelectron spectroscopy of hybrid 3T3 NIH cell structures with internalized porous silicon nanoparticles on substrates of various materials

The work is related to the study of a biohybrid material based on mammalian 3T3 NIH mouse fibroblast cells with immobilized porous silicon particles including nanocrystals about 10 nm in size by photoelectron spectroscopy. The influence of the surface material of the substrate on which the biohybrid material is grown on the possibility of conducting studies of the physico-chemical state of the developed surface is studied. Nickel as well as gold and titanium, known for their biocompatibility, were used as surface materials for cell growth and subsequent internalization of silicon particles. The method of optical microscopy in the reflected light mode was used to assess the distribution of cells on surfaces. It is shown that the nickel surface is not suitable for the synthesis and subsequent studies of biohybrid structures. At the same time, on the surface of gold and titanium, cellular material and structures based on it are available for measurements, including by photoelectron spectroscopy, a high-precision method for studying the atoms charge state and the physico-chemical state of the surface as a whole. The X-ray photoelectronic spectra show all the main components expected to be detected after drying and subsequent vacuuming of the studied objects: the surface material of the substrates and arrays of cell cultures grown on the substrates. No signal from silicon atoms was detected on the nickel surface. In the case of a gold surface, the proximity of the binding energies of the gold core levels (substrate) and silicon (internalized particles) leads to the fact that the signal of gold atoms, which is significant in its intensity, does not allow detecting a signal from silicon atoms, which is weaker in intensity. The signal of silicon atoms in biohybrid structures is reliably detected only when using titanium substrates, including for a control sample containing porous silicon nanoparticles without incubation in cells. Thus, it is shown that the surface of the titanium foil can be used for studies by photoelectron spectroscopy of a biohybrid material based on mammalian 3T3 NIH mouse fibroblast cells with immobilized porous silicon particles.The obtained result is important for high-precision diagnostics of the physico-chemical state of biohybrid materials and structures based on them with a low content of silicon atoms when solving problems of studying the compatibility and possibilities of using silicon nanomaterials for medical, including therapeutic and other applications

Peculiarities of electronic structure of silicon-on-insulator structures and their interaction with synchrotron radiation

SOI (silicon-on-insulator) structures with strained and unstrained silicon layers were studied by ultrasoft X-ray emission spectroscopy and X-ray absorption near edge structure spectroscopy with the use of synchrotron radiation techniques. Analysis of X-ray data has shown a noticeable transformation of the electron energy spectrum and local partial density of states distribution in valence and conduction bands in the strained silicon layer of the SOI structure. USXES Si L2,3 spectra analysis revealed a decrease of the distance between the L2v′ и L1v points in the valence band of the strained silicon layer as well as a shift of the first two maxima of the XANES first derivation spectra to the higher energies with respect to conduction band bottom Ec. At the same time the X-ray standing waves of synchrotron radiation (λ~12–20 nm) are formed in the silicon-on-insulator structure with and without strains of the silicon layer. Moreover changing the synchrotron radiation grazing angle θ by 2° leads to a change of the electromagnetic field phase to the opposite

The Oligomeric Form of the Escherichia coli Dps Protein Depends on the Availability of Iron Ions

The Dps protein of Escherichia coli, which combines ferroxidase activity and the ability to bind DNA, is effectively used by bacteria to protect their genomes from damage. Both activities depend on the integrity of this multi-subunit protein, which has an inner cavity for iron oxides; however, the diversity of its oligomeric forms has only been studied fragmentarily. Here, we show that iron ions stabilize the dodecameric form of Dps. This was found by electrophoretic fractionation and size exclusion chromatography, which revealed several oligomers in highly purified protein samples and demonstrated their conversion to dodecamers in the presence of 1 mM Mohr’s salt. The transmission electron microscopy data contradicted the assumption that the stabilizing effect is given by the optimal core size formed in the inner cavity of Dps. The charge state of iron ions was evaluated using Mössbauer spectroscopy, which showed the presence of Fe3O4, rather than the expected Fe2O3, in the sample. Assuming that Fe2+ can form additional inter-subunit contacts, we modeled the interaction of FeO and Fe2O3 with Dps, but the binding sites with putative functionality were predicted only for Fe2O3. The question of how the dodecameric form can be stabilized by ferric oxides is discussed

Localization of the E. coli Dps protein molecules in a silicon wires matrix according to scanning electron microscopy and X-ray photoelectron spectroscopy

The work is related to the study of the morphological features of silicon wires arrays combined with a nanomaterial of natural origin, a bacterial ferritin-like protein Dps, and their relationship with the composition of the surface and interior. A silicon wires array was formed by metal-assisted wet chemical etching. To obtain recombinant protein, Escherichia coli BL21*(DE3) cells were used as producers, and purification was carried out by the chromatography method. The combination of silicon wires with protein molecules was carried out by layering under laboratory conditions, followed by drying. The resulting hybrid material was studied by scanning electron microscopy and X-ray photoelectron spectroscopy. The initial silicon wires array had sharp boundaries on the surface. The diameter of the silicon wires was about 100 nm, while the distances between the wires can vary widely, reaching several hundred nanometres or be less than 100 nanometres, depending on the formation conditions, in the absence of noticeable transition layers. The pores formed in this way are available for filling with protein during deposition. The effectiveness of using the scanning electron microscopy method to study the morphology of the hybrid material “silicon wires – bacterial protein Dps” as well as X-ray photoelectron spectroscopy method together with ion etching for the investigation of the composition and physico-chemical of the hybrid material was demonstrated. Complementary results have shown that the molecular culture, which is a solution of oligomers of the recombinant Dps protein of E.coli bacterial cells, can penetrate deep into the pores of the silicon wires array with an extremely developed surface. The possibility of the control of the filling of silicon wires arrays by varying the pore morphology and other modes of formation of structures and their surface has been demonstrated. The obtained data can be used to study the possibilities of the functionalization of the developed surface of silicon wires by their driven coating with controlled delivery of biohybrid material