Thermally induced evolution of the structure and optical properties of silicon nanowires

In the present paper, we report on the investigation of thermal annealing (TA) effect on structural and optical properties of crystalline silicon nanowires produced by metal-assisted chemical etching approach. In particular, the impact of TA on nanowire length, relative volume and size distribution of voids is described in terms of Lifshitz-Slyozov-Wagner theory considering the TA induced Oswald ripening in the SiNW arrays. It was also found that TA leads to a decrease of the SiNWs total reflection in the wide UV–VIS-IR spectral range. The reported effects can be used for tuning of crystalline SiNWs arrays in view of their further applications in photonics related fields. © 2020 The Author

Nanostructured Silicon Matrix for Materials Engineering

Tin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications

Synchrotron studies of top-down grown silicon nanowires

Morphology of the top-down grown silicon nanowires obtained by metal-assisted wet-chemical approach on silicon substrates with different resistance were studied by scanning electron microscopy. Obtained arrays of compact grown Si nanowires were a subject for the high resolution electronic structures studies by X-ray absorption near edge structure technique performed with the usage of high intensity synchrotron radiation of the SRC storage ring of the University of Wisconsin-Madison. The different oxidation rates were found by investigation of silicon atoms local surrounding specificity of the highly developed surface and near surface layer that is not exceeded 70 nm. Flexibility of the wires arrays surface morphology and its composition is demonstrated allowing smoothly form necessary surface oxidation rate and using Si nanowires as a useful matrixes for a wide range of further functionalization

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

XPS investigations of MOCVD tin oxide thin layers on Si nanowires array

Tin oxide thin layers were grown by metal-organic chemical vapor deposition technique on the top-down nanostructured silicon nanowires array obtained by metal-assisted wet-chemical technique from single crystalline silicon wafers. The composition of the formed layers were studied by high-resolution X-ray photoelectron spectroscopy of tin (Sn 3d) and oxygen (O 1 s) atoms core levels. The ion beam etching was applied to study the layers depth composition profiles. The composition studies of grown tin oxide layers is shown that the surface of layers contains tin dioxide, but the deeper part contains intermediate tin dioxide and metallic tin phases

Influence of the substrate and precursor on the magnetic and magneto-transport properties in magnetite films

We have investigated the magnetic and transport properties of nanoscaled Fe3O4 films obtained from Chemical Vapor Deposition (CVD) technique using [FeIIFe2III(OBut)8] and [Fe2III(OBut)6] precursors. Samples were deposited on different substrates (i.e., MgO (001), MgAl2O4 (001) and Al2O3 (0001)) with thicknesses varying from 50 to 350 nm. Atomic Force Microscopy analysis indicated a granular nature of the samples, irrespective of the synthesis conditions (precursor and deposition temperature, Tpre) and substrate. Despite the similar morphology of the films, magnetic and transport properties were found to depend on the precursor used for deposition. Using [FeIIFe2III(OBut)8] as precursor resulted in lower resistivity, higher MS and a sharper magnetization decrease at the Verwey transition (TV). The temperature dependence of resistivity was found to depend on the precursor and Tpre. We found that the transport is dominated by the density of antiferromagnetic antiphase boundaries (AF-APB's) when [FeIIFe2III(OBut)8] precursor and Tpre = 363 K are used. On the other hand, grain boundary-scattering seems to be the main mechanism when [Fe2III(OBut)6] is used. The Magnetoresistance (MR(H)) displayed an approximate linear behavior in the high field regime (H > 796 kA/m), with a maximum value at room-temperature of \sim2-3% for H = 1592 kA/m, irrespective from the transport mechanism.Comment: 19 pages, 9 figure

Radiofrequency Hyperthermia of Cancer Cells Enhanced by Silicic Acid Ions Released during the Biodegradation of Porous Silicon Nanowires

The radiofrequency (RF) mild hyperthermia effect sensitized by biodegradable nanoparticles is a promising approach for therapy and diagnostics of numerous human diseases including cancer. Herein, we report the significant enhancement of local destruction of cancer cells induced by RF hyperthermia in the presence of degraded low-toxic porous silicon (PSi) nanowires (NWs). Proper selection of RF irradiation time (10 min), intensity, concentration of PSi NWs, and incubation time (24 h) decreased cell viability to 10%, which can be potentially used for cancer treatment. The incubation for 24 h is critical for degradation of PSi NWs and the formation of silicic acid ions H+ and H3SiO4- in abundance. The ions drastically change the solution conductivity in the vicinity of PSi NWs, which enhances the absorption of RF radiation and increases the hyperthermia effect. The high biodegradability and efficient photoluminescence of PSi NWs were governed by their mesoporous structure. The average size of pores was 10 nm, and the sizes of silicon nanocrystals (quantum dots) were 3-5 nm. Degradation of PSi NWs was observed as a significant decrease of optical absorbance, photoluminescence, and Raman signals of PSi NW suspensions after 24 h of incubation. Localization of PSi NWs at cell membranes revealed by confocal microscopy suggested that thermal poration of membranes could cause cell death. Thus, efficient photoluminescence in combination with RF-induced cell membrane breakdown indicates promising opportunities for theranostic applications of PSi NWs. © 2019 American Chemical Society

Surface deep profile synchrotron studies of mechanically modified top-down silicon nanowires array using ultrasoft X-ray absorption near edge structure spectroscopy

Atomic, electronic structure and composition of top-down metal-assisted wet-chemically etched silicon nanowires were studied by synchrotron radiation based X-ray absorption near edge structure technique. Local surrounding of the silicon and oxygen atoms in silicon nanowires array was studied on as-prepared nanostructured surfaces (atop part of nanowires) and their bulk part after, first time applied, in-situ mechanical removal atop part of the formed silicon nanowires. Silicon suboxides together with disturbed silicon dioxide were found in the composition of the formed arrays that affects the electronic structure of silicon nanowires. The results obtained by us convincingly testify to the homogeneity of the phase composition of the side walls of silicon nanowires and the electronic structure in the entire length of the nanowire. The controlled formation of the silicon nanowires array may lead to smart engineering of its atomic and electronic structure that influences the exploiting strategy of metal-assisted wet-chemically etched silicon nanowires as universal matrices for different applications