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

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

Peculiarities in XPS spectra of Sn/SiO2 layers as an effect of surface charge

X-ray photoelectron spectroscopy based on synchrotron radiation was used to investigate the composition of the observed SnO2-x/Sn:SiO2-x thin layer grown by organometallic chemical vapour deposition on single-crystalline silicon wafer with additional argon ions etching treatment. Due to the formation of a thermodynamic anomaly during in situ layer growth, an efficient oxygen exchange between silicon and tin oxide phases occurs. The present study addresses the effect of localized surface charging and its influence on the obtained XPS core level spectra. We found that due to the high electrical conductivity of metallic tin and the direct coupling of tin particles to the silicon wafer, the XPS Sn 3d5/2 core level spectrum is not affected by the surface charge compared to the highly charged dielectric silicon oxide matrix, as observed for the XPS O 1 s and Si 2p core level spectra. Our results show that the core level spectra of Si 2p and O 1 s are shifted up to 3 eV due to the presence of uncompensated positive charge on the surface of the silica matrix. These results provide insight into the influence of surface charge effects on the analysis of conductor/insulator composite materials and contribute to the application of Sn-based materials in various application concepts related to energy and surface functionalization