2019, Krause, A., Tkacheva, O., Omar, A., Langklotz, U., Giebeler, L., Dörfler, S., Fauth, F., Mikolajick, T., Weber, W.M.

Rapid decay of silicon anodes during lithiation poses a significant challenge in application of silicon as an anode material in lithium ion batteries. In situ Raman spectroscopy is a powerful method to study the relationship between structural and electrochemical data during electrode cycling and to allow the observation of amorphous as well as liquid and transient species in a battery cell. Herein, we present in situ Raman spectroscopy on high capacity electrode using uncoated and carbon-coated silicon nanowires during first lithiation and delithiation cycle in an optimized lithium ion battery setup and complement the results with operando X-ray reflection diffraction measurements. During lithiation, we were able to detect a new Raman signal at 1859 cm−1 especially on uncoated silicon nanowires. The detailed in situ Raman measurement of the first lithiation/delithiation cycle allowed to differentiate between morphology changes of the electrode as well as interphase formation from electrolyte components.

2012, Osminkina, L.A., Gonchar, K.A., Marshov, V.S., Bunkov, K.V., Petrov, D.V., Golovan, L.A., Talkenberg, F., Sivakov, V.A., Timoshenko, V.Y.

We study the structure and optical properties of arrays of silicon nanowires (SiNWs) with a mean diameter of approximately 100 nm and length of about 1-25 μm formed on crystalline silicon (c-Si) substrates by using metal-assisted chemical etching in hydrofluoric acid solutions. In the middle infrared spectral region, the reflectance and transmittance of the formed SiNW arrays can be described in the framework of an effective medium with the effective refractive index of about 1.3 (porosity, approximately 75%), while a strong light scattering for wavelength of 0.3 ÷ 1 μm results in a decrease of the total reflectance of 1%-5%, which cannot be described in the effective medium approximation. The Raman scattering intensity under excitation at approximately 1 μm increases strongly in the sample with SiNWs in comparison with that in c-Si substrate. This effect is related to an increase of the light-matter interaction time due to the strong scattering of the excitation light in SiNW array. The prepared SiNWs are discussed as a kind of 'black silicon', which can be formed in a large scale and can be used for photonic applications as well as in molecular sensing.

2016, Gonchar, Kirill A., Zubairova, Alsu A., Schleusener, Alexander, Osminkina, Liubov A., Sivakov, Vladimir

Silicon nanowires (SiNWs) were fabricated by metal-assisted chemical etching (MACE) where hydrofluoric acid (HF), which is typically used in this method, was changed into ammonium fluoride (NH4F). The structure and optical properties of the obtained SiNWs were investigated in details. The length of the SiNW arrays is about 2 μm for 5 min of etching, and the mean diameter of the SiNWs is between 50 and 200 nm. The formed SiNWs demonstrate a strong decrease of the total reflectance near 5-15 % in the spectral region λ < 1 μm in comparison to crystalline silicon (c-Si) substrate. The interband photoluminescence (PL) and Raman scattering intensities increase strongly for SiNWs in comparison with the corresponding values of the c-Si substrate. These effects can be interpreted as an increase of the excitation intensity of SiNWs due to the strong light scattering and the partial light localization in an inhomogeneous optical medium. Along with the interband PL was also detected the PL of SiNWs in the spectral region of 500-1100 nm with a maximum at 750 nm, which can be explained by the radiative recombination of excitons in small Si nanocrystals at nanowire sidewalls in terms of a quantum confinement model. So SiNWs, which are fabricated by environment-friendly chemistry, have a great potential for use in photovoltaic and photonics applications.

2018, Turishchev, S.Yu., Chuvenkova, Olga, Parinova, V.E., Koyuda, D.A., Chumakov, Ratibor G., Presselt, Martin, Schleusener, Alexander, Sivakov, Vladimir

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.

2014, Osminkina, L.A., Sivakov, V.A., Mysov, G.A., Georgobiani, V.A., Natashina, U.А., Talkenberg, F., Solovyev, V.V., Kudryavtsev, A.A., Timoshenko, V.Y.

Evaluation of cytotoxicity, photoluminescence, bio-imaging, and sonosensitizing properties of silicon nanoparticles (SiNPs) prepared by ultrasound grinding of porous silicon nanowires (SiNWs) have been investigated. SiNWs were formed by metal (silver)-assisted wet chemical etching of heavily boron-doped (100)-oriented single crystalline silicon wafers. The prepared SiNWs and aqueous suspensions of SiNPs exhibit efficient room temperature photoluminescence (PL) in the spectral region of 600 to 1,000 nm that is explained by the radiative recombination of excitons confined in small silicon nanocrystals, from which SiNWs and SiNPs consist of. On the one hand, in vitro studies have demonstrated low cytotoxicity of SiNPs and possibilities of their bio-imaging applications. On the other hand, it has been found that SiNPs can act as efficient sensitizers of ultrasound-induced suppression of the viability of Hep-2 cancer cells.

2018, Turishchev, S.Yu., Parinova, V.E., Nesterov, D.N., Koyuda, D.A., Sivakov, Vladimir, Schleusener, Alexander, Terekhov, V.A.

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.