Structural and Optical Properties of Silicon Nanowire Arrays Fabricated by Metal Assisted Chemical Etching With Ammonium Fluoride

Here we report on the metal assisted chemical etching method of silicon nanowires (SiNWs) manufacturing, where the commonly used hydrofluoric acid (HF) has been successfully replaced with ammonium fluoride (NH4F). The mechanism of the etching process and the effect of the pH values of H2O2: NH4F solutions on the structural and optical properties of nanowires were studied in detail. By an impedance and Mott-Schottky measurements it was shown that silver-assisted chemical etching of silicon can be attributed to a facilitated charge carriers transport through Si/SiOx/Ag interface. It was shown that the shape of nanowires changes from pyramidal to vertical with pH decreasing. Also it was established that the length of SiNW arrays non-linearly depends on the pH for the etching time of 10 min. A strong decrease of the total reflectance to 5–10% was shown for all the studied samples at the wavelength <800 nm, in comparison with crystalline silicon substrate (c-Si). At the same time, the intensities of the interband photoluminescence and the Raman scattering of SiNWs are increased strongly in compare to c-Si value, and also they were depended on both the length and the shape of SiNW: the biggest values were for the long pyramidal nanowires. That can be explained by a strong light scattering and partial light localization in SiNWs. Hereby, arrays of SiNWs, obtained by using weakly toxic ammonium fluoride, have great potential for usage in photovoltaics, photonics, and sensorics

Optical Properties of Silicon Nanowires Fabricated by Environment-Friendly Chemistry

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

Formation of Si/SiO2 Luminescent Quantum Dots From Mesoporous Silicon by Sodium Tetraborate/Citric Acid Oxidation Treatment

We propose a rapid, one-pot method to generate photoluminescent (PL) mesoporous silicon nanoparticles (PSiNPs). Typically, mesoporous silicon (meso-PSi) films, obtained by electrochemical etching of monocrystalline silicon substrates, do not display strong PL because the silicon nanocrystals (nc-Si) in the skeleton are generally too large to display quantum confinement effects. Here we describe an improved approach to form photoluminescent PSiNPs from meso-PSi by partial oxidation in aqueous sodium borate (borax) solutions. The borax solution acts to simultaneously oxidize the nc-Si surface and to partially dissolve the oxide product. This results in reduction of the size of the nc-Si core into the quantum confinement regime, and formation of an insulating silicon dioxide (SiO2) shell. The shell serves to passivate the surface of the silicon nanocrystals more effectively localizing excitons and increasing PL intensity. We show that the oxidation/dissolution process can be terminated by addition of excess citric acid, which changes the pH of the solution from alkaline to acidic. The process is monitored in situ by measurement of the steady-state PL spectrum from the PSiNPs. The measured PL intensity increases by 1.5- to 2-fold upon addition of citric acid, which we attribute to passivation of non-radiative recombination centers in the oxide shell. The measured PL quantum yield of the final product is up to 20%, the PL activation procedure takes &lt;20 min, and the resulting material remains stable in aqueous dispersion for at least 1 day. The proposed phenomenological model explaining the process takes into account both pH changes in the solution and the potential increase in solubility of silicic acid due to interaction with sodium cations

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

Raman Signal Enhancement Tunable by Gold-Covered Porous Silicon Films with Different Morphology

The ease of fabrication, large surface area, tunable pore size and morphology as well surface modification capabilities of a porous silicon (PSi) layer make it widely used for sensoric applications. The pore size of a PSi layer can be an important parameter when used as a matrix for creating surface-enhanced Raman scattering (SERS) surfaces. Here, we evaluated the SERS activity of PSi with pores ranging in size from meso to macro, the surface of which was coated with gold nanoparticles (Au NPs). We found that different pore diameters in the PSi layers provide different morphology of the gold coating, from an almost monolayer to 50 nm distance between nanoparticles. Methylene blue (MB) and 4-mercaptopyridine (4-MPy) were used to describe the SERS activity of obtained Au/PSi surfaces. The best Raman signal enhancement was shown when the internal diameter of torus-shaped Au NPs is around 35 nm. To understand the role of plasmonic resonances in the observed SERS spectrum, we performed electromagnetic simulations of Raman scattering intensity as a function of the internal diameter. The results of these simulations are consistent with the obtained experimental dat

Photoluminescent porous silicon nanowires as contrast agents for bioimaging

Porous silicon nanowires (pSi NWs) have attracted considerable interest due to their unique structural, optical properties and biocompatibility. The most common method for their top-down synthesis is metal-assisted chemical etching (MACE) of crystalline silicon (c-Si) wafers using silver nanoparticles as a catalyst. However, the replacement of silver with bioinert gold nanoparticles (Au NPs) markedly improves the efficiency of pSi NWs in biomedical applications. The present study demonstrates the fabrication of porous pSi NWs arrays using Au NPs as the catalyst in MACE of c-Si wafers with a resistivity of 1–5 mOhm·cm. Using scanning electron microscopy (SEM), the formation of arrays of porous nanowires with a diameter of 50 nm that consist of small silicon nanocrystals (nc-Si) and pores was observed. Raman spectroscopy analysis determined the size of nc-Si is about 4 nm. The pSi NWs exhibit effective photoluminescence (PL) with a peak in the red spectrum, which is attributed to the quantum confinement effect occurred in small 4 nm nc-Si. In addition, the pSi NWs exhibit low toxicity towards MCF-7 cancer cells, and their PL characteristics allow them to be used as contrast agents for bioimagin

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

Raman Signal Enhancement Tunable by Gold-Covered Porous Silicon Films with Different Morphology

The ease of fabrication, large surface area, tunable pore size and morphology as well surface modification capabilities of a porous silicon (PSi) layer make it widely used for sensoric applications. The pore size of a PSi layer can be an important parameter when used as a matrix for creating surface-enhanced Raman scattering (SERS) surfaces. Here, we evaluated the SERS activity of PSi with pores ranging in size from meso to macro, the surface of which was coated with gold nanoparticles (Au NPs). We found that different pore diameters in the PSi layers provide different morphology of the gold coating, from an almost monolayer to 50 nm distance between nanoparticles. Methylene blue (MB) and 4-mercaptopyridine (4-MPy) were used to describe the SERS activity of obtained Au/PSi surfaces. The best Raman signal enhancement was shown when the internal diameter of torus-shaped Au NPs is around 35 nm. To understand the role of plasmonic resonances in the observed SERS spectrum, we performed electromagnetic simulations of Raman scattering intensity as a function of the internal diameter. The results of these simulations are consistent with the obtained experimental data