Volcanic Eruption in the Nanoworld: Efficient Oxygen Exchange at the Si/SnO2 Interface.

Here, a phenomenon of efficient oxygen exchange between a silicon surface and a thin layer of tin dioxide during chemical vapor deposition is presented, which leads to a unique Sn:SiO2 layer. Under thermodynamic conditions in the temperature range of 725-735 °C, the formation of nanostructures with volcano-like shapes in "active" and "dormant" states are observed. Extensive characterization techniques, such as electron microscopy, X-ray diffraction, synchrotron radiation-based X-ray photoelectron, and X-ray absorption near-edge structure spectroscopy, are applied to study the formation. The mechanism is related to the oxygen retraction between tin(IV) oxide and silicon surface, leading to the thermodynamically unstable tin(II)oxide, which is immediately disproportionate to metallic Sn and SnO2 localized in the SiO2 matrix. The diffusion of metallic tin in the amorphous silicon oxide matrix leads to larger agglomerates of nanoparticles, which is similar to the formation of a magma chamber during the natural volcanic processes followed by magma eruption, which here is associated with the formation of depressions on the surface filled with metallic tin particles. This new effect contributes a new approach to the formation of functional composites but also inspires the development of unique Sn:SiO2 nanostructures for diverse application scenarios, such as thermal energy storage.

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.

Silicon Suboxides as Driving Force for Efficient Light-Enhanced Hydrogen Generation on Silicon Nanowires.

Efficient light-stimulated hydrogen generation from top-down produced highly doped n-type silicon nanowires (SiNWs) with silver nanoparticles (AgNPs) in water-containing medium under white light irradiation is reported. It is observed that SiNWs with AgNPs generate at least 2.5 times more hydrogen than SiNWs without AgNPs. The authors' results, based on vibrational, UV-vis, and X-ray spectroscopy studies, strongly suggest that the sidewalls of the SiNWs are covered by silicon suboxides, by up to a thickness of 120 nm, with wide bandgap semiconductor properties that are similar to those of titanium dioxide and remain stable during hydrogen evolution in a water-containing medium for at least 3 h of irradiation. Based on synchrotron studies, it is found that the increase in the silicon bandgap is related to the energetically beneficial position of the valence band in nanostructured silicon, which renders these promising structures for efficient hydrogen generation.

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.

Morphology and Microstructure Evolution of Gold Nanostructures in the Limited Volume Porous Matrices.

The modern development of nanotechnology requires the discovery of simple approaches that ensure the controlled formation of functional nanostructures with a predetermined morphology. One of the simplest approaches is the self-assembly of nanostructures. The widespread implementation of self-assembly is limited by the complexity of controlled processes in a large volume where, due to the temperature, ion concentration, and other thermodynamics factors, local changes in diffusion-limited processes may occur, leading to unexpected nanostructure growth. The easiest ways to control the diffusion-limited processes are spatial limitation and localized growth of nanostructures in a porous matrix. In this paper, we propose to apply the method of controlled self-assembly of gold nanostructures in a limited pore volume of a silicon oxide matrix with submicron pore sizes. A detailed study of achieved gold nanostructures' morphology, microstructure, and surface composition at different formation stages is carried out to understand the peculiarities of realized nanostructures. Based on the obtained results, a mechanism for the growth of gold nanostructures in a limited volume, which can be used for the controlled formation of nanostructures with a predetermined geometry and composition, has been proposed. The results observed in the present study can be useful for the design of plasmonic-active surfaces for surface-enhanced Raman spectroscopy-based detection of ultra-low concentration of different chemical or biological analytes, where the size of the localized gold nanostructures is comparable with the spot area of the focused laser beam.

Photoannealing of Merocyanine Aggregates.

In this work we elucidate the fundamental difference between aggregate formation of donor-π-acceptor merocyanines in their electronic ground and excited states. While increasing the π-bridge size favors formation of π-stacked aggregates in the dark, irradiation with visible light causes reorientation of the dyes to form prototype H-aggregates with compensating dipole moments. This photoannealing changes the supramolecular structure and its UV-vis spectroscopic properties dramatically, thus being of importance for the function of active layers composed of these dyes. Aggregates of the ground state dyes are bound cooperatively through ππ-London dispersion interactions and hydrogen bonds between the polar α-cyano-carboxylic acid groups. However, charge transfer upon photoexcitation leads to repulsion of the polar acid groups. Electronic excitation of the dyes approximately doubles the ground state dipole moment, thus driving molecular reorientation into prototype H-aggregate structures. We show that this photoinduced supramolecular rearrangement can disrupt the large polymeric aggregates formed in the dark. The photoinduced supramolecular structural changes reported in this work will influence the performance of optoelectronic devices composed of these structures and must be controlled to avoid morphological decomposition of active layers upon operation.

Antimicrobial Effect of Biocompatible Silicon Nanoparticles Activated Using Therapeutic Ultrasound.

In this study, we report a method for the suppression of Escherichia coli (E. coli) vitality by means of therapeutic ultrasound irradiation (USI) using biocompatible silicon nanoparticles as cavitation sensitizers. Silicon nanoparticles without (SiNPs) and with polysaccharide (dextran) coating (DSiNPs) were used. Both types of nanoparticles were nontoxic to Hep 2 cells up to a concentration of 2 mg/mL. The treatment of bacteria with nanoparticles and application of 1 W/cm2 USI resulted in the reduction of their viabilities up to 35 and 72% for SiNPs and DSiNPs, respectively. The higher bacterial viability reduction for DSiNPs as compared with SiNPs can be explained by the fact that the biopolymer shell of the polysaccharide provides a stronger adhesion of nanoparticles to the bacterial surface. Transmission electron microscopy (TEM) studies showed that the bacterial lipid shell was partially perforated after the combined treatment of DSiNPs and USI, which can be explained by the lysis of bacterial membrane due to the cavitation sensitized by the SiNPs. Furthermore, we have shown that 100% inhibition of E. coli bacterial colony growth is possible by coupling the treatments of DSiNPs and USI with an increased intensity of up to 3 W/cm2. The observed results reveal the application of SiNPs as promising antimicrobial agents.

Index matching at the nanoscale: light scattering by core-shell Si/SiO x nanowires.

Silicon nanowires (SiNWs) show strong resonant wavelength enhancement in terms of absorption as well as scattering of light. However, in most optoelectronic device concepts the SiNWs should be surrounded by a contact layer. Ideally, such a layer can also act as an index matching layer which could nearly halve the strong reflectance of light by silicon. Our results show that this reduction can be overcome at the nanometer scale, i.e. SiNWs embedded in a silica (SiO x ) layer can not only maintain their high scattering cross sections but also their strong polarization dependent scattering. Such effects can be useful for light harvesting or optoelectronic applications. Moreover, we show that it is possible to optically determine the diameters of the embedded nanoscale silicon (Si) cores.

Studies of silicon nanoparticles uptake and biodegradation in cancer cells by Raman spectroscopy.

In-vitro Raman micro-spectroscopy was used for diagnostics of the processes of uptake and biodegradation of porous silicon nanoparticles (SiNPs) in breast cancer cells (MCF-7 cell line). Two types of nanoparticles, with and without photoluminescence in the visible spectral range, were investigated. The spatial distribution of photoluminescent SiNPs within the cells obtained by Raman imaging was verified by high-resolution structured-illumination optical microscopy. Nearly complete biodegradation of SiNPs inside the living cells was observed after 13days of the incubation. The results reveal new prospects of multi-modal visualization of SiNPs inside cancer cells for theranostic applications.

Linear and Non-Linear Optical Imaging of Cancer Cells with Silicon Nanoparticles.

New approaches for visualisation of silicon nanoparticles (SiNPs) in cancer cells are realised by means of the linear and nonlinear optics in vitro. Aqueous colloidal solutions of SiNPs with sizes of about 10-40 nm obtained by ultrasound grinding of silicon nanowires were introduced into breast cancer cells (MCF-7 cell line). Further, the time-varying nanoparticles enclosed in cell structures were visualised by high-resolution structured illumination microscopy (HR-SIM) and micro-Raman spectroscopy. Additionally, the nonlinear optical methods of two-photon excited fluorescence (TPEF) and coherent anti-Stokes Raman scattering (CARS) with infrared laser excitation were applied to study the localisation of SiNPs in cells. Advantages of the nonlinear methods, such as rapid imaging, which prevents cells from overheating and larger penetration depth compared to the single-photon excited HR-SIM, are discussed. The obtained results reveal new perspectives of the multimodal visualisation and precise detection of the uptake of biodegradable non-toxic SiNPs by cancer cells and they are discussed in view of future applications for the optical diagnostics of cancer tumours.

Electronic levels in silicon MaWCE nanowires: evidence of a limited diffusion of Ag.

Deep level transient spectroscopy (DLTS) was performed on lowly n-doped silicon nanowires grown by metal-assisted wet chemical etching (MaWCE) with silver as the catalyst in order to investigate the energetic scheme inside the bandgap. To observe the possible diffusion of atoms into the bulk, DLTS investigation was also performed on the samples after removing the nanowires. Two of the four energy levels observed in the nanowires were also detected inside the substrate. Based on these results and on literature data about deep levels in bulk silicon, some hypotheses are advanced regarding the identification of the defects responsible for the energy levels revealed.

Influence of surface pre-treatment on the electronic levels in silicon MaWCE nanowires.

Deep level transient spectroscopy (DLTS) was performed on n-doped silicon nanowires grown by metal-assisted wet chemical etching (MaWCE) with gold as the catalyst in order to investigate the energetic scheme inside the bandgap. To observe the possible dependence of the level scheme on the processing temperature, DLTS measurements were performed on the nanowires grown on a non-treated Au/Si surface and on a thermally pre-treated Au/Si surface. A noticeable modification of the configuration of the energy levels was observed, induced by the annealing process. Based on our results on these MaWCE nanowires and on literature data about deep levels in bulk silicon, some hypotheses were advanced regarding the identification of the defects responsible of the energy levels revealed.

A time-resolved numerical study of the vapor-liquid-solid growth kinetics describing the initial nucleation phase as well as pulsed deposition processes.

Today, the vapor-liquid-solid (VLS) growth mechanism is a common process for the metal catalyzed bottom-up growth of semiconductor nanowires (NWs). Nevertheless, most of the literature only is concerned with the steady-state NW growth which applies when the amount of material supplied is equal to the amount consumed by the NW growth at the same time. While this description is suitable for chemical vapor deposition (CVD) or electron beam evaporation (EBE) processes after the initial nucleation time, problems arise when pulsed growth processes like pulsed laser deposition (PLD) are used since in this case the steady state growth condition cannot be applied. Moreover, the initial phase of NW growth cannot be described with steady state growth conditions, either. In this work, we present a modeling approach for VLS NW growth based on numerical simulations, which is capable of describing the nucleation phase of the VLS growth process as well as a pulsed deposition process.

SERS-based detection of the antibiotic ceftriaxone in spiked fresh plasma and microdialysate matrix by using silver-functionalized silicon nanowire substrates.

Therapeutic drug monitoring (TDM) is an important tool in precision medicine as it allows estimating pharmacodynamic and pharmacokinetic effects of drugs in clinical settings. An accurate, fast and real-time determination of the drug concentrations in patients ensures fast decision-making processes at the bedside to optimize the clinical treatment. Surface-enhanced Raman spectroscopy (SERS), which is based on the application of metallic nanostructured substrates to amplify the inherent weak Raman signal, is a promising technique in medical research due to its molecular specificity and trace sensitivity accompanied with short detection times. Therefore, we developed a SERS-based detection scheme using silicon nanowires decorated with silver nanoparticles, fabricated by means of top-down etching combined with chemical deposition, to detect the antibiotic ceftriaxone (CRO) in spiked fresh plasma and microdialysis samples. We successfully detected CRO in both matrices with an LOD of 94 µM in protein-depleted fresh plasma and 1.4 µM in microdialysate.

Tin/Tin Oxide Nanostructures: Formation, Application, and Atomic and Electronic Structure Peculiarities.

For a very long period, tin was considered one of the most important metals for humans due to its easy access in nature and abundance of sources. In the past, tin was mainly used to make various utensils and weapons. Today, nanostructured tin and especially its oxide materials have been found to possess many characteristic physical and chemical properties that allow their use as functional materials in various fields such as energy storage, photocatalytic process, gas sensors, and solar cells. This review discusses current methods for the synthesis of Sn/SnO2 composite materials in form of powder or thin film, as well as the application of the most advanced characterization tools based on large-scale synchrotron radiation facilities to study their chemical composition and electronic features. In addition, the applications of Sn/SnO2 composites in various fields are presented in detail.

Growth of axial SiGe heterostructures in nanowires using pulsed laser deposition.

Axial heterojunctions between pure silicon and pure germanium in nanowires have been realized combining pulsed laser deposition, chemical vapor deposition and electron beam evaporation in a vapor-liquid-solid nanowire growth experiment using gold nanoparticles as catalyst for the 1D wire growth. Energy dispersive x-ray mappings and line scans show a compositional transition from pure silicon to pure germanium and vice versa with exponential and thus comparably sharp transition slopes. Based on these results not only Si-Ge heterojunctions seem to be possible using the vapor-liquid-solid growth process but also heterojunctions in optoelectronic III-V compounds such as InGaAs/GaAs or group III nitride compounds such as InGaN/GaN as well as axial p-n junctions in Si nanowires.

Silver coated platinum core-shell nanostructures on etched Si nanowires: atomic layer deposition (ALD) processing and application in SERS.

A new method to prepare plasmonically active noble metal nanostructures on large surface area silicon nanowires (SiNWs) mediated by atomic layer deposition (ALD) technology has successfully been demonstrated for applications of surface-enhanced Raman spectroscopy (SERS)-based sensing. As host material for the plasmonically active nanostructures we use dense single-crystalline SiNWs with diameters of less than 100 nm as obtained by a wet chemical etching method based on silver nitrate and hydrofluoric acid solutions. The SERS active metal nanoparticles/islands are made from silver (Ag) shells as deposited by autometallography on the core nanoislands made from platinum (Pt) that can easily be deposited by ALD in the form of nanoislands covering the SiNW surfaces in a controlled way. The density of the plasmonically inactive Pt islands as well as the thickness of noble metal Ag shell are two key factors determining the magnitude of the SERS signal enhancement and sensitivity of detection. The optimized Ag coated Pt islands on SiNWs exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability and reproducibility. The plasmonic activity of the core-shell Pt//Ag system that will be experimentally realized in this paper as an example was demonstrated in numerical finite element simulations as well as experimentally in Raman measurements of SERS activity of a highly diluted model dye molecule. The morphology and structure of the core-shell Pt//Ag nanoparticles on SiNW surfaces were investigated by scanning- and transmission electron microscopy. Optimized core-shell nanoparticle geometries for maximum Raman signal enhancement is discussed essentially based on the finite element modeling.

Rapid detection of the bacterial biomarker pyocyanin in artificial sputum using a SERS-active silicon nanowire matrix covered by bimetallic noble metal nanoparticles.

Early stage detection of Pseudomonas infections is life-saving, especially in the case of patients with cystic fibrosis. Pyocyanin (PYO) is a specific metabolite of the Pseudomonas aeruginosa bacteria, and detection of it directly in the sputum can significantly reduce the diagnosis time of the infection. In the present study, aiming to achieve this goal, a simple and cost-effective surface-enhanced Raman spectroscopy (SERS) detection platform was proposed. For this, a silicon nanowire (SiNW) matrix, produced by metal-assisted chemical etching of silicon substrates was variously modified by noble metal (silver and gold) nanoparticles (NPs) and tested for the detection of the metabolite PYO in the complex matrix of artificial sputum. We found the SERS substrate with Ag NPs on the bottom of SiNWs and deposited bimetallic Ag/Au NPs on the top of them the best suited for the sensitive detection of PYO. The investigated plasmonic substrate showed good point-to-point and batch-to-batch signal reproducibility and allowed for the detection of PYO in artificial sputum down to 6.25 µM, which is the required sensitivity for clinical applications.

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.