In this work, we report a new stop-band formation mechanism by performing the atomistic Green's function calculation and the wave-packet molecular dynamics simulation for a system with germanium-nanoparticle array embedded in a crystalline silicon matrix. When only a single nanoparticle is embedded, the local resonance, induced through destructive interference between two different phonon wave paths, gives rise to several sharp and significant transmittance dips. On the other hand, when the number of embedded nanoparticles further increases to ten, a stop band with complete phonon reflection is formed due to the two-path resonance Bragg-like phonon interference. The wave packet simulations further uncover that the stop band originates from the collective phonon resonances at the embedded nanoparticles. Compared with the traditional stop-band formation mechanism that is the single-path Bragg reflection, the resonance mechanism has a significant advantage in not requiring the strict periodicity in the embedded nanoparticles array. We also demonstrate that the stop band can significantly suppress thermal conductance in the low-frequency regime. Our work provides a robust, scalable. and easily modulable stop-band formation mechanism. which opens a new degree of freedom for phononics-related heat control.
Thin films from the lanthanum vanadate nanoparticles were successfully grown by pulsed laser deposition method on glass and silicon substrates for the first time. Morphology and thickness of the films depend on a type of substrate and a number of pulses. The films are of 27 to 220 nm thickness and formed by very small particles up to 20 nm and also can contain single nanoparticles with dimensions 40 to 60 nm and sometimes agglomerates of nanoparticles. Spectral properties of the samples have been investigated and discussed. The vanadate films deposited on the silicon substrates lead to appeara…
Future decades will experience tons of silicon waste from various sources, with no reliable recycling route. The transformation of bulk silicon into SiO2 nanoparticles is environmentally significant because it provides a way to recycle residual silicon waste. To address the needs of silicon recycling, we develop a top-down approach that achieves 100% conversion of bulk silicon to silica nanoparticles with outcome sizes of 8-50 nm. In addition to upcycling the potential of silica, our method also possesses several advantages, such as simplicity, scalability and controllable particle size distri…
Vibrational mode frequencies and damping are calculated for an elastic sphere embedded in an infinite, homogeneous, isotropic elastic medium. Anisotropic elasticity of the sphere significantly shifts the frequencies in comparison to simplified calculations that assume isotropy. New low frequency Raman light scattering data are presented for silicon spheres grown in a SiO2 glass matrix. Principal features of the Raman spectrum are not correctly described by a simple model of the nanoparticle as a free, isotropic sphere, but require both matrix effects and the anisotropy of the silicon to be tak…
Crystalline Si substrates are doped by laser annealing of solution processed Si. For this experiment, dispersions of highly B-doped Si nanoparticles (NPs) are deposited onto intrinsic Si and laser processed using an 807.5nm cw-laser. During laser processing the particles as well as a surface-near substrate layer are melted to subsequently crystallize in the same orientation as the substrate. The doping profile is investigated by secondary ion mass spectroscopy revealing a constant B concentration of 2x10^18 cm^-3 throughout the entire analyzed depth of 5μm. Four-point probe measurements demons…
The vibrational density of states of silicon nanoparticles in the range from 2.3 to 10.3 nm is studied with the help of molecular-dynamics simulations. From these simulations the vibrational density of states and frequencies of bulk-like vibrational modes at high-symmetry points of the Brillouin-zone have been derived. The results show an increase of the density of states at low frequencies and a transfer of modes from the high-frequency end of the spectrum to the intermediate range. At the same time the peak of transverse optical modes is shifted to higher frequencies. These observations are …
A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions.
Silicon nanoparticles are experimentally investigated as a potential hyperpolarized, targetable MRI imaging agent. Nuclear T_1 times at room temperature for a variety of Si nanoparticles are found to be remarkably long (10^2 to 10^4 s) - roughly consistent with predictions of a core-shell diffusion model - allowing them to be transported, administered and imaged on practical time scales without significant loss of polarization. We also report surface functionalization of Si nanoparticles, comparable to approaches used in other biologically targeted nanoparticle systems.
The electromagnetic interaction between Ag nanoparticles on the top of the Si substrate and the incident light has been studied by numerical simulations. It is found that the presence of a dielectric layer with different thickness leads to varied resonance wavelength and scattering cross section, and consequently shifted photocurrent response over all wavelengths. These different behaviors are determined by whether the dielectric layer is beyond the domain where the near field of nanoparticles takes effect, and geometrical optics effects must be taken into account. It is revealed that for part…
We describe the synthesis, materials characterization and dynamic nuclear polarization (DNP) of amorphous and crystalline silicon nanoparticles for use as hyperpolarized magnetic resonance imaging (MRI) agents. The particles were synthesized by means of a metathesis reaction between sodium silicide (Na4Si4) and silicon tetrachloride (SiCl4) and were surface functionalized with a variety of passivating ligands. The synthesis scheme results in particles of diameter ~10 nm with long size-adjusted 29Si spin lattice relaxation (T1) times (> 600 s), which are retained after hyperpolarization by low …
Nanocrystalline bulk materials are desirable for many applications as they combine mechanical strength and specific electronic transport properties. Our bottom up approach starts with tailored nanoparticles. Compaction and thermal treatment are crucial, but usually the final stage sintering is accompanied by rapid grain growth which spoils nanocristallinity. For electrically conducting nanoparticles, field activated sintering techniques overcome this problem. Small grain sizes have been maintained in spite of consolidation. Nevertheless, the underlying principles, which are of high practical i…
We have investigated the formation of laser-induced periodic surface structures (LIPSS or ripples) on silicon upon excitation with p-polarized excimer laser pulses in the deep ultraviolet region (wavelength = 193 nm, pulse duration = 20 ns). Well-pronounced ripples with a period close to the laser wavelength were observed for pulse numbers N = 100 or higher, and the ripple period increased with the angle of incidence. While these results seem to be qualitatively consistent with the standard Sipe-theory, we observed a fundamentally different ripple formation mechanism and ripple morphology. At …
Embedding silicon nanoparticles in an intermetallic matrix is a promising strategy to produce remarkable bulk anode materials for lithium-ion (Li-ion) batteries with low potential, high electrochemical capacity and good cycling stability. These composite materials can be synthetized at a large scale using mechanical milling. However, for Si-Ni3Sn4 composites, milling also induces a chemical reaction between the two components leading to the formation of free Sn and NiSi2, which is detrimental to the performance of the electrode. To prevent this reaction, a modification of the surface chemistry…
Silicon nanoparticles are widely used in the medical area and until now they have not manifested toxicological effects in humans beings. In order to understand the physical properties that determine their low-toxicity, we perform ab initio computational simulations of silicon nanoclusters, pure, p-doped and hollow structured. The topological and electronic properties obtained pointed out to the number of dangling bonds and electronic density as fundamental parameters to locate active sites and directly related to toxicity, besides the size and surface chemistry of the silicon nanoparticle.
Confined acoustic and optical phonons in Si nanoclusters embedded in sapphire, synthesized using ion-beam implantation are investigated using Raman spectroscopy. The l = 0 and l = 2 confined acoustic phonons, found at low Raman shift, are analyzed using complex frequency model and the size of the nanoparticles are estimated as 4 and 6 nm. For the confined optical phonon, in contrast to expected red shift, the Raman line shape shows a substantial blue shift, which is attributed to size dependent compressive stress in the nanoparticles. The calculated Raman line shape for the stressed nanopartic…
Monocrystalline silicon solar cells with photo-absorbing morphology can amplify light-trapping properties within the absorber layer and help to fabricate cost-effective solar cells. In this paper, the effect of different parameters namely temperature and time of Cu-assisted chemical etching was thoroughly investigated for the optimization of the light absorption properties. P-type monocrystalline wafers were selectively treated with Cu(NO3)2.3H2O:HF:H2O2:DI water solution at 50 deg.C for five different time duration. The entire process was repeated at five different temperatures for 20min as w…
We show elasto-capillary folding of silicon nitride objects with accurate folding angles between flaps of 70.6$\pm$0.1° and demonstrate the feasibility of such accurate micro-assembly with a final folding angle of 90°. The folding angle is defined by stop-programmable hinges that are fabricated starting from silicon molds employing accurate three-dimensional corner lithography. This nano-patterning method exploits the conformal deposition and the subsequent timed isotropic etching of a thin film in a 3D shaped silicon template. The technique leaves a residue of the thin film in sharp concave c…
Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here we present an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-cry…
Ultrashort laser pulses allows to deliver electromagnetic energy to matter causing its localized heating that can be used for both material removal via ablation/evaporation and drive interface chemical reactions. Here, we showed that both mentioned processes can be simultaneously combined within straightforward laser nanotexturing of Si wafer in functionalizing solution to produce a practically relevant metal-semiconductor surface nano-morphology. Such unique hybrid morphology represent deep-subwavelength Si LIPSSs with a extremely short period down to 70 nm with their high-aspect-ratio nanotr…
We investigate the impact of water, a polar solvent, on the optical absorption of prototypical silicon clusters with oxygen passivation. We approach this complex problem by assessing the contributions of three factors: chemical reactivity; thermal equilibration and dielectric screening. We find that the silanone (Si=O) functional group is not chemically stable in the presence of water and exclude this as a source of significant red shift in absorption in aqueous environments. We perform first principles molecular dynamics simulations of the solvation of an oxygenated silicon cluster with expli…
The synthesis of Si3N4 nanowires from the reaction of silicon nanoparticles with N2 in the 1200-1440 C temperature range is reported. The nitridation conditions are such that the reaction with nitrogen is favoured by the presence of silicon oxide in the particles and by the active oxidation of silicon without a catalyst. It is shown that the Si to Si3N4 conversion rate depends on the amount of silicon particles used in the experiments and that, in general, the reaction slows down for greater amounts. This trend is explained by particle stacking, which restricts the exchange of gases between th…
Gold nanospheres, single wall carbon nanotubes (SWNT), and diamonoids were phyically incorporated into the negative photoresist SU-8. the mixtures were spin cast onto silicon or aluminium coated silicon wafers. ASTM standard D638 tensile specimens were lithographically patterned in the materials and then released from the substrate using Microchem'Omnicoat or an anodic metal dissolution process. the residual stresses, elastic moduli, and viscosity of the SU-8. Resistivity measurements of SU-8/SWNT nanocomposites were also investigates. We found the effective modulus and viscosity of the SU-8 t…
Which sizes of nanoparticles embedded in a crystalline solid yield the lowest thermal conductivity? Nanoparticles have long been demonstrated to reduce the thermal conductivity of crystals by scattering phonons, but most previous works assumed the nanoparticles to have a single size. Here, we use optimization methods to show that the best nanoparticle size distribution to scatter the broad thermal phonon spectrum is not a similarly broad distribution but rather several discrete peaks at well-chosen nanoparticle radii. For SiGe, the best size distribution yields a thermal conductivity below tha…
The shape of metal nanoparticles embedded in dielectric matrices influences the optical properties of the composite material. Swift heavy ion irradiation can induce a controllable shape transformation in gold and other metals embedded in amorphous silicon dioxide, where the particles elongate along the direction of the ion beam. The details of this transformation are not fully understood, but it is presumably related to nanometer-scale phase transitions induced by individual ion impacts. The phenomenon has been reproduced using atomistic simulations, although the time scale limitations and the…
Varying the amounts of silicon and carbon, different composites have been prepared by ball milling of Si, Ni$_{3.4}$Sn$_4$, Al and C. Silicon and carbon contents are varied from 10 to 30 wt.% Si, and 0 to 20 wt.% C. The microstructural and electrochemical properties of the composites have been investigated by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and electrochemical galvanostatic cycling up to 1000 cycles. Impact of silicon and carbon contents on the phase occurrence, electrochemical capacity and cycle-life are compared and discussed. For C-content comprised between 9 and…
We study the formation of nanometer thick oxide layers around nanoparticles (plateaus) in a wet nitrogen environment over 32 days. We determine both the plateau height and the lateral force needed to remove the particles with an atomic force microscope (AFM). The height is well described by the Deal-Grove model for a thermally activated diffusion limited oxidation process. Furthermore, we observe that height and force appear to be correlated suggesting that the rise in adhesion forces is mainly governed by an oxidation process. Since the plateaus are the result of a change in the chemical stru…
Formation of surface plasmon modes in sodium nanoclusters containing 20-300 atoms was studied using the GW method. It is shown that in the small Na nanoparticles up to 2 nm in size, the loss function $Im[ε^{-1}]$ is dominated by a single peak corresponding to localized surface plasmon resonance (LSPR). For particles of 2 nm and more, a resonance corresponding to surface plasmon polariton (SPP) oscillations begins to form, as well as a resonance corresponding to volume plasmon (VP) excitations. Considering the above, the linear size of a particle in the range of 0.7-3.7 nm can be estimated as t…
Experimental phonon imaging in diamond anvils cell is demonstrated to be an adequate tool to extract the complete set of elastic constants of single-crystalline silicon up to the ZB$\rightarrow β-$Sn transition (10 GPa). Contrary to what was commonly admitted, we demonstrate that the development of the strain-energy density in terms of strains cannot be stopped, for silicon, after the terms containing the third-order elastic constants. Nonlinear elasticity, degree of anisotropy and pressure-induced mechanical stability of the cubic silicon structure are thus revisited and investigated in more …
Silicon-based micro and nanoparticles have gained popularity in a wide range of biomedical applications due to their biocompatibility and biodegradability in-vivo, as well as a flexible surface chemistry, which allows drug loading, functionalization and targeting. Here we report direct in-vivo imaging of hyperpolarized 29Si nuclei in silicon microparticles by MRI. Natural physical properties of silicon provide surface electronic states for dynamic nuclear polarization (DNP), extremely long depolarization times, insensitivity to the in-vivo environment or particle tumbling, and surfaces favorab…
Using time-dependent density-functional theory, we investigate the electronic stopping power of self-irradiated silicon through non-adiabatic dynamics simulations. For specific velocities above 0.6 atom units, electronic stopping shows a generally assumed metallic behavior that is velocity-scaling. While in the lower velocity regime, the slope of electronic stopping power versus velocity changes and the overall magnitude are significantly greater than expectations, leading to a complete vanish of hard threshold. An analysis of the electron localization function allows us to arrive at the follo…
Silicon is one of the most promising anode materials for Lithium-ion batteries. Silicon endures volume changes upon cycling, which leads to subsequent pulverization and capacity fading. These drawbacks lead to a poor lifespan and hamper the commercialization of silicon anodes. In this work, a hybrid nanostructured anode based on silicon nanoparticles (SiNPs) anchored on vertically aligned carbon nanotubes (VACNTs) with defined spacing to accommodate volumetric changes is synthesized on commercial macroscopic current collector. Achieving electrodes with good stability and excellent electrochemi…
