Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.     

Influence of Liquid Medium on Optical Characteristics of the Si Nanoparticles Prepared by Submerged Electrical Spark Discharge

We have measured the size, structure, and optical properties for two sets of nanoparticles synthesized via electrical-spark discharge between two plane silicon electrodes immersed in deionized water (DI) and 97 % ethanol. The nanoparticles were characterized by X-ray diffraction (XRD), ultraviolet (UV)-visible absorption spectrometry, Raman spectrometry, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The size and optical features of the nanoparticles were studied as functions of nature of the liquid. Nearly spherical, single-crystal, and morphologically similar Si nanoparticles with diameters in the 3–8 and 6–13 nm ranges were formed in the colloidal solutions of water and ethanol, with estimated indirect bandgaps of approximately 1.5 and 1.3 eV, respectively. In both cases, the Raman peaks were blue shifted with respect to those of bulk silicon, a result consistent with the small diameters of the particles. The silicon nanoparticles synthesized in water exhibited strong emission in the violet-blue range, with a double peak near 417 and 439 nm. For those synthesized in ethanol, blue-green emission centered at 463 nm was detected.     

Video-frequency scanning transmission electron microscopy of moving gold nanoparticles in liquid

Immobilized gold nanoparticles were imaged in a liquid containing water and 50% glycerol with scanning transmission electron microscopy (STEM). The specimen was enclosed in a liquid compartment formed by two silicon microchips with electron transparent windows. A series of images was recorded at video frequency with a spatial resolution of 1.5nm. The nanoparticles detached from their support after imaging them for several seconds at a magnification of 250,000. Their movement was found to be much different than the movement of nanoparticles moving freely in liquid as described by Brownian Motion. The direction of motion was not random-the nanoparticles moved either in a preferred direction, or radially outwards from the center of the image. The displacement of the gold nanoparticles over time was three orders of magnitude smaller than expected on the basis of Brownian Motion. This finding implies that nanoscale objects of flexible structure or freely floating, including nanoparticles and biological objects, can be imaged with nanoscale resolution, as long as they are in close proximity to a solid support structure.     

Fluorescent Si nanoparticle-based electrode for sensing biomedical substances

We have been studying the miniaturization of silicon crystals and the transition from the solid state to the atomistic state. We demonstrated the existence of “sweet spots” in cluster size in the range 1-3 nm that have enhanced chemical, structural, and photo stability. The particles are produced by an electrochemical etching process as dispersion in liquid, and they are reconstituted in films, patterns, alloys, or spread on chips to produce super chips. Unlike bulk, these Si nanoparticle configurations have a spectacular ability to glow in distinct RGB colors. In this paper we describe an electrode sensor built by decorating metal or heavily doped silicon electrode with nanoparticles. We demonstrated amperometric response of the electrode to glucose and compared the response to that of heavily doped silicon wafer decorated with GOx. The all silicon electrode shows improved sensitivity, selectivity and stability. Light induced modulation of the response allows phase sensitive detection. The device is suitable for miniaturization, which may enable in vivo use.     

Formation process of Si nanoparticles in rare gas observed by a decomposition method

We have investigated the formation process of silicon nanoparticles after laser ablation of silicon targets in argon gas. The nanoparticles exhibit bright photoluminescence in the visible wavelength range and can be applied to opto-electronic devices. In order to observe silicon nanoparticles, we have developed a decomposition method. The nanoparticles were probed by detecting light emission resulting from decomposition using a second laser. This method enables us to observe nanoparticles that cannot be observed directly by the methods applied so far. We have observed that the nanoparticles grow in time periods of 1.0-1.8 ms following ablation in Ar gas at 5 Torr when Si targets are ablated at 5 J/cm² with a pulse width of 7 ns. The nanoparticles begin to grow above ablation spots slightly apart from the targets just after thermalization of the plume. We also found that the growth is delayed at higher fluxes of ablation laser light.     

Study of magnetite nanoparticle suspensions by photometry and NMR relaxometry

A method has been described for preparation of suspensions of magnetite nanoparticles stabilized by porous silicon dioxide. The process of sedimentation of nanoparticles in suspensions of different compositions and concentrations has been analyzed by transmission coefficient measurements. Spectra of the transmission coefficient have been obtained for suspensions containing composite nanoparticles, the initial silicon dioxide, and macroscopic magnetite particles. The average effective radius of nanoparticles has been calculated from the time dependences of the transmission coefficient. It has been demonstrated that the synthesized nanoparticles possess magnetic-resonance contrast properties.     

Sonochemical synthesis and rheological properties of shear thickening silica dispersions

A sonochemical method has been developed to synthesize shear thickening fluid. This shear thickening fluid (STF) is composed of hard silicon dioxide nanoparticles and polyethylene glycol (PEG) liquid polymer. The combination of flow-able and hard components at a particular composition, results a material with remarkable rheological properties that is suitable for liquid body armor applications. In the present study nine types of STF’s have been synthesized with two different types of silica nanoparticles (15 nm and 200 nm) and polyethylene glycol at various weight fractions using a high intensity ultrasonic irradiation. The resultant STF samples were tested for their rheological and thermal properties. The advantages and disadvantages of this process have been discussed.     

基于硅柱-磁性液体体系的光子晶体的可调谐负折射特性研究

本文研究了硅柱在MnFe₂O₄磁性液体背景中排列成六边形结构的二维光子晶体的可调谐负折射特性. 利用平面波展开法和时域有限差分法理论研究了硅柱-磁性液体体系二维光子晶体的带隙结构、等频曲线和负折射现象随外磁场强度的变化关系. 模拟结果表明, 硅柱-磁性液体体系二维光子晶体工作在TE模式时, 其负折射特性可由外磁场调节. 在固定背景溶液的磁性颗粒体积分数和入射光频率时, 所研究的折射光束的偏转角和光子晶体的负折射率绝对值随外磁场的增大而增大, 而在固定背景溶液的磁性颗粒体积分数和外磁场强度时, 负折射角和负折射率的绝对值随入射光归一化频率增大而减小. 固定外场强度和入射光频率时, 所研究结构的负折射特性随背景溶液的磁性颗粒体积分数增大而变弱.     

Coherent anti-Stokes Raman scattering in silicon nanowire ensembles

In this letter, we, for the first time, report on coherent anti-Stokes Raman scattering (CARS) spectroscopy of an ensemble of silicon nanowires (SiNWs) formed by wet chemical etching of crystalline silicon with a mask of silver nanoparticles. The fabricated SiNWs have diameter ranged from 30 to 200 nm and demonstrate both visible and infrared photolumine cence (PL) and spontaneous Raman signal, with their intensities depending on presence of silver nanoparticles in SiNWs. The efficiency of CARS in SiNW ensembles is found to be significantly higher than that in crystalline silicon. The results of CARS and PL measurements are explained in terms of resonant excitation of the electron states attributed to silicon nanoparticles.     

Preparation and characterization of silicon oil based ferrofluid

Stable silicon oil based ferrofluid was prepared in the present investigation. Silicon oil surfactant ethoxy terminated polydimethylsiloxane was used to modify the Fe₃O₄ nanoparticles. The Fe₃O₄ nanoparticles were firstly coated with a SiO₂ layer by the hydrolysis of tetraethoxysilane. Then using the active hydroxyl groups on the surface of the SiO₂, silicon oil surfactant was covalently grafted onto the Fe₃O₄ nanoparticles surface. The ethoxy terminated polydimethylsiloxane has similar molecular chain structure and good compatibility with that of the carrier liquid, thus ensuring stable dispersion of modified Fe₃O₄ in the carrier silicon oil. The interaction between Fe₃O₄ and the modifier was characterized by IR and XPS. The crystal structure and the magnetic properties of the Fe₃O₄ nanoparticles were determined by XRD and VSM, respectively. The size and morphology of the particles were observed using TEM. The properties of the silicon oil based ferrofluid were characterized by Gouy magnetic balance. The results indicated that the ferrofluid had high magnetism and good stability. The rheological properties and thermostability of the ferrofluid were also investigated.     

High-intensity near-field generation for silicon nanoparticle arrays with oblique irradiation for large-area high-throughput nanopatterning

We present near-field distributions around an isolated 800-nm silica or silicon nanoparticle, and nanoparticle arrays of 800-nm silica or silicon nanoparticles, on a silicon substrate by the finite-difference time-domain method when 800-nm light is irradiated obliquely to the substrate. Nanopatterning mediated with the nanoparticle system is promising for large-area, high-throughput patterning by using an enhanced localized near-field ablation by the nanoscattered light lens effect. The irradiation area cannot be extended for silica nanoparticles, because the optical field enhancement factor is low. Gold nanoparticles can generate highly enhanced near fields, although at present there are no useful ways to arrange the gold nanoparticles on the substrate at a high throughput. Silicon nanoparticles with high dielectric permittivity have optical characteristics of both silica and gold nanoparticles. The particle arrangement on the Si substrate is technically easy using a wet pulling process. From the calculation, high optical field intensity is acquired with oblique s-polarized irradiation to the substrate under silicon nanoparticle arrays, and the intensity is almost the same as that under gold nanoparticle arrays under the same condition. With this method, high-throughput nanopatterning for a large area would be achievable.     

Spectral features of composite oil-in-water emulsions containing silicon nanoparticles

A complex spectroscopic investigation of oil-in-water emulsions containing silicon nanoparticles synthesized by plasma chemical vapor deposition has been performed for the first time. It is established by electron microscopy and Raman and IR spectroscopy that nanoparticles synthesized by this method have a crystalline structure, sizes of about 10–15 nm, and an outer shell whose chemical composition depends on the powder synthesis atmosphere. Comparative measurements of the transmission spectra of silicon-containing emulsions showed that their transmission, taking into account scattering, decreases with a decrease in wavelength in the range below 450 nm. The wavelength dependences for particles with an oxynitride outer shell and particles having an oxide shell are significantly different. This result indicates a contribution of the outer shell of silicon nanoparticles to the transmission spectra of emulsions. This factor must be taken into account in design of UV protectors based on silicon powder. In addition, calculations performed for transparent media containing silicon nanoparticles predict the possibility of enhancement of the protective properties of such emulsions in the UV range with increasing sizes of particles above 10 nm.     

Silica encapsulation of luminescent silicon nanoparticles: stable and biocompatible nanohybrids

This article presents a process for surface coating and functionalization of luminescent silicon nanoparticles. The particles were coated with silica using a microemulsion process that was adapted to the fragile silicon nanoparticles. The as-produced core–shell particles have a mean diameter of 35 nm and exhibit the intrinsic photoluminescence of the silicon core. The silica layer protects the core from aqueous oxidation for several days, thus allowing the use of the nanoparticles for biological applications. The nanoparticles were further coated with amines and functionalized with polyethylene glycol chains and the toxicity of the particles has been evaluated at the different stages of the process. The core–shell nanoparticles exhibit no acute toxicity towards lung cells, which is promising for further development.     

银纳米颗粒/多孔硅复合材料的制备与气敏性能研究

采用双槽电化学腐蚀法以电阻率为10-15 Ω·cm的p型<100>晶向的单晶硅片制备了孔径约为1.5 μm, 孔深约为15-20 μm的p型多孔硅, 并以此多孔硅作为基底采用无电沉积法通过调控沉积时间在其表面沉积了不同厚度的银纳米颗粒薄膜. 采用扫描电子显微镜和X 射线衍射仪表征了银纳米颗粒/多孔硅复合材料的形貌和微观结构, 结果表明银纳米颗粒较均匀的分布于多孔硅的表面上且沉积时间对产物的形貌有重要影响. 采用静态配气法在室温下研究了银纳米颗粒/多孔硅复合材料对NH₃的气敏性能. 气敏测试结果表明沉积时间对产物的气敏性能影响较大. 当沉积时间较短时, 适量银纳米颗粒掺杂的多孔硅复合材料由于其较高的比表面积以及特殊的形貌和结构, 对NH₃气体表现出较高的灵敏度、优良的响应/恢复性能. 室温下, 其对50 ppm 的NH₃气体的气敏灵敏度可以达到5.8左右.     

氮化硅薄膜中硅纳米颗粒的形成机制研究

采用等离子体增强化学气相沉积技术,以SiH₄作为硅源, NH₃和N₂共同作为氮源,在单晶硅衬底上制备了不同的氮化硅薄膜. X射线衍射分析薄膜晶体结构,通过计算晶格尺寸大小证明了纳米硅颗粒的存在. 傅里叶变换红外光谱分析了薄膜中的键合作用的变化并结合化学反应过程对氮化硅薄膜中纳米硅颗粒的形成机制进行了研究,发现Si—Si键作为硅纳米颗粒的初始位置, 当反应朝着生成Si—Si的方向进行时,可以促进氮化硅薄膜中硅纳米颗粒的形成. X射线衍射分析和光致发光实验结果表明Si—Si键浓度增大时, 所形成的纳米硅颗粒的尺寸和浓度都随之增大.     

硅纳米颗粒在碳纳米管表面生长的分子动力学模拟

采用分子动力学模拟方法研究了硅纳米颗粒在碳纳米管上的生长，并分析了这种复合材料的基本结构.研究表明，由于硅原子和碳纳米管之间的相互作用以及碳纳米管的巨大的表面曲率，硅原子在碳纳米管表面不是形成覆盖碳纳米管的二维薄膜，而是生成具有三维结构的硅纳米颗粒.小纳米颗粒的结构和无基底条件下生成的颗粒结构基本一致.对于大纳米颗粒，不同于无基底条件下形成的球状纳米晶体硅结构，硅纳米颗粒沿管轴方向伸长，其结构为类似于硅晶体的无定形网络结构. 关键词： 纳米颗粒 碳纳米管 硅 分子动力学模拟     

Tunable photoluminescence of porous silicon by liquid crystal infiltration

The photoluminescence (PL) of porous silicon films has been investigated as a function of the amount of liquid crystal molecules that are infiltrated into the constricted geometry of the porous silicon films. A typical nematic liquid crystal 4-pentyl-4′-cyanobiphenyl was employed in our experiment as the filler to modify the PL of porous silicon. It is found that the originally red PL of porous silicon films can be tuned to blue by simply adjusting the amount of liquid crystal molecules in the microchannels of the porous films. The chromaticity coordinates are calculated for the recorded PL spectra. The mechanism of the tunable PL is discussed. Our results have demonstrated that the luminescent properties of porous silicon films can be efficiently tuned by liquid crystal infiltration.     

Fabrication and characterization of a granular film consisting of size-selected silver nanoparticles: application to a SERS substrate

Uniform-sized silver nanoparticles with average diameter of 13.7 nm have been prepared in the gas-phase by combining a pulsed laser ablation method with a low pressure-differential mobility analyzer (LP-DMA). By depositing the silver nanoparticles onto a silicon substrate, a granular film consisting of size-selected silver nanoparticles has been fabricated and its morphology and electronic properties have been examined using transmission electron microscopy (TEM) and UV-visible absorption spectroscopy. This granular silver film serves as a highly active substrate for surface-enhanced Raman scattering (SERS).     

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy,transmission electron microscopy,X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High‐resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)‐ and (100)‐oriented planes which stabilizes against further oxidation of the particles. X‐ray absorption spectroscopy (XANES) and X‐ray photoelectron spectroscopy (XPS) measurements at the O 1s‐edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milled for different times. XANES results reveal the presence of the +4 (SiO₂) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2p XPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub‐oxide, +1 (Si₂O), +2 (SiO) and +3 (Si₂O₃), states are present. The analysis of the change in the sub‐oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.     

Morphological, structural, and magnetic properties of Co nanoparticles in a silicon oxide matrix

We present a morphological, structural, and magnetic characterization of Co nanoparticles (mean diameter of 10.3 ± 1.8 nm) grown using a gas aggregation source and embedded in a silicon oxide matrix by sequential deposition of nanoparticles and silicon oxide. We show that the Co nanoparticles ??soft-land?? on the substrates and suffer a moderate oxidation in contact with the silicon oxide. Despite this moderate oxidation, it is found that, at room temperature, the magnetic volume of the resulting nanoparticles is below the superparamagnetic limit. The results presented in this article are compatible with the presence of an assembly of magnetically independent particles that also display a moderate exchange bias at low temperature.