Microstructural analysis of liquid and amorphous SiO2 nanoparticles

Microstructural properties of liquid and amorphous SiO₂ nanoparticles have been investigated via molecular dynamics (MD) simulations with the interatomic potentials that have weak Coulomb interaction and Morse-type short-range interaction under non-periodic boundary conditions. Structural properties of spherical nanoparticles with different sizes of 2, 4 and 6 nm obtained at 3500 K have been studied through partial radial distribution functions (PRDFs), coordination number and bond-angle distributions, and compared with those observed in the bulk. The core and surface structures of liquid SiO₂ nanoparticles have been studied in detail. We found significant size effects on structure of nanoparticles. Calculations also show that if the size is larger than 4 nm, liquid SiO₂ nanoparticles at the temperature of 3500 K have a lightly distorted tetrahedral network structure with the mean coordination number Z_Si-O≈4.0 and Z_O-Si≈2.0 like those observed in the bulk. Moreover, temperature dependence of structural defects and SiO_x stoichiometry in nanoparticles on cooling from the melt has been found and presented.     

Tuning the plasmon resonance of metallic tin nanocrystals in Si-based materials

The optical properties of metallic tin nanoparticles embedded in silicon-based host materials were studied. Thin films containing the nanoparticles were produced using RF magnetron sputtering followed by ex situ heat treatment. Transmission electron microscopy was used to determine the nanoparticle shape and size distribution; spherical, metallic tin nanoparticles were always found. The presence of a localized surface plasmon resonance in the nanoparticles was observed when SiO₂ and amorphous silicon were the host materials. Optical spectroscopy revealed that the localized surface plasmon resonance is at approximately 5.5 eV for tin nanoparticles in SiO₂, and at approximately 2.5 eV in amorphous silicon. The size of the tin nanoparticles in SiO₂ can be varied by changing the tin content of the films; this was used to tune the localized surface plasmon resonance.     

In vivo Monitoring of Organ-Selective Distribution of CdHgTe/SiO2 Nanoparticles in Mouse Model

CdHgTe/SiO₂ nanoparticles were prepared by SiO₂ capping on the surface of CdHgTe QDs. The characteristics, such as optical spectra, photostability, size and cell toxicity were investigated. The dynamic distribution of CdHgTe/SiO₂ nanoparticles was in vivo monitored by near infrared fluorescence imaging system. CdHgTe/SiO₂ nanoparticles acted as a novel fluorescence probe have a maximum fluorescence emission of 785 nm and high photo-stability. The hydrodynamic diameter of CdHgTe/SiO₂ nanoparticles could be adjusted to 122.3 nm. Compared to CdHgTe QDs, inhibitory effects of CdHgTe/SiO₂ nanoparticles on proliferation of HCT116 cells decreased to a certain extent. CdHgTe/SiO₂ nanoparticles had their specific dynamic distribution behavior, which provided new perspectives for bio-distribution of nanoparticles.     

Synthesis of well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization

We report on the synthesis of the well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization. At first, 3-(2-bromoisobutyramido)propyl(triethoxy)-silane (the ATRP initiator) was prepared by the reaction of 3-aminopropyltriethoxysilane with 2-bromoisobutyryl bromide. The ATRP initiator was covalently attached onto the nanosilica surface. The subsequent ATRP of HEMA from the initiator-attached SiO₂ surface was carried out in order to afforded functional nanoparticles bearing a hydroxyl moiety at the chain end, SiO₂-g-PHEMA-Br. The esterification reaction of pendent hydroxyl moieties of PHEMA segment with 2-bromoisobutyryl bromide afforded the SiO₂-based multifunctional initiator, SiO₂-g-PHEMA(-Br)-Br, bearing one bromine moiety on each monomer repeating unit within the PHEMA segment. Finally, the synthesis of SiO₂-g-PHEMA(-g-PSt)-b-PSt was accomplished by the ATRP of St monomer using SiO₂-g-PHEMA(-Br)-Br as multifunctional initiator. These organic/inorganic hybrid materials have been extensively characterized by FT-IR, XPS, TG, and TEM.     

Synthesis of carbon nanotubes by CVD: Effect of acetylene pressure on nanotubes characteristics

The effect of acetylene partial pressure on the structural and morphological properties of multi-walled carbon nanotubes (MWCNTs) synthesized by CVD on iron nanoparticles dispersed in a SiO₂ matrix as catalyst was investigated. The general growing conditions were: 110 cm³/min flow rate, 690 °C synthesis temperature, 180 Torr over pressure and two gas compositions: 2.5% and 10% C₂H₂/N₂. The catalyst and nanotubes were characterized by HR-TEM, SEM and DRX. TGA and DTA were also carried out to study degradation stages of synthesized CNTs. MWCNTs synthesized with low acetylene concentration are more regular and with a lower amount of amorphous carbon than those synthesized with a high concentration. During the synthesis of CNTs, amorphous carbon nanoparticles nucleate on the external wall of the nanotubes. At high acetylene concentration carbon nanoparticles grow, covering all CNTs’ surface, forming a compact coating. The combination of CNTs with this coating of amorphous carbon nanoparticles lead to a material with high decomposition temperature.     

不同生长环境下砷化镓纳米颗粒的应变场模拟

对于埋嵌在薄膜材料中的纳米颗粒,在其生长过程中总是不可避免地伴随着应变场的产生,而这种应变场的分布能反映纳米颗粒的结构变化,纳米颗粒结构与它的物理性能有重要的关系.研究埋嵌在不同薄膜材料中的纳米颗粒生长过程中的应变场分布对于调控纳米颗粒的物理性能有着重要的意义.本文利用有限元算法分别计算了埋嵌在非晶氧化铝薄膜和非晶二氧化硅薄膜材料中的砷化镓纳米颗粒生长过程中的应变场分布.砷化镓纳米颗粒在以上两薄膜材料生长过程中都受到非均匀偏应变作用.对于埋嵌在氧化铝薄膜中的砷化镓纳米颗粒,其生长过程中,纳米颗粒内部受到的应变大于纳米颗粒表面受到的应变;而对于埋嵌在二氧化硅薄膜中的砷化镓纳米颗粒,纳米颗粒内部受到的应变小于纳米颗粒表面受到的应变.选择砷化镓纳米颗粒生长的薄膜材料可以调控纳米颗粒生长过程中的应变场分布,从而进一步调控纳米颗粒的晶格结构和形貌及其物理性能.     

Surface phenomena involved in the formation of Co nanoparticles on amorphous carbon and SiO2 deposited by magnetron sputtering

High-pressure DC magnetron sputtering was used for the deposition of cobalt on amorphous carbon (a-C) and SiO₂. Deposition conditions, substrate surface morphology and annealing parameters are investigated in order to promote the synthesis of large arrays of nanoparticles, with regular size and shape. Uniformly distributed Co nanoparticles a few nanometers in size were formed under annealing at 700°C in H₂. Particle nucleation and growth are discussed based on X-ray photoelectron spectroscopy, transmission and scanning electron microscopy and kinetic Monte Carlo modeling (KMC).     

A versatile method for the preparation of end-functional polymers onto SiO2 nanoparticles by a combination of surface-initiated ATRP and Huisgen [3 + 2] cycloaddition

A versatile method was developed for the chain-end functionalization of the grafted polymer chains for surface modification of nanoparticles with functionalized groups through a combination of surface-initiated atom-transfer radical polymerization (ATRP) and Huisgen [3 + 2] cycloaddition. First, the surface of SiO₂ nanoparticles was modified with poly(methyl methacrylate) (PMMA) brushes via the “grafting from” approach. The terminal bromides of PMMA-grafted SiO₂ nanoparticles were then transformed into an azide function by nucleophilic substitution. These azido-terminated PMMA brushes on the nanoparticle surface were reacted with alkyne-terminated functional end group via Huisgen [3 + 2] cycloaddition. FTIR and ¹H NMR spectra indicated quantitative transformation of the chain ends of PMMA brushes onto SiO₂ nanoparticles into the desired functional group. And, the dispersibility of the end-functional polymer-grafted SiO₂ nanoparticles was investigated with a transmission electron microscope (TEM).     

Formation of nanoparticles containing zinc in Si(001) by ion-beam implantation and subsequent annealing

The formation of nanoparticles containing zinc in Si(001) substrates by the implantation of ⁶⁴Zn⁺ ions and subsequent annealing in dry oxygen at 800 and 1000°C for 1 h is studied. The structure of the samples is studied by high-resolution transmission electron microscopy, X-ray diffraction, and photoluminescence spectroscopy. 20-nm zinc nanoparticles located at a depth of about 50 nm are revealed in the as-implanted sample. 10–20-nm pores are observed in the surface layer. Annealing leads to oxidation of the Zn nanoparticles to the Zn₂SiO₄ state. It is shown that the oxidation of Zn nanoparticles begins on their surface and at an annealing temperature of 800°C results in the formation of nanoparticles with the “соre–shell” structure. The X-ray diffraction technique shows simultaneously two Zn and Zn₂SiO₄ phases. ZnO nanoparticles are not formed under the given implantation and annealing conditions.     

Preparation and characterization of size-controlled CeO2 nanoparticles coated with SiO2

CeO₂@SiO₂ (core@shell) nanoparticles were prepared by means of chemical precipitation technique. Results from X-ray diffraction, transmission electron microscopy (TEM), and Zeta-potential analyses provide strong microscopic and spectroscopic evidences to prove that CeO₂ particles have been encapsulated inside amorphous SiO₂ shell. As revealed from TEM investigations, the average grain size of CeO₂@SiO₂ is significantly smaller than that of uncoated CeO₂ nanoparticles prepared under the same conditions, indicating it is an effective method to restrict the grain enlargement of nanocrystalline CeO₂ by coating a thin layer of SiO₂ at elevated temperatures. The CeO₂@SiO₂ nanoparticles display a similar surface electric character behavior to that of SiO₂, and its dispersibility in water is improved.     

Dewetting process of Au films on SiO2 nanowires: Activation energy evaluation

SiO₂ nanowires gain scientific and technological interest in application fields ranging from nano-electronics, optics and photonics to bio-sensing. Furthermore, the SiO₂ nanowires chemical and physical properties, and so their performances in devices, can be enhanced if decorated by metal nanoparticles (such Au) due to local plasmonic effects.In the present paper, we propose a simple, low-cost and high-throughput three-steps methodology for the mass-production of Au nanoparticles coated SiO₂ nanowires. It is based on (1) production of the SiO₂ nanowires on Si surface by solid state reaction of an Au film with the Si substrate at high temperature; (2) sputtering deposition of Au on the SiO₂ nanowires to obtain the nanowires coated by an Au film; and (3) furnace annealing processes to induce the Au film dewetting on the SiO₂ nanowires surface. Using scanning electron microscopy analyses, we followed the change of the Au nanoparticles mean versus the annealing time extracting values for the characteristic activation energy of the dewetting process of the Au film on the SiO₂ nanowires surface. Such a study can allow the tuning of the nanowires/nanoparticles sizes for desired technological applications.     

Structural properties of amorphous Fe2O3 nanoparticles

We have investigated the microstructure of amorphous Fe₂O₃ nanoparticles by using molecular dynamics (MD) simulations. Non-periodic boundary conditions with Born-Mayer type pair potentials were used to simulate a spherical model of different diameters of 2, 3, 4 and 5 nm. Structural properties of an amorphous model obtained at 350 K have been analyzed in detail through the partial radial distribution functions (PRPFs), coordination number distributions, bond-angle distributions and interatomic distances. Calculations showed that structural characteristics of the model are in qualitative agreement with the experimental data. The observation of a large amount of structural defects as the particle size is decreased suggested that surface structure strongly depends on the size of nanoparticles. In addition, surface structure of amorphous Fe₂O₃ nanoparticles have been studied and compared with that observed in the core and in the bulk counterpart. Radial density profiles and stoichiometry in morphous Fe₂O₃ nanoparticles were also found and discussed.     

Preparation of MPS (mercaptopropyltrimethoxysilane)-coated SiO2 nanoparticle and its effect on mechanical properties of surface treated SiO2/EVA nanocomposite

SiO₂ nanoparticles were synthesized from different three precursors, namely, TEOS (tetraethyl orthosilicate), sodium metasilicate and sodium silicate. First, SiO₂ nanoparticles were prepared by a controlled hydrolysis of TEOS. In another method, SiO₂nanoparticles were prepared by precipitation in an emulsion medium from sodium metasilicate and hydrochloric acid solution. Finally, SiO₂ nanoparticles were also synthesized from sodium silicate by an emulsion method. In this study, we concentrated on dispersion and compatibility between nanosized SiO₂ particles and EVA (ethylene vinyl acetate). Therefore, surface modification of synthesized SiO₂ nanoparticles was accomplished with MPS (3-mercaptopropyl trimethoxysilane) to enhance homogeneous dispersion and compatibility between the obtained SiO₂ nanoparticles and EVA. Finally, nanocomposites of surface treated SiO₂ nanoparticles and EVA were prepared. By inserting the MPS-coated SiO₂ nanoparticles into EVA, abrasion resistance and hardness were increased remarkably. On the other hand, insertion of SiO₂ nanoparticles barely decreased original tensile strength and elongation of EVA. Consequently, MPS-coated SiO₂/EVA nanocomposite can have an improved abrasion resistance and hardness compared with raw EVA, without decrease tensile strength and elongation. The characterization of synthesized SiO₂ nanoparticles and their nanocomposite with EVA was conducted by TEM, SEM, FTIR photography and mechanical property tests such as abrasion, hardness, tensile strength and elongation.     

The effect of packing density on luminescence of amorphous SiO<Subscript>2</Subscript> nanoparticles

Photoluminescence of amorphous SiO₂ nanoparticles compressed in the form of tablets is studied under exposure to UV radiation. The observed luminescence spectrum is a broad band extending from the excitation wavelength to 700 nm and with a maximum at ~470 nm. The spectrum can be decomposed into two Gaussian components with maxima at ~460 and ~530 nm. As the pressure applied for sample preparation increases, the integrated intensities of these bands change in opposite directions—the intensity of the short-wavelength band increases, while that of the long-wavelength band decreases. It is concluded that these bands are due to different luminescence centers of silicon dioxide located on the surface and in the bulk of SiO₂ nanoparticles.     

Computational study on the structural and surface properties of amorphous hydroxylated TiO<Subscript>2</Subscript> spherical nanoparticles

Monte Carlo simulations were carried out on amorphous titanium dioxide (TiO₂) for both bulk and hydroxylated nanoparticles with particle sizes ranging from 1 to 10 nm. The potential developed by the Matsui and Akaogi (MA) was used to model the interatomic interactions of TiO₂ in both cases (bulk and nanoparticles). Besides, Angular and Morse potentials proposed by the Tether, Cormack, Du et. al. (TCD) were introduced to model the interactions of hydroxyl groups on the TiO₂ surfaces, i.e., the Ti-O-H groups with an experimental and theoretical angles of 125 ^o . The bulk system was developed using periodic boundary conditions. The TiO₂ nanoparticles were extracted by applying a spherical cut section in the bulk TiO₂ melt structure to obtain the required size. Free valences on the nanoparticle surfaces were saturated via additional hydroxyl groups and then quenched to 300 K under free boundary conditions. The bulk and surface properties of the nanoparticles were calculated at 300 K and zero pressure and characterized via radial distribution functions, bond angle distributions, bond distances, coordination numbers, OH group concentrations and radial density profiles. In addition, to understand the difference in properties of amorphous hydroxylated TiO₂ nanoparticles and bulk amorphous TiO₂, a comparative study was done at the same thermodynamic conditions. The study shows that the bulk properties of amorphous hydroxylated TiO₂ nanoparticles are strongly size-dependent and different from those of the bulk TiO₂. As expected, increasing the particle size leads to an approach of the particle’s bulk properties to the bulk properties of the (quasi) infinite system. The size effects show that decreasing the particle size results in increasing the surface effects and surface OH group concentrations. Accordingly, small-sized TiO₂ nanoparticles have higher surface OH group concentrations and larger surface effects than large-sized TiO₂ nanoparticles. Larger surface effects result significant changes in their bond angles, bond distances, and coordination numbers. The simulation results of the surface properties reveal that the surface titanium atoms in the TiO2 nanoparticles have the capability of accommodating up to 5 hydroxyl groups. The mean surface hydroxyl group density of the amorphous TiO₂ spherical nanoparticles is estimated to be around 8.1/nm ², which lies in the range of 8–16/nm ², found by experimental and other simulation studies. Details of the modelling, simulations results and the study are presented in this paper.     

One-step flame method for the synthesis of coated composite nanoparticles

A simple in situ flame coating method has been developed by designing a new type of coflow diffusion flame burner having a sliding unit. The sliding unit was shown to be very effective in finding a right position where the precursor for coating layer should meet with core particles. SiO₂-coated TiO₂ nanoparticles were first prepared and whether most surfaces of particles were coated was examined by both direct observation of particles through a transmission electron microscope and Zeta potential measurements. Mean core sizes varied from 28 to 109 nm and mean coating thickness was about 2.4 nm for silica-coated titania particles. By simply changing chemical precursors, we demonstrated that SiO₂-coated SnO₂, SnO₂-coated TiO₂, SiO₂–SnO₂-coated TiO₂ nanoparticles could be also synthesized.     

离子注入Zn的Si(001)基片热氧化制备纳米ZnO团簇及其生长行为研究

采用离子注入技术将Zn离子注入Si（001）基片,并在大气环境下加热氧化制备了ZnO纳米团簇.利用电子探针、薄膜X射线衍射仪、原子力显微镜和透射电子显微镜,对注入和热氧化后的薄膜成分、表面形貌和微观结构进行表征,探讨了热氧化温度以及注入剂量对纳米ZnO团簇的成核过程及生长行为的影响.结果表明,Zn离子注入到Si基片表面后形成了Zn纳米团簇,热氧化过程中Zn离子向表面扩散,在表面SiO₂非晶层和Si基片多晶区的界面处形成纳米团簇.热氧化温度是影响ZnO纳米团簇结晶质量的一个重要参数.随着热氧化温度的升高,金属Zn的衍射峰强度逐渐变弱并消失,而ZnO的（101）衍射峰强度逐渐增强.当热氧化温度高于800 ℃以后,ZnO与SiO₂之间开始发生化学反应形成Zn₂SiO₄. 关键词： ZnO纳米团簇 离子注入 微观结构 形貌分析     

Surface Plasmon Resonance of Au Nanoparticles Fabricated by Negative Ion Implantation and Grid Structure toward Plasmonic Applications

Optical properties of Au nanoparticle composites and a grid structure of Cu nanoparticle composite were studied. Negative ion implantation was applied to synthesize Au and Cu nanoparticles in amorphous SiO₂ and Al₂O₃. Au nanoparticles were embedded within a depth of 30 nm by 60keV Au⁻ implantation. The surface plasmon resonance (SPR) of Au:SiO₂ and Au: Al₂O₃ composites shifted to red and to blue, respectively, compared to calculated ones by the Mie theory. Optical nonlinearity was measured with pump-probe femtosecond spectroscopy and the transient spectrum of Au: Al₂O₃ composite presented a large red shift from the SPR peak. Image mapping of far-field transmitted intensity of Cu-implanted SiO₂ with a fine grid structure drawn by laser-lithography was observed by a scanning near-field optical microscopy (SNOM) system.     

Low temperature CEMS of Sn-implanted SiO2

Conversion electron Mössbauer spectroscopy (CEMS) at room and low temperature has been used to study thin SiO₂ films implanted with Sn atoms and annealed at 900°C. This work focuses on the determination of the Debye temperature (θ _D) and Debye–Waller factors (f) of the Sn oxidized phases formed in this system. The Sn²⁺ oxidation state is the predominant one, even if a small percentage of the Sn atoms is in the Sn⁴⁺ oxidation state. The real Sn-oxides fractions are calculated by normalizing the resonant areas to the f values, as calculated from the temperature dependence of the related resonant areas within a Debye model. The Sn⁴⁺ oxidation state, possibly related to Sn atoms close to the SiO₂ surface, represents less than 20% of the Sn atoms. For the Sn²⁺ oxidation state, two different electronics configurations a and b, having different Debye temperature and hyperfine parameters are identified. The component a, with a lower θ _D (137 K), is the predominant one and might be related to small (2–3 nm) amorphous SnO _x clusters in the SiO₂ matrix. The component b could be related to substitutional Sn atoms in the SiO₂ network forming a local Sn environment similar to the SnO amorphous compound.     

Nanocomposites of magnetic cobalt nanoparticles and cellulose

Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH₄ and NaH₂PO₂, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH₄ reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH₂PO₂ reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.