Evaporation of free PbS nanoparticles: evidence of the Kelvin effect

The size-dependent evaporation of free-spherical PbS nanoparticles has been investigated by in-flight sintering of size-classified aerosols. The temperature (T(ev)) at which the particle size decreases due to evaporation is found to be size dependent and decreases with decreasing particle size. A linear relationship between the evaporation temperature and the inverse of the particle size is obtained as is the case with size-dependent melting of nanoparticles. This gives a direct evidence of the Kelvin effect and allows one to estimate the surface energy of nanoparticles. The surface energy of PbS nanoparticles has been found to be 2.45 J m(2).     

Proof‐of‐Concept Studies Directed toward the Formation of Metallic Ag Nanostructures from Ag3PO4 Induced by Electron Beam and Femtosecond Laser

In this work, for the first time, the instantaneous nucleation and growth processes of Ag nanoparticles on Ag₃PO₄ mediated by femtosecond laser pulses are reported and analyzed. The investigated samples are pure Ag₃PO₄ sample, electron‐irradiated Ag₃PO₄ sample, and laser‐irradiated sample. Complete characterization of the samples is performed using X‐ray diffraction (XRD), Rietveld refinements, field emission scanning electron microscopy, and energy dispersive spectroscopy (EDS). XRD confirms that the irradiated surface layer remains crystalline, and according to EDS analysis, the surface particles are composed primarily of Ag nanoparticles. This method not only offers a one‐step route to synthesize Ag nanoparticles using laser‐assisted irradiation with particle size control, but also reports a complex process involving the formation and subsequent growth of Ag nanoparticles through an unexpected additive‐free in situ fabrication process.     

Synthesis and formation mechanism of Ag–Ni alloy nanoparticles at room temperature

Ag–Ni nanoparticles were prepared with a chemical reduction method in the presence of polyvinylpyrrolidone (PVP) used as a stabilizing agent. During the synthesis of Ag–Ni nanoparticles, silver nitrate was used as the Ag⁺ source while nickel sulfate hexahydrate was used as Ni²⁺ source. Mixed solutions of Ag⁺ source and Ni²⁺ source were used as the precursors and sodium borohydride was used as the reducing agent. Five ratios of Ag⁺/Ni²⁺ (9:1, 3:1, 1:1, 1:3, and 1:9) suspensions were prepared in the corresponding precursors. Ag–Ni alloy nanoparticles were obtained with this method at room temperature. Scanning electronic microscope (SEM), energy dispersive spectrum (EDS), high resolution transmission electron microscope (HRTEM) were used to characterize the morphology, composition and crystal structure of the nanoparticles. The crystal structure was also investigated with X-ray diffraction (XRD). In all five Ag/Ni ratios, two kinds of particle structures were observed that are single crystal structure and five-fold twinned structure respectively. Free energy of nanoparticles with different crystal structures were calculated at each Ag/Ni ratio. Calculated results revealed that, with identical volume, free energy of single crystal particle is lower than multi-twinned particle and the difference becomes smaller with the increase of particle size; increase of Ni content will lead the increase of free energy for both structures. Formation of different crystal structures are decided by the structure of the original nuclei at the very early stage of the reduction process.     

复合纳米金属间化合物Ag2Al的制备及其结构表征

采用自悬浮定向流法制备出Ag2Al复合金属间化合物的纳米微粉,通过透射电子显微镜、X射线衍射仪和X射线能谱仪对纳米微粉的显微结构、粒度、相组成和成分构成进行研究。结果表明:所制备出的复合金属间化合物纳米颗粒呈规则球形,粒径分布在20～110 nm之间;纳米合金颗粒的主要组成相为Ag2Al,并伴有少量的Al;样品中的Ag,Al原子数比约为66.5∶33.5,金属间化合物纳米颗粒中Ag2Al晶粒尺寸约为33 nm,Al的约为21 nm。     

复合纳米金属间化合物Ag2Al的制备及其结构表征

采用自悬浮定向流法制备出Ag2Al复合金属间化合物的纳米微粉,通过透射电子显微镜、X射线衍射仪和X射线能谱仪对纳米微粉的显微结构、粒度、相组成和成分构成进行研究。结果表明：所制备出的复合金属间化合物纳米颗粒呈规则球形,粒径分布在20～110 nm之间;纳米合金颗粒的主要组成相为Ag2Al,并伴有少量的Al;样品中的Ag,Al原子数比约为66.5∶33.5,金属间化合物纳米颗粒中Ag2Al晶粒尺寸约为33 nm,Al的约为21 nm。     

Cohesive energy and physical properties of nanocrystals

Recently, a lattice-type-sensitive model, free of any adjustable parameter, for the size dependence of the cohesive energy of nanocrystals (nanodisks, -films, -wires and -particles) has been developed, taking into account the effects of the averaged structural and energetic properties of their surface and volume. These effects are related to the first- and second-nearest-neighbor atomic interactions. Now, considering the intimate relation between cohesive energy and other physical properties of materials, the recently obtained formula for the cohesive energy of nanocrystals has been applied to the cases of melting point (In, Bi, Si and Ag), evaporation temperature (Ag and Au), vacancy formation energy (Au), diffusion activation energy (Au), surface energy (Au, Al and Na), liquid–vapor interfacial energy (Al and Na), Curie temperature (Pb), Debye temperature (Au and Fe) and band gap energy (Si) of nanocrystals. In general, good agreement between the present model and the data has been obtained. Moreover, the surface-area-difference (SAD) model has been derived as a first-order approximation of the present model.     

Highly Luminescent Material Based on Alq3:Ag Nanoparticles

Tris (8-hydroxyquinoline) aluminum (Alq₃) is an organic semiconductor molecule, widely used as an electron transport layer, light emitting layer in organic light-emitting diodes and a host for fluorescent and phosphorescent dyes. In this work thin films of pure and silver (Ag), cupper (Cu), terbium (Tb) doped Alq₃ nanoparticles were synthesized using the physical vapor condensation method. They were fabricated on glass substrates and characterized by X-ray diffraction, scanning electron microscope (SEM), energy dispersive spectroscopy, atomic force microscope (AFM), UV-visible absorption spectra and studied for their photoluminescence (PL) properties. SEM and AFM results show spherical nanoparticles with size around 70–80 nm. These nanoparticles have almost equal sizes and a homogeneous size distribution. The maximum absorption of Alq₃ nanoparticles is observed at 300 nm, while the surface plasmon resonant band of Ag doped sample appears at 450 nm. The PL emission spectra of Tb, Cu and Ag doped Alq₃ nanoparticles show a single broad band at around 515 nm, which is similar to that of the pure one, but with enhanced PL intensity. The sample doped with Ag at a concentration ratio of Alq₃:Ag?=?1:0.8 is found to have the highest PL intensity, which is around 2 times stronger than that of the pure one. This enhancement could be attributed to the surface plasmon resonance of Ag ions that might have increased the absorption and then the quantum yield. These remarkable result suggest that Alq₃ nanoparticles incorporated with Ag ions might be quite useful for future nano-optoelectronic devices.     

[(Fe/Pt/Fe)/Ag]n多层膜低温合成分离的L10相FePt纳米颗粒

制备了［（Fe/Pt/Fe）/Ag］n多层膜,研究了不同温度退火后的微结构和磁特性.实验结果表明温度高于400℃退火后,样品开始形成L10相的FePt纳米颗粒与Ag基体的复合结构.ΔM曲线的测量表明FePt颗粒之间不存在交换作用,非常清楚地说明非磁基体Ag有效地隔离了FePt磁性颗粒.有序相的低温合成可能和多层膜结构所造成的界面扩散以及Ag层引入的界面缺陷有关,同时,Ag原子较强的迁移性以及FePt与Ag之间表面自由能的显著差异,使FePt纳米颗粒被Ag隔离. 关键词： L10相 FePt 交换作用     

微乳液法制备纳米银粒子的结构及其荧光现象研究

采用微乳液法合成了不同粒径的纳米银粒子,考察了环己烷和甲苯作为油相对制备纳米银的影响.对纳米银粒子的尺寸与结构进行了表征,观察到近球形多晶粒子,并有孪晶结构存在,对晶体结构的分析表明银粒子存在不同程度的点阵畸变,晶面间距增大.不同粒径的纳米银粒子氯仿体系可呈现荧光光谱,而纳米银甲苯体系则无荧光发射.结合紫外—可见吸收光谱和电子自旋共振谱对该体系的荧光发射机理进行了分析 关键词： 微乳液 纳米银粒子 纳米晶结构 荧光     

Surface‐enhanced Raman scattering characteristics of CuO : Mn/Ag heterojunction probed by methyl orange: effect of Mn2+ doping

Interest in the synthesis of hybrid substrates for surface‐enhanced Raman scattering (SERS) has surged recently. Hereof, in the present work, a hybrid SERS substrate CuO : Mn/Ag heterojunction has been synthesised. To accomplish this, the nanostructred Ag island film and CuO : Mn nanoparticles are synthesised by vacuum thermal evaporation method and sol–gel method respectively, and thereafter, a heterojunction between the CuO : Mn and Ag is fabricated by adsorption of CuO : Mn (10^‐3 m in ethanol) on Ag island film. Further, the SERS sensitivity of CuO : Mn/Ag heterojunctions has been studied by probing methyl orange. We observed that with Mn‐doping in the lattice of CuO, the SERS signal is enhanced considerably because of ferromagnetic ordering in CuO : Mn. DFT/B3LYP/6‐311 G(d, p) method is used to calculate the energy of HOMO and LUMO level of methyl orange. Copyright © 2016 John Wiley & Sons, Ltd.     

Growth of Ag nanostructures on TiO2(1 1 0)

We present a study of the growth of silver nanoparticles or clusters on a TiO₂(1 1 0) substrate in ultra-high vacuum. The growth is monitored in situ by ion and neutral scattering spectroscopy using He⁺ scattering and Auger spectroscopy. The scattering measurements show that only part of the surface is covered by Ag suggesting formation of clusters. Additionally an ex-situ study was performed by scanning electron microscopy and atomic force microscopy to determine the size distribution of these clusters. The average size distributions were found to range from about 5 to about 20 nm as a function of the evaporation flux. At the higher evaporation flux we observe formation of the smaller sized clusters.     

Grain size-dependent diffusion activation energy in nanomaterials

We report a unified model, free of any adjustable parameter, for size-dependence of intrinsic diffusion activation energy of elements in crystals. It is found that as the size of the nanocrystals decreases, the diffusion activation energy of atoms decreases and the corresponding diffusion coefficient strongly increases due to the Arrhenius relationship between them, which leads to evident diffusion at the room temperature. The model prediction is in agreement with the experimental diffusion results of N into bcc Fe and Ag into Au nanoparticles.     

Surface free energy of platinum nanoparticles at zero pressure: A molecular dynamic study

Metallic nanoparticles are interesting because of their use in catalysis and sensors. The surface energy of the FCC platinum nanoparticles are investigated via molecular dynamics simulation using Quantum Sutton–Chen (QSC) potential. We have calculated the Gibbs free energy for the FCC platinum bulk and also for its nanoparticle. All calculations have been carried out at zero pressure. We have used the thermodynamic integration method to obtain the Gibbs free energy. The total Gibbs free energy is taken as the sum of its central bulk and its surface free energy. We have calculated the free energy of a platinum nanoparticle as a function of temperature.     

Intense X-ray induced formation of silver nanoparticles stabilized by biocompatible polymers

Colloidal Ag nanoparticles were formed by X-ray irradiation in the presence of a polymer. This new synthesis method is simple, rapid and leads to a high production yield. Compared to the citrate-reduced Ag colloidal, polymer-protected Ag nanoparticles are smaller in size and more stable—and therefore suitable for biomedical application—as verified by TEM observation, XAFS measurement and optical characterization. Ag nanoparticles so produced were also visualized in solution and in real time by a visible light microscope based on dark field light scattering. The color-derived size and distribution of Ag nanoparticles correlates well with the hydrodynamic size data.     

Controlling SERS intensity by tuning the size and height of a silver nanoparticle array

It is demonstrated that the surface-enhanced Raman scattering (SERS) intensity of R6G molecules adsorbed on a Ag nanoparticle array can be controlled by tuning the size and height of the nanoparticles. A firm Ag nanoparticle array was fabricated on glass substrate by using nanosphere lithography (NSL) combined with reactive ion etching (RIE). Different sizes of Ag nanoparticles were fabricated with seed polystyrene nanospheres ranging from 430 nm to 820 nm in diameter. By depositing different thicknesses of Ag film and lifting off nanospheres from the surface of the substrate, the height of the Ag nanoparticles can be tuned. It is observed that the SERS enhancement factor will increase when the size of the Ag nanoparticles decreases and the deposition thickness of the Ag film increases. An enhancement factor as high as 2×10⁶ can be achieved when the size of the polystyrene nanospheres is 430 nm in diameter and the height of the Ag nanoparticles is 96 nm. By using a confocal Raman mapping technique, we also demonstrate that the intensity of Raman scattering is enhanced due to the local surface plasmon resonance (LSPR) occurring in the Ag nanoparticle array.     

Spontaneous formation of polymer nanoparticles by good-solvent evaporation as a nonequilibrium process

In recent years, polymer nanoparticles have been investigated with great interest due to their potential applications in the fields of electronics, photonics, and biotechnology. Here, we report the spontaneous formation of polymer nanoparticles from a clear solution containing a nonvolatile poor solvent by slow evaporation of a volatile good solvent. During evaporation of the good solvent, the solution gradually turns turbid. After evaporation, polymer nanoparticles of homogeneous shape and size are dispersed in the poor solvent. Homogeneous nucleation and successive growth of polymer particles takes place during the dynamic nonequilibrium process of solvent evaporation. The size of the particles, ranging from tens of nanometers to micrometer scale, depends on both polymer concentration and the solvent mixing ratio. Because of the physical generality of the particle formation mechanism, this procedure is applicable to a wide variety of polymers with suitable combinations of solvents. Here, we also show unique features, surface structures and surface properties of polymer nanoparticles prepared by this method.     

Computational study of the surface properties of aluminum nanoparticles

We calculate the surface energy, surface stress, and lattice contraction of Al nanoparticles using ab initio density functional and empirical computational techniques. Ab initio calculations are carried out using the siesta pseudopotential method combined with the generalized gradient approximation. Empirical calculations are conducted using the embedded atom method. The ab initio density functional approach predicts the surface energies of Al nanoclusters to be in the range of 0.9-2.0 J/m². These values are consistent with the surface energy of bulk aluminum and are close to the surface energies of silver nanoparticles calculated in our previous study. In contrast to our previous results for Ag nanoparticles, we found a significant discrepancy between the theoretical values of surface energy and stress for Al nanoclusters. This result could be explained by a greater degree of surface reconstruction in Al clusters than in Ag clusters.     

Luminescence enhancement of ZnO nanoparticles on metal surface

We have studied luminescence enhancement of zinc oxide (ZnO) nanoparticles with the average size of 30 nm on several metal surfaces at low temperatures. Bandedge luminescence originated from bound exciton (BE) annihilation is observed at 3.360 eV, and strongly depends on the kind and surface roughness of metal. The luminescence intensity is about 10 times larger for Ag surface than that for quartz surface. Furthermore, the luminescence increases remarkably when the roughness of Ag surface is almost the same as the particle size. The intensity ratio of the fast decay component to the slow one decreases for Ag surface compared with quartz. These results suggest that the luminescence enhancement is partially attributed to suppressing of the nonradiative recombination process in ZnO nanoparticles on metal surface.     

Assemblies from metallic and semiconducting nanocrystals

Optical properties of nanomaterials such as semiconductor and metal quantum dots are important for sensors and photovoltaic applications. We report on optical, microscopic, and AFM investigations on bulk and single nanoobjects such as metal and semiconducting nanoparticles. Firstly, of special interest is the investigation of Ag metal nanoaggregates formed in zeolites. Here, the defined structure of the zeolite serves both as size directing and a stabilizing agent. The size selected Ag aggregates fluoresce in the zeolite cages even after storage under ambient conditions for almost one year. In addition, single Ag particles escape the cages and can be investigated by fluorescence microscopy also with respect to sensor applications. Secondly, with respect to photovoltaic applications, energy transfer among organic dye molecules and semiconductor quantum dots is of great importance. We report on the extension of the optical absorption of ZnSe quantum dots into the UV regime and investigate excitation energy transfer within self-assembled nanoaggregates of surface functionalized QDs and fluorescent styrylpyridine dyes.     

A facile method to prepare monodispersed ZnO–Ag core-shell microspheres

Monodispersed and core-shell structured ZnO–Ag microspheres were realized by coating the Ag nanoparticles onto the surface of ZnO microspheres via a novel solution method. The obtained materials were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–Vis) absorption measurement. It was shown that face-center-cubic Ag nanoparticles with the mean size of 20 nm were successfully grown on the surface of ZnO microspheres. The absorption band of ZnO–Ag core-shell microspheres showed a large redshift comparing to pure Ag nanoparticles, indicating the strong interfacial interaction between ZnO and Ag. The effects of Ag coating thickness on the structure, morphology and optical absorption of ZnO–Ag core-shell microspheres were investigated. The discussion on the growth process of ZnO–Ag core-shell microspheres revealed the important role of Sn²⁺. This approach was simple, mild and readily scaled up, affording a simple method for the synthesis of size-tunable inorganic-metal core-shell nanostructures.