Surface Modification of Silver Iodide Films by Electron Irradiation

It has been found experimentally that electron irradiation of polycrystalline AgI films leads to the formation of a nanocrystalline silver particle monolayer. With an increase in the irradiation time, the nanoparticle size grows but the concentration of the particles first increases and then drops. Formation mechanisms of the nanoparticles and the dynamics of their growth have been considered. Ostwald’s ripening, fieldinduced migration, and nanoparticle charge variation during irradiation by low-energy electrons have been shown to be the main processes responsible for the above effects.     

Mechanisms of heteroepitaxial growth of cadmium telluride thin films in a thermal field of a temperature gradient

The processes of forming cadmium telluride films upon vapor-phase deposition onto a substrate in a thermal field of the temperature gradient along the substrate plane are studied. The results of technological, geometric, electron diffraction, and electron microscopic investigations are reported. It is found that the thermal field of temperature gradient leads to a change in the duration of the Ostwald ripening stage and, under certain conditions, enhances the perfection of the formed structure. The mechanism of the influence of a thermal field on the Ostwald ripening is established. The results obtained are in agreement with the current theory of film formation.     

Electron transport in semiconducting nanoparticle and nanocluster carbon-polymer composites

The electron transport properties of two types of carbon-polyimide (C-PI) nanocomposite thin films have been evaluated. Conductive nanocomposites formed by incorporation of 30 nm carbon particles prior to polymer cross linking (ex situ formation) has been compared to high energy ion beam irradiation in situ formation of nanoscale carbon clusters within the polymer composite. Addition of carbon nanoparticles were able to reduce the resistivity by 13 orders of magnitude for 8 vol% carbon content. The irradiated in situ formed film showed a comparable resistivity to this 8% C-PI film. All the films exhibited negative temperature coefficient of resistance (NTCR) behaviour. While in the ex situ films the NTCR decreased progressively with increasing temperature above 350 K, the in situ film exhibited a constant NTCR value at ambient as well as elevated temperatures indicating that films formed by ion beam irradiation eliminate possible clustering of nanoparticles prior to crosslinking seen in the ex situ films. The optimum hop energies for the ex situ films ranged from 23.1 to 8.05 meV when carbon content increased from 1 to 8 vol% and the corresponding value for the in situ formed film was 34.94 meV. These films had appreciable NTCR values, and were evaluated for their thermistor behaviour as a class of material with potential for temperature sensing devices.     

Ostwald Ripening of Concentrated Alkane Emulsions: A preliminary report

Fiber optic dynamic light scattering (FODLS) was used to study the kinetics of aging processes in emulsions of n-alkanes stabilized by a surfactant. The method is particularly useful for this purpose because it permits measurements in concentrated emulsions. Complications that may occur in traditional DLS due to the extreme dilution, such as solubilization of the particles in the medium, can be easily avoided in this way. The experimental results show that the main aging process is Ostwald ripening. The results are in agreement with theoretical predictions based on the Lifshitz-Slyozov-Wagner (LSW) theory as far as it concerns the relation between the molecular solubility of the n-alkanes (in the aqueous phase) and the Ostwald ripening rate. This illustrates that the main rate-determining factor is the molecular diffusion of the alkane molecules through the continuous (aqueous) phase. The Ostwald ripening rate is affected by the concentration of surfactant but in all situations is higher than expected from LSW theory.     

Ostwald ripening of beta-carotene nanoparticles

Ostwald ripening, the interfacial-energy-driven dissolution and reprecipitation of solutes, becomes an increasingly significant problem for nanoparticle formulations. We present the first quantitative study of Ostwald ripening for nanoparticle dispersions. The Lifshitz-Slyozov-Wagner (LSW) theory of particle growth driven by diffusion is applied to study beta-carotene nanoparticles with sizes of O(100 nm) formed by our block-copolymer protected Flash Nanoprecipitation process. A numerical implementation of the LSW theory that accounts for the original particle size distribution is presented. The predicted particle sizes from the numerical simulation are compared with the experimental results measured by dynamical light scattering. The results show quantitative agreement with no adjustable parameters. The addition of antisolvent results in the reduction of the ripening rate by dramatically decreasing bulk solubility.     

One-pot synthesis of uniform hollow cuprous oxide spheres fabricated by single-crystalline particles via a simple solvothermal route

Uniform Cu₂O hollow spheres fabricated by single-crystalline particles (smaller than 20 nm) are facile synthesized in ethylene glycol (EG) solution by a simple solvothermal route without using pre-fabricated templates and reductive agents. EG in this protocol is not only used as a solvent, complexing agent, and reducing agent, but also served as a structure-directing agent for the formation of hollow structure. By control of reaction conditions, such as reaction time, temperature, and the anions, the morphology and structure of the hollow spheres can be tuned. A coordination adsorption and oriented attachment and Ostwald ripening mechanism is proposed for explaining the formation process of hollow Cu₂O spheres in EG solution; and importantly, the hollow Cu₂O spheres exhibit an excellent property for the electro-catalytic oxidization of ascorbic acid in acetic acid buffer solution. Moreover, the hollow spherical Cu₂O particles could be potentially applied in catalysis, sensor, and as model for fundamental research.     

Formation of small particles of gold on alumina support films and their behaviour in oxygen and hydrogen atmospheres

Attempt has been successfully made to disperse ultrafine gold particles on alumina support films by keeping the substrate at elevated temperatures during metal deposition under vacuum of ≈ 10^-5 Torr. It is found that reasonable dispersion of particles occurs for a mean thickness of 0.5 nm at a substrate temperature of 125 °C. The resulting samples turn out to be quite suitable for model studies of the behaviour of gold/alumina catalyst. Electron microscope observations coupled with diffraction have provided evidence for emergence of gold particles without any compound formation with the residual gases present during deposition at 10^-5 Torr. The nature of dispersion and average particle size are shown to depend on substrate temperature and the amount of metal evaporated. Heat treatments in hydrogen and oxygen at 200–500 °C for various lengths of time led to an increase in particle size with a simultaneous decrease in number density (i.e. coarsening of particles) following, in all probability, the Ostwald ripening mechanism. The oxidizing atmosphere has been shown to be more favourable to coarsening or deactivation of the catalyst. Finally, it is indicated that gold particles prefer to facet giving well-defined shapes (e.g. hexagonal, pentagonal or rhombohedral) with faces corresponding to planes of relatively smaller interfacial energies.     

纳米氧化锌的过饱和控制生长与大小分布控制.

"在非水介质中合成了纳米氧化锌,测定了纳米氧化锌的紫外吸收光谱,并用有效质量模型计算了粒子大小,开发并命名了一种称之为纳米粒子过饱和控制生长的技术,该技术涉及将小的纳米粒子悬浊液加入到大的粒子悬浊液中,结果因为不同大小粒子间的溶解度差异小的粒子将全部溶解,大的粒子将整体长大,大粒子悬浊液的粒子数将保持不变,大粒子的生长速度显著比Ostwald老化的高．该技术最显著的特征是只要最初两悬浊液粒子大小的差异足够大,分布不是太宽,则粒子大小的分布将会因为粒子如此长大而变窄．"     

Highly ordered Ga nanodroplets on a GaAs surface formed by a focused ion beam

The morphological evolution of a GaAs surface induced by a focused ion beam (FIB) has been investigated by in situ electron microscopy. Under off-normal bombardment without sample rotation, Ga droplets with sizes from 70 to 25 nm in diameter on the GaAs surface can self-assemble into a highly ordered hexagonal pattern instead of Ostwald ripening or coalescence. The mechanism relies on a balance between anisotropic loss of atoms on the surface of droplets due to sputtering and an anisotropic supply of atoms on the substrate surface due to preferential sputtering of As. The ratio of wavelength to the droplet diameter predicted by this model is in excellent agreement with experimental observations.     

Dynamics of gold clusters on amorphous carbon films induced by annealing in a transmission electron microscope

The change of the size distribution of Au clusters induced by annealing was studied in situ by transmission electron microscopy. Starting from statistically distributed Au clusters on a thin amorphous carbon film, “islands” are formed within a few months storage at room temperature, which consist of Au clusters with sizes <4 nm embedded in a thin Au film. These islands cover originally areas with sizes around 25 × 70 nm². If the temperature is increased in the transmission electron microscope two different processes can be clearly distinguished that lead to the coarsening of the cluster size distribution: cluster coalescence and (contactless) Ostwald ripening. The degree and rate of the coarsening are found to depend on the underlying surface (Au film or amorphous carbon) and the exposure to the high-flux high-energy electron beam, which can be estimated to lead to high-temperature excursions in a cluster on a 10⁻¹² s time scale. The experimental findings are confirmed by Monte-Carlo simulations using the many-body Gupta potentials in order to calculate the Au/Au interaction. Moreover, the results of MC simulations suggest an electron-beam induced formation of a “quasi-two-dimensional gas” of small highly mobile Au species on the Au film, which promotes Ostwald ripening.     

Digestive Ripening,Nanophase Segregation and Superlattice Formation in Gold Nanocrystal Colloids

A novel digestive ripening process is shown to narrow the particle size distribution from a highly polydisperse dodecanethiol ligated gold colloid. Unlike the Ostwald ripening process, the digestion occurs through transferring materials from large particles to small particles. Temperature-induced size segregation can further select the particle sizes. By using these two methods, highly ordered superlattices using nanocrystals as building blocks can be synthesized directly from a polydisperse colloid.     

The effects of catalyst treatment on fast growth of millimeter-long multi-walled carbon nanotube arrays

An optimized strategy was developed for fast growth of millimeter-long CNT arrays using chemical vapor deposition (CVD). Growth temperature of 800 °C was firstly determined, and catalyst heat treatment conditions were then optimized to probe the full potential of growth rate. 1.5 mm long CNT arrays were obtained in 10 min under optimized growth and catalyst heat treatment conditions. The growth rate of CNT arrays strongly depends on the growth temperature and catalyst heat treatment. Insufficient reduction could not reduce iron oxide into metallic state or/and crack down catalyst film into particles, but excessive treatment may result in large particles due to Ostwald ripening process. This method would offer more freedoms in designing the fast growth of high-purity, long CNT arrays.     

The theory of Ostwald ripening

Developments in the theory of Ostwald ripening since the classic work of I. M. Lifshitz and V. V. Slyozov (LS) are reviewed and directions for future work are suggested. Recent theoretical work on the role of a finite volume fraction of coarsening phase on the ripening behavior of two-phase systems is reformulated in terms of a consistent set of notation through which each of the theories can be compared and contrasted. Although more theoretical work is necessary, these theories are in general agreement on the effects of a finite volume fraction of coarsening phase on the coarsening behavior of two-phase systems. New work on transient Ostwald ripening is presented which illustrates the broad range of behavior which is possible in this regime. The conditions responsible for the presence of the asymptotic state first discovered by LS, as well as the manner in which this state is approached, are also discussed. The role of elastic fields during Ostwald ripening in solid-solid mixtures is reviewed, and it is shown that these fields can play a dominant role in determining the coarsening behavior of a solid-solid system.     

Evolution of gas-filled nanocracks in crystalline solids

In this work, the evolution of gas-filled cracks under gas implantation and subsequent annealing is studied on the basis of an elastic continuum approach. The observed growth limitation of He-filled nanocracks in SiC is attributed to their stabilization by the formation of circular dislocation dipoles. The formation and Ostwald ripening of bubble-loop complexes at elevated temperatures is modeled in terms of gas atom exchange between such complexes coupled with local matrix atom exchange between bubbles and loops of the same complex. The scaling laws derived for the time dependence of bubble and loop sizes are found to be in good agreement with experimental data.     

A novel hydrothermal route to synthesize solid SnO2 nanospheres and their photoluminescence property

Solid tin oxide (SnO₂) nanospheres were fabricated via one-step hydrothermal treatment of tin foil in aqueous alkaline solutions at 180°C. Based on the time-dependent experiments, the evolution behavior of Ostwald ripening is proposed to explain the formation mechanism. Besides a broad emission band at 600 nm, the SnO₂ nanospheres, synthesized for 24 h, show an additional emission band at 490 nm that has a great sensitivity to the content of oxygen. Spectral examinations and analyses reveal that the two emission bands originate from the electronic states determined by the oxygen interstitials, intrinsic surface states, and oxygen vacancies.     

Ostwald ripening under conditions of mixed-type diffusion

The Ostwald ripening in metallic alloys and quasi-zero-dimensional semiconductor structures is investigated under conditions of mixed dislocation-matrix diffusion, when none of the terms j _d and j _v in the expression for the total diffusion flux can be ignored. The size distribution functions and time dependences of the maximum size r _g and critical (average) size r _k(〈r〉) of particles for different ratios x between the fluxes are obtained. It is demonstrated that mixed dislocation-matrix diffusion can occur in the course of the formation of CdS quantum dots prepared through chemical deposition.     

Growth of Co nanoparticles on a nanostructured θ-Al2O3 film on CoAl(1 0 0)

We have investigated the growth of Co nanoparticles on θ-Al₂O₃/CoAl(1 0 0) by means of Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (EELS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Due to Volmer-Weber growth, Co forms particles with a mean diameter of approximately 2.5 nm and height of 0.8 nm. Even on the entirely covered oxide, there is no Ostwald ripening and Co particles stay structurally isolated. The nanoparticles exhibit a small size distribution and tend to form chains, as predetermined by the streak structure of the oxide template. For sufficient high coverages Co-core-CoO-shell nanoparticles may be evidenced, which is explained as a result of surfactant oxygen. The nanostructured particles may open the door to numerous applications, such as in catalysis and magnetoelectronic applications, where large areas of ordered nanodots are desired.     

Evolution of the heterogeneous structure of model sodium silicate glasses during binodal decomposition: X-ray small-angle scattering investigation

The kinetics of binodal decomposition in model glasses of the Na₂O-SiO₂ system from the initial stage to the stage of the Ostwald ripening inclusive has been investigated in situ. It has been found that the spatial-temporal evolution of the heterogeneous structure during binodal decomposition has a multistage character. The characteristic size of the phase regions at each stage of the binodal decomposition varies with time according to the power law L ～ t ^β. The values of exponents β for different stages of the binodal decomposition are as follows: 1/20 (fluctuation stage), 1/2 (growth stage), 0 (transient stage), and 1/3 (Ostwald ripening stage). The particle size distributions for all stages of the binodal decomposition have been presented.     

Construction of Ag/AgCl nanostructures from Ag nanoparticles as high-performance visible-light photocatalysts

A combined strategy of in situ oxidation and assembly is developed to prepare Ag/AgCl nanospheres and nanocubes from Ag nanoparticles under room temperature. It is a new facile way to fabricate Ag/AgCl with small sizes and defined morphologies. Ag/AgCl nanospheres with an average size of 80 nm were achieved without any surfactants, while Ag/AgCl nanocubes with a mean edge length of 150 nm were obtained by introduction of N-dodecyl-N,N-dimethyl-2-ammonio-acetate. The possible formation mechanism involves the self-assembly of AgCl nanoparticles, Ostwald ripening and photoreduction of Ag⁺ into Ag⁰ by the room light. The as-prepared Ag/AgCl nanospheres and nanocubes exhibit excellent photocatalytic activity and stability toward degradation of organic pollutants under visible-light irradiation. It is demonstrated that Ag/AgCl nanocubes display enhanced photocatalytic activity in comparison with Ag/AgCl nanospheres due to the more efficient charge transfer. This work may pave an avenue to construct various functional materials via the assembly strategy using nanoparticles as versatile building blocks.

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Graphical abstract A combined strategy of in situ oxidation and assembly was developed to construct Ag/AgCl nanospheres and nanocubes from Ag nanoparticles, which exhibited highly photocatalytic activity and good stability for degrading methyl orange under visible light irradiation.

     

Controlled growth of uniform nanoflakes-built pyrite FeS<Subscript>2</Subscript> microspheres and their electrochemical properties

Nanoflakes-built pyrite FeS₂ microspheres were synthesized through a simple solvothermal process in mixed solvents of N, N-dimethytformamide and ethylene glycol without using any surfactant. Both the composition of the solvents and urea were key factors for the formation of the uniform products. It was found that the flake-like intermediate products transformed into FeS₂ nanoflakes in situ in the early stage and Ostwald ripening growth mechanism would contribute to the uniformity of the final products. Electrochemical studies revealed that the nanoflakes-built pyrite FeS₂ microspheres exhibited large lithium storage capacities. This method can be easily controlled and is expected to be extendable to the fabrication of other metal chalcogenides with controlled shape and structure.