Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

Effect of growth time on morphology and photovoltaic properties of ZnO nanowire array films

Single-crystalline ZnO nanowire arrays with different aspect ratios and nanowire densities were prepared by the hydrothermal growing method using polyethyleneimine （PEI） as a surfactant. PEI can only hinder the lateral growth of the ZnO nanowires, which is observed by high resolution transmission electron microscopy （HRTEM） analysis. Dye-sensitized solar cells were assembled by the ZnO nanowire arrays with different thicknesses, which can be controlled by the growing time and characterized using photocurrent-voltage measurements. Their photocurrent densities and energy allover conversion efficiencies increased with increasing ZnO nanowire lengths. Short-circuit current density of 4.31 mA.cm-2 and allover energy conversion efficiency of 0.87% were achieved with 12.9-μm-long ZnO nanowire arrays.

Preparation and growth mechanism of nickel nanowires under applied magnetic field

Nickel nanowires with large aspect ratio of up to 300 have been prepared by a hydrazine hydrate reduction method under applied magnetic field. The diameter of nickel nanowires is about 200 nm and length up to 60 μm. The role of magnetic field on the growth of magnetic nanowires is discussed and a magnetic nanowire growth mechanism has been proposed. Nickel ions are firstly reduced to nickel atoms by hydrazine hydrates in a strong alkaline solution and grow into tiny spherical nanoparticles. Then, these magnetic particles will align under a magnetic force and form linear chains. Furthermore, the as-formed chains can enhance the local magnetic field and attract other magnetic particles nearby, resulting finally as linear nanowires. The formation and the size of nanowires depend strongly on the magnitude of applied magnetic field.

Ⅲ–Ⅴ ternary nanowires on Si substrates: growth, characterization and device applications

Over the past decades, the progress in the growth of materials which can be applied to cutting-edge technologies in the field of electronics, optoelectronics and energy harvesting has been remarkable. Among the various materials, group Ⅲ–Ⅴ semiconductors are of particular interest and have been widely investigated due to their excellent optical properties and high carrier mobility. However, the integration of Ⅲ–Ⅴ structures as light sources and numerous other optical components on Si,which is the foundation for most optoelectronic and electronic integrated circuits, has been hindered by the large lattice mismatch between these compounds. This mismatch results in substantial amounts of strain and degradation of the performance of the devices. Nanowires(NWs) are unique nanostructures that induce elastic strain relaxation, allowing for the monolithic integration of Ⅲ–Ⅴ semiconductors on the cheap and mature Si platform. A technique that ensures flexibility and freedom in the design of NW structures is the growth of ternary Ⅲ–Ⅴ NWs, which offer a tuneable frame of optical characteristics, merely by adjusting their nominal composition. In this review, we will focus on the recent progress in the growth of ternary Ⅲ–Ⅴ NWs on Si substrates. After analysing the growth mechanisms that are being employed and describing the effect of strain in the NW growth, we will thoroughly inspect the available literature and present the growth methods, characterization and optical measurements of each of the Ⅲ–Ⅴ ternary alloys that have been demonstrated. The different properties and special treatments required for each of these material platforms are also discussed. Moreover, we will present the results from the works on device fabrication, including lasers, solar cells, water splitting devices, photodetectors and FETs, where ternary Ⅲ–Ⅴ NWs were used as building blocks. Through the current paper, we exhibit the up-to-date state in this field of research and summarize the important accomplishments of the past few years.

Solute drag-controlled grain growth in magnesium investigated by quasi in-situ orientation mapping and level-set simulations

Critical properties of metallic materials,such as the yield stress,corrosion resistance and ductility depend on the microstructure and its grain size and size distribution.Solute atoms that favorably segregate to grain boundaries produce a pinning atmosphere that exerts a drag pressure on the boundary motion,which strongly affects the grain growth behavior during annealing.In the current work,the characteristics of grain growth in an annealed Mg-1 wt.%Mn-1 wt.%Nd magnesium alloy were investigated by advanced experimental and modeling techniques.Systematic quasi in-situ orientation mappings with a scanning electron microscope were performed to track the evolution of local and global microstructural characteristics as a function of annealing time.Solute segregation at targeted grain boundaries was measured using three-dimensional atom probe tomography.Level-set computer simulations were carried with different setups of driving forces to explore their contribution to the microstructure development with and without solute drag.The results showed that the favorable growth advantage for some grains leading to a transient stage of abnormal grain growth is controlled by several drivers with varying importance at different stages of annealing.For longer annealing times,residual dislocation density gradients between large and smaller grains are no longer important,which leads to microstructure stability due to predominant solute drag.Local fluctuations in residual dislocation energy and solute concentration near grain boundaries cause different boundary segments to migrate at different rates,which affects the average growth rate of large grains and their evolved shape.

Controlled growth of large＇scale silver nanowires

Large-scale silver nanowires with controlled aspect ratio were synthesized via reducing silver nitrate with 1, 2- propanediol in the presence of poly （vinyl pyrrolidone） （PVP）. Scanning electron microscopy, transmission electron microscopy and x-ray powder diffraction were employed to characterize these silver nanowires. The diameter of the silver nanowires can be readily controlled in the range of 100 to 400 nm by varying the experimental conditions. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy results show that there exists no chemical bond between the silver and the nitrogen atoms. The interaction between PVP and silver nanowires is mainly through the oxygen atom in the carbonyl group.

An in-situ study of static recrystallization in Mg using high temperature EBSD

It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization and grain growth is critical to the success of the technique.In the present work,by using in-situ high temperature EBSD,the mechanisms that control recrystallization and grain growth of an extruded pure Mg were studied.The experimental results revealed that the grains of priority for dynamic recrystallization exhibit fading competitiveness under static recrystallization.It is also found that grain boundary movement or grain growth is likely to show an inverse energy gradient effect,i.e.,low energy grains tend to swallow or grow into high energy grains,and grain boundaries of close to 30°exhibit superior growth advantage to others.Another finding is that{10-12}tensile twin boundaries are sites of hardly observed for recrystallization,and are finally swallowed by adjacent recrystallized grains.The above findings may give comprehensive insights of static recrystallization and grain growth of Mg,and may guide the design of advanced materials processing in microstructural engineering.

TBAB hydrate formation and growth in a microdevice under static and dynamic conditions

The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydrate formation and growth processes in the porous medium is of significance for the exploitation of natural gas hydrate. The micro-packed bed device is one of the efficient microfluidic devices in the engineering field, but it has been rarely used for the hydrate-based research. In this study, a transparent micro-packed bed device filled with glass beads was developed to mimic the porous condition of sediments, and used to in-situ visualize the hydrate formation and growth habits in the pore spaces under both static and dynamic conditions. For the static experiment, two types of hydrate growth patterns in porous medium were observed and identified in the micro-packed bed device, which were the graincoating growth and pore-filling growth. For the dynamic condition, the hydrate formation, growth,distribution habits and hydrate blockage phenomena in the pore spaces were in-situ visually captured.The impacts of flowrate and subcooling on the pressure variation of the micro-packed bed and the duration of the hydrate growth under dynamic flow condition in pores were in-situ monitored and analyzed. The higher flowrate could result in the faster hydrate growth and more severe blockage in pores, but the effect of subcooling condition might be less significant at the high flowrate.

The Self-Assembling Growth of Copper Nanowires for Transparent Electrodes

Long(15-40 μm), thin(diameter of 20 ± 5 nm), and well-dispersed CuNWs Cu nanowires were prepared. The high-resolution TEM and selected area electron diffraction showed that the CuNWs were single-crystalline. To investigate the growth mechanism, we examined the microstructure of these CuNWs at different reaction time. It was found that the CuNWs were actually formed through the self-assembling of Cu nanoparticles along the [110] direction. The transparent electrodes fabricated using the CuNWs achieved a high transparency of 76 % at 31±5 Ω/□.

The influence of ablation products on the ablation resistance of C/C-SiC composites and the growth mechanism of SiO_2 nanowires

Ablation under oxyacetylene torch with heat flux of 4186.8（10%kW/m2 for 20 s was performed to evaluate the ablation resistance of C/C-SiC composites fabricated by chemical vapor infiltration（CVI） combined with liquid silicon infiltration（LSI） process.The results indicated that C/C-SiC composites present a better ablation resistance than C/C composites without doped SiC.The doped SiC and the ablation products SiO2 derived from it play key roles in ablation process.Bulk quantities of SiO2 nanowires with diameter of 80 nm-150 nm and length of tens microns were observed on the surface of specimens after ablation.The growth mechanism of the SiO_2 nanowires was interpreted with a developed vapor-liquid-solid（VLS） driven by the temperature gradient.

Wrinkling and Growth Mechanism of CuO Nanowires in Thermal Oxidation of Copper Foil

We report a systematic study on wrinkling and CuO nanowires （NWs） growth in the thermal oxidation of copper foil. Copper foils with thickness of 0.5 mm were thermally oxidized in air at 500℃ for 0.5-10 h. It is found that all the samples have wrinkles and the size of the wrinkles increases with the oxidation time increasing. CuO NWs can grow on both the sidehill and hilltop of wrinkle. The CuO NWs on sidehill are longer and denser than those on hilltop. The growth direction of the CuO NWs on sidehill is not vertical to the substrate but vertical to their growth surfaces. The process of wrinkling and CuO NWs growth can be divided into three stages： undulating, voiding, and cracking. The CuO NWs on both sidehill and hilltop grow at the undulating stage. However, only the CuO NWs on sidehill grow and those on hilltop stop growing at the voiding and cracking stages because of the void in hilltop. The local electric field in a wrinkle at undulating stage was calculated, and it is found that the difference of local electric field strengths between hilltop and sidehill is small, which indicates that the predominant driving force for the diffusion of Cu ion during CuO NWs growth is internal stress.

Role of Chromium Intermediate Thin-Film on the Growth of Silicon Oxide (SiO_x) Nanowires

In the present work, one-dimensional nanostructures of silicon oxide (SiOx) have been synthesized by thermal annealing method with and without chromium thin film on silicon substrate. The synthesis was carried out at different process temperatures ranging from 1000°C to 1100°C by using gold/chromium (Au/Cr) catalysts stack layer on the Si substrate in nitrogen (N2) ambience. The as-synthesized SiOx nanostructures have tetragonal rutile structure and show polycrystalline nature. The SEM images reveal wire-like nanostructures on the substrate with and without chromium thin film. Under the catalytic reaction of the gold/chromium metal, the density of SiOx nanowires is enhanced, since the Cr layer serves as a diffusion barrier for the diffusion of the gold downwards into the Si substrate. The vapor-liquid solid (VLS) growth mechanism is found to be dominant in the growth of SiOx nanowires. Furthermore, X-Ray diffraction microscopy (XRD) and Photoluminescence spectroscopy (PL) analysis conclude the defect free growth of the SiOx nanowires on gold/chrome/silicon substrate.

Wet-Chemical Synthesis and Optical Property of ZnSe Nanowires by Ag₂Se-Catalyzed Growth Mechanism

High-quality II-VI semiconductor ZnSe nanowires were facilely prepared in the oleic acid and oleylamine mixed solution at low temperatures of 130°C-200°C through an Ag2Se-catalyzed growth mechanism. Oleylamine served as an effective reducing agent and a surfactant in the synthesis. Many of the resultant nanowires were terminated by an Ag2Se catalyst particle at one of their ends, confirming that the nanowire growth followed a catalytic mechanism. The crystal structure of Ag2Se catalyst was examined, which exhibited a metastable tetragonal phase, not the common orthorhombic phase. Meanwhile, the optical properties of as-synthesized ZnSe nanowire solid powder were evaluated by the UV-Visible diffuse reflectance and photoluminescence spectroscopy and a significant blue shift was observed compared to the bulk ZnSe with a band gap of 2.7 eV. This work would provide an alternative and effective catalytic route for the preparation of one-dimensional (1D) nanostructures of ZnSe and other metal selenides.

Characterization of SiC nanowires prepared on C/C composite without catalyst by CVD

SiC nanowires were prepared on C/C composite surface without catalyst by chemical vapor deposition（CVD） using CH3 SiCl3 as precursor.SEM images of the CVD-product reveal that some long nanowires have grown to tens of micrometers with some gathered as a ball.Some short nanowires agglomerate like chestnut shell with many thorns accompanied by some deposited nano-particles.XRD,Raman-spectrum and FTIR patterns indicate that the product is a typical β-SiC.TEM images show that the nanowires have a wide diameter range from 10 to 100 nm,and some thin nanowires are bonded to the thick one by amorphous CVD-SiC.A SiC branch generates from an amorphous section of a thick one with an angle of 70° between them,which is consistent with the [111] axis stacking angle of the crystal.SAED and fast Fourier transform（FFT） patterns reveal that the nanowires can grow along with different axes,and the bamboo-nodes section is full of stacking faults and twin crystal.The twisted SiC lattice planes reveal that the screw dislocation growth is the main mechanism for the CVD-SiC nanowires.

Interface catalytic reduction of alumina by nickle for the aluminum nanowire growth: Dynamics observed by in situ TEM

Metal nanowires show promise in a broad range of applications and can be fabricated via a number of methods,such as vapor–liquid–solid process and template-based electrodeposition.However,the synthesis of Al nanowires(NWs)is still challenging from the stable alumina substrate.In this work,the Ni-catalyzed fabrication of Al NWs has been realized using various Al_(2)O_(3) substrates.The growth dynamics of Al NWs on Ni/Al_(2)O_(3) was studied using in situ transmission electron microscopy(TEM).The effect of alumina structures,compositions,and growth temperature were investigated.The growth of Al NWs correlates with the Na addition to the alumina support.Since no eutectic mixture of nickel aluminide was formed,a mechanism of Ni-catalyzed reduction of Al_(2)O_(3) for Al NWs growth has been proposed instead of the vapor–liquid–solid mechanism.The key insights reported here are not restricted to Ni-catalyzed Al NWs growth but can be extended to understanding the dynamic change and catalytic performance of Ni/Al_(2)O_(3) under working conditions.

Growth mechanism of reinforcements in in-situ synthesized (TiB+TiC)/Ti composites

The growth mechanism of reinforcement in in situ synthesized (TiB+TiC)/Ti composites was investigated. The results show that reinforcements nucleate and grow in a way of dissolution precipitation. The morphologies of reinforcements are closely related to the solidification paths and crystal structure of reinforcements. TiB, as a reinforcement, is liable to grow along [010] direction and forms in short fibre shape due to its B27 structure, whereas primary TiC is liable to form composition undercooling and grow in dendritic shape. TiC phases precipitated in binary eutectic and ternary eutectic reactions grow in equiaxial shape. The addition of aluminum element refines TiB and TiC particles, and makes TiC reinforcements grow into the equiaxial particles easily. The addition of graphite adjusts the solidification paths and forms more TiC with dendritic shape. [

Facile Preparation of Mn_2O_3 Nanowires by Thermal Decomposition of MnCO_3

Mn2O3 nanowires with diameters of about 130 nm and lengths up to tens of micrometers were synthesized by the thermal decomposition of MnCO3 precursors. It was identified that the growth of the cubic Mn2O nanowires was preferential along the [001] direction. The intermediate stage containing melting state and the particles of manganese oxide played an important role for the formation of Mn2O3 with one-dimensional structure. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to characterize the morphology and crystal structure of the precursors and final products. Thermogravimetry analysis was also carried out to find the mechanism for the formation of Mn2O3 nanowires. The growth of the nanowires was proposed to be dominated by the conventional melt-growth mechanism.

Synthesis of large-scale GaN nanowires by ammoniating Ga_2O_3 films on Co layer deposited on Si(111) substrates

A mass of GaN nanowires has been successfully synthesized on Si（111） substrates by magnetron sputtering through ammoniating Ga2O3/Co films at 950℃. X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscope and Fourier transformed infrared spectra are used to characterize the samples. The results demonstrate that the nanowires are of single-crystal GaN with a hexagonal wurtzite structure and possess relatively smooth surfaces. The growth mechanism of GaN nanowires is also discussed.

Optimization of the in-situ growth conditions based on a novel photo-microcalorimeter for the sustainable cultivation of photosynthetic microorganisms

Despite the great potential of photosynthetic microbes in the production of renewable fuels,value-adding chemicals,and water treatment,etc.,commercial utilization of them is significantly hindered by the lack of techniques to accurately monitor the thermodynamic and kinetic characteristics of the in-situ growth of microbes under controlled light illumination for optimal cultivation.Herein,we demonstrated that a newly developed highly sensitive photo-microcalorimetric system successfully captured the impacts of the light wavelength and strength on the thermodynamic and kinetic parameters of the in-situ growth of Rhodopseudomonas palustris,a representative photosynthetic microorganism.To our best knowledge,this is the first time that highly precise microcalorimetry is employed to monitor exam the in-situ growth of photosynthetic microorganisms under controllable photo illumination.We envision this technique can help for the optimization of the growth conditions of photosynthetic microorganisms for scale-up applications.

Optically manipulated nanomechanics of semiconductor nanowires

Opto–electromechanical coupling at the nanoscale is an important topic in new scientific studies and technical applications. In this work, the optically manipulated electromechanical behaviors of individual cadmium sulfide(CdS) nanowires are investigated by a customer-built optical holder inside transmission electron microscope, wherein in situ electromechanical resonance took place in conjunction with photo excitation. It is found that the natural resonance frequency of the nanowire under illumination becomes considerably lower than that under darkness. This redshift effect is closely related to the wavelength of the applied light and the diameter of the nanowires. Density functional theory(DFT) calculation shows that the photoexcitation leads to the softening of CdS nanowires and thus the redshift of natural frequency, which is in agreement with the experimental results.