原子尺度材料三维结构、磁性及动态演变的透射电子显微学表征

原子表征与操控是实现原子制造必须突破的物理瓶颈之一.像差校正电子显微学方法因其优异的空间分辨率,为实现原子精细制造提供了有力的表征手段.因此,利用电子显微学手段,在原子尺度对原子制造的材料及器件进行三维结构和性能的协同表征,对于深入理解原子水平材料操控的物理机理具有非常重要的意义.纳米团簇及纳米颗粒是原子制造材料与器件研究的主要对象之一,具有丰富的物理化学性质和较高的可操纵性.本文探讨纳米团簇/颗粒结构三维定量表征、使役条件下纳米团簇/颗粒结构演变定量表征、纳米颗粒/晶粒结构-成分-磁性协同定量表征等诸多方法与实例,阐明了电子显微学表征手段的突破和发展为实现精细控制的原子制造材料提供了坚实基础.     

Hybrid polymer nanosystems based on selenium and zinc-selenide nanoparticles: Morphology,electronic structure,and thermodynamic properties

The structure and morphology of hybrid nanosystems based on selenium and zinc-selenide nano-particles stabilized by water-soluble polymers—polyvinylpyrrolidone and polymethacrylic acid, are studied by methods of atomic force microscopy (AFM), high-resolution electron microscopy, transmission and scanning electron microscopy (TEM and SEM), X-ray photoelectron spectroscopy, X-ray structural analysis, and static light scattering. Comparison of the size characteristics of the nanostructures in the nanoparticle/polymer systems upon an increase in the weight ratio (ν) of the system components, using static light scattering in a solution and AFM, SEM, and TEM on the substrate surface, shows that the sizes of the forming nano-structures change nonmonotonically. The thermodynamic characteristics of the nanostructures in the solution are determined. It is shown that depending on ν, nanostructures of various morphologies may be formed, including spheres and irregularly shaped micelles with cores of different sizes.     

Understanding CeO2‐Based Nanostructures through Advanced Electron Microscopy in 2D and 3D

Engineering morphology and size of CeO₂‐based nanostructures on a (sub)nanometer scale will greatly influence their performance; this is because of their high oxygen storage capacity and unique redox properties, which allow faster switching of the oxidation state between Ce⁴⁺ and Ce³⁺. Although tremendous research has been carried out on the shape‐controlled synthesis of CeO₂, the characterization of these nanostructures at the atomic scale remains a major challenge and the origin of debate. The rapid developments of aberration‐corrected transmission electron microscopy (AC‐TEM) have pushed the resolution below 1 Å, both in TEM and in scanning transmission electron microscopy (STEM) mode. At present, not only morphology and structure, but also composition and electronic structure can be analyzed at an atomic scale, even in 3D. This review summarizes recent significant achievements using TEM/STEM and associated spectroscopic techniques to study CeO₂‐based nanostructures and related catalytic phenomena. Recent results have shed light on the understanding of the different mechanisms. The potential and limitations, including future needs of various techniques, are discussed with recommendations to facilitate further developments of new and highly efficient CeO₂‐based nanostructures.     

Atomic force microscopy and transmission electron microscopy of biocompatible magnetic fluids: A comparative analysis

The present study provides a comparative analysis of the size dispersity of magnetic nanoparticles (MNPs) within magnetic fluids as obtained from atomic force microscopy (AFM) and transmission electron microscopy (TEM). Whereas the mean particle diameter obtained from the AFM data presented a reduction of about 34% as compared to the value obtained from the TEM data, the standard deviation obtained from the AFM data is twice the value found from the TEM data. Similarities and differences in the size dispersity parameters are discussed in terms of sample preparation and tip characteristics. A two-dimensional mode for the deposition of the MNPs on top of the mica substrate is discussed as well.     

Effect of ultrasonic treatment on the morphology of casein particles

In this study, the effect of ultrasonic treatment duration on the morphology of self-assembled casein particles was investigated by atomic force microscopy (AFM), low vacuum scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the case of AFM images, the particle analysis which was carried out by the SPIP program showed that the self-assembled casein particles after being ultrasonically treated for 2 min got smaller in size compared to the casein particles that have not been exposed to any ultrasonic treatment. Surprisingly, however, increasing the ultrasonic time exposure of the particles resulted in an opposite effect where larger particles or aggregates seemed to be present. We show that by comparing the results obtained by AFM, SEM and TEM, the information extracted from the AFM images and analyzed by SPIP program give more detailed insights into particle sizes and morphology at the molecular level compared to SEM and TEM images, respectively.     

AFM and TEM study of hydrogenated sputtered Si/Ge multilayers

Multilayers of hydrogenated ultrathin (3 nm) amorphous a-Si and a-Ge layers prepared by sputtering have been studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM) to check the influence of annealing on their structural stability. The annealed multilayers exhibit surface and bulk degradation with formation of bumps and craters whose density and size increase with increasing hydrogen content and/or annealing temperature and time. Bumps are due to the formation of H₂ bubbles in the multilayer. The craters are bumps blown up very likely because of too high a gas pressure inside. The release of H from its bonds to Si and Ge occurs within cavities very likely present in the samples. The necessary energy is supplied by the heat treatment and by the recombination of thermally generated carriers. Results by energy filtered TEM on the interdiffusion of Si and Ge upon annealing are also presented.     

A comparative study of conventional type II and inverted core–shell nanostructures based on CdSe and ZnS

The objective of this work is to investigate structural, morphological and optical properties of conventional CdSe/ZnS core–shell and inverted ZnS/CdSe core–shell nanostructures for opto-electronic device applications. For this purpose both nanostructures were synthesized using chemical bath deposition technique in thin film form. The structural properties were studied using X-ray diffraction technique with Rietveld refinement and transmission electron microscopy (TEM). The surface morphology of synthesized thin film was illustrated in the form 2D and 3D images using atomic force microscopy (AFM). The optical properties were explained using UV–Vis absorption spectroscopy and photo luminescence (PL) spectroscopy in in situ monitoring process. A comparison of estimated particle size from XRD, high resolution AFM and TEM images was resulted in good agreement as 2.1, 2.4 and 2.1 nm respectively for conventional CdSe/ZnS core–shell and as 2.5, 2.5 and 2.2 nm respectively for inverted ZnS/CdSe core–shell nanostructures.     

Electron microscopy of nanoemulsions: an essential tool for characterisation and stability assessment

The characterisation of pharmaceutical formulations by microscopic techniques is essential to obtain reliable data about the actual morphology of the system. Since the size range of colloidal drug delivery systems has long ago reached the lower end of the nanometer scale, classical light microscopy has been replaced by electron microscopy techniques which provide sufficient resolution for the visualisation of nano-sized structures. Indeed, the superior resolution and methodological versatility of electron microscopy has rendered this technique an indispensable tool for the analysis of nanoemulsions. Microscopic analysis of these lipid-based drug delivery systems with particle sizes in the lower submicron range provides critical information about the size, shape and internal structure of the emulsion droplets. Moreover, surfactant aggregates such as liposomes or multilamellar structures which remain unnoticed during particle size measurements can be detected in this fashion. This review provides a brief overview about both transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques which have been employed to characterise nanoemulsions. Of special interest are sophisticated cryo techniques of sample preparation for both TEM and SEM which deliver high-quality images of nanoemulsions in their natural state. An overview about the instrumentation and sample preparation for all presented methods is given. Important practical aspects, sources of error and common artefacts as well as recent methodological advances are discussed. Selected examples of electron microscopic studies of nanoemulsions are presented to illustrate the potential of this technique to reveal detailed and specific information.     

Composition of the “GaAs” quantum dot,grown by droplet epitaxy

Self-assembled strain-free quantum dot (QD) structures were grown on AlGaAs surface by the droplet epitaxal method. The QDs were developed from pure Ga droplets under As pressure. The QDs were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Both techniques show that the QDs are very uniform in size and their distribution on the surface is also homogeneous. The high resolution cross-sectional TEM investigation shows perfect lattice matching between the QD and the substrate, and also the faceting of the side walls of QD can be identified exactly by lattice planes. Analytical TEM (elemental mapping by EELS) unambiguously identifies the presence of Al in the QD.     

Atomic origins of solid helium bubbles in tungsten

Solid helium bubbles were directly observed in the helium ion implanted tungsten（W）, by different transmission electron microscopy（TEM） techniques at room temperature. The diameters of these solid helium bubbles range from1 nm to 8 nm in diameter with the mean bubble size about 3 nm. The selected area electron diffraction（SAED） and fast Fourier transform（FFT） images revealed that solid helium bubbles possess body-centered cubic（bcc） structure with a lattice constant of 0.447 nm. High-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）images further confirmed the existence of helium bubble in tungsten. The present findings provide an atomic level view of the microstructure evolution of helium in the materials, and revealed the existence of solid helium bubbles in materials.     

High contrast hollow-cone dark field transmission electron microscopy for nanocrystalline grain size quantification

In this paper, we describe hollow-cone dark field (HCDF) transmission electron microscopy (TEM) imaging, with a slightly convergent beam, as an improved technique that is suitable to form high contrast micrographs for nanocrystalline grain size quantification. We also examine the various factors that influence the HCDF TEM image quality, including the conditions of microscopy (alignment, focus and objective aperture size), the properties of the materials imaged (e.g., atomic number, strain, defects), and the characteristics of the TEM sample itself (e.g., thickness, ion milling artifacts). Sample preparation was found to be critical and an initial thinning by wet etching of the substrate (for thin film samples) or tripod polishing (for bulk samples), followed by low-angle ion milling was found to be the preferred approach for preparing high-quality electron transparent samples for HCDF imaging.     

Optical measurements of ZnS nanoparticles aqueous solution

We synthesized zinc sulfide (ZnS) nanopowders with size ranging from 2 to 100 nm by a simple, low-cost, and mass production chemical method. The nanoparticles (NPs) were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and UV-vis absorption spectroscopy. Our study concerns also the change in the refractive index of deionized water in presence of ZnS nanospheres. We present experimental results on effective index variation of water dispersed ZnS NPs at different wavelengths in visible spectrum.     

UHV-HREM and diffraction of surfaces

Characterization of the structure of surfaces is very important in order to develop a fundamental understanding of the electronic, mechanical and chemical properties of a material. While transmission electron microscopy imaging (TEM) and diffraction (TED) techniques are capable of providing surface structural information at the atomic level, such data would be suspect if obtained under conventional vacuum conditions (10^-6–10^-8 Torr). Ultrahigh vacuum (UHV) conditions are imperative during both preparation and observation of clean surfaces/interfaces. Conventional TEM techniques are very powerful for UHV-TEM investigations; however, the marriage of surface science and conventional TEM to yield an UHV-TEM is a complex task. These complexities and some of the results obtained using UHV-TEM and UHV-TED techniques for surfaces i.e. solid-vacuum interfaces will be illustrated.     

Photo-chemical synthesis and deposition of noble metal nanoparticles

Highly dispersed nanoparticles of transition and noble metals are utilized for hydrocarbon reactions and rearrangements important to the chemical industry. The need to obtain 1 to 3 nm particles with narrow size distributions has prompted the development of alternative processing methods. In this paper, a novel, dry method to synthesize nanoparticles from a frozen salt solution is reported. Pd nanoparticles were synthesized by photo-chemical decomposition of palladium acetate (PdAc) within a host matrix of chloroform using an excimer laser operating at 248 nm. Frozen composite targets were ablated at fluences ranging from 0.25 J/cm² to 0.75 J/cm² at a processing pressure of 10 mTorr. The ejected nanoparticles were deposited on continuous carbon coated and lacey carbon transmission electron microscopy (TEM) grids at ambient temperature. Characterization was performed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDXS). High-resolution TEM analysis showed definitive evidence that the size distributions of the nanoparticles were narrow, exhibiting mean diameters ranging from 2.15 nm to 2.62 nm. PACS 81.15.Fg; 68.37.Lp; 81.07.Wx; 81.07.Bc; 81.10.Dn     

Structural and optical properties of chemically synthesized monodispersed CdCr2S4 films

Alkaline chemical synthesis of amorphous CdCr₂S₄ (CCS) thin films of different thicknesses using cadmium chloride, chromic acid, disodium salt of ethylenediaminetetra acetic acid and thiourea precursors is reported, and the structural and surface morphological properties of CCS using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM) techniques are discussed. Films of aggregated grains with some void spaces are obtained. Change in band gap energy and electrical resistivity of CCS films are discussed as a function of film thickness. n-type conductivity is confirmed from the sign of thermally generated voltage across the cold and hot junctions.     

Direct Synthesis of ZIF-8 on Transmission Electron Microscopy Grids Allows Structure Analysis and 3D Reconstruction

The first example of layer-by-layer growth of a metal–organic framework (MOF) directly on transmission electron microscopy (TEM) grids is described. ZIF-8 is deposited on thin amorphous carbon films and subjected to a structure analysis by (scanning) TEM ((S)TEM). This method serves as a two-in-one synthesis and TEM sample-preparation technique and allows straightforward analysis of ZIF-8 crystallites. Artifacts resulting from sample preparation are completely avoided by this approach. The morphological properties, crystal structure, and the chemical composition of the material are investigated with high spatial resolution by a variety of methods of (analytical) electron microscopy. Furthermore, the incorporation of metallic nanoparticles in ZIF-8 by integrating a corresponding step into the layer-by-layer deposition process is examined. The formation of ZIF-8 crystals on the film proceeds as under the absence of nanoparticle-forming synthesis steps. However, the nanoparticles rather cover the supporting amorphous carbon film than being incorporated in the ZIF-8 material. This information cannot be obtained from standard characterization techniques but requires the application of analytical (S)TEM techniques.     

Elaboration and characterization of TiO2 nanoparticles incorporated in SiO2 host matrix

Nanometer-scale TiO₂ particles have been synthesized by sol-gel method. It was incorporated in a glass-based silica aerogel. The composite was characterized by various techniques such as particle size analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and photoluminescence (PL). The bulk glass presents a strong luminescence at wavelengths ranging from 750 to 950 nm. This PL was attributed to various non-bridging oxygen hole centers (NBOHCs) defects resulting from thermal treatment and crystallization of TiO₂ at the interface between titania nanoparticles and silica host matrix.     

Nanoporous AlN particles production from a solid-state metathesis reaction

This paper reports that nanoporous AlN particles are synthesized from solid-state metathesis reactions using AlCl₃ and Mg₃N₂ as reactants. The samples are characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, high-resolution transmission electron microscopy (HRTEM), ultraviolet--visible (UV--vis) absorption spectroscopy and Raman spectroscopy. The results show that samples with walls 10 nm in thickness and pores between 10 nm and 100 nm in diameter were produced successfully from these reactions, and their band gap and vibration modes agree with those of AlN bulk crystal.     

Characterization challenges for a cellulose nanocrystal reference material: dispersion and particle size distributions

Cellulose nanocrystals (CNCs) have high aspect ratios, polydisperse size distributions, and a strong propensity for aggregation, all of which make them a challenging material for detailed size and morphology characterization. A CNC reference material produced by sulfuric acid hydrolysis of softwood pulp was characterized using a combination of dynamic light scattering (DLS), atomic force microscopy (AFM), transmission electron microscopy, and X-ray diffraction. As a starting point, a dispersion protocol using ultrasonication was developed to provide CNC suspensions with reproducible size distributions as assessed by DLS. Tests of various methods for AFM sample preparation demonstrated that spin coating on a positively charged substrate maximizes the number of individual particles for size analysis, while minimizing the presence of agglomerates. The effects of sample-to-sample variability, analyst bias, and sonication on size distributions were assessed by AFM. The latter experiment indicated that dispersion of agglomerates by sonication did not significantly change the size distribution of individual CNCs in suspension. Comparison with TEM data demonstrated that the two microscopy methods provide similar results for CNC length (mean ~?80 nm); however, the particle width as measured by TEM is approximately twice that of the CNC height (mean 3.5 nm) measured by AFM. The individual crystallite size measured by X-ray diffraction is intermediate between the two values, although closer to the AFM height, possibly indicating that laterally agglomerated CNCs contribute to the TEM width. Overall, this study provides detailed information that can be used to assess the factors that must be considered in measuring CNC size distributions, information that will be useful for benchmarking the performance of different industrially sourced materials.     

ESTEM imaging of single atoms under controlled temperature and gas environment conditions in catalyst reaction studies

Heterogeneous gas‐solid catalyst reactions occur on the atomic scale and there is increasing evidence single atoms and very small clusters can act as primary active sites in chemical reactions. Aberration corrected environmental scanning transmission electron microscope (AC ESTEM) has been developed for novel studies of nanoparticle catalysts with Angstrom (0.1 nm) resolution in gas. It extends high vacuum analyses with full analytical facilities and unrestricted high angle annular dark field (HAADF) imaging of single atoms, small clusters and nanoparticles in dynamic in‐situ experiments with controlled gas reaction environments at initial operating temperatures up to > 500 °C.