Exploring the environmental transmission electron microscope

The increasing interest and development in the field of in situ techniques have now reached a level where the idea of performing measurements under near realistic conditions has become feasible for transmission electron microscopy (TEM) while maintaining high spatial resolution. In this paper, some of the opportunities that the environmental TEM (ETEM) offers when combined with other in situ techniques will be explored, directly in the microscope, by combining electron-based and photon-based techniques and phenomena. In addition, application of adjacent setups using sophisticated transfer methods for transferring the specimen between specialized in situ equipment without compromising the concept of in situ measurements will be exploited. The opportunities and techniques are illustrated by studies of materials systems of Au/MgO and Cu(2)O in different gaseous environments.     

Study of local density of electron states in InGaAs/GaAs quantum rings by combined STM/AFM

The electronic structure of self-assembled InGaAs/GaAs(001) quantum rings grown by atmospheric pressure metal-organic vapor phase epitaxy has been investigated by combined scanning tunneling/atomic force microscopy (STM/AFM) in ultrahigh vacuum (UHV) for the first time. The current images and the tunnel spectra of contact of Pt-coated Si AFM probe to the quantum ring heterostructure surface revealing the spatial distribution of the local density of states and the electron size quantization spectra in the quantum rings have been obtained.     

Image resolution and sensitivity in an environmental transmission electron microscope

An environmental transmission electron microscope provides unique means for the atomic-scale exploration of nanomaterials during the exposure to a reactive gas environment. Here we examine conditions to obtain such in situ observations in the high-resolution transmission electron microscopy (HRTEM) mode with an image resolution of 0.10nm. This HRTEM image resolution threshold is mapped out under different gas conditions, including gas types and pressures, and under different electron optical settings, including electron beam energies, doses and dose-rates. The 0.10nm resolution is retainable for H(2) at 1-10mbar. Even for N(2), the 0.10nm resolution threshold is reached up to at least 10mbar. The optimal imaging conditions are determined by the electron beam energy and the dose-rate as well as an image signal-to-noise (S/N) ratio that is consistent with Rose's criterion of S/N≥5. A discussion on the electron-gas interactions responsible for gas-induced resolution deterioration is given based on interplay with complementary electron diffraction (ED), scanning transmission electron microscopy (STEM) as well as electron energy loss spectroscopy (EELS) data.     

Current image formation in combined STM/AFM of metal nanoclusters in dielectric films

Current imaging in studying metal nanoclusters in thin dielectric films by combined scanning tunneling and atomic-force microscopy was simulated. It was shown that sizes of increased conductivity regions in current images, caused by electron tunneling through nanoclusters, are controlled by the size of the probe-film surface contact area.     

Scanning probe microscope with interchangeable AFM-FFM and STM heads

Summary A scanning probe microscope operating in air with interchangeable atomic force-friction force (AFM-FFM) and electronic-tunnelling (STM) heads is presented. Our AFM operates in the so-called contact mode and utilizes the optical-lever detection method which allows simultaneous measurement of the topography as well as the lateral force. The set-up also contains an optical microscope to control both the sample and the probe laser spot on the cantilever. The experimental method to change from AFM to STM operation is based on the use of the probe laser beam and the optical microscope. The maximum scanning area is (24×24) μm² and it is well embraced in the optical-microscope visual field. The microscope attains atomic resolution in air in both AFM and STM configuration. Its performance is demonstrated on the surface of different samples. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Strain mapping of semiconductor specimens with nm-scale resolution in a transmission electron microscope

The last few years have seen a great deal of progress in the development of transmission electron microscopy based techniques for strain mapping. New techniques have appeared such as dark field electron holography and nanobeam diffraction and better known ones such as geometrical phase analysis have been improved by using aberration corrected ultra-stable modern electron microscopes. In this paper we apply dark field electron holography, the geometrical phase analysis of high angle annular dark field scanning transmission electron microscopy images, nanobeam diffraction and precession diffraction, all performed at the state-of-the-art to five different types of semiconductor samples. These include a simple calibration structure comprising 10-nm-thick SiGe layers to benchmark the techniques. A SiGe recessed source and drain device has been examined in order to test their capabilities on 2D structures. Devices that have been strained using a nitride stressor have been examined to test the sensitivity of the different techniques when applied to systems containing low values of deformation. To test the techniques on modern semiconductors, an electrically tested device grown on a SOI wafer has been examined. Finally a GaN/AlN superlattice was tested in order to assess the different methods of measuring deformation on specimens that do not have a perfect crystalline structure. The different deformation mapping techniques have been compared to one another and the strengths and weaknesses of each are discussed.     

Quantitative measurement of image intensity in transmission electron microscope images

We have made a thorough comparison of the ability of image simulations to predict the contrast in high-resolution electron microscope lattice images of GaAs. Simulations of the diffracted beam intensities from thickness fringes generally agreed with observations to within ∼20% over a range of GaAs thicknesses up to 150 nm. Likewise, simulations of lattice images agreed qualitatively with experimental lattice images over a range of defocus and sample thicknesses up to 20 nm. However, using the same parameters as for the diffracted beam intensities, lattice fringe amplitudes were calculated to be typically two to three times higher than observed experimentally.     

On the oxidation of CaF2 in transmission electron microscope

Electron stimulated oxidation of CaF₂ in transmission electron microscope has been thoroughly studied using various electron microscopy techniques, including imaging, electron diffraction and electron energy-loss spectroscopy. It found that the electron irradiation induced CaO locate on the edge of specimen. The oxidation process is associated with desorption of F by electron irradiation, and originates from O impurities in the specimen. Driven by electric field produced by electron irradiation, the O ions inside bulk diffuse to the edge region, occupying the interstitials of metallized Ca lattice. Therefore, the accumulation of O along the edge of specimen results in forming CaO.     

Observation of charges on specimens in a transmission electron microscope

In the introduction the paper gives the unfavourable consequences of localized charges in irradiated thin non-conducting foils and on isolated particles. It describes the arrangement of the optical system enabling the observation of charges on the specimen by means of shadow microscopy without changing the normal position of the preparation. This method is applied to the electron microscope Tesla BS 413 and illustrated by two examples.The authors express their thanks to Mr. J. Komrska for his comments on the text of the paper.     

Microstructure characterization of Al matrix composite reinforced with Ti-6Al-4V meshes after compression by scanning electron microscope and transmission electron microscope

Compressive properties of Al matrix composite reinforced with Ti-6Al-4V meshes (TC4(m)/5A06 Al composite) under the strain rates of 10(-3)S(-1) and 1S(-1) at different temperature were measured and microstructure of composites after compression was characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). Compressive strength decreased with the test temperature increased and the strain-rate sensitivity (R) of composite increased with the increasing temperature. SEM observations showed that grains of Al matrix were elongated severely along 45° direction (angle between axis direction and fracture surface) and TC4 fibres were sheared into several parts in composite compressed under the strain rate of 10(-3)S(-1) at 25°C and 250°C. Besides, amounts of cracks were produced at the interfacial layer between TC4 fibre and Al matrix and in (Fe, Mn)Al(6) phases. With the compressive temperature increasing to 400°C, there was no damage at the interfacial layer between TC4 fibre and Al matrix and in (Fe, Mn)Al(6) phases, while equiaxed recrystal grains with sizes about 10 μm at the original grain boundaries of Al matrix were observed. However, interface separation of TC4 fibres and Al matrix occurred in composite compressed under the strain rate of 1S(-1) at 250°C and 400°C. With the compressive temperature increasing from 25°C to 100°C under the strain rate of 10(-3) S(-1), TEM microstructure in Al matrix exhibited high density dislocations and slipping bands (25°C), polygonized dislocations and dynamic recovery (100°C), equiaxed recrystals with sizes below 500 μm (250°C) and growth of equiaxed recrystals (400°C), respectively.     

STM and AFM of bio/organic molecules and structures

Applications of scanning tunneling and atomic force microscopes in bio/organic researches are reviewed with a special emphasis on the types of researches that are expected to contribute to the creation of a new field of “single molecule biochemistry” in the near future. The reviewed articles within the scope as stated above actually include a fairly broad spectrum of researches. It is, therefore, a hope of the author that this review will be useful to those who are considering biological applications of the probe microscopy techniques but are not quite familiar with the types of experiments that have been done in the past. In the section on scanning tunneling microscopy, identification of chemically distinct functional groups by the difference in their tunneling properties will be discussed as a main focus because it is fundamental for biochemists to identify molecules by their shapes and properties. In the section on atomic force microscopy, recent progresses in the imaging techniques of proteins and DNAs are closely reviewed, and rapidly advancing technologies of single molecule measurements and manipulation of nanometer sized structures are given extensive coverage because the author considers that such new applications are extremely promising to open an entirely new field in biological sciences.     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Transition edge sensor system for material analysis using transmission electron microscope

We have developed a Transition Edge Sensor (TES) – Energy Dispersive Spectroscopy (EDS) for Transmission Electron Microscope (TEM) based on a dilution refrigerator. The dilution refrigerator was cooled by liquid helium (L-He), which was supplied from an L-He container separated from the dilution refrigerator. We adopted the hybrid magnetic shields combining a permalloy shield and a NbTi/Nb/Cu superconducting shield to operate the TEM–TES system under a magnetic field of 200 mT. The permalloy shield was used to prevent the ambient magnetic field until the NbTi superconducting shield cooled from room temperature (RT) to 2 K. The critical magnetic field was 220 mT for the TES change from a superconducting state to a normal state. The SQUID – current vs. bias current curve, under the condition that the snout was inserted in the TEM, was equal to the curve of the snout that was out of the TEM. The C (0 0 2) planes could be observed at 120 kV under the condition the snout was inserted in the TEM.     

In situ synthesis of cobalt nanocrystal hierarchies in a transmission electron microscope

We report a versatile electron beam (e-beam) synthesis method for the local fabrication of ferromagnetic nanocrystals “on demand”. A localized irradiation in a transmission electron microscope (TEM) is used to convert a raw cobalt fluoride material into ferromagnetic metal by means of formation of a short-range ordered distribution of well-defined faceted three-dimensional (3D) cobalt nanocrystals on the carbon substrate. A range of sizes and morphologies can be obtained, depending on the size, intensity, and acceleration voltage of the e-beam and on the initial size/thickness of the 3D raw fluoride materials, with 300 kV acceleration voltage and thermionic LaB₆ emission found most favorable. The nanofabrication of locally quasi-monodispersed, small sized, and well-distributed 3D nanocrystals opens up the possibility to generate particle arrays on demand with desirable magnetic properties.     

Solid-gas reactions of complex oxides inside an environmental high-resolution transmission electron microscope

In a gas reaction cell (GRC), installed in a high-resolution transmission electron microscope (HRTEM) (JEOL 4000EX), samples can be manipulated in an ambient atmosphere (p<50mbar). This experimental setup permits not only the observation of solid-gas reactions in situ at close to the atomic level but also the induction of structural modifications under the influence of a plasma, generated by the ionization of gas particles by an intense electron beam. Solid state reactions of non-stoichiometric niobium oxides and niobium tungsten oxides with different gases (O2, H2 and He) have been carried out inside this controlled environment transmission electron microscope (CETEM), and this has led to reaction products with novel structures which are not accessible by conventional solid state synthesis methods.Monoclinic and orthorhombic Nb(12)O(29) crystallize in block structures comprising [3x4] blocks. The oxidation of the monoclinic phase occurs via a three step mechanism: firstly, a lamellar defect of composition Nb(11)O(27) is formed. Empty rectangular channels in this defect provide the diffusion paths in the subsequent oxidation. In the second step, microdomains of the Nb(22)O(54) phase are generated as an intermediate state of the oxidation process. The structure of the final product Nb(10)O(25), which consists of [3x3] blocks and tetrahedral coordinated sites, is isostructural to PNb(9)O(25). Microdomains of this apparently metastable phase appear as a product of the Nb(22)O(54) oxidation. The oxidation reaction of Nb(12)O(29) was found to be a reversible process: the reduction of the oxidation product with H(2) results in the formation of the starting Nb(12)O(29) structure. On the other hand, the block structure of Nb(12)O(29) has been destroyed by a direct treatment of the sample with H(2) while NbO in a cubic rock salt structure is produced.This in situ technique has also been applied to niobium tungsten oxides which constitute the solid solution series Nb(8-n)W9(+n)O47 with 0< or =n< or =4. All of these phases crystallize in the threefold tetragonal tungsten bronze (TTB) superstructure of Nb(8)W(9)O(47) (n=0). In the main reaction, these phases decompose in a gas plasma (O2, H2 or He, p=20mbar) into WO(3-x), which evaporates and solidifies again near the irradiated crystallite, and (Nb,W)(24)O(64), which crystallizes in a 2a superstructure of the TTB type observed here for the first time in the system Nb-W-O. Nb(8)W(9)O(47), Nb(7)W(10)O(47) and Nb(6)W(11)O(47) always react in this way, independent of the applied gas. On the other hand, the treatment of Nb(5)W(12)O(47) (n=3) and Nb(4)W(13)O(47) (n=4) in an oxygen atmosphere often caused a different reaction: these phases have been oxidized and a heavily disordered bronze-type structure has been formed. The oxygen excess in these products is largely accommodated in segregated domains of WO(3).     

Forces with submolecular resolution between the probing tip and Cu-TBPP molecules on Cu(100) observed with a combined AFM/STM

Combined STM/AFM experiments were performed on monolayer islands of Cu-TBPP molecules on Cu(100). Pulling of single molecules on the substrate was observed and the imaging parameters were compared to STM studies. Local frequency shift vs. distance curves reveal three types of curves, which can be related to the interaction of the tip above the Cu(100) substrate, the centre of the molecule and the leg of the molecule. The frequency vs. distance curves above the legs reveal two minima, which are associated with the bending of the legs above a certain threshold value. Quantitative analysis yields force values of about 0.4 nN.     

微氮直拉硅单晶中氧化诱生层错透射电镜研究

利用透射电镜研究了热氧化过程中含氮（NCZ）和不含氮（CZ）直拉硅单晶的氧化诱生缺陷.研究表明，NCZ中的氧化诱生层错的尺寸随着湿氧氧化时间的延长而减小，并有冲出型位错产生.而在CZ中，生成了大量的多面体氧沉淀，并且随着热氧化时间的延长，层错的尺寸逐渐增大. 关键词： 直拉硅 透射电镜 氧化诱生层错     

Impact of dynamical scattering on quantitative contrast for aberration-corrected transmission electron microscope images

Aberration-corrected transmission electron microscope images taken under optimum-defocus conditions or processed offline can correctly reflect the projected crystal structure with atomic resolution. However, dynamical scattering, which will seriously influence image contrast, is still unavoidable. Here, the multislice image simulation approach was used to quantify the impact of dynamical scattering on the contrast of aberration-corrected images for a 3C-SiC specimen with changes in atomic occupancy and thickness. Optimum-defocus images with different spherical aberration (C_S) coefficients, and structure images restored by deconvolution processing, were studied. The results show that atomic-column positions and the atomic occupancy for SiC ‘dumbbells’ can be determined by analysis of image contrast profiles only below a certain thickness limit. This limit is larger for optimum-defocus and restored structure images with negative C_S coefficient than those with positive C_S coefficient. The image contrast of C (or Si) atomic columns with specific atomic occupancy changes differently with increasing crystal thickness. Furthermore, contrast peaks for C atomic columns overlapping with neighboring peaks of Si atomic columns with varied Si atomic occupancy, which is enhanced with increasing crystal thickness, can be neglected in restored structure images, but the effect is substantial in optimum-defocus images.     

Approaches for ultrafast imaging of transient materials processes in the transmission electron microscope

The growing field of ultrafast materials science, aimed at exploring short-lived transient processes in materials on the microsecond to femtosecond timescales, has spawned the development of time-resolved, in situ techniques in electron microscopy capable of capturing these events. This article gives a brief overview of two principal approaches that have emerged in the past decade: the stroboscopic ultrafast electron microscope and the nanosecond-time-resolved single-shot instrument. The high time resolution is garnered through the use of advanced pulsed laser systems and a pump-probe experimental platforms using laser-driven photoemission processes to generate time-correlated electron probe pulses synchronized with laser-driven events in the specimen. Each technique has its advantages and limitations and thus is complementary in terms of the materials systems and processes that they can investigate. The stroboscopic approach can achieve atomic resolution and sub-picosecond time resolution for capturing transient events, though it is limited to highly repeatable (>10(6) cycles) materials processes, e.g., optically driven electronic phase transitions that must reset to the material's ground state within the repetition rate of the femtosecond laser. The single-shot approach can explore irreversible events in materials, but the spatial resolution is limited by electron source brightness and electron-electron interactions at nanosecond temporal resolutions and higher. The first part of the article will explain basic operating principles of the stroboscopic approach and briefly review recent applications of this technique. As the authors have pursued the development of the single-shot approach, the latter part of the review discusses its instrumentation design in detail and presents examples of materials science studies and the near-term instrumentation developments of this technique.     

High resolution transmission electron microscope observation of zero-strain deformation twinning mechanisms in Ag

We have observed a new deformation-twinning mechanism using the high resolution transmission electron microscope in polycrystalline Ag films, zero-strain twinning via nucleation, and the migration of a Σ3{112} incoherent twin boundary (ITB). This twinning mechanism produces a near zero macroscopic strain because the net Burgers vectors either equal zero or are equivalent to a Shockley partial dislocation. This observation provides new insight into the understanding of deformation twinning and confirms a previous hypothesis: detwinning could be accomplished via the nucleation and migration of Σ3{112} ITBs. The zero-strain twinning mechanism may be unique to low staking fault energy metals with implications for their deformation behavior.