A brief overview of transmission electron microscopy as it applies specifically to obtaining surface crystallographic information is presented. This review will encompass many of the practical aspects of obtaining surface crystal information from a transmission electron microscope, including equipment requirements, experimental techniques, sample preparation methods, data extraction and image processing, and complimentary techniques.

Recent progress in in situ observation of solid–liquid interfaces by means of transmission electron microscopy, carried out by the Nagoya group, was reviewed. The results obtained on pure materials are discussed based on Jackson's theory. The structure of the solid–liquid interfaces of eutectic alloys was also observed. The in situ observation technique of solid–liquid interface is applied to industrially important reactions which include liquid phases.

High electric fields were delivered to specimens during imaging in the transmission electron microscopy (TEM) chamber to reveal details of electric field-induced phenomena in ferroelectric oxides. These include the polarization switching in nanometer-sized ferroelectric domains and the grain boundary cavitation in a commercial lead zirconate titanate (PZT) polycrystalline ceramic, the domain wall fracture in a Pb(Mg1/3Nb2/3)O3–PbTiO3 single crystal, and the transformation of incommensurate modulations in Pb0.99Nb0.02[(Zr1−xSnx)1−yTiy]0.98O3 (PZST100x/100y/2) polycrystalline ceramics. In the PZT ceramic, a cavitation process was uncovered for the electric field-induced intergranular fracture. In the ferroelectric single crystal, a preexisting crack was observed to deflect and to follow a 90° domain wall, indicating the presence of severe incompatible piezoelectric strains at thedomain wall. In the antiferroelectric PZST ceramics, the electric field-induced antiferroelectric-to-ferroelectric phase transformation was accompanied with the disappearance of incommensurate modulations.

In situ observation is of great value in the study of radiation damage utilizing electron or ion irradiation. We summarize the facilities and give examples of work found around the world. In situ observations of irradiation behavior have fallen into two broad classes. One class consists of long-term irradiation, with observations of microstructural evolution as a function of the radiation dose in which the advantage of in situ observation has been the maintenance of specimen position, orientation, and temperature. A second class has involved the recording of individual damage events in situations in which subsequent evolution would render the correct interpretation of ex situ observations impossible. In this review, examples of the first class of observation include ion-beam amorphization, damage accumulation, plastic flow, implant precipitation, precipitate evolution under irradiation, and damage recovery by thermal annealing. Examples of the second class of observation include single isolated ion impacts that produce defects in the form of dislocation loops, amorphous zones, or surface craters, and single ion impact-sputtering events. Experiments in both classes of observations attempt to reveal the kinetics underlying damage production, accumulation, and evolution.

The initial oxidation stages of Cu(100), (110), and (111) surfaces have been investigated by using in situ ultra-high-vacuum transmission electron microscopy (TEM) techniques to visualize the nucleation and growth of oxide islands. The kinetic data on the nucleation and growth of oxide islands shows a highly enhanced initial oxidation rate on the Cu(110) surface as compared with Cu(100), and it is found that the dominant mechanism for the nucleation and growth is oxygen surface diffusion in the oxidation of Cu(100) and (110). The oxidation of Cu(111) shows a dramatically different behavior from that of the other two orientations, and the in situ TEM observation reveals that the initial stages of Cu(111) oxidation are dominated by the nucleation of oxide islands at temperatures lower than 550 °C, and are dominated by two-dimensional oxide growth at temperatures higher than 550 °C. This dependence of the oxidation behavior on the crystal orientation and temperature is attributed to the structures of the oxygen-chemisorbed layer, oxygen surface diffusion, surface energy, and the interfacial strain energy.

The world of nanomaterials has become the real world for most applications in the area of nanotechnology. As postsynthesis handling of materials at the nanoscale level is impractical, nanomaterials must be synthesized directly as part of a device or circuit. The demands of nanotechnology have led to modifications in the design of transmission electron microscopes (TEMs) that enable in situ synthesis and characterization simultaneously. The environmental TEM (ETEM) is one such modified instrument that has often been used to follow gas–solid and/or liquid–solid interactions at elevated temperatures. Although the history and development of the ETEM, also called the controlled atmosphere or environmental cell TEM, is as old as transmission electron microscopy itself, developments in the design of medium-voltage TEMs have succeeded in bringing resolutions down to the subnanometer level. A modern ETEM equipped with a field-emission gun, energy filter or electron energy-loss spectrometer, scanning transmission electron microscopy coils, and bright-field and dark-field detectors can be a versatile tool for understanding chemical processes at the nanometer level. This article reviews the design and operations of a dedicated ETEM. Its applications range from the in situ characterization of reaction steps, such as oxidation-reduction and hydroxylation, to the in situ synthesis of nanomaterials, such as quantum dots and carbon nanotubes. Some examples of the current and the future applications for the synthesis and characterization of nanomaterials are also discussed.

From the study of alloy phase formation in nanometer-sized particles by in situ transmission electron microscopy, it is revealed that not only the surface energy but also the interface energy of an interface between two different phases (solid–solid or solid–liquid) significantly changes the phase equilibrium of nanometer-sized particles. These energies result in large suppression of the eutectic point, structural instability, and unique solid/liquid two-phase structures in isolated nanometer-sized alloy particles. A theoretical study based on thermodynamics, which is modified in such a manner that Gibbs free energies for bulk materials were modified by taking factors affecting the phase equilibrium of nanometer-sized alloy particles into consideration, was proved useful to evaluate the results obtained from experiments.

The commercial nickel base alloy NIMONIC PE16 is strengthened by nano-scale spherical coherent precipitates of the intermetallic γ′-phase Ni3(Al,Ti). A bulk polycrystalline specimen of NIMONIC PE16 was aged such that it was in the transition range from the peak- to the overaged state. This transition limits the duration of technically useful aging treatments of structural particle strengthened materials. Thin foils prepared from this specimen were stretched inside a transmission electron microscope, and the dislocation processes were observed under full load. Two dislocations with identical Burgers vectors of the type 1/2〈110〉 form a pair and glide together. The leading 1/2〈110〉 dislocation bypasses the γ′-precipitates and the trailing one shears them. These dislocation processes are also discussed with reference to the results of computer simulations.

The crystallization and phase transformations of amorphous NiTi thin films were studied using in situ transmission electron microscopy (TEM). These films were sputter-deposited onto micromachined silicon-nitride membranes and subjected to heating and cooling conditions. The microstructural evolution was monitored and recorded. Kinetic parameters such as the nucleation rate, growth rate, and area-fraction transformed were independently determined by noting the number of grains per frame and their change in size. Using the Johnson–Mehl–Avrami–Kolmogorov analysis, fitted kinetic parameters were determined and found to be consistent with TEM observations. To explore the compositional sensitivity of crystallization, samples near-equiatomic and slightly Ti-rich were studied with these methods. TEM micrographs show that equiatomic films exhibit polymorphic crystallization while samples that are slightly off-stoichiometry showed more complicated behavior.

The mechanical properties of ultrafine-grained and nanograined materials have received a great deal of recent attention because of their unusual and promising values. However, some of the most important mechanisms of deformation remain unclear. In this work, the deformation behavior of ultrafine-grained Al films and ultrafine-grained Fe is studied through in situ nanoindentation in a transmission electron microscope. Deformation-induced coarsening by grain boundary migration was observed in the ultrafine-grained Al films during deformation at room temperature, whereas no grain boundary motion was found in ultrafine-grained Fe. The lack of grain boundary motion in Fe was attributed to the pinning effect of nano-sized particles at the Fe grain boundaries.

The thermal stability of amorphous Zr:Al mixed oxide films of different composition, produced on (001) silicon wafers by the atomic layer deposition method is studied by transmission electron microscopy during in situ heating experiments. The temperatures at which phase separation and crystallization occur are composition dependent. The crystallization of thick films (55–70 nm), deposited on HF-treated silicon surfaces covered with a 15 cycles Al2O3 layer, results in the formation of cubic ZrO2 and cubic γ–Al2O3. In very thin films (5 nm), deposited on silicon surfaces covered with a 0.5 nm SiO2 thin film, the formation of tetragonal zirconium disilicide (ZrSi2) is observed in the microscope vacuum, at temperatures above 900 °C. This effect depends on the thickness of the as deposited thin film.

Thin film specimens of austenitic 304 stainless steel implanted with 100 keV Xe ions at room temperature were investigated. Microstructural evolution and phase transformation were characterized and analyzed in situ with conventional and high-resolution transmission electron microscopy. The phase transformation in a sequence from austenitic γ face-centered cubic (fcc) to hexagonal close-packed (hcp), and then to a martensitic α body-centered cubic (bcc) structure was observed in the implanted specimens. The fraction of the induced α(bcc) phase increased with increasing Xe ion fluence. Orientation relationships between the induced α(bcc) phase and austenitic γ(fcc) matrix were determined to be (011)α//(111)γ and [111]α//[011]γ. The relationship was independent of the induced process of the martensitic phase transformation for austenitic 304 stainless steel specimen, in agreement with the Kurdjumov–Sachs (K-S) rule. It is suggested that the phase transformation is induced mainly by the formation of the highly pressurized Xe precipitates, which generate a large stress level in stainless steels.

Crucial features of materials evolution due to ion beam irradiation are often revealed only through studies of process dynamics. We review some significant examples of such experiments performed over the last 25 years with the Orsay in situ facility: a transmission electron microscope setup (with temperature stages operating between 4 and 1000 K) on a medium energy (3–570 keV) ion beam line. New results on nanocavity evolution and metal silicide nanoprecipitates in Si are presented briefly.We show that CoSi2 nanoprecipitate growth is mainly due to the constant Co atom contribution from the ion beam, and CoSi2 platelet growth is the result of a three-dimensional to two-dimensional growth mode transition.

The unique capability of rendering opaque specimens transparent with atomic resolution makes transmission electron microscopy (TEM) an indispensable toolfor microstructural and crystallographic analysis of materials. Conventional TEM specimens are placed on grids about 3 mm in diameter and 10–100 μm thick. Such stringent size restriction has precluded mechanical testing inside the TEM chamber.So far, in situ testing of nanoscale thin foils has been mostly qualitative. Micro-electro-mechanical systems (MEMS) offer an unprecedented level of miniaturization to realize sensors and actuators that can add TEM visualization to nano-mechanical characterization. We present a MEMS-based uniaxial tensile experiment setup that integrates nanoscale freestanding specimens with force and displacement sensors, which can be accommodated by a conventional TEM straining stage. In situ TEM testing on 100-nm-thick freestanding aluminum specimens (with simultaneous stress measurement) show limited dislocation activity in the grain interior and consequent brittle mode of fracture. Plasticity at this size scale is contributed by grain boundary dislocations and partial dislocations.

Perovskite-based SrNb0.2Ti0.8O3/La0.7Sr0.3MnO3 bilayer films were grown on (001) SrTiO3 substrate. By means of in situ transmission electron microscopy, lattice expansion and double periodicity were identified in both plan-view and cross-section La0.7Sr0.3MnO3 films under electron irradiation for 25 s. After the electron beam was removed from specimens, the original perovskite structure recovered within 10 min. However, when irradiation time was more than 1 min, the original perovskite structure could not recover and became an amorphous phase or a cavity created by irradiation. According to first-principle calculation and electron diffraction pattern simulation, formation mechanism of the lattice expansion and double periodicity is proposed based on oxygen deficiency during electron irradiation.

The structural stability of transition metal nanoclusters has been scrutinized with in situ transmission electron microscopy as a function of temperature. In particular iron, cobalt, niobium, and molybdenum clusters with diameters around 5 nm have been investigated. During exposure to air, a thin oxide shell with a thickness of 2 nm is formed around the iron and cobalt clusters, which is thermally unstable under moderate high vacuum annealing above 200 °C. Interestingly, niobium clusters oxidize only internally at higher temperatures without the formation of an oxide shell. They are unaffected under electron beam irradiation, whereas iron and cobalt undergo severe structural changes. Further, no cluster coalescence of niobium takes place, even during annealing up to 800 °C, whereas iron and cobalt clusters coalesce after decomposition of the oxide, as long as the clusters are in close contact. In contrast to niobium, molybdenum clusters do not oxidize upon annealing; they are stable under electron beam irradiation and coalesce at temperatures higher than 800 °C. In all cases, the coalescence process indicates a strong influence of the local environment of the cluster.

The fundamental processes controlling the high-temperature interaction of dislocations with precipitates in Al-alloys were investigated in real time by deforming specimens in situ in the transmission electron microscope at elevated temperature. The observations support a bypass mechanism involving the interaction of lattice dislocations with the precipitate–matrix interface dislocations, where the rate-limiting step in the interaction is the release of the dislocation from the particle. These observations are discussed in relation to high-temperature deformation processes and models.

We have designed and fabricated a standardized specimen holder that allows the operation of a microelectromechanical system (MEMS) device inside a transmission electron microscope (TEM). The details of the design and fabrication processes of the holder are presented. The sample loading mechanism is simple and allows reliable electrical contact to eight signal lines on the device. Using a MEMS-based, nanojoule calorimeter, we performed rapid-heating experiments on Bi nanoparticles to demonstrate the functionality of the holder. We show that the heat capacity can be measured simultaneously with TEM observations. The size-dependent melting of Bi nanoparticles was observed simultaneously by nanocalorimetry and selected area diffraction measurements. We believe this approach will open up new experimental pathways to researchers, combining the speed and resolution of transmission electron microscopy with the flexibility, precision, and compactness of MEMS-based sensors and actuators.

Transmission electron microscopy (TEM) and nanoindentation, both with in situ heating capability, and electrical resistivity measurements were used to investigate phase transformation phenomena and thermomechanical behavior of shape-memory titanium-nickel (TiNi) films. The mechanisms responsible for phase transformation in the nearly equiatomic TiNi films were revealed by heating and cooling the samples inside the TEM vacuum chamber. Insight into the deformation behavior of the TiNi films was obtained from the nanoindentation response at different temperatures. A transition from elastic-plastic to pseudoelastic deformation of the martensitic TiNi films was encountered during indentation and heating. In contrast to the traditional belief, the martensitic TiNi films exhibited a pseudoelastic behavior during nanoindentation within a specific temperature range. This unexpected behavior is interpreted in terms of the evolution of martensitic variants and changes in the mobility of the twinned structures in the martensitic TiNi films, observed with the TEM during in situ heating.