Protocols for conducting in situ transmission electron microscopy (TEM) reactions using an environmental TEM with dry gases have been well established. However, many important reactions that are relevant to catalysis or high-temperature oxidation occur at atmospheric pressure and are influenced by the presence of water vapor. These experiments necessitate using a closed-cell gas reaction TEM holder. We have developed protocols for introducing and controlling water vapor concentrations in experimental gases from 2% at a full atmosphere to 100% at ~17 Torr, while measuring the gas composition using a residual gas analyzer (RGA) on the return side of the in situ gas reactor holder. Initially, as a model system, cube-shaped MgO crystals were used to help develop the protocols for handling the water vapor injection process and confirming that we could successfully inject water vapor into the gas cell. The interaction of water vapor with MgO triggered surface morphological and chemical changes as a result of the formation of Mg(OH)2, later validated with mass spectra obtained with our RGA system with and without water vapor. Integrating an RGA with an in situ scanning/TEM closed-cell gas reaction system can thus provide critical measurements correlating gas composition with dynamic surface restructuring of materials during reactions.

In prior research, specimen holders that employ a novel MEMS-based heating technology (AduroTM) provided by Protochips Inc. (Raleigh, NC, USA) have been shown to permit sub-Ångström imaging at elevated temperatures up to 1,000°C during in situ heating experiments in modern aberration-corrected electron microscopes. The Aduro heating devices permit precise control of temperature and have the unique feature of providing both heating and cooling rates of 106°C/s. In the present work, we describe the recent development of a new specimen holder that incorporates the Aduro heating device into a “closed-cell” configuration, designed to function within the narrow (2 mm) objective lens pole piece gap of an aberration-corrected JEOL 2200FS STEM/TEM, and capable of exposing specimens to gases at pressures up to 1 atm. We show the early results of tests of this specimen holder demonstrating imaging at elevated temperatures and at pressures up to a full atmosphere, while retaining the atomic resolution performance of the microscope in high-angle annular dark-field and bright-field imaging modes.

The aberration-corrected scanning transmission electron microscope can provide information on nanostructures with sub-Ångström image resolution. The relatively intuitive interpretation of high-angle annular dark-field (HAADF) imaging technique makes it a popular tool to image a variety of samples and finds broad applications to characterizing nanostructures, especially when combined with electron energy-loss spectroscopy and X-ray energy-dispersive spectroscopy techniques. To quantitatively interpret HAADF images, however, requires full understanding of the various types of signals that contribute to the HAADF image contrast. We have observed significant intensity enhancement in HAADF images, and large expansion of lattice spacings, of surface atoms of atomically flat ZnO surfaces. The surface-resonance channeling effect, one of the electron-beam channeling phenomena in crystalline nanostructures, was invoked to explain the observed image intensity enhancement. A better understanding of the effect of electron beam channeling along surfaces or interfaces on HAADF image contrast may have implications for quantifying HAADF images and may provide new routes to utilize the channeling phenomenon to study surface structures with sub-Ångström spatial resolution.

The recent advent of a novel design of in situ heating technology for electron microscopes has permitted unprecedented control of elevated temperature studies of catalytic materials, particularly when coupled with the sub-Ångström imaging performance of a modern aberration-corrected scanning transmission electron microscope (STEM). Using micro-electro-mechanical-systems (MEMS)-based Aduro™ heating chips from Protochips, Inc. (Raleigh, NC, USA) allows nearly instantaneous heating and cooling of catalyst powders, avoiding effects of temperature ramping as experienced with standard heating stages. The heating technology also provides stable operation limited only by the inherent drift in the microscope stage, thus allowing full image resolution to be achieved even at elevated temperatures. The present study details the use of both the high X-Y spatial resolution in both dark-field and simultaneous bright-field imaging, along with the high resolution in Z (depth sectioning) provided by the large probe incidence semiangle in the aberration-corrected instrument, to characterize the evolution of microstructure in a commercial Au/Fe2O3 water-gas shift catalyst during elevated temperature treatment. The phenomenon of Au diffusion to the surface of hematite support particles to form discrete crystalline Au nanoparticles in the 1–2 nm size range, after a prior leaching treatment to remove surface Au species has been characterized.

Capabilities for in-situ studies of materials at elevated temperatures and under gaseous environments have received increasing attention in recent years [1]. With the advent of electron microscopes that provide routine imaging at the atomic level (e.g. aberration-corrected TEM and STEM instruments), it is of particular interest to be able to record images at high temperatures while retaining the inherent resolution of the microscope; that is, the resolution is not limited by drift in the heating holder or other instabilities associated with its operation. A number of commercial and experimental heating devices have been used over the years; some holders are designed with miniature furnaces that heat entire grids [2], while a more recent development used a tiny spiral filament coated with a carbon film as the heater element [3]. These devices, while very useful for some applications (particularly in “environmental microscopes” that employ differential pumping to allow gases at some elevated pressure to be injected around the specimen), are invariably not as stable as might be desired for sub-Ångström imaging experiments. They are also limited by the speed at which the sample can be heated to temperature for stable operation. In collaboration with Protochips Inc. (Raleigh, NC), our laboratory is developing a novel new technology for in-situ heating experiments that overcomes a number of performance problems associated with standard heating stage technologies [4].

Ag on γ-alumina is a promising catalyst for hydrocarbon selective catalytic reduction in lean-burn gasoline and diesel engines for transportation applications. Although much is known about the mechanism of NOx reduction and the various intermediates, little agreement exists on the nature of the active silver species. In the present work, aberration-corrected STEM has provided new information about the nature of Ag on alumina both as impregnated and following treatments at various temperatures with exposure to simulated exhaust gas. Ex situ techniques have provided new insights into the evolution of Ag on alumina following exposure to temperature and simulated exhaust gas.

The resolution-limiting aberrations of round electromagnetic lenses can now be successfully overcome via the use of multipole element “aberration correctors.” The installation and performance of a hexapole-based corrector (CEOS GmbH) integrated on the probe-forming side of a JEOL 2200FS FEG STEM/TEM is described. For the resolution of the microscope not to be severely compromised by its environment, a new, specially designed building at Oak Ridge National Laboratory has been built. The Advanced Microscopy Laboratory was designed with the goal of providing a suitable location for aberration-corrected electron microscopes. Construction methods and performance of the building are discussed in the context of the performance of the microscope. Initial performance of the microscope on relevant specimens and modifications made to eliminate resolution-limiting conditions are also discussed.

A biomimetic approach is employed to deposit ceramic films on organic self-assembled monolayers (SAMs) coated substrates. Specifically, zirconia (ZrO2) films are grown in a zirconium sulfate precursor solution at near room temperatures (∼70°C). This process, directed by the nanoscale organic template, mimics the controlled nucleation and growth of the biominerals such as bones and teeth. The resultant zirconia films consist of nanosized particles (5-10 nm) that are precipitated out in a supersaturated precursor solution. Cross-sectional TEM and STEM works were performed to quantitatively analyze the film structure and chemistry, as well as interfacial region of the ceramic-SAM films. A stepwise deposition process was developed to avoid excessive formation of aggregation. Further, the dynamic nanoindentation testing was employed to assess the thickness and film-only intrinsic mechanical properties for direct comparison among the films processed with different processing parameters and microstructures. The films with finer particulate structure displayed higher intrinsic modulus than did those with coarser structure.

Extended abstract of a paper presented at the Pre-Meeting Congress: Materials Research in an Aberration-Free Environment, at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, July 31 and August 1, 2004.