Transmission Electron Microscopy Specimen Preparation Research Articles

Intergranular corrosion in AA5083 alloy: The influence of grain boundary segregation and its detection via TEM

The influence of grain boundary segregation on corrosion behaviour of AA5083 alloy remains unclear. In the present work, the segregation in both as-received and sensitized AA5083 alloys was examined via transmission electron microscopy (TEM). The influence of TEM specimen preparation methods on grain boundary segregation detection was explored. It is revealed that focussed ion beam (FIB) is reliable for the detection of grain boundary segregation. Further, the influence of grain boundary segregation on intergranular corrosion (IGC) of AA5083 alloy was examined. It is indicated that Mg segregation at grain boundary is decisive for IGC development in AA5083-H116 alloy, which also benefits IGC development in sensitized AA5083-H116 alloy by increasing the continuity of grain boundary micro-chemistry.

Fs-laser preparation of half grid specimens for atom probe tomography and transmission electron microscopy

For atom probe tomography (APT) and transmission electron microscopy (TEM) half grids are commonly applied as specimen carriers, serving as mount for focused ion beam (FIB) processed lift-outs. This technical note presents an alternative way to fabricate half grids directly from the material to be investigated using femtosecond (fs)-laser ablation. After cutting ∼200 µm thin in-plane and cross-plane slices from a TiN coated cemented carbide substrate using a precision cutting saw, two different half grid geometries, one suitable for APT and the other for TEM, were cut via fs-laser processing. Freestanding posts for APT were further sharpened and the areas intended for TEM were thinned top-down using the fs-laser system followed by final annular FIB milling of the APT and thinning of the TEM specimens. For proof of concept, the TiN APT half grid specimens in in- and cross-plane direction were successfully measured in voltage and laser-assisted mode, utilizing a local electrode atom probe, while electron transparency of the in- and cross-plane TEM half grid specimens was proven using a scanning electron microscope equipped with a scanning transmission electron microscopy (STEM) detector. The herein presented method is simple, fast and omits the necessity of a lift-out, reducing the complexity of FIB operations. Additionally, a frequently considered weak point of APT lift-out specimens, the Pt weld between specimen and half grid or microtip coupon is avoided, whilst a wide range of materials can be processed and consumables consumption is reduced. Thus, this work clearly demonstrates the great potential of fs-laser processing for APT and TEM specimen preparation.

Optimized procedure for conventional TEM sample preparation using birefringence

Specimens for quality transmission electron microscopy (TEM) analyses must fulfil a range of requirements, which demand high precision during the prior preparation process. In this work, an optimized procedure for conventional TEM specimen preparation is presented that exploits the thickness-dependence of interference colors occurring in birefringent materials. It facilitates the correct estimation of specimen thickness to avoid damage or breaking during mechanical thinning and reduces ion-milling times below 30minutes. The benefits of the approach are shown on sapphire and silicon carbide cross-section samples. The presented method is equally suitable for assessing specimen thickness during dimpling and wedge-polishing, and is particularly useful at thicknesses below 20 μm, where the accuracy of mechanical techniques is insufficient. It is precise enough to be employed for a visual thickness estimation during the thinning process, but can be additionally optimized by analyzing the RGB spectrum of the occurring interference colors.

High-quality TEM specimen preparation for lithium-ion conducting solid electrolytes by low-energy ion milling

Focused ion beam (FIB) is a widely used method to prepare transmission electron microscopy (TEM) specimen from bulk materials. However, the surface amorphous layer induced by ion beam is an obstacle to obtain high-quality atomic-scale images for quantitative analysis, especially for the analysis of light elements such as lithium in lithium-ion conducting solid electrolytes. Here, taking lithium-ion conducting solid electrolyte materials as an example, the advantages and disadvantages of applying low-energy Ar+ ion for fine milling after FIB are investigated. Combining Monte-Carlo simulations with ion milling experiments, the milling parameters are evaluated and discussed in detail. With optimized parameters, TEM specimens with less beam damage and thinner amorphous layer were prepared, enabling the acquisition of high-quality atomic-scale images. Furthermore, low-energy Ar+ ion milling is also able to remove hydrocarbon contamination formed during the electron beam illumination inside the microscope, making the contaminated TEM specimens reusable.

Transmission electron microscopy studies of organic–inorganic hybrid perovskites: Advances, challenges, and prospects

In the last few years, organic–inorganic hybrid perovskites (OIHPs) have attracted immense research and industry attention for their application as light absorbers in solar cells and light-emitting diodes. Characterizing OIHP materials and optoelectronic devices using transmission electron microscopy (TEM)-based techniques has played a large role in understanding their structural, compositional, and electronic properties. However, the highly energetic and electrically charged electron beam radiation used in TEM can result in damage to the pristine structure, as OIHPs are unstable and highly sensitive to electron beams. This damage potentially obscures intrinsic information and leads to a serious misunderstanding of the microscopic structure–property–performance relationship for OIHP optoelectronic devices. To address this issue, we first review the electron and ion beam-induced degradation mechanism of OIHPs, followed by a review of the development of ultra-low-dose TEM techniques that can able to minimize this damage, thus can able to obtain reliable, intrinsic structural information about OIHPs from the atomic to micrometer length scales. Finally, we suggest a protocol for appropriate TEM specimen preparation and characterization techniques. This protocol can help ensure that future TEM studies of OIHPs give reliable information, thereby enabling a deeper understanding and optimization of the performance and long-term stability of OIHP optoelectronic devices.

Major Factors Influencing the Size Distribution Analysis of Cellulose Nanocrystals Imaged in Transmission Electron Microscopy.

Size distributions of cellulose nanocrystals (CNCs), extracted from softwood pulp via strong sulfuric acid hydrolysis, exhibit large variability when analyzed from transmission electron microscopy (TEM) images. In this article, the causes of this variability are studied and discussed. In order to obtain results comparable with those reported, a reference material of CNCs (CNCD-1) was used to evaluate size distribution. CNC TEM specimens were prepared as-stained and dried with a rapid-flushing staining method or hydrated and embedded in vitreous ice with the plunge-freezing method. Several sets of bright-field TEM (BF-TEM), annular dark-field scanning TEM (ADF-STEM) and cryogenic-TEM (cryo-TEM) images were acquired for size distribution analysis to study the contributing factors. The rapid-flushing staining method was found to be the most effective for contrast enhancement of CNCs, not only revealing the helical structure of single CNCs but also resolving the laterally jointed CNCs. During TEM specimen preparation, CNCs were fractionated on TEM grids driven by the coffee-ring effect, as observed from contrast variation of CNCs with a stain-depth gradient. From the edge to the center of the TEM grids, the width of CNCs increases, while the aspect ratio (length to width) decreases. This fractionated dispersion of CNCs suggests that images taken near the center of a droplet would give a larger mean width. In addition to particle fractionation driven by the coffee-ring effect, the arrangement and orientation of CNC particles on the substrate significantly affect the size measurement when CNC aggregation cannot be resolved in images. The coexistence of asymmetric cross-section CNC particles introduces a large variation in size measurement, as TEM images of CNCs are mixed projections of the width and height of particles. As a demonstration of how this contributes to inflated size measurement, twisted CNC particles, rectangular cross-section particles and end-to-end jointed CNCs were revealed in reconstructed three-dimensional (3D) micrographs by electron tomography (ET).

Comparing Xe+ pFIB and Ga+ FIB for TEM sample preparation of Al alloys: Minimising FIB-induced artefacts.

Recently, the dual beam Xe+ plasma focused ion beam (Xe+pFIB) instrument has attracted increasing interest for site‐specific transmission electron microscopy (TEM) sample preparation for a local region of interest as it shows several potential benefits compared to conventional Ga+FIB milling. Nevertheless, challenges and questions remain especially in terms of FIB‐induced artefacts, which hinder reliable S/TEM microstructural and compositional analysis. Here we examine the efficacy of using Xe+ pFIB as compared with conventional Ga+ FIB for TEM sample preparation of Al alloys. Three potential source of specimen preparation artefacts were examined, namely: (1) implantation‐induced defects such as amophisation, dislocations, or ‘bubble’ formation in the near‐surface region resulting from ion bombardment of the sample by the incident beam; (2) compositional artefacts due to implantation of the source ions and (3) material redeposition due to the milling process. It is shown that Xe+pFIB milling is able to produce improved STEM/TEM samples compared to those produced by Ga+ milling, and is therefore the preferred specimen preparation route. Strategies for minimising the artefacts induced by Xe+pFIB and Ga+FIB are also proposed.Lay Description FIB (focused ion beam) instruments have become one of the most important systems in the preparation of site‐specific TEM specimens, which are typically 50‐100 nm in thickness. TEM specimen preparation of Al alloys is particularly challenging, as convention Ga‐ion FIB produces artefacts in these materials that make microstructural analysis difficult or impossible. Recently, the use of noble gas ion sources, such as Xe, has markedly improved milling speeds and is being used for the preparation of various materials. Hence, it is necessary to investigate the structural defects formed during FIB milling and assess the ion‐induced chemical contamination in these TEM samples. Here we explore the feasibility and efficiency of using Xe+PFIB as a TEM sample preparation route for Al alloys in comparison with the conventional Ga+FIB.

Strain determination in heterostructures by TEM in selected area electron diffraction mode

The technique for determination of strain and elemental composition distribution across the graded layer in heterostructures by means of selected area electron diffraction in transmission electron microscope (TEM) is proposed. The approach accounts for the modification in the residual elastic strain due to sample thinning during TEM specimen preparation. The technique is approved using In0,7Ga0,3As/InxAl1-xAs/GaAs(001) and Al0,75Ga0,25N/AlN/Al2O3 heterostructures, and the results are in a good agreement with those obtained by alternative ways.

Geometrical Characterization of Glass Nanopipettes with Sub-10 nm Pore Diameter by Transmission Electron Microscopy.

Glass nanopipettes are widely used for various applications in nanosciences. In most of the applications, it is important to characterize their geometrical parameters, such as the aperture size and the inner cone angle at the tip region. For nanopipettes with sub-10 nm aperture and thin wall thickness, transmission electron microscopy (TEM) must be most instrumental in their precise geometrical measurement. However, this measurement has remained a challenge because heat generated by electron beam irradiation would largely deform sub-10 nm nanopipettes. Here, we provide methods for preparing TEM specimens that do not cause deformation of such tiny nanopipettes.

Twin-jet electropolishing for damage-free transmission electron microscopy specimen preparation of metallic microwires.

A method to prepare TEM specimens from metallic microwires and based on conventional twin-jet electropolishing is introduced. The wire is embedded in an opaque epoxy resin medium and the hardened resin is mechanically polished to reveal the wire on both sides. The resin containing wire is then cut into discs of the appropriate size. The obtained embedded wire is electropolished in a conventional twin-jet electropolishing machine until electron transparency in large areas without radiation damage is achieved.

Ultra-Microtome for the Preparation of TEM Specimens from Battery Cathodes.

With the wide application of ultra-microtome sectioning in the preparation of transmission electron microscopy (TEM) specimens with bio- and organic materials, here, we report an ultra-microtome-based method for the preparation of TEM specimens from cathodes of Li-ion batteries. The ultra-microtome sectioning reduces the sample thickness to tens of nanometers and yields atomic resolution from the core region of particles of hundreds of nanometers. Analysis indicates that the mechanical cross-sectioning introduces no observable microstructural artifacts or structural damage, such as microcracking and nanoporosity. These results demonstrate the high efficiency of the ultra-microtome approach in preparing well-thinned specimens of particulate materials that allow for atomic-scale TEM imaging of a large number of sectioned particles in one single TEM specimen, thereby providing statistically significant results of the TEM analysis.

Specimen preparation optimization for size and morphology characterization of nanocellulose by TEM

Nanoparticle morphology, size and dispersion are key parameters for the application of cellulose nanomaterials in various areas, such as polymer nanocomposites, catalysts, gel and so on. Transmission electron microscopy (TEM) is the most suitable technique for the morphological characterization of these particles. However, nanocellulose low contrast in TEM images is the major drawback for their adequate morphological characterization and size determination. Even though it is widespread knowledge that negative staining using uranyl acetate is the best approach for intensifying cellulose contrast, up to now few have succeeded in achieving high quality images and reliable size measurements of these nanomaterials. This protocol presents an optimization of the standard uranyl acetate protocol commonly used for biological specimens in order to suit cellulose nanomaterials. Drying method and grid conditions were proven to be the most significant variables for effective TEM specimen preparation. These guidelines could also be successfully applied to enhance the cellulose nanomaterial contrast in polymer matrices.

Application of focused ion-beam sampling for sidewall-roughness measurement of free-standing sub-μm objects by atomic force microscopy.

In the present study, a free-standing object-sampling technique for microelectromechanical systems (MEMS) is developed to measure their sidewall surface roughnesses by atomic force microscopy (AFM). For this purpose, a conventional focused ion beam (FIB) sampling technique widely used for cross-sectional transmission electron microscope specimen preparation was applied. The sub-nm-order roughness parameters were quantitatively measured for sidewalls of Si-bridge test samples. The roughness parameters were compared before and after H2 annealing treatment, which induced smoothing of the surface by migration of the Si atoms. The reduction in the surface roughness by a factor of approximately one-third with 60-s H2 annealing was quantitatively evaluated by AFM. The present study confirms that the developed FIB-AFM technique is one potential approach for quantitatively evaluating the surface-roughness parameters on the oblique faces of free-standing objects in MEMS devices.

Combined Focused Ion Beam-Ultramicrotomy Method for TEM Specimen Preparation of Porous Fine-Grained Materials.

A new transmission electron microscopy (TEM) specimen preparation method that utilizes a combination of focused ion beam (FIB) methods and ultramicrotomy is demonstrated. This combined method retains the benefit of site-specific sampling by FIB but eliminates ion beam-induced damage except at specimen edges and allows recovery of many consecutive sections. It is best applied to porous and/or fine-grained materials that are amenable to ultramicrotomy but are located in bulk samples that are not. The method is ideal for unique samples from which every specimen is precious, and we demonstrate its utility on fine-grained material from the one-of-a-kind Paris meteorite. Compared with a specimen prepared by conventional FIB methods, the final sections are uniformly thin and free from re-deposition and curtaining artifacts common in FIB specimens prepared from porous, heterogeneous samples.

Migration Pinning and Roughening Transition of a Ni Grain Boundary

To date, much research has been conducted into the effect of migration pinning on the grain size in polycrystalline materials. However, effects of migration pinning on the grain-boundary structure and its transition have not been illuminated. Here, using transmission electron microscopy (TEM) we have explored the pinning effects for the grain boundary in a Ni bicrystal. During TEM specimen preparation, a hole was intentionally drilled in the middle of the grain boundary as a pinning point against grain-boundary migration. The specimen was heated to 600 °C. The grain boundary is driven to migrate by both the surface energy anisotropy and the total strain energy reduction. Grain-boundary facets with a plane orientation of {0 3 2}//{1 1 1} appear near the hole. The facets undergo a structural transition from atomically flat to rough with increasing distance from the hole. A pinning force exerted by the hole suppresses the migration of the grain boundary near the hole, indicating that the grain-boundary region away from the hole is subjected to a higher driving force. It certainly appears that the phenomenon originates from a change in driving force with the distance from the hole, being a signature of kinetic roughening.

Signature of Kinetic Roughening Revealed by Migration Pinning in a Ni Grain Boundary

To date much research has been conducted into the effect of migration pinning on the grain size in polycrystalline materials. However, effects of migration pinning on the grain-boundary structure and its transition have not been illuminated. Here, using transmission electron microscopy (TEM) we have explored the pinning effects for the grain boundary in a Ni bicrystal. During TEM specimen preparation, a hole was intentionally drilled in the middle of the grain boundary as a pinning point against grain-boundary migration. The specimen was heated to 600oC. The grain boundary is driven to migrate by both the surface energy anisotropy and the total strain energy reduction. Grain-boundary facets with a plane orientation of {0 3 2}//{1 1 1} appear near the hole. The facets undergo a structural transition from atomically flat to rough with increasing distance from the hole. A pinning force exerted by the hole suppresses the migration of the grain boundary near the hole, indicating that the grain-boundary region away from the hole is subjected to a higher driving force. It certainly appears that the phenomenon originates from a change in driving force with the distance from the hole, being a signature of kinetic roughening. The same argument applies to the formation of short (0 1 0)//(1 -1 0) facets developing between {0 3 2}//{1 1 1} facets.

Liftout of High-Quality Thin Sections of a Perovskite Oxide Thin Film Using a Xenon Plasma Focused Ion Beam Microscope.

It is shown that a xenon plasma focused ion beam (FIB) microscope is an excellent tool for high-quality preparation of functional oxide thin films for atomic resolution electron microscopy. Samples may be prepared rapidly, at least as fast as those prepared using conventional gallium FIB. Moreover, the surface quality after 2 kV final polishing with the Xe beam is exceptional with only about 3 nm of amorphized surface present. The sample quality was of a suitably high quality to allow atomic resolution high-angle annular dark field imaging and integrated differential phase contrast without any further preparation, and the resulting images were good enough for quantitative evaluation of atomic positions to reveal the oxygen octahedral tilt pattern. This suggests that such xenon plasma FIB instruments may find widespread application in transmission electron microscope and scanning transmission electron microscope specimen preparation.

Transmission Electron Microscopy Specimen Preparation for Two Dimensional Material Using Electron Beam Induced Deposition of a Protective Layer in the Focused Ion Beam Method

Transmission Electron Microscopy Specimen Preparation for Two Dimensional Material Using Electron Beam Induced Deposition of a Protective Layer in the Focused Ion Beam Method

Transmission Electron Microscope Specimen Preparation of Si-Based Anode Materials for Li-Ion Battery by Using Focused Ion Beam and Ultramicrotome

Transmission Electron Microscope Specimen Preparation of Si-Based Anode Materials for Li-Ion Battery by Using Focused Ion Beam and Ultramicrotome

A new oxidation based technique for artifact free TEM specimen preparation of nuclear graphite

Graphite is a key component in designs of current and future nuclear reactors whose in-service lifetimes are dependent upon the mechanical performance of the graphite. Irradiation damage from fast neutrons creates lattice defects which have a dynamic effect on the microstructure and mechanical properties of graphite. Transmission electron microscopy (TEM) can offer real-time monitoring of the dynamic atomic-level response of graphite subjected to irradiation; however, conventional TEM specimen-preparation techniques, such as argon ion milling itself, damage the graphite specimen and introduce lattice defects. It is impossible to distinguish these defects from the ones created by electron or neutron irradiation. To ensure that TEM specimens are artifact-free, a new oxidation-based technique has been developed. Bulk nuclear grades of graphite (IG-110 and NBG-18) and highly oriented pyrolytic graphite (HOPG) were initially mechanically thinned to ∼60 μm. Discs 3 mm in diameter were then oxidized at temperatures between 575 °C and 625 °C in oxidizing gasses using a new jet-polisher-like set-up in order to achieve optimal oxidation conditions to create self-supporting electron-transparent TEM specimens. The quality of these oxidized specimens were established using optical and electron microscopy. Samples oxidized at 575 °C exhibited large areas of electron transparency and the corresponding lattice imaging showed no apparent damage to the graphite lattice.