High-voltage Transmission Electron Microscopy Research Articles

Real-time observation of the thermally-induced phase transformation in GeTe and its thermal expansion properties

The GeTe-based system has long been considered as a promising candidate system for various functional applications; many of which are directly related to the polymorphic phase transformation in their crystalline forms. Consequently, the microstructure underlying their intriguing phase transition has been the subject of numerous studies. Here we provide real-time observation of the microstructural changes associated with the reversible pseudo-cubic (or rhombohedral) to cubic GeTe phase transition using high-voltage transmission electron microscopy (HV-TEM) operating at 1,250 kV and complementary high-temperature X-ray diffraction (XRD). As a result of the phase transition, the pseudo-cubic GeTe domain's configuration significantly changes from its original band-like to a spike-like morphology with a different orientation after a heating/cooling cycle. The coefficients of thermal expansion (CTE) properties as a function of temperature are also explored in relation to the GeTe phase transition.

Observation of Fatigue Dislocation Structures Formed in [001] Multi-slip Oriented Copper Single Crystals by High-voltage Scanning Transmission Electron Microscopy

Observation of Fatigue Dislocation Structures Formed in [001] Multi-slip Oriented Copper Single Crystals by High-voltage Scanning Transmission Electron Microscopy

Imaging the Polymorphic Transformation in a Single Cu₆Sn₅ Grain in a Solder Joint.

In-situ observations of the polymorphic transformation in a single targeted Cu6Sn5 grain constrained between Sn-0.7 wt % Cu solder and Cu-Cu3Sn phases and the associated structural evolution during a solid-state thermal cycle were achieved via a high-voltage transmission electron microscope (HV-TEM) technique. Here, we show that the monoclinic η′-Cu6Sn5 superlattice reflections appear in the hexagonal η-Cu6Sn5 diffraction pattern upon cooling to isothermal 140 °C from 210 °C. The in-situ real space imaging shows that the η′-Cu6Sn5 contrast pattern is initiated at the grain boundary. This method demonstrates a new approach for further understanding the polymorphic transformation behavior on a real solder joint.

Probing Crystal Dislocations in a Micrometer-Thick GaN Film by Modern High-Voltage Electron Microscopy.

We report on extreme penetration power of relativistic electrons in a micrometer-thick gallium nitride epitaxial film and its application to probing threading dislocations, which were introduced during crystal growth. Maximum usable thickness of the specimen was quantitatively evaluated using high-voltage transmission electron microscopy (TEM) operating at 1 MV. The width of dislocation images was used as a measure for the evaluation of usable thickness. Superior maximum usable thickness was obtained in scanning transmission electron microscopy (STEM) than in TEM mode; the results were 6.9 μm for STEM and 4.4 μm for TEM. In STEM, dislocations can be imaged with an almost constant width of 15–20 nm in a wide thickness range 1–4 μm. The latest high-voltage STEM is thus useful for observing dislocations in micrometer-thick inorganic materials.

Putative Neural Network Within an Olfactory Sensory Unit for Nestmate and Non-nestmate Discrimination in the Japanese Carpenter Ant: The Ultra-structures and Mathematical Simulation.

Ants are known to use a colony-specific blend of cuticular hydrocarbons (CHCs) as a pheromone to discriminate between nestmates and non-nestmates and the CHCs were sensed in the basiconic type of antennal sensilla (S. basiconica). To investigate the functional design of this type of antennal sensilla, we observed the ultra-structures at 2D and 3D in the Japanese carpenter ant, Camponotus japonicus, using a serial block-face scanning electron microscope (SBF-SEM), and conventional and high-voltage transmission electron microscopes. Based on the serial images of 352 cross sections of SBF-SEM, we reconstructed a 3D model of the sensillum revealing that each S. basiconica houses > 100 unbranched dendritic processes, which extend from the same number of olfactory receptor neurons (ORNs). The dendritic processes had characteristic beaded-structures and formed a twisted bundle within the sensillum. At the “beads,” the cell membranes of the processes were closely adjacent in the interdigitated profiles, suggesting functional interactions via gap junctions (GJs). Immunohistochemistry with anti-innexin (invertebrate GJ protein) antisera revealed positive labeling in the antennae of C. japonicus. Innexin 3, one of the five antennal innexin subtypes, was detected as a dotted signal within the S. basiconica as a sensory organ for nestmate recognition. These morphological results suggest that ORNs form an electrical network via GJs between dendritic processes. We were unable to functionally certify the electric connections in an olfactory sensory unit comprising such multiple ORNs; however, with the aid of simulation of a mathematical model, we examined the putative function of this novel chemosensory information network, which possibly contributes to the distinct discrimination of colony-specific blends of CHCs or other odor detection.

Characterising the polymorphic phase transformation at a localised point on a Cu6Sn5 grain

Cu6Sn5 is an important intermetallic for electric interconnects and anode material of Li-ion batteries, with a polymorphic transformation from hexagonal eta-Cu6Sn5 at temperatures higher than 186 °C to monoclinic eta′-Cu6Sn5 at lower temperatures. The polymorphic transformation of Cu6Sn5 has the potential to generate internal stresses in soldered joints during both the soldering process and subsequent device operation involving thermal cycling. Here we developed a systematic method to characterise the polymorphic transformations at localised points in a single grain of Cu6Sn5 that is in intimate contact with adjacent Sn rich and Cu3Sn phases to establish a time–temperature transformation (TTT) diagram of the eta to eta′-Cu6Sn5 transformation. The method involves in situ temperature-controlled high-voltage transmission electron microscopy (HVTEM) of a single-targeted Cu6Sn5 grain with observation of diffraction patterns during multiple heating and cooling experiments on a 0.5 μm thick sample made by focused ion beam milling (FIB). The results are compared to previously reported powder X-ray diffraction data. It is concluded that there is good agreement between both techniques and the transformations observed in the powder are representative of those in individual grains present in polycrystalline structures. Based on the newly developed TTT, it was established that the high-temperature eta-Cu6Sn5 could be stablised down to room temperature if the cooling rate exceeded 20 °C min−1.

Maximum usable thickness revisited: Imaging dislocations in Si by modern high-voltage scanning transmission electron microscopy

We have quantitatively evaluated the usable thickness of specimens in scanning transmission electron microscopy (STEM) at 1 MV using a wedge-shaped Si(110) single crystal including artificially introduced high-density dislocations. The width of dislocation images was employed as a criterion for the quantitative evaluation of usable thickness. Superior usable thickness in STEM than in TEM was found; the obtained results were 14.7 µm for STEM and 5.8 µm for TEM. In particular, in STEM, dislocations can be observed as thin lines with 10–15 nm width in the thickness range up to 10 µm. The latest high-voltage STEM is useful for imaging crystal defects in thick semiconductors.

Femtosecond laser-induced modification at aluminum/diamond interface

We investigated femtosecond-laser-induced modification at an Al/diamond interface. The interface was irradiated from the backside through the diamond substrate, which is transparent to the laser beam. Extremely high pulse energies, i.e., 200 and 100 µJ/pulse, were used to irradiate the interface. The cross-section of the laser-irradiated line was observed with conventional and high-voltage transmission electron microscopy. The modification of the laser-irradiated interface was characterized by the formation of an amorphous phase sandwiched between the deformed Al film and the diamond substrate. The major chemical component of the amorphous phase was identified as carbon, blown from the diamond substrate. The newly formed interface between the amorphous phase and the diamond substrate was concave. In addition, a fine ripple structure with an average spacing one-quarter the wavelength of the laser light was formed only in the sample irradiated by the higher-energy pulses.

Detection of one-dimensional migration of single self-interstitial atoms in tungsten using high-voltage electron microscopy.

The dynamic behaviour of atomic-size disarrangements of atoms—point defects (self-interstitial atoms (SIAs) and vacancies)—often governs the macroscopic properties of crystalline materials. However, the dynamics of SIAs have not been fully uncovered because of their rapid migration. Using a combination of high-voltage transmission electron microscopy and exhaustive kinetic Monte Carlo simulations, we determine the dynamics of the rapidly migrating SIAs from the formation process of the nanoscale SIA clusters in tungsten as a typical body-centred cubic (BCC) structure metal under the constant-rate production of both types of point defects with high-energy electron irradiation, which must reflect the dynamics of individual SIAs. We reveal that the migration dimension of SIAs is not three-dimensional (3D) but one-dimensional (1D). This result overturns the long-standing and well-accepted view of SIAs in BCC metals and supports recent results obtained by ab-initio simulations. The SIA dynamics clarified here will be one of the key factors to accurately predict the lifetimes of nuclear fission and fusion materials.

Direct evaluation of grain boundary hydrogen embrittlement: A micro-mechanical approach

In order to directly investigate the grain boundary (GB) hydrogen embrittlement in polycrystalline materials, a novel micro-mechanical testing method was developed. By combining a site-specific sampling technique and a high-voltage environmental transmission electron microscope (HV ETEM), the fracture property of micro-cantilever specimens fabricated from the same GB in a nickel-aluminide (Ni3Al) polycrystal was critically compared in environments with/without hydrogen (H2) gas. For randomly oriented GBs, brittle fracture nucleation accompanied by plastic deformation was observed in a H2-containing environment except for ones with small orientation difference. No GB fracture was observed for coherent Σ3 boundaries. It also appeared that the similitude of the hydrogen-enhanced decohesion (HEDE) mechanism was still valid even for the submicron-scale specimens.

Evaluation of Interfacial Fracture Strength in Micro-Scale Components Combined with High-Voltage Environmental Electron Microscopy

A novel experimental method that enables evaluation of interfacial strength of micro-components subjected to well-controlled various environments is proposed. The method combines a high-voltage transmission electron microscope (HVEM) equipped with an open type environmental cell (EC) and a quantitative nano-mechanical holder. The experiments were conducted by using focused-ion-beam-processed micro-cantilever specimens containing interfaces of dissimilar materials (silicon (Si) and copper (Cu)). The in situ observation of fracture phenomenon along a target interface (Si/Cu) and the simultaneous measurement of fracture load were successfully implemented under vacuum and gaseous environments (N2 gas and N2/H2 mixed gas) whose maximum pressure was controlled at 5 × 103 Pa. The stress distribution at the onset of fracture was calculated in detail by finite element analysis. The strength against interfacial debonding was then evaluated by the local normal stress value at the interface free-edge. The proposed technique, which can also be combined with simultaneous electron probe analyses, is highly versatile when compared to the conventional nano-mechanical strength evaluations under limited environments.

Development of TEM and SEM high brightness electron guns using cold-field emission from a carbon nanotip

A newly developed carbon cone nanotip (CCnT) has been used as field emission cathode both in low voltage SEM (30kV) electron source and high voltage TEM (200kV) electron source. The results clearly show, for both technologies, an unprecedented stability of the emission and the probe current with almost no decay during 1h, as well as a very small noise (rms less than 0.5%) compared to standard sources which use tungsten tips as emitting cathode. In addition, quantitative electric field mapping around the FE tip have been performed using in situ electron holography experiments during the emission of the new tip. These results show the advantage of the very high aspect ratio of the new CCnT which induces a strong enhancement of the electric field at the apex of the tip, leading to very small extraction voltage (some hundred of volts) for which the field emission will start. The combination of these experiments with emission current measurements has also allowed to extract an exit work function value of 4.8eV.

Three-dimensional reconstruction of the axon extending from the dermal photoreceptor cell in the extraocular photoreception system of a marine gastropod, onchidium.

The marine gastropod Onchidium has a multiple photoreceptive system consisting of stalk eyes, dorsal eyes, photosensitive neurons, and extraocular dermal photoreceptor cells (DPCs). The DPCs were widespread all over the dorsal mantle and distributed singly or in groups in the dermis, but were not discernible by the naked eye. The DPC was oval in shape and large in size, and characterized by features specific to gastropod photoreceptor cells such as massive microvilli, photic vesicles, and a depolarized response. DPC-17, one of a group of 19 DPCs, was examined on serial semi-thin sections of 0.4 µm in thickness with a high-voltage transmission electron microscope (HVTEM). The axon emerged specifically from the lateral side between the distal microvillous portion and proximal cytoplasm, travelled through the connective tissue, and joined a small nerve bundle (NB). Two types of supportive cells were found along the length of the axon. The first type was a covering cell (CC) surrounding the surface of the DPC body and continuing onward to the axon sheath. DPC-17 was covered by 11 CCs, while the larger DPC-6 was only covered by four CCs. The second type was a sheath cell (ShC) wrapping the surface of the small NB where the axon of the DPC merged with undefined nerve fibers. The axon extending directly from DPC-17 was reconstructed three-dimensionally (3D) using DeltaViewer software. The 3D-reconstructed image of the sheath of the axon and the CC demonstrated the continuity between the two structures, especially when the image was rotated using DeltaViewer.

Development of an environmental high voltage electron microscope and its application to nano and bio-materials

Environmental transmission electron microscopy has recently emerged as topics of great interest as well as ultra-high resolution electron microscopy using aberration correctors. Current research in this area has been focusing on dynamic observation with atomic resolution under gaseous atmospheres and in liquids. Nagoya University has been developing a new 1-MV high voltage (scanning) transmission electron microscope, which can be used to observe nano-materials under conditions that include the presence of gases, liquids and illuminating lights, and it can be also used to perform mechanical operations to nm-sized areas as well as electron tomography and elemental analysis by electron energy loss spectroscopy.

Characterization of Vacant Broken Line Defects in A-Face Grown Crystals of Silicon Carbide

A new type of defects, vacant broken line defects, was found to occur in a-face grown crystals of 4H-Silicon Carbide. We characterized the vacant broken line defects by high voltage transmission electron microscope (HV-TEM). The HV-TEM image revealed that the edges of broken line defects were connected by a bundle of dislocations, which elongated to the growth direction on the basal plane. The analysis by gb method for determining Burgers vector indicated that the dislocations were not pure screw dislocations, but complex of screw and edge dislocations. The vacant broken line defect was considered to be a quasi-stable state of a bundle of basal plane dislocations in a-face growth, similar to a micropipe defect in c-face growth.

A Method to Determine Energy and Power of a Fracture Process in Polycrystals by Means of HVTEM

Main crack propagation process in polycrystalline materials is very complex due to intercrystalline sliding mechanism effects. Multiple factors make it considerably difficult to analyze the state of stresses in the crack tip within the theoretical scope of linear fracture mechanics (LFM). As a basis for the suggested Bilby-Cottrell-Swinden model, we propose a method to determine the state of stresses in the tip of a propagating crack in microspecimens subjected to tension and measured inside a high voltage transmission electron microscope (HVTEM). Based on the electron microscopy observations of a main crack and the formation of microcracks in the plastic zone, theJ-integral was determined.

Development of an environmental high-voltage electron microscope for reaction science

Environmental transmission electron microscopy and ultra-high resolution electron microscopic observation using aberration correctors have recently emerged as topics of great interest. The former method is an extension of the so-called in situ electron microscopy that has been performed since the 1970s. Current research in this area has been focusing on dynamic observation with atomic resolution under gaseous atmospheres and in liquids. Since 2007, Nagoya University has been developing a new 1-MV high voltage (scanning) transmission electron microscope that can be used to observe nanomaterials under conditions that include the presence of gases, liquids and illuminating lights, and it can be also used to perform mechanical operations to nanometre-sized areas as well as electron tomography and elemental analysis by electron energy loss spectroscopy. The new instrument has been used to image and analyse various types of samples including biological ones.

The Multilayered Interlaced Network (MIN) in the sporoplasm of the Microsporidium Anncaliia algerae is derived from Golgi

This study provides evidence for the Golgi-like activity of the multilayered interlaced network (MIN) and new ultrastructural observations of the MIN in the sporoplasm of Anncaliia algerae, a microsporidium that infects both insects and humans. The MIN is attached to the end of the polar tubule upon extrusion from the germinating spore. It surrounds the sporoplasm, immediately below its plasma membrane, and most likely maintains the integrity of the sporoplasm, as it is pulled through the everting polar tube. Furthermore, the MIN appears to deposit its dense contents on the surface of the sporoplasm within minutes of spore discharge thickening the plasma membrane. This thickening is characteristic of the developmental stages of the genus Anncaliia. The current study utilizes transmission electron microscopy (TEM), enzyme histochemistry, and high voltage TEM (HVEM) with 3D tomographic reconstruction to both visualize the structure of the MIN and demonstrate that the MIN is a Golgi-related structure. The presence of developmentally regulated Golgi in the Microsporidia has been previously documented. The current study extends our understanding of the microsporidial Golgi and is consistent with the MIN being involved in the extracellular secretion in Anncaliia algerae. This report further illustrates the unique morphology of the MIN as illustrated by HVEM using 3D tomography.

Development of Novel Optical Fiber System for Cathodoluminescence Detection in High Voltage Transmission Electron Microscope

We have installed a new system to observe cathodoluminescence (CL) in a high voltage transmission electron microscope (HVTEM). The system is constructed of a ball lens for collection of CL, an optical fiber and a multi-channel optical detector. The system can be operated without any disturbance of TEM observation. The system was proved to be very useful to observe CL in HVTEM and will be a powerful tool to investigate production mechanisms of luminescence centers by observing CL changes with incident electron energy and flux (displacement damage effect), and temperature, together with simultaneous TEM observations of microstructure changes. [doi:10.2320/matertrans.M2013025]

The role of non-stoichiometric defects in radiation damage evolution of SrTiO3

The response of polycrystalline SrTiO3, fabricated by the flash sintering method, to ion beam irradiation was investigated by means of transmission electron microscopy (TEM) and atomic scale modeling. The samples were implanted with 250 keV Ne ions at fluences between 1.11 × 1016 and 2.25 × 1016 ions per cm2 at room temperature and then characterized using scanning transmission electron microscopy and high voltage TEM. We observed that this material has a large number of Ruddlesden–Popper (RP) faults, related to the non-stoichiometry of the material, in a random and sometimes complicated arrangement. These faults have a significant impact on the radiation damage evolution of the material. In particular, the faults amorphize more quickly than the surrounding SrTiO3 matrix. We examined the interaction of point defects with the RP faults using atomistic modeling and determined that both the thermodynamic and kinetic properties of defects are significantly influenced by the presence of the faults, providing insight into the experimental observations. We conclude that planar defects such as RP faults can have a significant impact on the radiation damage evolution of SrTiO3 and might be one avenue for controlling radiation tolerance in complex materials.