Conventional Electron Diffraction Research Articles

A new rhombohedral phase and its 48 variants in β titanium alloy

A new rhombohedral phase (termed R′) in a solution−aging-treated titanium alloy (Ti−4.5Al−6.5Mo−2Cr− 2Nb−1V−1Sn−1Zr, wt.%) was identified. Its accurate Bravais lattice parameters were determined by a novel unit cell reconstruction method based on conventional selected-area electron diffraction (SAED) technique. The orientation relationship between R′ phase and BCC phase was revealed. The results show that the R′ phase is found to have 48 crystallographically equivalent variants, resulting in rather complicated SAED patterns with high-order reflections. A series of in-situ SAED patterns were taken along both low- and high-index zone axes, and all weak and strong reflections arising from the 48 variants were properly explained and directly assigned with self-consistent Miller indices, confirming the presence of the rhombohedral phase. Additionally, some criteria were also proposed for evaluating the indexed results, which together with the Bravais lattice reconstruction method shed light on the microstructure characterization of even unknown phases in other alloys.

Investigation of the structural stability of polycrystalline cBN under near-industrial grinding process conditions

Cubic boron nitride (cBN) is an important material in the cutting and metal processing industries due to its exceptional hardness and high thermal stability, which allows it to withstand temperatures up to 1400 °C without decomposing. These properties make cBN and, with that, polycrystalline cBN (PcBN) ideal materials for high-speed machining and other applications, resulting in increased efficiency and reduced costs in production processes. Despite its established importance, the possibility of phase transformations into hexagonal boron nitride phases or partial amorphization during industrial PcBN grinding processes remains unclear and, due to the deteriorated mechanical characteristics, raised recently some concerns about possible losses of cBN's hardness, wear resistance, and abrasive properties. In order to address this issue and for identifying such potential structural changes, a commercial PcBN grade was exposed to near-industrial grinding process conditions and then characterized in detail by conventional (scanning) transmission electron microscopy (S)TEM and (scanning) electron diffraction techniques. To understand the influence of the PcBN machining on the material, the grinding process also needs to be assessed via the identification of chip formation mechanisms, which is as well addressed in this work. The main outcome of this study, combining a material analysis and a manufacturing technology point of view, is that there is so far no evidence of any structural instabilities of PcBN under usual processing conditions.

Revisiting the Crystallography of {225}γ Martensite: How EBSD Can Help to Solve Long-Standing Controversy

Explaining the crystallography of iron alloys martensite with a {225}γ habit plane remains a challenging task within the phenomenological theory of martensite crystallography. The purpose of this study is to re-examine the martensite formed in a Fe-8Cr-1.1C alloy using EBSD, which has a better angular resolution than the conventional transmission electron diffraction techniques previously used. The results show that the single morphological plates, which hold a near {225}γ habit plane, are bivariant composites made up of two twin-related variants. It is shown that a {113}γ plane is systematically parallel to one of the three common 112α planes between the two twin-related crystals. This observation suggests that the lattice invariant strain of transformation occurs through a dislocation glide on the {113}γ ⟨110⟩γ system, rather than through twinning as is commonly accepted. Based on this assumption, the predictions of Bowles and Mackenzie’s original theory are in good agreement with the crystallographic features of {225}γ martensite. Unexpectedly, it is the high shear solution of the theory that gives the most accurate experimental predictions.

Structural analysis of nanocrystals by pair distribution function combining electron diffraction with crystal tilting.

As an important characterization method, pair distribution function (PDF) has been extensively used in structural analysis of nanomaterials, providing key insights into the degree of crystallinity, atomic structure, local disorder etc. The collection of scattering signals with good statistics is necessary for a reliable structural analysis. However, current conventional electron diffraction experiments using PDF (ePDF) are limited in their ability to acquire continuous diffraction rings for large nanoparticles. Herein, a new method - tilt-ePDF - is proposed to improve the data quality and compatibility of ePDF by a combination of electron diffraction and specimen tilting. In the present work, a tilt-series of electron diffraction patterns was collected from gold nanoparticles with three different sizes and a standard sample polycrystalline aluminium film for ePDF analysis. The results show that tilt-ePDF can not only enhance the continuity of diffraction rings, but can also improve the signal-to-noise ratio in the high scattering angle range. As a result, compared with conventional ePDF data, tilt-ePDF data provide structure parameters with a better accuracy and lower residual factors in the refinement against the crystal structure. This method provides a new way of utilizing ePDF to obtain accurate local structure information from nanoparticles.

Local structure analysis of disordered materials via contrast variation in scanning transmission electron microscopy

The crystallographic structures of disordered materials are typically analyzed using diffractometry techniques, such as x-ray diffraction (XRD), neutron diffraction (ND), and electron diffraction (ED). Here, we demonstrate a novel technique to analyze the local structure of disordered materials via scanning transmission electron microscopy (STEM) under a contrast variation scheme. Contrast variation is a scheme used for the analysis of bulk materials, which combines two different diffractometry techniques with discrete scattering factors, such as ND and XRD. The STEM image contrasts of annular dark-field (ADF) and annular bright-field (ABF) imaging, which are characterized by different atomic number dependences, are simultaneously utilized. Simulated STEM images of amorphous SiO2 are examined using Fourier transform and autocorrelation operations, revealing that the Fourier transforms of ADF and ABF images are consistent with the results of conventional XRD/ED and ND techniques, respectively. The autocorrelation of the ABF image indicates the short-range ordering of light elements, which cannot be accomplished using conventional TEM, ED, and XRD techniques. As such, employing the contrast variation scheme in STEM imaging paves the way for analyzing the local crystallographic structure of non-monoatomic materials.

Evaluation of accuracy in the determination of crystal structure factors using large-angle convergent-beam electron diffraction patterns.

The accuracy of electron density distribution analysis using large-angle convergent-beam electron diffraction (LACBED) patterns is evaluated for different convergence angles. An orbital ordered state of FeCr2O4 is used as an example of the analysis. Ideal orbital-ordered and non-ordered states are simulated by using orbital scattering factors. LACBED patterns calculated for the orbital-ordered state were used as hypothetical experimental data sets. Electron density distribution of the Fe 3d orbitals has been successfully reconstructed with a higher accuracy from LACBED patterns with convergence angles larger than 15.2 mrad, which is 4 times as large as that for conventional convergent-beam electron diffraction patterns. Excitation of particular Bloch waves with the aid of LACBED patterns has a key role in the accurate analysis of electron density distributions.

Effect of Coulomb field on laser-induced ultrafast imaging methods

By performing a joint theoretical and experimental investigation on the high-order above-threshold ionization (HATI) spectrum, the dominant role of the 3rd-return-recollision trajectories in the region near the cutoff due to the ionic Coulomb field is identified. This invalidates the key assumption adopted in the conventional laser-induced electron diffraction (LIED) approach that the 1st-returnrecollision trajectories dominate the spectrum according to strong field approximation (SFA). Our results show that the incident (return) electron beams produced by the 1st and 3rd returns possess distinct characteristics of beam energy, beam diameter and temporal evolution law due to the influence of Coulomb field, and therefore the extracted results in the LIED will be altered if the significance of the 3rd-return-recollision trajectories is properly considered in the analysis. Such Coulomb field effect should be taken into account in all kinds of laser-induced imaging schemes based on recollision.

Atomic-resolution imaging of carbonyl sulfide by laser-induced electron diffraction.

Measurements on the strong-field ionization of carbonyl sulfide molecules by short, intense, 2 µm wavelength laser pulses are presented from experiments where angle-resolved photoelectron distributions were recorded with a high-energy velocity map imaging spectrometer, designed to reach a maximum kinetic energy of 500 eV. The laser-field-free elastic-scattering cross section of carbonyl sulfide was extracted from the measurements and is found in good agreement with previous experiments, performed using conventional electron diffraction. By comparing our measurements to the results of calculations, based on the quantitative rescattering theory, the bond lengths and molecular geometry were extracted from the experimental differential cross sections to a precision better than ±5 pm and in agreement with the known values.

Fabrication and structural characterization of diamond-coated tungsten tips

Coating metal nanotips with a negative electron affinity material like hydrogen-terminated diamond bears promise for a high brightness photocathode. We report a recipe on the fabrication of diamond-coated tungsten tips. A tungsten wire is etched electrochemically to a nanometer sharp tip, dip-seeded in diamond suspension and subsequently overgrown with a diamond film by plasma-enhanced chemical vapor deposition. With dip-seeding only, the seeding density declines towards the tip apex due to seed migration during solvent evaporation. The migration of seeds can be counteracted by nitrogen gas flow towards the apex, which makes coating of the apex with nanometer-thin diamond possible. At moderate gas flow, diamond grows homogeneously at shaft and apex whereas at high flow diamond grows in the apex region only. With this technique, we achieve a thickness of a few tens of nanometers of diamond coating within less than 1 μm away from the apex. Conventional transmission electron microscopy (TEM), electron diffraction and electron energy loss spectroscopy confirm that the coating is composed of dense nanocrystalline diamond with a typical grain size of 20 nm. High resolution TEM reveals graphitic paths between the diamond grains.

Wet-chemistry synthesis of shape-controlled Ag3PO4 crystals and their 3D surface reconstruction from SEM imagery

A simple chemical solution-based synthesis route has been developed to prepare uniform and shape-controllable Ag3PO4 crystals. Tetrapod- and cube-shaped crystals having a size of about 9–10 μm were prepared from AgNO3 and NH4H2PO4 precursors, and pseudo-octahedral (equiaxial) crystals were prepared from AgNO3 and (NH4)2HPO4. TEM analysis revealed Ag3PO4 crystals to be electron beam sensitive materials, which under a voltage of 200 kV decompose to the metallic Ag, thereby demonstrating the difficulty in determining crystal facets and structural defects using conventional electron diffraction studies. UV–Vis diffuse reflectance spectroscopy was used to study the correlation between structural and optical properties of surfaces of Ag3PO4 crystals. Furthermore, a spatial 3-dimentional (3D) reconstruction of Ag3PO4 surface structures was performed from SEM images. The reconstruction produced realistic 3D mesh models, insomuch that the 3D reconstructed structures provided extra information about the examined crystals. Results suggested that the proposed synthesis route and performed spatial reconstruction of Ag3PO4 had the potential for simulating processing conditions to produce various microcrystals and explore material surface structures and reconstruction of microstructures.

Quantification of crystallinity using zero-loss filtered electron diffraction.

The quantity of the crystalline phases present in a nanomaterial is an important parameter that governs the correlation between its properties and microstructure. However, quantification of crystallinity in nanoscale-level applications by conventional methods (Raman spectroscopy and X-ray diffraction) is difficult because of the spatial limitations of sampling. Therefore, we propose a technique that involves using energy-filtered electron diffraction in transmission electron microscopy which offers improved spatial resolution. The degree of crystallinity (DOC) was calculated by separating the crystalline and amorphous intensities from the total intensity histogram acquired by the azimuthal averaging of the zero-loss filtered signals from electron diffraction. In order to validate the method, it was demonstrated that the DOC calculated by zero-loss filtered electron diffraction was consistent with the DOC measured by the area ratio using an amorphous silicon on crystalline silicon standard sample. In addition, the results obtained from zero-loss filtered and conventional electron diffractions were compared. The zero-loss filtered electron diffraction successfully provided the reliable results of the crystallinity quantification. In contrast, the DOC measured using conventional electron diffraction yielded extremely variable results. Therefore, our results provide a crystallinity quantification technique that can extract quantitative information about crystallinity of nanoscale devices by using zero-loss filtered electron diffraction with better reliability than conventional electron diffraction. RESEARCH HIGHLIGHTS: The degree of crystallinity can be measured by separating the crystalline and amorphous intensities from the total intensity histogram acquired by the azimuthal averaging of the zero-loss filtered signals from selected area electron diffraction.

Machining protein microcrystals for structure determination by electron diffraction

We demonstrate that ion-beam milling of frozen, hydrated protein crystals to thin lamella preserves the crystal lattice to near-atomic resolution. This provides a vehicle for protein structure determination, bridging the crystal size gap between the nanometer scale of conventional electron diffraction and micron scale of synchrotron microfocus beamlines. The demonstration that atomic information can be retained suggests that milling could provide such detail on sections cut from vitrified cells.

An advanced three-dimensional RHEED mapping approach to the diffraction study of Co/MnF2/CaF2/Si(001) epitaxial heterostructures

An advanced three-dimensional mapping approach utilizing reflection high-energy electron diffraction (RHEED) is introduced. The application of the method is demonstrated in detail by resolving the crystal structure and epitaxial relations of individual components within epitaxially grown magnetically ordered Co/MnF2/CaF2/Si(001) heterostructures. The electron diffraction results are cross-checked using synchrotron X-ray diffraction measurements. A number of advantages of the three-dimensional mapping technique as compared to conventional electron diffraction are demonstrated. Not least amongst these is the possibility to build arbitrary planar cross sections and projections through reciprocal space, including the plan-view projection onto the plane parallel to the sample surface, which is otherwise impossible to obtain.

Extracting conformational structure information of benzene molecules via laser-induced electron diffraction.

We have measured the angular distributions of high energy photoelectrons of benzene molecules generated by intense infrared femtosecond laser pulses. These electrons arise from the elastic collisions between the benzene ions with the previously tunnel-ionized electrons that have been driven back by the laser field. Theory shows that laser-free elastic differential cross sections (DCSs) can be extracted from these photoelectrons, and the DCS can be used to retrieve the bond lengths of gas-phase molecules similar to the conventional electron diffraction method. From our experimental results, we have obtained the C-C and C-H bond lengths of benzene with a spatial resolution of about 10 pm. Our results demonstrate that laser induced electron diffraction (LIED) experiments can be carried out with the present-day ultrafast intense lasers already. Looking ahead, with aligned or oriented molecules, more complete spatial information of the molecule can be obtained from LIED, and applying LIED to probe photo-excited molecules, a “molecular movie” of the dynamic system may be created with sub-Ångström spatial and few-ten femtosecond temporal resolutions.

Precession Electron Diffraction

The strong Coulombic interaction between a high energy electron and a thin crystal film gives rise to electron diffraction patterns encoded with information that is remarkably sensitive to the crystal potential. That exquisite sensitivity can be advantageous, for example in the determination of local symmetry and bonding, but can also be problematic in that in general the dynamical scattering inherent in electron diffraction prohibits the use of conventional crystallographic methods to recover structure factor phase information and solve unknown structures. One way to reduce this problem is to use precession electron diffraction (PED), introduced 20 years ago [1] as the electron analogue of Buerger's X-ray technique, in which the electron beam is first rocked in a hollow cone above the sample and then de-rocked below, the net effect of which is equivalent to precessing the sample about a stationary electron beam. PED is now used almost routinely as a starting point to solve crystal structures that cannot be solved for a variety of reasons using x-ray or neutron methods. In this keynote lecture we explore why the PED technique has been successful for structure determination, focussing on the PED geometry, the variation of intensities with precession angle and specimen thickness, and how this `mimics' kinematic behaviour, and the use of unconventional structure solution and refinement approaches [2]. New acquisition geometries will be discussed that rely on tilt series of PED patterns to yield a more complete 3D data set. The lecture will focus on how PED has been used also as a method for nanoscale orientation mapping [3], providing more information than conventional electron diffraction and a robust method with which to determine local crystallographic orientation. By scanning the beam, accurate orientation images can be derived from series of PED patterns and, by combining with tomographic methods, sub-volume orientation information is also available.

Time-dependent density-functional theory simulation of electron wave-packet scattering with nanoflakes

Low-energy electron scattering with nanoflakes is investigated using a time-dependent density functional theory (TDDFT) simulation in real time and real space. By representing the incident electron as a finite-sized wave packet, we obtain diffraction patterns that show not only the regular features of conventional low-energy electron diffraction (LEED) for periodic structures but also special features resulting from the local atomic inhomogeneity. We have also found a signature of $\ensuremath{\pi}$ plasmon excitation upon electron impact on a graphene flake. The present study shows the remarkable potential of TDDFT for simulating the electron scattering process, which is important for clarifying the local and periodic atomic geometries as well as the electronic excitations in nanostructures.

A complex pseudo-decagonal quasicrystal approximant, Al37(Co,Ni)15.5, solved by rotation electron diffraction

Electron diffraction is a complementary technique to single-crystal X-ray diffraction and powder X-ray diffraction for structure solution of unknown crystals. Crystals too small to be studied by single-crystal X-ray diffraction or too complex to be solved by powder X-ray diffraction can be studied by electron diffraction. The main drawbacks of electron diffraction have been the difficulties in collecting complete three-dimensional electron diffraction data by conventional electron diffraction methods and the very time-consuming data collection. In addition, the intensities of electron diffraction suffer from dynamical scattering. Recently, a new electron diffraction method, rotation electron diffraction (RED), was developed, which can overcome the drawbacks and reduce dynamical effects. A complete three-dimensional electron diffraction data set can be collected from a sub-micrometre-sized single crystal in less than 2 h. Here the RED method is applied forab initiostructure determination of an unknown complex intermetallic phase, the pseudo-decagonal (PD) quasicrystal approximant Al37.0(Co,Ni)15.5, denoted as PD2. RED shows that the crystal is F-centered, witha= 46.4,b= 64.6,c= 8.2 Å. However, as with other approximants in the PD series, the reflections with oddlindices are much weaker than those withleven, so it was decided to first solve the PD2 structure in the smaller, primitive unit cell. The basic structure of PD2 with unit-cell parametersa= 23.2,b= 32.3,c= 4.1 Å and space groupPnmmhas been solved in the present study. The structure withc= 8.2 Å will be taken up in the near future. The basic structure contains 55 unique atoms (17 Co/Ni and 38 Al) and is one of the most complex structures solved by electron diffraction. PD2 is built of characteristic 2 nm wheel clusters with fivefold rotational symmetry, which agrees with results from high-resolution electron microscopy images. Simulated electron diffraction patterns for the structure model are in good agreement with the experimental electron diffraction patterns obtained by RED.

Femtosecond streaking of electron diffraction patterns to study structural dynamics in crystalline matter

A table-top femtosecond, non-relativistic, electron diffraction setup is combined with a low-jitter, photo-triggered streak camera to follow the optically induced structural dynamics in complex solids. A temporal resolution of 550 fs is experimentally demonstrated, while the route to streaking with sub-250 fs temporal resolution is outlined. The streaking technique allows for parallel capturing of temporal information as opposed to the serial data acquisition in a conventional scanning femtosecond electron diffraction. Moreover, its temporal resolution is not corrupted by increasing the number of electrons per pulse. Thus, compared to the conventional scanning approach, a substantial increase in signal-to-noise ratio (SNR) can be achieved. These benefits are demonstrated by studying a photo-induced charge density wave phase transition in 4Hb-TaSe2 using both methods. Within the same data acquisition time a three-fold increase in SNR is achieved when compared to the scanning method, with ways for a further improvement outlined.

Structure analysis of a precipitate phase in an Ni-rich high-temperature NiTiHf shape memory alloy

Thermal aging of the high-temperature shape memory alloy 50.3Ni–29.7Ti–20Hf (at.%) introduces a novel precipitate phase that plays an important role in improving shape memory properties. The precipitate phase was investigated by conventional electron diffraction, high-resolution scanning transmission electron microscopy (STEM) and three-dimensional atom probe tomography. An unrelaxed orthorhombic atomic structural model is proposed based on these observations. This model was subsequently relaxed by ab initio calculations. As a result of the relaxation, atom shuffle displacements occur, which in turn yields improved agreement with the STEM images. The relaxed structure, which is termed the “H phase”, has also been verified to be thermodynamically stable at 0K.

Structure refinement from precession electron diffraction data

Electron diffraction is a unique tool for analysing the crystal structures of very small crystals. In particular, precession electron diffraction has been shown to be a useful method for ab initio structure solution. In this work it is demonstrated that precession electron diffraction data can also be successfully used for structure refinement, if the dynamical theory of diffraction is used for the calculation of diffracted intensities. The method is demonstrated on data from three materials - silicon, orthopyroxene (Mg,Fe)(2)Si(2)O(6) and gallium-indium tin oxide (Ga,In)(4)Sn(2)O(10). In particular, it is shown that atomic occupancies of mixed crystallographic sites can be refined to an accuracy approaching X-ray or neutron diffraction methods. In comparison with conventional electron diffraction data, the refinement against precession diffraction data yields significantly lower figures of merit, higher accuracy of refined parameters, much broader radii of convergence, especially for the thickness and orientation of the sample, and significantly reduced correlations between the structure parameters. The full dynamical refinement is compared with refinement using kinematical and two-beam approximations, and is shown to be superior to the latter two.