Nanobeam Electron Diffraction Research Articles

Crystallization induced ordering of hard magnetic L1 phase in melt-spun FeNi-based ribbons

The microstructure of newly developed hard magnetic Fe42Ni41.3SixB12-xP4Cu0.7 (x = 2 to 8 at%) nanocrystalline alloy ribbons has been studied by transmission electron microscopy (TEM) and electron diffraction. A high-density polycrystalline grains, ∼30 nm in size, were formed in a ribbon after annealing at 673 K for 288 hours. Elemental mapping of the annealed specimen revealed the coexistence of three regions, Fe-rich, Ni-rich, and nearly equiatomic Fe-Ni, with areal fractions of 37%, 40%, and 23 %, respectively. The equiatomic L10-type ordered phase of FeNi was detected in between the Fe and Ni-rich phases. The presence of superlattice reflections in nanobeam electron diffraction patterns confirmed the formation of the hard magnetic L10 phase beyond any doubt. The L10 phase of FeNi was detected in alloys annealed in the temperature range of 673 to 813 K. The present results suggest that the order-disorder transition temperature of L10 FeNi is higher than the previously reported value (593 K). The high diffusion rates of the constituent elements induced by the crystallization of an amorphous phase at relatively low temperature (∼673K) are responsible for the development of atomic ordering in FeNi.

High-resolution analytical imaging and electron holography of magnetite particles in amyloid cores of Alzheimer's disease.

Abnormal accumulation of brain metals is a key feature of Alzheimer’s disease (AD). Formation of amyloid-β plaque cores (APC) is related to interactions with biometals, especially Fe, Cu and Zn, but their particular structural associations and roles remain unclear. Using an integrative set of advanced transmission electron microscopy (TEM) techniques, including spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM), nano-beam electron diffraction, electron holography and analytical spectroscopy techniques (EDX and EELS), we demonstrate that Fe in APC is present as iron oxide (Fe3O4) magnetite nanoparticles. Here we show that Fe was accumulated primarily as nanostructured particles within APC, whereas Cu and Zn were distributed through the amyloid fibers. Remarkably, these highly organized crystalline magnetite nanostructures directly bound into fibrillar Aβ showed characteristic superparamagnetic responses with saturated magnetization with circular contours, as observed for the first time by off-axis electron holography of nanometer scale particles.

Crystallization behavior of ZrO2[sbnd]3Y2O3[sbnd]xSrO precursor powders synthesized by a coprecipitation process

Crystallization behaviors of ZrO23Y2O3xSrO precursor powders were studied with zirconium nitrate (Zr(NO3)4·xH2O), yttrium nitrate (Y(NO3)3·6H2O) and strontium nitrate (Sr(NO3)2) constituting the initial materials. Differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED) and high-resolution TEM (HRTEM) were utilized to characterize the crystallization behavior of ZrO23Y2O3xSrO precursor powders. The activation energies of tetragonal ZrO2 (t-ZrO2) crystallization were 389.1, 327.6, and 315.1 kJ/mol with SrO content for 1, 2, and 3 mol%, respectively, obtained with a non-isothermal method. The growth morphology parameter and growth mechanism index were close to 2.0 and 1.0, respectively, showing that t-ZrO2 had a plate-like morphology.

Effect of SrO addition on the growth behavior of ZrO2–3Y2O3 precursor powders synthesized by a coprecipitation process

Effect of SrO addition on the crystalline growth behavior of ZrO2–3Y2O3 precursor powders using a coprecipitation process has been studied. Zirconium nitrate (Zr(NO3)4·xH2O), yttrium nitrate (Y(NO3)3·6H2O) and strontium nitrate (Sr(NO3)2) were used as the initial materials. Crystalline growth behavior was investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED) and high-resolution TEM (HRTEM). The XRD results showed the ZrO2–3Y2O3–xSrO only contained single phase of tetragonal ZrO2 (t-ZrO2) when the precursor powders were calcined at different temperatures for various durations. The crystallite size increased from 22.91 to 27.44nm when the ZrO2–3Y2O3–1SrO precursor powders after calcination at 823K from 15 to 120min. The activation energy values obtained are 9.98, 9.04 and 7.43kJ/mol for SrO addition amount of 1, 2 and 3mol%, respectively, and the kinetics equations of t-ZrO2 crystalline growth with SrO addition are also expressed as follows: D1SrO2=6.00×t0.13exp(−9.98×103RT),D2SrO2=6.02×t0.11exp(−9.04×103RT) and D3SrO2=6.13×t0.10exp(−7.43×103RT) with SrO content for 1, 2 and 3mol%, respectively, for 15≤t≤120min and 773≤T≤923K.

In‐depth structural and chemical characterization of engineered TiO2 films

Analytical routines for a comprehensive in‐depth morphological, structural, and chemical characterization of functionalized TiO2 films by using different state‐of‐the‐art analytical techniques are presented and discussed with the main objective to identify potential reference TiO2 coating parameters able to be certified at a later stage. TiO2 films fabricated by two different synthetic procedures as representative for two main large‐scale applications were selected: (i) pulsed d.c. magnetron sputtering for photocatalytic applications and (ii) screen printing from preformed anatase nanoparticles. The screen‐printed films were further loaded with a sensitizing dye for application as a dye‐sensitized solar cell. Film properties such as microstructure and crystallographic texture of pulsed d.c. magnetron sputtering synthesized films were systematically studied by means of scanning nanobeam electron diffraction in a transmission electron microscope and the surface and inner morphology by scanning electron microscopy. The dye distribution over the depth of screen‐printed TiO2 layers was analyzed before and after dye‐loading by means of energy dispersive X‐ray spectroscopy at scanning electron microscope, Auger electron spectroscopy and time‐of‐flight secondary ion mass spectrometry. The long‐term goal of the present study is the improvement of quality of the TiO2 film parameters as measured by using different types of reference TiO2 coatings having specific parameters certified. Copyright © 2016 John Wiley & Sons, Ltd.

Structure Determination of Superatom Metallic Clusters Using Rapid Scanning Electron Diffraction

Experimental analysis of electron diffraction patterns for ligand-stabilized gold clusters in transmission electron microscopy is a cumbersome procedure, due to electron beam–induced irradiation damage. We propose herein a method for instantaneous data collection using scanning nanobeam electron diffraction and the subsequent determination of the crystal metallic clusters. The procedure has been tested on a known structure, namely Au102(p-MBA)44 nanoclusters and has been compared with their structure theoretically determined by ones previously obtained from X-ray diffraction analysis. The method can be unambiguously applied for the case of any nanoscale system susceptible to electron beam damage and it is capable to register the rotation effect on the metallic clusters caused due to the electron beam interaction during the raster scanning on the sample.

三方位からの透過形電子顕微鏡観察と構造因子計算によるBiFeO<sub>3</sub>エピタキシャル薄膜の結晶対称性の決定

Despite extensive studies on crystal structure of thin film BiFeO3 (BFO) thin film, it remains debated primarily due to its structural complexity as well as stress effect from underlying substrates. We have examined comprehensive crystal structure analysis for BFO thin layer (30 nm) grown on SrTiO3 (STO) substrate using cross-sectional transmission electron microscopy technique along three different zone axes. Nano-beam electron diffraction (NBED) patterns combined with structure factor (SF) calculations and high-resolution transmission electron microscopy images unambiguously reveal that BFO thin layer grows with rhombohedral structure that is identical to its bulk form. No evidence of monoclinic and/or tetragonal distortion is found. The rhombohedral BFO thin layer is found to grow onto STO by maintaining an epitaxial relationship in a manner that can minimize lattice mismatch at BFO/STO interface. Our current work clearly demonstrates that multiple-zone axes NBED combined with SF calculation is highly effective for precise crystal structure analysis of thin film BFO.

Comprehensive characterization of ball-milled powders simulating a tribofilm system

A model system was used to simulate the properties of tribofilms which form during automotive braking. The model system was prepared by ball milling of a blend of 70vol.% iron oxides, 15vol.% molybdenum disulfide and 15vol.% graphite. The resulting mixture was characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and various transmission electron microscopic (TEM) methods, including energy dispersive X-ray spectroscopy (EDXS), high resolution investigations (HRTEM) with corresponding simulation of the HRTEM images, diffraction methods such as scanning nano-beam electron diffraction (SNBED) and selected area electron diffraction (SAED). It could be shown that the ball milling caused a reduction of the grain size of the initial components to the nanometer range. Sometimes even amorphization or partial break-down of the crystal structure was observed for MoS2 and graphite. Moreover, chemical reactions lead to a formation of surface coverings of the nanoparticles by amorphous material, molybdenum oxides, and iron sulfates as derived from XPS.

Two-dimensional strain mapping in semiconductors by nano-beam electron diffraction employing a delay-line detector

A delay-line detector is established for electron detection in the field of scanning transmission electron microscopy (STEM) and applied to two-dimensional strain mapping in Si-based field effect transistors. We initially outline the functional principle of position-sensitive delay-line detection, based on highly accurate time measurements for electronic pulses travelling in meandering wires. In particular, the detector is a single-counting device essentially providing an infinite time stream of position-resolved events so that acquisition speed is not hindered by detector read-outs occurring in conventional charge-coupled devices. By scanning the STEM probe over stressor- and gate regions of a field effect transistor on a 100 × 100 raster, 10 000 diffraction patterns have been acquired within 3–6.5 min, depending on the scan speed. Evaluation of the 004 and 220 reflections yields lateral and vertical strain at a spatial resolution of 1.6 nm. Dose-dependent strain precisions of 1.2−1.8×10−3 could be achieved for frame times of 40 and 20 ms, respectively. Finally, the detector is characterised as to quantum efficiency and further scopes of application are outlined.

Discontinuous Precipitation Reaction Front of Cellular Recrystallization for a Single-Crystal Superalloy Studied by Electron Microscopy**Supported by the Scientific Research Foundation of Xi'an University of Technology under Grant No 101-451115007, the National Natural Science Foundation of China under Grant No 51174161, and the Pivot Innovation Team of Shaanxi Electric Materials and Infiltration Technique under Grant No 2012KCT-25.

Combining analytical transmission electron microscopy systematic tilting, scanning transmission electron microscopy mapping and nano-beam electron diffraction operations, we obtain direct experimental proofs on the boundary type, elemental distribution and structure of the cellular recrystallization reaction front for a single-crystal superalloy. It is demonstrated that the cellular recrystallization reaction front usually corresponds to coincidence site lattice boundaries, and a thin layer of γ-forming elements such as Re, Cr, Mo and Co invariably exists in the direct reaction front. Furthermore, the thin layer with γ-forming elements is proved to be γ phase, with the same orientation as the neighboring original matrix.

Natural attenuation of arsenic in the environment by immobilization in nanostructured hematite

Iron (hydr)oxides are known to play a major role in arsenic fixation in the environment. The mechanisms for long-term fixation into their crystal structure, however, remain poorly understood, especially arsenic partitioning behavior during transformation from amorphous to crystalline phases under natural conditions. In this study, these mechanisms are investigated in Fe–Al-oxisols exposed over a period of 10years to a sulfide concentrate in tailings impoundments. The spatial resolution necessary to investigate the markedly heterogeneous nanoscale phases found in the oxisols was achieved by combining three different, high resolution electron microscopy techniques – Nano-Beam Electron Diffraction (NBD), Electron Energy-Loss Spectroscopy (EELS), and High Resolution Transmission Electron Microscopy (HRTEM). Arsenic (1.6±0.5wt.%) was unambiguously and precisely identified in mesocrystals of Al-hematite with an As/Fe atomic ratio of 0.026±0.006. The increase in the c-axis (c=1.379±0.009nm) compared to standard hematite (c=1.372nm) is consistent with the presence of arsenic in the Al-hematite structure. The As-bearing Al-hematite is interpreted as a secondary phase formed from oxyhydroxides, such as ferrihydrite, during the long-term exposure to the sulfide tailings. The proposed mechanism of arsenic fixation in the Al-hematite structure involves adsorption onto Al-ferrihydrite nanoparticles, followed by Al-ferrihydrite aggregation by self-assembly oriented attachment and coalescence that ultimately produces Al-hematite mesocrystals. Our results illustrate for the first time the process of formation of stable arsenic bearing Al-hematite for the long-term immobilization of arsenic in environmental samples.

Strain mapping at nanometer resolution using advanced nano-beam electron diffraction

We report on the development of a nanometer scale strain mapping technique by means of scanning nano-beam electron diffraction. Only recently possible due to fast acquisition with a direct electron detector, this technique allows for strain mapping with a high precision of 0.1% at a lateral resolution of 1 nm for a large field of view reaching up to 1 μm. We demonstrate its application to a technologically relevant strain-engineered GaAs/GaAsP hetero-structure and show that the method can even be applied to highly defected regions with substantial changes in local crystal orientation. Strain maps derived from atomically resolved scanning transmission electron microscopy images were used to validate the accuracy, precision and resolution of this versatile technique.

Theoretical study of precision and accuracy of strain analysis by nano-beam electron diffraction

Measurement of lattice strain is important to characterize semiconductor nanostructures. As strain has large influence on the electronic band structure, methods for the measurement of strain with high precision, accuracy and spatial resolution in a large field of view are mandatory. In this paper we present a theoretical study of precision and accuracy of measurement of strain by convergent nano-beam electron diffraction. It is found that the accuracy of the evaluation suffers from halos in the diffraction pattern caused by a variation of strain within the area covered by the focussed electron beam. This effect, which is expected to be strong at sharp interfaces between materials with different lattice plane distances, will be discussed for convergent-beam electron diffraction patterns using a conventional probe and for patterns formed by a precessing electron beam. Furthermore, we discuss approaches to optimize the accuracy of strain measured at interfaces. The study is based on the evaluation of diffraction patterns simulated for different realistic structures that have been investigated experimentally in former publications. These simulations account for thermal diffuse scattering using the frozen-lattice approach and the modulation-transfer function of the image-recording system. The influence of Poisson noise is also investigated.

Spatially and momentum resolved energy electron loss spectra from an ultra-thin PrNiO3 layer

We present an experimental approach which allows for the acquisition of spectra from ultra-thin films at high spatial, momentum, and energy resolutions. Spatially and momentum (q) resolved electron energy loss spectra have been obtained from a 12 nm ultra-thin PrNiO3 layer using a nano-beam electron diffraction based approach which enabled the acquisition of momentum resolved spectra from individual, differently oriented nano-domains and at different positions of the PrNiO3 thin layer. The spatial and wavelength dependence of the spectral excitations are obtained and characterized after the analysis of the experimental spectra using calculated dielectric and energy loss functions. The presented approach makes a contribution towards obtaining momentum-resolved spectra from nanostructures, thin film, heterostructures, surfaces, and interfaces.

(Invited) 14nm FDSOI Technology for High-Speed and Energy-Efficient CMOS

As CMOS technology scales down, two paths are pursued by the industry to overcome the fundamental limits of traditional planar bulk transistors. One is the introduction of a Tri-Gate or FinFET transistor at the 22 and 16 nm nodes [1, 2]. These architectures provide impressive drive currents per footprint at low supply voltages because of the 3-D conduction channel and excellent electrostatic control. Conversely, they have high gate and parasitic capacitances, proportional to the 3-D effective W increase, which negatively impacts both the speed and active power consumption. Alternatively FDSOI provides an evolutionary path. First introduced at the 28nm node [3], FDSOI includes excellent mismatch properties, a simplified planar manufacturing process vs 3-D finFET technology and capitalization of existing design techniques. It also extends the possibility of back biasing and therefore offers unique “smart” solutions for dynamic power optimization [4]. The technology presented in this paper furthers the appeal of FDSOI to the 14nm node [5]. Compared to the 28nm technology, new Front-End process elements include a dual SOI/SiGeOI N/P channel, a dual workfunction gate-first HKMG integration scheme and a dual in-situ doped Si:CP/SiGeB N/P raised source-drain [5]. Additionally hybrid bulk areas, formed before Shallow Trench Isolation (STI), provide a space for passive devices and ESD FETs to be built [6]. The strained-SiGe channel (cSiGe) is realized before STI patterning to avoid SiGeOI over-thinning linked to the Ge condensation process at active edges [7] (Fig.1). As shown in Fig.1, strain into the channel has been experimentally measured by Nano-Beam Electron Diffraction (NBED) : 1% compressive strain in the 6nm thin SiGeOI channel (25%Ge) is demonstrated. After gate patterning, a N/P dual spacer/dual epitaxy scheme is used, as illustrated in Fig.2.Since gate-to-drain capacitance (Cgd) is of high importance for the circuit speed and power, spacer, poly thickness and raised source-drain epitaxy (Fig.2) has been optimised to minimize Cgd down to ~0.3fF/µm for both n and pMOS devices. cSiGe and SiGeB source-drain implementation in 14nm FDSOI provides a large pMOS drive current enhancement when compared to FDSOI technology at the 28nm node. As a result of low Cgd and large pMOS drive current, 14FDSOI technology demonstrated in [5] a -20% delay gain with the Fan-Out 3 (FO3) RO inverters at the same static leakage and a 100mV Vdd reduction (0.8V vs 0.9V) over the 28nm FDSOI technology (Fig.3). From this previous work, the transistor performance has further progressed and the delay boost is now established at -34% with -100mV Vdd operation, as shown in Fig.3. It means >50% speed frequency in 14FDSOI at 0.8V Vdd vs 28FDSOI at 0.9V Vdd. These large performance enhancements over 28FDSOI make 14FDSOI as a leading edge technology for the 14nm node and a highly competitive technology for low voltage and energy efficient CMOS applications.

Evidence of rhombohedral structure within BiFeO3 thin film grown on SrTiO3

Comprehensive crystal structure analysis was performed for a BiFeO3 thin layer (∼30 nm) grown on a SrTiO3 substrate using cross-sectional transmission electron microscopy along three different zone axes. Nano-beam electron diffraction patterns combined with structure factor calculations and high-resolution transmission electron microscopy images unambiguously revealed that the BiFeO3 thin layer grew with a rhombohedral structure identical to its bulk form. No evidence of monoclinic and/or tetragonal distortion was found. The rhombohedral BiFeO3 thin layer was found to grow onto SrTiO3 by maintaining an epitaxial relationship in a manner minimizing the lattice mismatch at the BiFeO3/SrTiO3 interface.

Structural Heterogeneity of the Melt-spun (Fe, Co)-Si-B-P-Cu Alloy with Excellent Soft Magnetic Properties

A structural heterogeneity of a newly developed soft magnetic Fe81.2Co4Si0.5B9.5P4Cu0.8 melt-spun alloy has been studied by transmission electron microscopy (TEM) and electron diffraction. Hollow-cone dark-field TEM imaging revealed that the density of coherent scattering regions in the as-quenched Fe81.2Co4Si0.5B9.5P4Cu0.8 alloy is as high as that in the Fe85.2Si2B8P4Cu0.8 hetero-amorphous alloy (NANOMET®). According to the aberration-corrected high-resolution TEM, crystalline atomic clusters, typically of ∼1nm in diameter, are densely distributed in an amorphous matrix of Fe81.2Co4Si0.5B9.5P4Cu0.8 alloy, while nanobeam electron diffraction detected weak Bragg reflections from Fe clusters with the body centered cubic structure. These results unambiguously reveal structural heterogeneity of the as-quenched Fe81.2Co4Si0.5B9.5P4Cu0.8 alloy, which is similar to that observed in the NANOMET®.

Insights from STEM and NBED studies into the local structure and growth mechanism of misfit layered compounds prepared using modulated reactants

Abstract X-ray diffraction and transmission electron microscopy were used to probe the structure of the misfit compound [(SnSe)1.15]1(VSe2)1 grown using an elementally modulated precursor. The specular X-ray diffraction pattern contained only 00l reflections, which yielded a c lattice parameter of 1.203(1) nm. Cross-section STEM revealed alternating layers of SnSe and VSe2, in agreement with the structure model refined from the X-ray diffraction pattern using Rietveld refinement. Plan-view transmission electron microscopy revealed the in-plane grain structure of the films, yielding grain sizes in agreement with previously reported in plane X-ray diffraction studies and the cross-section STEM images. The plan view images also contained Moiré fringes resulting from grains with different relative tilting on both sides of interfaces as well as Moiré fringes resulting from different relative rotations between domains. An energy-filtered nano-beam electron diffraction pattern obtained from at least one domain in the [(SnSe)1.15]1(VSe2)1 sample investigated in cross section contained a series of resolvable supercell reflections along the c axis that indicated that the supercell c-axis lattice parameter was a multiple of three times that determined using X-ray diffraction. Energy filtered NBED of plan-view samples showed diffraction patterns from select regions with 12-fold symmetry, indicating that the arrangement of the layers is not rotationally random from layer to layer. This suggests that during the self-assembly of the amorphous modulated elemental precursor, the SnSe and VSe2 constituent layers must nucleate off the adjacent interfaces of the growing crystal, yielding layers that are locally rotationally aligned with growing crystal. Different processing conditions during the precursor to crystal self-assembly might enable the domain size and/or the extent of order to be controlled.

Comprehensive transmission electron microscopy study on Cu–Al intermetallic compound formation at wire bond interface

Abstract

Electron holography of devices with epitaxial layers

Applicability of electron holography to deep submicron Si devices with epitaxial layers is limited due to lack of the mean inner potential data and effects of the sample tilt. The mean inner potential V0 = 12.75 V of the intrinsic epitaxial SiGe was measured by electron holography in devices with Ge content CGe = 18%. Nanobeam electron diffraction analysis performed on the same device structure showed that SiGe is strain-free in [220] direction. Our results showed good correlation with simulations of the mean inner potential of the strain-free SiGe using density function theory. A new method is proposed in this paper to correct electron holography data for the overlap of potentials of Si and the epitaxial layer, which is caused by the sample tilt. The method was applied to the analysis of the dopant diffusion in p-Field-effect Transistor devices with the identical gate length L = 30 nm, which had alternative SiGe geometry in the source and drain regions and was subjected to different thermal processing. Results have helped to understand electrical data acquired from the same devices in terms of dopant diffusion.