James M. LeBeau

Standardless atom counting in scanning transmission electron microscopy.

We demonstrate that high-angle annular dark-field imaging in scanning transmission electron microscopy allows for quantification of the number and location of all atoms in a three-dimensional, crystalline, arbitrarily shaped specimen without the need for a calibration standard. We show that the method also provides for an approach to directly measure the finite effective source size of a scanning transmission electron microscope.

Revolving scanning transmission electron microscopy: Correcting sample drift distortion without prior knowledge

We report the development of revolving scanning transmission electron microscopy--RevSTEM--a technique that enables characterization and removal of sample drift distortion from atomic resolution images without the need for a priori crystal structure information. To measure and correct the distortion, we acquire an image series while rotating the scan coordinate system between successive frames. Through theory and experiment, we show that the revolving image series captures the information necessary to analyze sample drift rate and direction. At atomic resolution, we quantify the image distortion using the projective standard deviation, a rapid, real-space method to directly measure lattice vector angles. By fitting these angles to a physical model, we show that the refined drift parameters provide the input needed to correct distortion across the series. We demonstrate that RevSTEM simultaneously removes the need for a priori structure information to correct distortion, leads to a dramatically improved signal-to-noise ratio, and enables picometer precision and accuracy regardless of drift rate.

On the structural origins of ferroelectricity in HfO2 thin films

Here, we present a structural study on the origin of ferroelectricity in Gd doped HfO2 thin films. We apply aberration corrected high-angle annular dark-field scanning transmission electron microscopy to directly determine the underlying lattice type using projected atom positions and measured lattice parameters. Furthermore, we apply nanoscale electron diffraction methods to visualize the crystal symmetry elements. Combined, the experimental results provide unambiguous evidence for the existence of a non-centrosymmetric orthorhombic phase that can support spontaneous polarization, resolving the origin of ferroelectricity in HfO2 thin films.

Spin-driven ordering of Cr in the equiatomic high entropy alloy NiFeCrCo

Spin-driven ordering of Cr in an equiatomic fcc NiFeCrCo high entropy alloy (HEA) was predicted by first-principles calculations. Ordering of Cr is driven by the reduction in energy realized by surrounding anti-ferromagnetic Cr with ferromagnetic Ni, Fe, and Co in an alloyed L12 structure. The fully Cr-ordered alloyed L12 phase was predicted to have a magnetic moment that is 36% of that for the magnetically frustrated random solid solution. Three samples were synthesized by milling or casting/annealing. The cast/annealed sample was found to have a low temperature magnetic moment that is 44% of the moment in the milled sample, which is consistent with theoretical predictions for ordering. Scanning transmission electron microscopy measurements were performed and the presence of ordered nano-domains in cast/annealed samples throughout the equiatomic NiFeCrCo HEA was identified.

Ferroelectric phenomena in Si-doped HfO2 thin films with TiN and Ir electrodes

Ferroelectric HfO2 is an attractive candidate for future ferroelectric random access memory devices due to its compatibility with the complementary metal-oxide-semiconductor process, conformal deposition, and scaling ability. Crystallization of HfO2 with different dopants and annealing conditions can produce the stabilization of the monoclinic, tetragonal, cubic, or orthorhombic crystal phases. In this work, the authors observe ferroelectric behavior in Si-doped hafnium oxide with TiN and Ir electrodes. Atomic layer deposited 10 nm HfO2 capacitors doped with varying concentrations of SiO2 have been fabricated in the metal–ferroelectric–insulator–semiconductor (MFIS) structure. The ferroelectric characteristics of thin film HfO2 are compared in the MFIS and metal–ferroelectric–metal configurations. Post-metallization anneals were applied to all thin film ferroelectric HfO2 capacitors, resulting in a remanent polarization of up to 22 μC/cm2 and a range of observed coercive voltages, emphasizing the importan...

Atom column indexing: atomic resolution image analysis through a matrix representation.

Here, we report the development of an approach to map atomic resolution images into a convenient matrix representation. Through the combination of two-dimensional Gaussian fitting and the projective standard deviation, atom column locations are projected onto two noncollinear reference lattice vectors that are used to assign each a unique (i, j) matrix index. By doing so, straightforward atomic resolution image analysis becomes possible. Using practical examples, we demonstrate that the matrix representation greatly simplifies categorizing atom columns to different sublattices. This enables a myriad of direct analyses, such as mapping atom column properties and correlating long-range atom column pairs. MATLAB source code can be downloaded from https://github.com/subangstrom/aci.

Detector non-uniformity in scanning transmission electron microscopy.

A non-uniform response across scanning transmission electron microscope annular detectors has been found experimentally, but is seldom incorporated into simulations. Through case study simulations, we establish the nature and scale of the discrepancies which may arise from failing to account for detector non-uniformity. If standard detectors are used at long camera lengths such that the detector is within or near to the bright field region, we find errors in contrast of the order of 10%, sufficiently small for qualitative work but non-trivial as experiments become more quantitative. In cases where the detector has been characterized in advance, we discuss the detector response normalization and how it may be incorporated in simulations.

Quantitative atomic resolution elemental mapping via absolute-scale energy dispersive X-ray spectroscopy.

Quantitative agreement on an absolute scale is demonstrated between experiment and simulation for two-dimensional, atomic-resolution elemental mapping via energy dispersive X-ray spectroscopy. This requires all experimental parameters to be carefully characterized. The agreement is good, but some discrepancies remain. The most likely contributing factors are identified and discussed. Previous predictions that increasing the probe forming aperture helps to suppress the channelling enhancement in the average signal are confirmed experimentally. It is emphasized that simple column-by-column analysis requires a choice of sample thickness that compromises between being thick enough to yield a good signal-to-noise ratio while being thin enough that the overwhelming majority of the EDX signal derives from the column on which the probe is placed, despite strong electron scattering effects.

Al-doped HfO2/In0.53Ga0.47As metal-oxide-semiconductor capacitors

Hafnium oxide gate dielectrics doped with a one to two percent of aluminum are grown on In0.53Ga0.47As channels by codeposition of trimethylaluminum TMA and hafnium tertbutoxide HTB. It is shown that the addition of TMA during growth allows for smooth, amorphous films that can be scaled to 5 nm physical thickness. Metal-oxide-semiconductor capacitors MOSCAPs with this dielectric have an equivalent oxide thickness of 1 nm, show an unpinned, efficient Fermi level movement and lower interface trap densities than MOSCAPs with HfO2 dielectrics grown by sequential TMA/HTB deposition.

Accurate Nanoscale Crystallography in Real-Space Using Scanning Transmission Electron Microscopy

Here, we report reproducible and accurate measurement of crystallographic parameters using scanning transmission electron microscopy. This is made possible by removing drift and residual scan distortion. We demonstrate real-space lattice parameter measurements with <0.1% error for complex-layered chalcogenides Bi2Te3, Bi2Se3, and a Bi2Te2.7Se0.3 nanostructured alloy. Pairing the technique with atomic resolution spectroscopy, we connect local structure with chemistry and bonding. Combining these results with density functional theory, we show that the incorporation of Se into Bi2Te3 causes charge redistribution that anomalously increases the van der Waals gap between building blocks of the layered structure. The results show that atomic resolution imaging with electrons can accurately and robustly quantify crystallography at the nanoscale.