Yongsoo Yang

Three-dimensional coordinates of individual atoms in materials revealed by electron tomography

Crystallography, the primary method for determining the 3D atomic positions in crystals, has been fundamental to the development of many fields of science. However, the atomic positions obtained from crystallography represent a global average of many unit cells in a crystal. Here, we report, for the first time, the determination of the 3D coordinates of thousands of individual atoms and a point defect in a material by electron tomography with a precision of ∼19 pm, where the crystallinity of the material is not assumed. From the coordinates of these individual atoms, we measure the atomic displacement field and the full strain tensor with a 3D resolution of ∼1 nm(3) and a precision of ∼10(-3), which are further verified by density functional theory calculations and molecular dynamics simulations. The ability to precisely localize the 3D coordinates of individual atoms in materials without assuming crystallinity is expected to find important applications in materials science, nanoscience, physics, chemistry and biology.

Deciphering chemical order/disorder and material properties at the single-atom level

Perfect crystals are rare in nature. Real materials often contain crystal defects and chemical order/disorder such as grain boundaries, dislocations, interfaces, surface reconstructions and point defects. Such disruption in periodicity strongly affects material properties and functionality. Despite rapid development of quantitative material characterization methods, correlating three-dimensional (3D) atomic arrangements of chemical order/disorder and crystal defects with material properties remains a challenge. On a parallel front, quantum mechanics calculations such as density functional theory (DFT) have progressed from the modelling of ideal bulk systems to modelling ‘real’ materials with dopants, dislocations, grain boundaries and interfaces; but these calculations rely heavily on average atomic models extracted from crystallography. To improve the predictive power of first-principles calculations, there is a pressing need to use atomic coordinates of real systems beyond average crystallographic measurements. Here we determine the 3D coordinates of 6,569 iron and 16,627 platinum atoms in an iron-platinum nanoparticle, and correlate chemical order/disorder and crystal defects with material properties at the single-atom level. We identify rich structural variety with unprecedented 3D detail including atomic composition, grain boundaries, anti-phase boundaries, anti-site point defects and swap defects. We show that the experimentally measured coordinates and chemical species with 22 picometre precision can be used as direct input for DFT calculations of material properties such as atomic spin and orbital magnetic moments and local magnetocrystalline anisotropy. This work combines 3D atomic structure determination of crystal defects with DFT calculations, which is expected to advance our understanding of structure–property relationships at the fundamental level.

Determination of the intrinsic ferroelectric polarization in orthorhombic HoMnO3

Whether or not a large ferroelectric polarization P exists in the orthorhombic HoMnO3 with E-type antiferromagnetic spin ordering remains one of the unresolved, challenging issues in the physics of multiferroics. The issue is closely linked to an intriguing experimental difficulty in determining the P of polycrystalline specimens, namely that conventional pyroelectric current measurements performed after a poling procedure under high dc electric fields are subject to large errors due to the problems caused by leakage currents or space charges. To overcome the difficulty, we employed the positive-up negative-down (PUND) method, which uses successively the two positive and two negative electrical pulses, to directly measure electrical hysteresis loops in several polycrystalline HoMnO3 specimens below their Neel temperatures. We found that all the HoMnO3 samples had similar remnant polarization Pr values at each temperature, regardless of their variation in resistivity, dielectric constant and pyroelectric current levels. Moreover, the Pr value of 0.07µCcm 2 at 6K is consistent with the P value obtained from the pyroelectric current measurement performed after a short pulse poling. Our findings suggest that the intrinsic P of polycrystalline HoMnO3 can be determined through the PUND method and P at 0K may reach 0.24µCcm 2 in a single crystalline specimen. This P value is still much smaller than the theoretically predicted one but is one of the largest observed in magnetism induced ferroelectrics.

Intrinsic ferroelectric polarization of orthorhombic manganites with E-type spin order

By directly measuring electrical hysteresis loops using the Positive-Up Negative-Down (PUND) method, we determined accurately the remanent ferroelectric polarization P-r of orthorhombic RMnO3 (R = Ho, Tm, Yb, and Lu) compounds below their E-type spin ordering temperatures. We found that LuMnO3 has the largest P-r of 0.17 mu C/cm(2) at 6 K in the series, the value of which allows us to predict that its single-crystal form can produce a P-r of at least 0.6 mu C/cm(2) at 0 K. Furthermore, at a fixed temperature, P-r decreases systematically with increasing rare earth ion radius from R = Lu to Ho, exhibiting a strong correlation with the variation of the in-plane Mn-O-Mn bond angle and Mn-O distances. Our experimental results suggest that the contribution of the Mn t(2g) orbitals may dominate the ferroelectric polarization.

Nanomaterial datasets to advance tomography in scanning transmission electron microscopy

Electron tomography in materials science has flourished with the demand to characterize nanoscale materials in three dimensions (3D). Access to experimental data is vital for developing and validating reconstruction methods that improve resolution and reduce radiation dose requirements. This work presents five high-quality scanning transmission electron microscope (STEM) tomography datasets in order to address the critical need for open access data in this field. The datasets represent the current limits of experimental technique, are of high quality, and contain materials with structural complexity. Included are tomographic series of a hyperbranched Co2P nanocrystal, platinum nanoparticles on a carbon nanofibre imaged over the complete 180° tilt range, a platinum nanoparticle and a tungsten needle both imaged at atomic resolution by equal slope tomography, and a through-focal tilt series of PtCu nanoparticles. A volumetric reconstruction from every dataset is provided for comparison and development of post-processing and visualization techniques. Researchers interested in creating novel data processing and reconstruction algorithms will now have access to state of the art experimental test data.

Untilting BiFeO3: The influence of substrate boundary conditions in ultra-thin BiFeO3 on SrTiO3

We report on the role of oxygen octahedral tilting in the monoclinic-to-tetragonal phase transition in ultra-thin BiFeO3 films grown on (001) SrTiO3 substrates. Reciprocal space maps clearly show the disappearance of the integer-order Bragg peak splitting associated with the monoclinic phase when the film thickness decreases below 20 unit cells. This monoclinic-to-tetragonal transition is accompanied by the evolution of the half-order diffraction peaks, which reflects untilting of the oxygen octahedra around the [110] axis, proving that the octahedral tilting is closely correlated with the transition. This structural change is thickness-dependent, and different from a strain-induced transition in the conventional sense.

Origin of stress and enhanced carrier transport in solution-cast organic semiconductor films

Molecular packing in laterally directed solution deposition is a strong function of variables such as printing speed, substrate temperature, and solution concentration. Knowledge of the ordering mechanisms impacts on the development of new processes and materials for improved electronic devices. Here, we present real-time synchrotron x-ray scattering results combined with optical video microscopy, revealing the stages of ordering during the deposition of organic thin films via hollow capillary writing. Limited long range ordering is observed during the initial crystallization, but it gradually develops over 3–4 s for a range of deposition conditions. Buckling of thin films is typically observed for deposition above room temperature. We infer that compressive stress originates from thermal transients related to solvent evaporation on timescales similar to the development of long range ordering. Under optimized conditions, elimination of cracks and other structural defects significantly improves the average...

GENFIRE: A generalized Fourier iterative reconstruction algorithm for high-resolution 3D imaging

Tomography has made a radical impact on diverse fields ranging from the study of 3D atomic arrangements in matter to the study of human health in medicine. Despite its very diverse applications, the core of tomography remains the same, that is, a mathematical method must be implemented to reconstruct the 3D structure of an object from a number of 2D projections. Here, we present the mathematical implementation of a tomographic algorithm, termed GENeralized Fourier Iterative REconstruction (GENFIRE), for high-resolution 3D reconstruction from a limited number of 2D projections. GENFIRE first assembles a 3D Fourier grid with oversampling and then iterates between real and reciprocal space to search for a global solution that is concurrently consistent with the measured data and general physical constraints. The algorithm requires minimal human intervention and also incorporates angular refinement to reduce the tilt angle error. We demonstrate that GENFIRE can produce superior results relative to several other popular tomographic reconstruction techniques through numerical simulations and by experimentally reconstructing the 3D structure of a porous material and a frozen-hydrated marine cyanobacterium. Equipped with a graphical user interface, GENFIRE is freely available from our website and is expected to find broad applications across different disciplines.

Understanding strain-induced phase transformations in BiFeO3 thin films

Experiments demonstrate that under large epitaxial strain a coexisting striped phase emerges in BiFeO3 thin films, which comprises a tetragonal‐like (T′) and an intermediate S′ polymorph. It exhibits a relatively large piezoelectric response when switching between the coexisting phase and a uniform T′ phase. This strain‐induced phase transformation is investigated through a synergistic combination of first‐principles theory and experiments. The results show that the S′ phase is energetically very close to the T′ phase, but is structurally similar to the bulk rhombohedral (R) phase. By fully characterizing the intermediate S′ polymorph, it is demonstrated that the flat energy landscape resulting in the absence of an energy barrier between the T′ and S′ phases fosters the above‐mentioned reversible phase transformation. This ability to readily transform between the S′ and T′ polymorphs, which have very different octahedral rotation patterns and c/a ratios, is crucial to the enhanced piezoelectricity in strained BiFeO3 films. Additionally, a blueshift in the band gap when moving from R to S′ to T′ is observed. These results emphasize the importance of strain engineering for tuning electromechanical responses or, creating unique energy harvesting photonic structures, in oxide thin film architectures.

Growth and modelling of spherical crystalline morphologies of molecular materials

Crystalline, yet smooth, sphere-like morphologies of small molecular compounds are desirable in a wide range of applications but are very challenging to obtain using common growth techniques, where either amorphous films or faceted crystallites are the norm. Here we show solvent-free, guard flow-assisted organic vapour jet printing of non-faceted, crystalline microspheroids of archetypal small molecular materials used in organic electronic applications. We demonstrate how process parameters control the size distribution of the spheroids and propose an analytical model and a phase diagram predicting the surface morphology evolution of different molecules based on processing conditions, coupled with the thermophysical and mechanical properties of the molecules. This experimental approach opens a path for exciting applications of small molecular organic compounds in optical coatings, textured surfaces with controlled wettability, pharmaceutical and food substance printing and others, where thick organic films and particles with high surface area are needed.