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

• Published in: Nature (London) Vol. 542; no. 7639; pp. 75 - 79
• Main Authors: Yang, Yongsoo, Chen, Chien-Chun, Scott, M. C., Ophus, Colin, Xu, Rui, Pryor, Alan, Wu, Li, Sun, Fan, Theis, Wolfgang, Zhou, Jihan, Eisenbach, Markus, Kent, Paul R. C., Sabirianov, Renat F., Zeng, Hao, Ercius, Peter, Miao, Jianwei
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 02.02.2017; Nature Publishing Group
• Subjects: 639/301/357/537; 639/638/298/920; 639/766/119/997; 639/925/930/2735; Anisotropy; ATOMIC AND MOLECULAR PHYSICS; Atoms & subatomic particles; Boundaries; Chemical properties; Chemical speciation; Crystal defects; Crystallography; Crystals; Density functional theory; Humanities and Social Sciences; imaging techniques; Intermetallic compounds; Iron compounds; letter; magnetic materials; magnetic properties and materials; MATERIALS SCIENCE; multidisciplinary; Nanoparticles; Platinum; Platinum compounds; Science; structural properties; Structure
• ISSN: 0028-0836; 1476-4687
• DOI: 10.1038/nature21042

The three-dimensional coordinates of more than 23,000 atoms in an iron-platinum nanoparticle are determined with 22 picometre precision to correlate chemical order/disorder and crystal defects with magnetic properties. Material properties at the single-atom level FePt nanoparticles have practical potential in fields as diverse as catalysis and magnetic storage media. But far from being pristine crystalline materials, these nanoparticles are structurally heterogeneous with grain boundaries and other crystal defects. In this paper, Jianwei Miao and colleagues reveal the complex atomic-scale structure of a single FePt nanoparticle containing more than 22,000 atoms. They do this by generating a high-resolution tomographic tilt series of 68 images of the nanoparticle and reconstructing it using a new algorithm, achieving resolution with 22 picometre precision. The resulting structure reveals the complexity of the nanoparticle, and the chemistry and crystal structure of the grains within the material. When analysing the order/disorder character, the authors find that the grains are more ordered towards the core of the nanoparticle and less ordered towards the surface. They use data from the boundary between two grains to calculate local magnetocrystalline anisotropy energies using density functional theory, revealing how these energies vary across the grain with order parameter and across a grain boundary. 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 1 , 2 , 3 . Such disruption in periodicity strongly affects material properties and functionality 1 , 2 , 3 . Despite rapid development of quantitative material characterization methods 1 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 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 19 , 20 ; 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.