Chemical Nanoanalyses at Grain Boundaries By Joint Use of Scanning Transmission Electron Microscopy and Atom Probe Tomography
Authors: Ohno Yutaka , Inoue Kaihei , Fujiwara Kozo , Kutsukake Kentaro , Deura Momoko , Yonenaga Ichiro , Ebisawa Naoki , Shimizu Yasuo , Inoue Koji , Nagai Yasuyoshi , Yoshida Hideto , Takeda Seiji , Tanaka Shingo , Kohyama Masanori 
Published: February 2020

Polycrystalline materials with grain boundaries (GBs), involving excess free energy because of their structural imperfection, can reduce their energy by the nanoscopic structural changes of the GBs via impurity segregation. Those local changes at GBs can stabilize non-equilibrium nanostructures, resulting in the drastic change in the macroscopic properties of those materials. The mechanism of GB segregation is, however, far from being understood due to difficulties in characterizing both crystallographic and chemical properties of the same GB at atomistic levels. We have therefore developed an analytical method to determine the impurity segregation ability on the same GB at the same nanoscopic location by a joint use of scanning transmission electron microscopy (STEM) and atom probe tomography (APT) combined with ab-initio calculations, and discussed the segregation mechanism in terms of bond distortions at the GB.
In the present work, we examined the GBs in Si ingots used for solar cells. They have serious impacts on the solar cell efficiency via the segregation of detrimental impurity atoms, such as oxygen and transition metals introduced inevitably during crystal growth and cell processing, depending on their structural condition at those GBs. Accordingly, precise understanding of the segregation mechanism of impurity atoms is one important issue to produce cost-effective solar cells by engineering the structural condition of impurity atoms segregating at GBs. Three-dimensional distribution of impurity atoms was systematically determined at the typical large-angle GBs (i.e., Σ3{111}, Σ5{013}, Σ9{221}, Σ9{114}, Σ9{111}/{115}, and Σ27{552}) [1-3] and small-angle GBs [3-5] by APT with a low impurity detection limit (0.01 at.% on a GB plane) simultaneously with a high spatial resolution (about 0.4 nm), and it was correlated with the atomic stresses around the GBs estimated by ab-initio calculations based on atomic-resolution scanning TEM data (for large-angle GBs [2]) and by calculations with the elastic theory based on dark-field TEM data (for small-angle GBs [4]). It was hypothesized that oxygen atoms segregate at the bond-centered positions under tensile stresses above about 2 GPa so as to attain more stable bonding network by reducing the local stresses [6]. The number of segregating atoms per unit GB area (N
GB
) is in proportion to both the number of the stressed positions per unit GB area (n
bc) and the average concentration of oxygen atoms around the GB ([Oi]) with N
GB ~ 50n
bc[Oi]. This indicates that the probability of oxygen atoms at the segregation positions would be, on average, fifty times larger than in bond-centered positions in defect-free regions. This nanoscopic finding may provide a general guidance to control compositions and band structures at GBs via oxygen segregation.
References: [1] Y. Ohno, et al., Appl. Phys. Lett. 103 (2013) 102102; [2] Y. Ohno, et al., Appl. Phys. Lett. 110 (2017) 062105; [3] Y. Ohno, et al., Appl. Phys. Lett. 109 (2016) 142105; [4] Y. Ohno, et al., Appl. Phys. Lett. 106 (2015) 251603; [5] Y. Ohno, et al., Phys. Rev. B 91 (2015) 235315; [6] Y. Ohno, et al., J. Microsc. 268 (2017) 230.
Acknowledgments: This work was supported by “Multicrystalline informatics toward establishment of general grain boundary physics & realization of high-quality silicon ingot with ideal microstructures” in “Revolutional material development by fusion of strong experiments with theory/data science” project in JST/CREST, Grant No. JPMJCR17J1 (2017-2023). STEM and APT were, respectively, performed at ISIR under the Cooperative Research Program of "Network Joint Research Center for Materials and Devices: Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials" and at The Oarai Center under under the Inter-University Cooperative Research Program in IMR.
Figure caption: Analyses of oxygen segregation at large-angle GBs in Si [2]. (a, c) Bonding network and (b, d) distribution of atomic stress P
atomic at (a, b) Σ9{221} and (c, d) Σ9{114} GBs. (e, f) Number of bond-centered positions under a tensile stress P
bc above 1.5 GPa and (g, h) oxygen density across the GB plane for (e, g) Σ9{221} and (f, h) Σ9{114} GBs.

Figure 1