journal article·2022-05-11Open access

Low-energy electronic structure of perovskite and Ruddlesden-Popper semiconductors in the Ba-Zr-S system probed by bond-selective polarized x-ray absorption spectroscopy, infrared reflectivity, and Raman scattering

Kevin Ye, Nathan Z. Koocher, Stephen Filippone, Shanyuan Niu, Boyang Zhao, Matthew Yeung, Sharon Bone, Adam J. Robinson, Patrick Vora, André Schleife, Long Ju, Alexey Boubnov, James M. Rondinelli, Jayakanth Ravichandran, R. Jaramillo

Physical Review B· Volume 105· Issue 19

Abstract

Chalcogenides in perovskite and the related layered Ruddlesden-Popper crystal structures (chalcogenide perovskites for brevity) are an exciting family of semiconductors but remain experimentally little studied. Chalcogenide perovskites share crystal structures and some physical properties with ionic compounds such as oxide and halide perovskites, but the metal-chalcogen bonds responsible for semiconducting behavior are substantially more covalent than in these more-studied perovskites. Here, we use complementary experimental and theoretical methods to study how the mixed ionic-covalent Zr-S bonds support the electronic structure and physical properties of perovskite ${\mathrm{BaZrS}}3$ and Ruddlesden-Popper ${\mathrm{Ba}}3{\mathrm{Zr}}2{\mathrm{S}}7$. We apply theoretical methods to assign features of experimentally measured x-ray absorption spectroscopy (XAS) to particular orbital transitions, enabling a clear physical interpretation of angle-dependent, polarized XAS data measured on single-crystal samples, and an atomistic view of the covalent bonding network that facilitates charge transport. Polarized Raman measurements identify signatures of crystalline anisotropy in ${\mathrm{Ba}}3{\mathrm{Zr}}2{\mathrm{S}}7$ and enable the first assignments of mode symmetry in this material. Infrared reflectivity reveals electronic transport properties that augur well for the use of chalcogenide perovskites in optoelectronic and energy-conversion technologies.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Perovskite Materials and Applications · Advanced Thermoelectric Materials and Devices · Chalcogenide Semiconductor Thin Films

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA

Mork Family Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089, USA

Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

Department of Physics and Astronomy and Quantum Science and Engineering Center, George Mason University, Fairfax, Virginia 22030, USA

Department of Materials Science and Engineering, Materials Research Laboratory, and National Center for Supercomputing Applications, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

Institute of Nanotechnology, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen 76344, Germany

Funding

National Science Foundation · Army Research Office · U.S. Department of Energy

References (41)

Show source-provided references
1. 10.1016/j.nanoen.2021.10595910.1016/j.nanoen.2021.105959 ↗
2. 10.1021/acs.jpclett.1c0017710.1021/acs.jpclett.1c00177 ↗
3. 10.1002/adfm.20200138710.1002/adfm.202001387 ↗
4. 10.1016/j.nanoen.2019.10431710.1016/j.nanoen.2019.104317 ↗
5. 10.1021/acsaem.9b0242810.1021/acsaem.9b02428 ↗
6. 10.1002/solr.20190055510.1002/solr.201900555 ↗
7. 10.1021/jacs.8b1362210.1021/jacs.8b13622 ↗
8. 10.1021/acs.chemmater.8b0170710.1021/acs.chemmater.8b01707 ↗
9. 10.1002/adma.20160473310.1002/adma.201604733 ↗
10. 10.1103/PhysRevMaterials.3.10160110.1103/PhysRevMaterials.3.101601 ↗
11. 10.1557/jmr.2018.41910.1557/jmr.2018.419 ↗
12. 10.1039/D0NR08078K10.1039/D0NR08078K ↗
13. 10.1063/1.512479510.1063/1.5124795 ↗
14. 10.1103/PhysRevMaterials.4.09160110.1103/PhysRevMaterials.4.091601 ↗
15. 10.1021/acs.chemmater.1c0220210.1021/acs.chemmater.1c02202 ↗
16. 10.1002/adfm.20210556310.1002/adfm.202105563 ↗
17. 10.1557/jmr.2019.34810.1557/jmr.2019.348 ↗
18. 10.1107/S090904950501271910.1107/S0909049505012719 ↗
19. 10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
20. 10.1103/PhysRevB.59.175810.1103/PhysRevB.59.1758 ↗
21. 10.1103/PhysRevLett.100.13640610.1103/PhysRevLett.100.136406 ↗
22. 10.1103/PhysRevB.98.23520510.1103/PhysRevB.98.235205 ↗
23. 10.1103/PhysRevB.73.04511210.1103/PhysRevB.73.045112 ↗
24. 10.1103/PhysRevMaterials.2.10540610.1103/PhysRevMaterials.2.105406 ↗
25. 10.1016/j.scriptamat.2015.07.02110.1016/j.scriptamat.2015.07.021 ↗
26. 10.1103/PhysRevB.89.04140710.1103/PhysRevB.89.041407 ↗
27. 10.1103/PhysRevB.91.04111610.1103/PhysRevB.91.041116 ↗
28. 10.1088/0953-8984/21/34/34550110.1088/0953-8984/21/34/345501 ↗
29. 10.1021/acs.jctc.5b0032710.1021/acs.jctc.5b00327 ↗
30. 10.1088/0953-8984/15/45/01410.1088/0953-8984/15/45/014 ↗
31. 10.1021/jp410644j10.1021/jp410644j ↗
32. K. W. Böer · 2014
33. 10.1063/1.506180910.1063/1.5061809 ↗
34. 10.1016/0025-5408(93)90132-W10.1016/0025-5408(93)90132-W ↗
35. 10.1524/zkri.2006.221.1.1510.1524/zkri.2006.221.1.15 ↗
36. 10.1107/S010876730504028610.1107/S0108767305040286 ↗
37. 10.1038/s41578-021-00289-w10.1038/s41578-021-00289-w ↗
38. 10.1016/0079-6786(71)90018-510.1016/0079-6786(71)90018-5 ↗
39. 10.1038/nphys290710.1038/nphys2907 ↗
40. 10.1103/PhysRevResearch.1.03313810.1103/PhysRevResearch.1.033138 ↗
41. 10.1103/PhysRevB.54.70010.1103/PhysRevB.54.700 ↗