Two-Dimensional Robust Ferromagnetic Semiconductors via Assembly of Magnetic Superatoms [Fe6S8(CN)6]5

Jing Cheng; Qingqing Feng; Xingxing Li; Jinlong Yang

doi:10.1021/acs.jpclett.3c00960

Two-Dimensional Robust Ferromagnetic Semiconductors via Assembly of Magnetic Superatoms [Fe₆S₈(CN)₆]⁵

J Phys Chem Lett. 2023 Jun 1;14(21):5048-5054. doi: 10.1021/acs.jpclett.3c00960. Epub 2023 May 25.

Authors

Jing Cheng^{1

2}, Qingqing Feng^{1

2}, Xingxing Li^{1

2

3

4}, Jinlong Yang^{1

2

3

4}

Affiliations

¹ Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
² Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
³ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
⁴ Hefei National Laboratory, University of Science and Technology of China, Hefei, Anhui 230088, China.

PMID: 37227122
DOI: 10.1021/acs.jpclett.3c00960

Abstract

Cluster-assembled materials are of considerable interest owing to their unique properties and extensive application prospects. Nevertheless, the majority of cluster-assembled materials developed to date are nonmagnetic, limiting their applications in spintronics. Thus, two-dimensional (2D) cluster-assembled sheets with intrinsic ferromagnetism are very desirable. Here, via first-principles calculations, utilizing the recently synthesized magnetic superatomic cluster [Fe₆S₈(CN)₆]^5- as a building block, we design a series of thermodynamically stable 2D nanosheets [NH₄]₃[Fe₆S₈(CN)₆]TM (TM = Cr, Mn, Fe, Co) with robust ferromagnetic ordering (Curie temperatures (T_c) up to 130 K), medium band gaps (from 1.96 to 2.01 eV), and sizable magnetic anisotropy energy (up to 0.58 meV per unit cell). Among these nanosheets, the [NH₄]₃[Fe₆S₈(CN)₆]Cr is a bipolar magnetic semiconductor, whereas the other three ([NH₄]₃[Fe₆S₈(CN)₆]TM (TM = Mn, Fe, Co) are half semiconductors. Additionally, the electronic and magnetic properties of [NH₄]₃[Fe₆S₈(CN)₆]TM (TM = Cr, Mn, Fe, Co) nanosheets can be easily modulated by electron and hole doping via simply controlling the number of ammonium counterions. Furthermore, the Curie temperatures of the 2D nanosheets can be improved to 225 and 327 K by choosing 4d/5d transition metals TM = Ru and Os, respectively.