Tailoring magnetic ordering in solid-state materials is essential for emerging spintronics1,2. However, substitutional lattice doping in magnetic semiconductors is often constrained by the low solubility of magnetic elements3-5, limiting the maximum achievable doping concentration (for example, less than 5%) and ferromagnetic ordering temperature6. The intercalation of magnetic elements in layered two-dimensional atomic crystals (2DACs) without breaking in-plane covalent bonds offers an alternative approach to incorporate a much higher concentration of magnetic atoms (for example, up to 50%) beyond the typical solubility limit. However, commonly used chemical and electrochemical intercalation methods are largely confined to a few isolated examples so far. Here we report a general two-step intercalation and cation-exchange strategy to produce a library of highly ordered magnetic intercalation superlattices (MISLs) with tunable magnetic ordering. Monovalent transition-metal cations Cu+ and Ag+, divalent magnetic cations Mn2+, Fe2+, Co2+ and Ni2+, and trivalent rare-earth cations Eu3+ and Gd3+ have been successfully incorporated into group-VIB 2DACs, including MoS2, MoSe2, MoTe2, WS2, WSe2 and WTe2, and group-IVB, -VB, -IIIA, -IVA and -VA 2DACs, including TiS2, NbS2, NbSe2, TaS2, In2Se3, SnSe2, Bi2Se3 and Bi2Te3. We show that these MISLs can be prepared with tunable concentrations of magnetic intercalants, enabling tailored magnetic ordering across a diverse array of functional 2DACs, including semiconductors, topological insulators, and superconductors. This work establishes a versatile material platform for both fundamental investigations and spintronics applications.

California NanoSystems Institute University of California Los Angeles Los Angeles CA USA

Department of Chemistry and Biochemistry University of California Los Angeles Los Angeles CA USA

Department of Chemistry University of Wisconsin Madison Madison WI USA

Department of Inorganic Chemistry University of Chemistry and Technology Prague Prague Czech Republic

Department of Materials Science and Engineering University of California Irvine Irvine CA USA

Department of Materials Science and Engineering University of California Los Angeles Los Angeles CA USA

Department of Materials Science and Engineering University of Wisconsin Madison Madison WI USA

Department of Physics and Astronomy University of California Irvine Irvine CA USA

Department of Physics University of Wisconsin Madison Madison WI USA

Irvine Materials Research Institute University of California Irvine Irvine CA USA

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