Probing Magnetic Ordering in Air Stable Iron‐Rich Van der Waals Minerals

Abstract

Magnetic monolayers show great promise for future applications in nanoelectronics, data storage, and sensing. The research in magnetic two‐dimensional (2D) materials focuses on synthetic iodides and tellurides, which suffer from a lack of ambient stability. So far, naturally occurring layered magnetic materials have been overlooked. These minerals offer a unique opportunity to explore complex air‐stable layered systems with high concentration of magnetic ions. Magnetic ordering in iron‐rich phyllosilicates is demonstrated, focusing on minnesotaite, annite, and biotite. These naturally occurring layered materials integrate local moment baring ions of iron via magnesium/aluminum substitution in their octahedral sites. Self‐inherent capping by silicate/aluminate tetrahedral groups enables air stability of ultra‐thin layers. Their structure and iron oxidation states are determined via Raman and X‐ray spectroscopies. Superconducting quantum interference device magnetometry measurements are performed to examine the magnetic ordering. Paramagnetic or superparamagnetic characteristics at room temperature are observed. Below 40 K ferrimagnetic or antiferromagnetic ordering occurs. In‐field magnetic force microscopy on exfoliated flakes confirms that the paramagnetic response at room temperature persists down to monolayers. Further, a correlation between the mixture of the oxidation states of iron and the critical ordering temperature is established, indicating a path to design materials with higher critical temperatures via oxidation state engineering.