Linear Magnetoelectric Phase in Ultrathin MnPS3 Probed by Optical Second Harmonic Generation

The transition metal thiophosphates M PS₃ (M =Mn , Fe, Ni) are a class of van der Waals stacked insulating antiferromagnets that can be exfoliated down to the ultrathin limit. MnPS₃ is particularly interesting because its Néel ordered state breaks both spatial-inversion and time-reversal symmetries, allowing for a linear magnetoelectric phase that is rare among van der Waals materials. However, it is unknown whether this unique magnetic structure of bulk MnPS₃ remains stable in the ultrathin limit. Using optical second harmonic generation rotational anisotropy, we show that long-range linear magnetoelectric type Néel order in MnPS₃ persists down to at least 5.3 nm thickness. However an unusual mirror symmetry breaking develops in ultrathin samples on SiO₂ substrates that is absent in bulk materials, which is likely related to substrate induced strain.