Manipulation of localized excitons in CrPS₄ by temperature and magnetic field

Layered van der Waals magnetic semiconductors provide a versatile platform for exploring excitonic phenomena intertwined with spin and lattice degrees of freedom, enabling excitons to act as sensitive probes of magnetic order. CrPS₄ is a layered antiferromagnetic semiconductor that hosts rich excitonic features whose microscopic origin and connection to magnetic ordering remain incompletely understood. Here, we investigate the electronic and excitonic properties of bulk CrPS₄ using a combination of many-body perturbation theory, dynamical mean-field theory, and photoluminescence-based experiments. Our calculations establish CrPS₄ as a direct-gap semiconductor with a bandgap of 2.48 eV in the antiferromagnetic phase. Several subbandgap excitonic transitions are predicted by theory, comprising multiple spin-allowed excitons and an additional spin-flip excitation, predominantly localized on the Cr³⁺ ions. Temperature- and magnetic-field-dependent optical measurements reveal thermally driven exciton redistribution among localized states and identify characteristic energy shifts that provide clear optical signatures of magnetic phase transitions in CrPS₄. These results provide insights into the excitonic transitions of antiferromagnets and suggest potential routes for all-optical sensing and light-driven control of their magnetic order.