Person:

Larson, Daniel

Molecular-scale manipulation of electronic/ionic charge accumulation in materials is a preeminent challenge, particularly in electrochemical energy storage. Layered van der Waals (vdW) crystals exemplify a diverse family of materials that permit ions to reversibly associate with a host atomic lattice by intercalation into interlamellar gaps. Motivated principally by the search for high-capacity battery anodes, ion intercalation in composite materials is a subject of intense study. Yet the precise role and ability of heterolayers to modify intercalation reactions remains elusive. Previous studies of vdW hybrids represented ensemble measurements at macroscopic films/powders, which do not permit the isolation and investigation of the chemistry at individual 2-dimensional (2D) interfaces. Here, we demonstrate the intercalation of lithium at the level of individual atomic interfaces of dissimilar vdW layers. Electrochemical devices based on vdW heterostructures comprised of deterministically stacked hexagonal boron nitride, graphene (G) and molybdenum dichalcogenide (MoX2; X = S, Se) layers are fabricated, enabling the direct resolution of intermediate stages in the intercalation of discrete heterointerfaces and the extent of charge transfer to individual layers. Operando magnetoresistance and optical spectroscopy coupled with low-temperature quantum magneto-oscillation measurements show that the creation of intimate vdW heterointerfaces between G and MoX2 engenders over 10-fold accumulation of charge in MoX2 compared to MoX2/MoX2 homointerfaces, while enforcing a more negative intercalation potential than that of bulk MoX2 by at least 0.5 V. Beyond energy storage, our new combined experimental and computational methodology to manipulate and characterize the electrochemical behavior of layered systems opens up new pathways to control the charge density in 2D (opto)electronic devices.

Following the recent isolation of monolayer CrI3 [1], there has been a surge of new two-dimensional van der Waals magnetic materials [2-12], whose incorporation in van der Waals heterostructures offers a new platform for spintronics [5-9], proximity magnetism [13], and quantum spin liquids [14]. A primary question in this burgeoning field is how exfoliating crystals to the few-layer limit influences their magnetism. Studies on CrI3 have shown a different magnetic ground state for ultrathin exfoliated films [1,5,6] but the origin is not yet understood. Here, we use electron tunneling through few-layer crystals of the layered antiferromagnetic insulator CrCl3 to probe its magnetic order, finding a ten-fold enhancement in the interlayer exchange compared to bulk crystals. Moreover, temperature- and polarization-dependent Raman spectroscopy reveal that the crystallographic phase transition of bulk crystals does not occur in exfoliated films. This results in a different low temperature stacking order and, we hypothesize, increased interlayer exchange. Our study provides new insight into the connection between stacking order and interlayer interactions in novel two-dimensional magnets, which may be relevant for correlating stacking faults and mechanical deformations with the magnetic ground states of other more exotic layered magnets, such as RuCl3 [14].

Following the recent isolation of monolayer CrI3, many more two-dimensional van der Waals magnetic materials have been isolated. Their incorporation in van der Waals heterostructures offers a new platform for spintronics proximity magnetism and quantum spin liquids. A primary question in this field is how exfoliating crystals to the few-layer limit influences their magnetism. Studies of CrI3 have shown a different magnetic ground state for ultrathin exfoliated films compared with the bulk, but the origin is not yet understood. Here, we use electron tunnelling through few-layer crystals of the layered antiferromagnetic insulator CrCl3 to probe its magnetic order and find a tenfold enhancement of the interlayer exchange compared with bulk crystals. Moreover, temperature- and polarization-dependent Raman spectroscopy reveals that the crystallographic phase transition of bulk crystals does not occur in exfoliated films. This results in a different low-temperature stacking order and, we hypothesize, increased interlayer exchange. Our study provides insight into the connection between stacking order and interlayer interactions in two-dimensional magnets, which may be relevant for correlating stacking faults and mechanical deformations with the magnetic ground states of other more exotic layered magnets such as RuCl3.