Realizing solution-processed heterostructures is a long-enduring challenge in halide perovskites because of solvent incompatibilities that disrupt the underlying layer. By leveraging the solvent dielectric constant and Gutmann donor number, we could grow phase-pure two-dimensional (2D) halide perovskite stacks of the desired composition, thickness, and bandgap onto 3D perovskites without dissolving the underlying substrate. Characterization reveals a 3D–2D transition region of 20 nanometers mainly determined by the roughness of the bottom 3D layer. Thickness dependence of the 2D perovskite layer reveals the anticipated trends for n-i-p and p-i-n architectures, which is consistent with band alignment and carrier transport limits for 2D perovskites. We measured a photovoltaic efficiency of 24.5%, with exceptional stability ofT₉₉(time required to preserve 99% of initial photovoltaic efficiency) of >2000 hours, implying that the 3D/2D bilayer inherits the intrinsic durability of 2D perovskite without compromising efficiency.

Due to the strong in-plane but weak out-of-plane bonding, it is relatively easy to separate nanosheets of two-dimensional (2D) materials from their respective bulk crystals. This exfoliation of 2D materials can yield large 2D nanosheets, hundreds of micrometers wide, that can be as thin as one or a few atomic layers thick. However, the underlying physical mechanisms unique to each exfoliation technique can produce a wide distribution of defects, yields, functionalization, lateral sizes, and thicknesses, which can be appropriate for specific end applications. The five most commonly used exfoliation techniques include micromechanical cleavage, ultrasonication, shear exfoliation, ball milling, and electrochemical exfoliation. In this review, we present an overview of the field of 2D material exfoliation and the underlying physical mechanisms with emphasis on progress over the last decade. The beneficial characteristics and shortcomings of each exfoliation process are discussed in the context of their functional properties to guide the selection of the best technique for a given application. Furthermore, an analysis of standard applications of exfoliated 2D nanosheets is presented including their use in energy storage, electronics, lubrication, composite, and structural applications. By providing detailed insight into the underlying exfoliation mechanisms along with the advantages and disadvantages of each technique, this review intends to guide the reader toward the appropriate batch-scale exfoliation techniques for a wide variety of industrial applications.