Spatially controlled two-dimensional heterostructures via solution-phase growth

The research in two-dimensional (2D) materials, such as graphene, transition metal dichalcogenides (TMDs) and black phosphorus, has been further flourished with the recent emergence of heterostructures composed of dissimilar 2D materials. The interfacing/coupling between different constituent components in a heterostructure has given rise to interesting phenomena and useful properties. For example, depending on the type of 2D materials, the distance and the kind of bonding between them, as well as the crystalline property of the hetero-interface, the interface may provide charge traps, exciton recombination centers, or bridges for effective charge/energy transfer. It has also been found that the spatial arrangement in addition to the composition of the constituents is an important factor influencing the overall properties of the heterostructures. Although many methods, such as dry transfer and vapor-phased growth are able to yield heterostructures from pristine or highly crystalline 2D crystals with spatial control, such as vertical heterostructures and lateral heterostructures, these methods are generally not scalable, which has restricted the use of the obtained heterostructures mostly to fundamental studies. The solution-phased synthesis methods, such as solvothermal/hydrothermal synthesis, electrochemical deposition and hot-injection method, may be more suitable for mass production of functional heterostructures despite the relatively low product quality. In the past couple of years, a diverse kinds of hetero/hybrid structures of 2D materials have been prepared successfully in wet-chemical processes. However, precise control over the geometric arrangement of the constituent components has been challenging in solution. Currently, four types of heterostructures including 2D crystals grown on a larger 2D template, vertical heterostructures, lateral heterostructures, and core-shell heterostructures have been prepared in solution. For the first type, flexible 2D nanosheets such as graphene and monolayer TMDs are used as synthesis templates to support the nucleation and growth of other 2D crystals. For vertical heterostructures, relatively rigid nanoplates are used to allow continuous deposition of 2D layers of other materials to form sandwich-like structures. The formation of lateral heterostructures requires edge growth on existing 2D materials without basal deposition, and therefore other methods such as cation exchange can be used as alternative routes. The preparation of core-shell 2D heterostructures generally involves both epitaxial edge growth and basal deposition and has been realized in both metallic and semiconductor structures. In this review, these kinds of heterostructures based on 2D materials will be discussed in terms of their synthesis methods, properties and possible applications. In addition, we will discuss the challenges and possible opportunities in this research direction.