Designable excitonic effects in van der Waals artificial crystals with exponentially growing thickness

When disassembled into monolayers from their bulk crystals, two-dimensional (2D) transition metal dichalcogenides (TMDCs) exhibit exotic optical properties dominated by strong excitonic effects. Reassembling 2D TMDC layers to build bulk excitonic crystals can significantly boost their optical performance and introduce emerging functionalities toward optoelectronic and valleytronic applications. However, maintaining or manipulating 2D excitonic properties in bulk structures or superlattices is challenging. Herein, we developed a method to precisely construct m∙2N-layer artificial excitonic crystals with only a number N of stacking operations (m denotes the layer number of the initial material unit), referred to as the “2^N method”. We successfully fabricated a millimeter-scale weakly coupled 16-layer MoS2 single crystal with zero interlayer twist angle, which retains monolayer-like exciton properties and exhibits remarkable enhancements up to 643% and 646% in their absorption and photoluminescence (PL) features, respectively. Moreover, we created a WSe2/(MoS2/WSe2)3/MoS2 superlattice starting from monolayer WSe2 and MoS2, which demonstrated an intensity increase of up to 400% in quadrupolar interlayer exciton (IX) emission as compared to dipolar IXs in its bilayer counterpart. Our work shows a promising approach for the design and bottom-up fabrication of excitonic crystals, promoting the exploration of excitonic physics in complex van der Waals (vdW) structures and their applications in optoelectronic devices. The fabrication of artificial crystals by reassembling monolayer semiconductors enables on-demand engineering of their excitonic properties. Here, the authors report an efficient stacking method to fabricate millimetre-scale van der Waals homo-/hetero-crystals, demonstrating enhanced monolayer-like photoluminescence emission and quadrupolar interlayer exciton emission.