Two-dimensional materials from layered van der Waals (vdW) crystals hold great promise for electronic, optoelectronic, and quantum devices, but technological implementation will be hampered by the lack of high-throughput techniques for exfoliating single-crystal monolayers with sufficient size and high quality. Here, we report a facile method to disassemble vdW single crystals layer by layer into monolayers with near-unity yield and with dimensions limited only by bulk crystal sizes. The macroscopic monolayers are comparable in quality to microscopic monolayers from conventional Scotch tape exfoliation. The monolayers can be assembled into macroscopic artificial structures, including transition metal dichalcogenide multilayers with broken inversion symmetry and substantially enhanced nonlinear optical response. This approach takes us one step closer to mass production of macroscopic monolayers and bulk-like artificial materials with controllable properties.

Colloidal nanoplatelets (NPLs) have shown great potentials for lasing applications due to their sharp absorption and emission peaks, large absorption cross sections, large radiative decay rates, and long multiexciton lifetimes. How multiexciton lifetimes depend on material dimensions remains unknown in two-dimensional (2D) materials, despite being a key parameter affecting optical gain threshold and many other properties. Herein, we report a study of room-temperature biexciton Auger recombination time of CdSe NPLs as a function of thickness and lateral area. Comparison of all NPLs shows that the biexciton lifetime does not increase linearly with volume, unlike previously reported "universal volume scaling law" for quantum dots. For NPLs of the same thickness (∼1.8 nm), the biexciton lifetime increase linearly with their lateral area (from 143.7 ± 12.6 to 320.1 ± 17.1 ps when the area increases from 90.5 ± 21.4 to 234.2 ± 41.9 nm). The biexciton lifetime depends linearly on (1/E) (E is the electron confinement energy) or nearly linearly on d (d is NPL thickness). The observed dependence is consistent with a model in which biexciton Auger recombination rate scales with the product of exciton binary collision frequency and Auger recombination probability in biexciton complexes. The linear increase of Auger lifetimes with NPL lateral areas reflects a 1/area dependence of the binary collision frequency for 2D excitons and the thickness-dependent biexciton Auger recombination time is attributed to its strong dependence on the degree of quantum confinement. This model may be generally applicable to exciton Auger recombination in quantum confined 1D and 2D nanomaterials.

Colloidal cadmium chalcogenide nanosheets with atomically precise thickness of a few atomic layers and size of 10-100 nm are two-dimensional (2D) quantum well materials with strong and precise quantum confinement in the thickness direction. Despite their many advantageous properties, excitons in these and other 2D metal chalcogenide materials are short-lived due to large radiative and nonradiative recombination rates, hindering their applications as light harvesting and charge separation/transport materials for solar energy conversion. We showed that these problems could be overcome in type-II CdSe/CdTe core/crown heteronanosheets (with CdTe crown laterally extending on the CdSe nanosheet core). Photoluminesence excitation measurement revealed that nearly all excitons generated in the CdSe and CdTe domains localized to the CdSe/CdTe interface to form long-lived charge transfer excitons (with electrons in the CdSe domain and hole in the CdTe domain). By ultrafast transient absorption spectroscopy, we showed that the efficient exciton localization efficiency could be attributed to ultrafast exciton localization (0.64 ± 0.07 ps), which was facilitated by large in-plane exciton mobility in these 2D materials and competed effectively with exiton trapping at the CdSe or CdTe domains. The spatial separation of electrons and holes across the CdSe/CdTe heterojunction effectively suppressed radiative and nonradiative recombination processes, leading to a long-lived charge transfer exciton state with a half-life of ∼ 41.7 ± 2.5 ns, ∼ 30 times longer than core-only CdSe nanosheets.

Large in-plane exciton mobility in CdSe nanosheets leads to ultrafast exciton quenching by energy transfer to Pt.