We demonstrate that the intrinsic properties of monolayer graphene allow it to act as a more effective saturable absorber for mode-locking fiber lasers when compared to multilayer graphene. The absorption of monolayer graphene can be saturated at lower excitation intensity compared to multilayer graphene, graphene with wrinkle-like defects, or functionalized graphene. Monolayer graphene has a remarkably large modulation depth of 65.9%, whereas the modulation depth of multilayer graphene is greatly reduced due to nonsaturable absorption and scattering loss. Picosecond ultrafast laser pulses (1.23 ps) can be generated using monolayer graphene as a saturable absorber. Due to the ultrafast relaxation time, larger modulation depth and lower scattering loss of monolayer graphene, it performs better than multilayer graphene in terms of pulse shaping ability, pulse stability, and output energy.

At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe₂, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of ‘design-and-build’ 2D layered heterojunctions for large-scale exploration and applications.