Printed 2D materials, derived from solution‐processed inks, offer scalable and cost‐effective routes to mechanically flexible optoelectronics. With micrometer‐scale control and broad processing latitude, aerosol‐jet printing (AJP) is of particular interest for all‐printed circuits and systems. Here, AJP is utilized to achieve ultrahigh‐responsivity photodetectors consisting of well‐aligned, percolating networks of semiconducting MoS2 nanosheets and graphene electrodes on flexible polyimide substrates. Ultrathin (≈1.2 nm thick) and high‐aspect‐ratio (≈1 μm lateral size) MoS2 nanosheets are obtained by electrochemical intercalation followed by megasonic atomization during AJP, which not only aerosolizes the inks but also further exfoliates the nanosheets. The incorporation of the high‐boiling‐point solvent terpineol into the MoS2 ink is critical for achieving a highly aligned and flat thin‐film morphology following AJP as confirmed by grazing‐incidence wide‐angle X‐ray scattering and atomic force microscopy. Following AJP, curing is achieved with photonic annealing, which yields quasi‐ohmic contacts and photoactive channels with responsivities exceeding 103 A W−1 that outperform previously reported all‐printed visible‐light photodetectors by over three orders of magnitude. Megasonic exfoliation coupled with properly designed AJP ink formulations enables the superlative optoelectronic properties of ultrathin MoS2 nanosheets to be preserved and exploited for the scalable additive manufacturing of mechanically flexible optoelectronics.

Inks based on two-dimensional (2D) materials could be used to tune the properties of printed electronics while maintaining compatibility with scalable manufacturing processes. However, a very wide range of performances have been reported in printed thin-film transistors in which the 2D channel material exhibits considerable variation in microstructure. The lack of quantitative physics-based relationships between film microstructure and transistor performance limits the codesign of exfoliation, sorting, and printing processes to inefficient empirical approaches. To rationally guide the development of 2D inks and related processing, we report a gate-dependent resistor network model that establishes distinct microstructure-performance relationships created by near-edge and intersheet resistances in printed van der Waals thin-film transistors. The model is calibrated by analyzing electrical output characteristics of model transistors consisting of overlapping 2D nanosheets with varied thicknesses that are mechanically exfoliated and transferred. Kelvin probe force microscopy analysis on the model transistors leads to the discovery that the nanosheet edges, not the intersheet resistance, limit transport due to their impact on charge carrier depletion and scattering. Our model suggests that when transport in a 2D material network is limited by the near-edge resistance, the optimum nanosheet thickness is dictated by a trade-off between charged impurity screening and gate screening, and the film mobilities are more sensitive to variations in printed nanosheet density. Removal of edge states can enable the realization of higher mobilities with thinner nanosheets due to reduced junction resistances and reduced gate screening. Our analysis of the influence of nanosheet edges on the effective film mobility not only examines the prospects of extant exfoliation methods to achieve the optimum microstructure but also provides important perspectives on processes that are essential to maximizing printed film performance.