A Precursor-Limited Nanoparticle Coalescence Pathway for Tuning the Thickness of Laterally-Uniform Colloidal Nanosheets: The Case of SnSe

Abstract

The availability of high-quality colloidal nanosheets underpins a diverse range of applications and investigations into dimension-dependent physical properties. To facilitate this, synthetic methods that yield single-crystal colloidal nanosheets with regular shapes, uniform lateral dimensions, and tunable thicknesses are critically important. Most strategies that yield colloidal nanosheets achieve some, but not all, of these morphological characteristics. Here, we describe a synthetic pathway that generates colloidal nanosheets of SnSe with uniform lateral dimensions and tunable thicknesses. SnSe represents an excellent prototype system for studying the formation of colloidal nanosheets because of its layered crystal structure and the growing interest in its potential application as an absorption layer in low-cost photovoltaic devices. Freestanding colloidal SnSe nanosheets were synthesized by slowly heating a one-pot reaction mixture of SnCl(2), oleylamine, trioctylphosphine selenide (TOP-Se), and hexamethyldisilazane (HMDS) to 240 °C. The SnSe nanostructures adopt a uniform square-like morphology with lateral dimensions of approximately 500 nm × 500 nm, and the average nanosheet thicknesses can be tuned from approximately 10 to 40 nm by adjusting the concentrations of the SnCl(2) and TOP-Se reagents. Aliquot studies reveal fundamental insights into how the nanosheets form: they first "grow out" laterally via coalescence of individual nanoparticle building blocks to yield a single-crystal nanosheet template and then "grow up" vertically (through nanoparticle attachment to the nanosheet template) in a pseudo layer-by-layer fashion. Vertical growth is therefore limited, and can be controlled, by reagent concentration. Drop-cast films of the SnSe nanosheets are photoactive and have a bandgap of approximately 1 eV. These studies, demonstrated for SnSe but potentially applicable to other systems, establish a straightforward pathway for tuning the thicknesses of colloidal nanosheets while maintaining lateral uniformity.