Single-Crystal Colloidal Nanosheets of GeS and GeSe

Narrow-band-gap IV-VI semiconductors offer promising optoelectronic properties for integration as light-absorbing components in field-effect transistors, photodetectors, and photovoltaic devices. Importantly, colloidal nanostructures of these materials have the potential to substantially decrease the fabrication cost of solar cells because of their ability to be solution-processed. While colloidal nanomaterials formed from IV-VI lead chalcogenides such as PbS and PbSe have been extensively investigated, those of the layered semiconductors SnS, SnSe, GeS, and GeSe have only recently been considered. In particular, there have been very few studies of the germanium chalcogenides, which have band-gap energies that overlap well with the solar spectrum. Here we report the first synthesis of colloidal GeS and GeSe nanostructures obtained by heating GeI(4), hexamethyldisilazane, oleylamine, oleic acid, and dodecanethiol or trioctylphosphine selenide to 320 °C for 24 h. These materials, which were characterized by TEM, SAED, SEM, AFM, XRD, diffuse reflectance spectroscopy, and I-V conductivity measurements, preferentially adopt a two-dimensional single-crystal nanosheet morphology that produces fully 100-oriented films upon drop-casting. Optical measurements indicated indirect band gaps of 1.58 and 1.14 eV for GeS and GeSe, respectively, and electrical measurements showed that drop-cast films of GeSe exhibit p-type conductivity.