Atomic-Resolution Imaging of Small Organic Molecules on Graphene.

Here, we demonstrate atomic-resolution scanning transmission electron microscopy (STEM) imaging of light elements in small organic molecules on graphene. We use low-dose, room-temperature, aberration-corrected STEM to image 2D monolayer and bilayer molecular crystals, followed by advanced image processing methods to create high-quality composite images from ∼102-104 individual molecules. In metalated porphyrin and phthalocyanine derivatives, these images contain an elementally sensitive contrast with up to 1.3 Å resolution─sufficient to distinguish individual carbon and nitrogen atoms. Importantly, our methods can be applied to molecules with low masses (∼0.6 kDa) and nanocrystalline domains containing just a few hundred molecules, making it possible to study systems for which large crystals cannot easily be grown. Our approach is enabled by low-background graphene substrates, which we show increase the molecules' critical dose by 2-7×. These results indicate a new route for low-dose, atomic-resolution electron microscopy imaging to solve the structures of small organic molecules.

Combinatorial Synthesis of Magnesium Tin Nitride Semiconductors.

Nitride materials feature strong chemical bonding character that leads to unique crystal structures, but many ternary nitride chemical spaces remain experimentally unexplored. The search for previously undiscovered ternary nitrides is also an opportunity to explore unique materials properties, such as transitions between cation-ordered and -disordered structures, as well as to identify candidate materials for optoelectronic applications. Here, we present a comprehensive experimental study of MgSnN2, an emerging II-IV-N2 compound, for the first time mapping phase composition and crystal structure, and examining its optoelectronic properties computationally and experimentally. We demonstrate combinatorial cosputtering of cation-disordered, wurtzite-type MgSnN2 across a range of cation compositions and temperatures, as well as the unexpected formation of a secondary, rocksalt-type phase of MgSnN2 at Mg-rich compositions and low temperatures. A computational structure search shows that the rocksalt-type phase is substantially metastable (>70 meV/atom) compared to the wurtzite-type ground state. Spectroscopic ellipsometry reveals optical absorption onsets around 2 eV, consistent with band gap tuning via cation disorder. Finally, we demonstrate epitaxial growth of a mixed wurtzite-rocksalt MgSnN2 on GaN, highlighting an opportunity for polymorphic control via epitaxy. Collectively, these findings lay the groundwork for further exploration of MgSnN2 as a model ternary nitride, with controlled polymorphism, and for device applications, enabled by control of optoelectronic properties via cation ordering.