arXiv subjects

Chad A. Mirkin

Publications and source records attributed to Chad A. Mirkin.

4 recordsLinked to original sources

arXiv2024

Electron-Induced Radiation Chemistry in Environmental Transmission Electron Microscopy

Environmental transmission electron microscopy (E-TEM) enables direct observation of nanoscale chemical processes crucial for catalysis and materials design. However, the high-energy electron probe can dramatically alter reaction pathways through radiolysis - the dissociation of molecules under electron beam irradiation. While extensively studied in liquid-cell TEM, the impact of radiolysis in gas-phase reactions remains unexplored. Here, we present a numerical model elucidating radiation chemistry in both gas and liquid E-TEM environments. Our findings reveal that while gas-phase E-TEM generates radiolytic species with lower reactivity than liquid-phase systems, these species can accumulate to reaction-altering concentrations, particularly at elevated pressures. We validate our model through two case studies: the radiation-promoted oxidation of aluminum nanocubes and disproportionation of carbon monoxide. In both cases, increasing the electron beam dose rate directly accelerates their reaction kinetics, as demonstrated by enhanced AlOx growth and carbon deposition. Based on these insights, we establish practical guidelines for controlling radiolysis in closed-cell nanoreactors. This work not only resolves a fundamental challenge in electron microscopy but also advances our ability to rationally design materials with sub-Angstrom resolution.

cond-mat.mtrl-sci↗

arXiv2024

Surface-Functionalization of Oleate-Capped Nano-Emitters for Stable Dispersion in 3D-Printable Polymers

Two-photon polymerization (2PP) 3D printing is a well-known technique for fabricating passive micro/nanoscale structures, such as microlenses and inversely designed polarization splitters. The integration of light emitting nanoparticle (NP) dopants, such as quantum dots (QDs) and rare-earth doped nanoparticles (RENPs), into a polymer resist would enable 3D printing of active polymer micro-photonic devices, including sensors, lasers, and solid-state displays. Many NPs are stabilized with oleic acid ligands to prevent degradation, but oleate-capped NPs (oc-NPs) tend to agglomerate in nonpolar media despite the hydrophobicity of the ligand. This results in an uneven distribution of NPs in polymers and increased optical extinction properties. In this work, we propose a general approach for dispersing various oc-NPs in commercial 3D printable polymers. We achieve controlled growth of small carbon chains around the oc-NPs by functionalizing the NPs with methyl-methacrylate monomers. The proposed approach is validated on RENPs (~65 nm) and CdSe/ZnS quantum dots (~12 nm) using different commercial polymer resists (IP-Dip and IP-Visio). Dispersions of functionalized NPs (f-NPs) have improved NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. Our approach is generalizable to a variety of oc-NPs and ultimately leads to higher quality polymer-based optical and electronic devices.

physics.app-ph↗

arXiv2018

Windowless Observation of Evaporation-Induced Coarsening of Au-Pt Nanoparticles in Polymer Nanoreactors

The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. In such reactors, homogeneous Au-Pt nanoparticles are synthesized from metal ion precursors in situ under electron irradiation. The non-uniform evaporation of the thin polymer film not only concentrates the nanoparticles, but also accelerates the coalescence kinetics at the receding polymer edges. Qualitative analysis of the particle forces influencing coalescence suggests that capillary dragging by the polymer edges plays a significant role in accelerating this process. Taken together, this work: 1) provides fundamental insight into the role of solvents in the chemistry and coarsening behavior of nanoparticles during the synthesis of polyelemental nanostructures, 2) provides insight into how particles form via the SPBCL process, and 3) shows how SPBCL-generated domes, instead of liquid cells, can be used to study nanoparticle formation. More generally, it shows why conventional models of particle coarsening, which do not take into account solvent evaporation, cannot be used to describe what is occurring in thin film, liquid-based syntheses of nanostructures.

physics.chem-ph↗

arXiv2017

The Structural Fate of Individual Multicomponent Metal-Oxide Nanoparticles in Polymer Nanoreactors

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized via scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely due to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems.

physics.chem-ph↗