Microfluidic reactors are investigated as a mechanism to control the growth of semiconductor nanocrystals and characterize the structural evolution of colloidal quantum dots. Due to their short diffusion lengths, low thermal masses, and predictable fluid dynamics, microfluidic devices can be used to quickly and reproducibly alter reaction conditions such as concentration, temperature, and reaction time, while allowing for rapid reagent mixing and product characterization. These features are particularly useful for colloidal nanocrystal reactions, which scale poorly and are difficult to control and characterize in bulk fluids. To demonstrate the capabilities of nanoparticle microreactors, a size series of spherical CdSe nanocrystals was synthesized at high temperature in a continuous-flow, microfabricated glass reactor. Nanocrystal diameters are reproducibly controlled by systematically altering reaction parameters such as the temperature, concentration, and reaction time. Microreactors with finer control over temperature and reagent mixing were designed to synthesize nanoparticles of different shapes, such as rods, tetrapods, and hollow shells. The two major challenges observed with continuous flow reactors are the deposition of particles on channel walls and the broad distribution of residence times that result from laminar flow. To alleviate these problems, I designed and fabricated liquid-liquid segmented flow microreactors in which the reaction precursors are encapsulated in flowing droplets suspended in an immiscible carrier fluid. The synthesis of CdSe nanocrystals in such microreactors exhibited reduced deposition and residence time distributions while enabling the rapid screening a series of samples isolated in nL droplets. Microfluidic reactors were also designed to modify the composition of existing nanocrystals and characterize the kinetics of such reactions. The millisecond kinetics of the CdSe-to-Ag2Se nanocrystal cation exchange reaction are measured in situ with micro-X-ray Absorption Spectroscopy in silicon microreactors specifically designed for rapid mixing and time-resolved X-ray spectroscopy. These results demonstrate that microreactors are valuable for controlling and characterizing a wide range of reactions in nL volumes even when nanoscale particles, high temperatures, caustic reagents, and rapid time scales are involved. These experiments provide the foundation for future microfluidic investigations into the mechanisms of nanocrystal growth, crystal phase evolution, and heterostructure assembly.

The high-temperature synthesis of CdSe nanocrystals in nanoliter-volume droplets flowing in a perfluorinated carrier fluid through a microfabricated reactor is presented. A flow-focusing nanojet structure with a step increase in channel height reproducibly generated octadecene droplets in Fomblin Y 06/6 perfluorinated polyether at capillary numbers up to 0.81 and with a droplet:carrier fluid viscosity ratio of 0.035. Cadmium and selenium precursors flowing in octadecene droplets through a high-temperature (240-300 degrees C) glass microreactor produced high quality CdSe nanocrystals, as verified by optical spectroscopy and transmission electron microscopy. Isolating the reaction solution in droplets prevented particle deposition and hydrodynamic dispersion, allowing the reproducible synthesis of nanocrystals at three different temperatures and four different residence times in the span of four hours. Our synthesis of a wide range of nanocrystals at high temperatures, high capillary numbers, and low viscosity ratio illustrates the general utility of droplet-based microfluidic reactors to encapsulate nanoliter volumes of organic or aqueous solutions and to precisely control chemical or biochemical reactions.

We describe the use of a flow-focusing microfluidic reactor to measure the kinetics of the CdSe-to-Ag2Se nanocrystal cation exchange reaction using micro-X-ray absorption spectroscopy (mu XAS). The small microreactor dimensions facilitate the millisecond mixing of CdSe nanocrystal and Ag+ reactant solutions, and the transposition of the reaction time onto spatial coordinates enables the in situ observation of the millisecond reaction with mu XAS. XAS spectra show the progression of CdSe nanocrystals to Ag2Se over the course of 100 ms without the presence of long-lived intermediates. These results, along with supporting stopped flow absorption experiments, suggest that this nanocrystal cation exchange reaction is highly efficient and provide insight into how the reaction progresses in individual particles. This experiment illustrates the value and potential of in situ microfluidic X-ray synchrotron techniques for detailed studies of the millisecond structural transformations of nanoparticles and other solution-phase reactions in which diffusive mixing initiates changes in local bond structures or oxidation states.