Synthesis and characterization of infrared quantum dots

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2014.116Cataloged from PDF version of thesis.Includes bibliographical references (pages 147-159).This thesis focuses on the development of synthetic methods to create application ready quantum dots (QDs) in the infrared for biological imaging and optoelectronic devices. I concentrated primarily on controlling the size and size distribution of indium arsenide and cadmium arsenide QDs. In the nanocrystal community, classical nucleation and growth is often invoked to explain size focusing. However, this model lacks predictive power and contradicts what is known about the chemistry of QD growth. I try to relate my experimental approach and my conclusions to our understanding of the mechanism of particle growth. This approach led me to explore the role of precursor conversion rate in the growth of III-V QDs and to develop a continuous injection synthesis method that I used to make both III-V and cadmium arsenide QDs. Cadmium arsenide (Cd 3As 2 ) is a narrow gap semiconductor that can form QDs with tunable emission between 530nm and 2000nm. I developed a synthetic strategy to precisely control the size of Cd3As 2 QDs while maintaining a narrow size distribution. Continuous precursor injection was used to drive growth and suppress size broadening. The quantum yields of Cd3As 2 QDs produced using this method ranged as high as 80%, and their emission is tunable over a broad range with narrow linewidths. However, they were found to be unstable in ambient conditions. Nevertheless, by processing in inert conditions we were able to make a crude photodetector that demonstrates that Cd3As 2 QDs are sufficiently stable for use in optoelectronic devices. Although growth of a Cd3 P2 shell provided enough added stability to observe emission after ligand exchange into water, these core-shell structures do not seem to be robust enough for biological applications. Indium arsenide (InAs) QDs are more easily stabilized with a core-shell structure. However, the spectral linewidths are broad and existing synthetic techniques produce only small particles with limited spectral tunability. Models predicted that decreasing precursor reactivity would produce larger, more monodisperse particles. Therefore, I chemically modified the group-V precursor to reduce reactivity. I made a library of group-V precursors, and I developed a framework for comparing the QDs that they produced and measuring the kinetics of precursor conversion and particle growth. Although we successfully reduced precursor reactivity, we found that the effect on particle size was minimal and that the least reactive precursors produced particles with inferior size distributions. To find another way to try to improve III-V synthesis, I adapted the continuous injection method developed for making Cd3As 2. Using this strategy, I was able to produce InAs QDs with broadly tunable size and narrow spectral features. However, continuous injection ceases to drive particle growth beyond about 5nm in diameter. We examined why particle growth stops, and proposed a strategy to prolong growth and size focusing. Ultimately, the continuous injection technique allowed us to produce InAs QDs with infrared emission and narrow spectral features that were ideally suited for producing QDs optimized for deep tissue imaging in mice. By adding a shell of CdSe, CdS, or ZnSe, the quantum yield and stability were enhanced. These emitters allowed us to see biodistribution and biological processes occurring inside live mice. Although we found that precursor chemistry did not affect particle growth to the degree we hoped, we were able to produce application ready QDs via a continuous injection procedure. Continuous injection synthesis of QDs is a precise way to tune QD size while maintaining narrow size distributions. We have used this technique to produce QDs with the specifications required for high impact applications.by Daniel Kelly Harris.Ph. D