Self-assembly of anisotropic nanostructures and interferometric spectroscopy

With the development of controlled and predictable nanoparticle fabrication, assembling multiple nano-objects into larger functional nanostructure has attracted increasing attention. As the most basic structure, assembly of one-dimensional (1D) structures is a good model for investigating the assembly mechanism of a nanostructure's formation from individual particles. In this dissertation, the dynamics and the growth mechanism of anisotropic 1D nanostructures is investigated. In our first study, we demonstrate a simple method for assembling superparamagnetic nanoparticles (SPIONs) into structure-controlled 1D chains in a rotating magnetic field. The length of the SPION chains can be well described by an exponential distribution, as is also seen in SPION chains in a static field. In addition, the maximum chain length is limited by the field's rotational speed, as is seen in micro-sized beads forming chains in a rotating field. However, due to a combination of thermal fluctuations and hydrodynamic forces, the chain length in our case is shorter than either limit. In addition to chain length, the disorder of chains was also studied. Because of the friction between particles, kinetic potential traps prevent relaxation to the global free energy minimum. The traps are too deep to be overcome through thermal fluctuations, and assemblies captured by the kinetic traps therefore form disordered chains. We demonstrate that this disorder gradually heals over a timescale of tens of minutes and that the healing process can be promoted by increasing particle concentration or solution ionic strength, suggesting that the chain growth process provides the energy required to overcome the kinetic trapping. Next, we introduce a novel optical technique we term Quantitative Optical Anisotropy Imaging (QOAI). A fast and precise single-particle characterizing technique for anisotropic nanostructures, QOAI allows real-time tracking of particle orientation as well as the spectroscopic characterization of polarizabilities of nanoparticles on a microsecond timescale. The abilities of QOAI are demonstrated by the detection and the characterization of single gold nanorods. We also show that single particle diffusions and the process of particle binding to a wall can be tracked through QOAI. The rotational diffusivities of gold nanorods near the wall were determined by autocorrelation analysis, which shows that the diffusivity in the polar direction is slightly smaller than in the azimuthal direction. This result demonstrates that a detailed correlation analysis with QOAI may provide the opportunity to analyze both the translational and rotational motion of particles simultaneously, enabling true 3-dimensional orientation tracking. Finally, optical methods including QOAI are applied to the investigation of magnetic assembly, demonstrating that optical anisotropy is generated during particle binding, which can be used as a probe of the magnetic assembly process. QOAI is employed to track the dynamics of magnetic clusters in real time, attempting to capture insights on the self-assembly of the magnetic nanoparticles. By turning the external magnetic field on and off, the processes of combining superparamagnetic colloidal nanoparticle clusters into chain assemblies are monitored along with the chain growth. This fast and orientation-sensitive single-particle measurement opens the door to detailed studies of self-assembly away from equilibrium.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Physics

Department dc:contributor.department

Physics

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2020

Author dc:creator

• He, Zhixing

Chair dc:contributor.committeechair

• Robinson, Hans D.

Committee members dc:contributor.committeemember

• Khodaparast, Giti
• Park, Kyungwha
• Tao, Chenggang

• Nanotechnology
• Plasmon
• Plasmonics
• Self-Assembly
• nanoparticle
• Superparamagnetism
• interferometry
• spectroscopy

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:24395

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/97402