Makiko Quint

Tuning Quantum-Dot Organization in Liquid Crystals for Robust Photonic Applications

Mesogenic ligands have the potential to provide control over the dispersion and stabilization of nanoparticles in liquid crystal (LC) phases. The creation of such hybrid materials is an important goal for the creation of soft tunable photonic devices, such as the LC laser. Herein, we present a comparison of isotropic and mesogenic ligands attached to the surface of CdSe (core-only) and CdSe/ZnS (core/shell) quantum dots (QDs). The mesogenic ligands flexible arm structure enhances ligand alignment, with the local LC director promoting QD dispersion in the isotropic and nematic phases. To characterize QD dispersion on different length scales, we apply fluorescence microscopy, X-ray scattering, and scanning confocal photoluminescent imaging. These combined techniques demonstrate that the LC-modified QDs do not aggregate into the dense clusters observed for dots with simple isotropic ligands when dispersed in liquid crystal, but loosely associate in a fluid-like droplet with an average interparticle spacing >10 nm. Embedding the QDs in a cholesteric cavity, we observe comparable coupling effects to those reported for more closely packed isotropic ligands.

Plasmon-actuated nano-assembled microshells

We present three-dimensional microshells formed by self-assembly of densely-packed 5 nm gold nanoparticles (AuNPs). Surface functionalization of the AuNPs with custom-designed mesogenic molecules drives the formation of a stable and rigid shell wall, and these unique structures allow encapsulation of cargo that can be contained, virtually leakage-free, over several months. Further, by leveraging the plasmonic response of AuNPs, we can rupture the microshells using optical excitation with ultralow power (<2 mW), controllably and rapidly releasing the encapsulated contents in less than 5 s. The optimal AuNP packing in the wall, moderated by the custom ligands and verified using small angle x-ray spectroscopy, allows us to calculate the heat released in this process, and to simulate the temperature increase originating from the photothermal heating, with great accuracy. Atypically, we find the local heating does not cause a rise of more than 50 °C, which addresses a major shortcoming in plasmon actuated cargo delivery systems. This combination of spectral selectivity, low power requirements, low heat production, and fast release times, along with the versatility in terms of identity of the enclosed cargo, makes these hierarchical microshells suitable for wide-ranging applications, including biological ones.

Effect of mesogenic ligands on short and long-term spectral dynamics and stability of core-shell CdSe/ZnS quantum dots

Surface modification is a versatile and effective route towards improving functional and structural characteristics of chemically synthesized nanomaterials. In the specific case of semiconducting nanoparticles (quantum dots (QDs)) the photophysical properties are strongly tied to surface conditions. Therefore, a careful monitoring of photoluminescent (PL) behavior, both short and long term, is critical following alterations to their surface chemistry. We observe several noteworthy changes in the static and dynamic PL spectra of CdSe/ZnS core–shell QDs when the as-grown native ligands are exchanged with two different mesogenic ligands—rod-like molecules attached to the particle by a flexible alkyl chain. These include reduced inter-dot energy transfer, stable recombination rates and steady emission color over more than an hour of continuous photo-excitation, all effects being more prominent in the sample with the longer attachment chain. Temperature dependence of PL and recombination rates reveals further differences. Thermally activated PL recovery threshold is pushed to a higher temperature in the modified dots, while PL lifetime does not show the expected increase with decreasing temperature. Our results indicate that increased charge separation induced by the longer ligands is responsible for these effects, and this may be a route to fabricating QD films for specific applications demanding long term emission color stability.

Optical switching of nematic liquid crystal film arising from induced electric field of localized surface plasmon resonance

We have developed an all-optical method to control the in- and out-of-plane spatial orientation of nematic liquid crystal (NLC) molecules by leveraging the highly localized electric fields produced in the near-field regime of gold nanoparticle (AuNP) layers. A 1-2 micron thick NLC film is deposited on a close-packed drop-cast AuNP layer, excited with tunable optical sources and the transmission of white light through it analyzed using polarization optics as a function of incident light wavelength, excitation power and sample temperature. Our findings, supported by simulations using discrete-dipole approximations, establish the optical switching effect to be repeatable, reversible, spectrally-selective, operational over a broad temperature range, including room temperature, and requiring very small on-resonance excitation intensity (0.3 W/cm2). For the case of the in-plane switching we have additionally demonstrated that controlling the incident excitation polarization can continuously vary the alignment of the NLC molecules, allowing for grayscale transmission.