Nematic liquid crystals of achiral molecules or racemic mixtures of chiral ones form flat films and show uniform textures between circular polarizers when suspended in sub-millimeter size grids and submersed under water. Recently it was shown that on addition of chiral dopants to the liquid crystal, the films exhibit optical textures with concentric ring patterns with radial variation of the birefringence color, while the films become biconvex. The curved shape together with degenerate planar anchoring leads to a radial variation of the optical axis along the plane of the film, providing a Pancharatnam-Berry type phase lens that dominates the imaging. Here we describe preliminary results of nematic liquid crystal microlenses formed by the addition of chiral nanoparticles. It is found that the helical twisting power of the nanoparticles, the key factor to form the lens, is an order of magnitude greater than that of the strongest molecular chiral dopants. From the observations we present here, we were able to estimate the shape and the geometric focal length of the lens and demonstrated its performance as an optical device. The use of chiral nanoparticles to make microlenses may allow tuning by light that the nanoparticles absorb or, for magnetic NPs, by magnetic fields. Further, the measurement of focal length at known NP concentration offers a new method to measure the helical twisting power of chiral nanoparticles.
Studies of chiroptical effects of chiral ligand-capped gold nanoparticles (Au NPs) are a fascinating and rapidly evolving field in nanomaterial research with promising applications of such chiral metal NPs in catalysis and metamaterials as well as chiral sensing and separation. The aim of our studies was to seek out a system that not only allows the detection and understanding of Au NP chirality but also permits visualization and ranking — considering size, shape and nature as well as density of the ligand shell — of the extent of chirality transfer to a surrounding medium. Nematic liquid crystal (N-LC) phases are an ideal platform to examine these effects, exhibiting characteristic defect textures upon doping with a chiral additive. To test this, we synthesized series of Au NPs capped with two structurally different chiral ligands and studied well-dispersed mixtures in two nematic liquid crystal hosts. Induced circular dichroism (ICD) spectropolarimetry and polarized light optical microscopy (POM) confirmed that all Au NPs induce chiral nematic (N*-LC) phases, and measurements of the helical pitch as well as calculation of the helical twisting power (HTP) in various cell geometries allowed for an insightful ranking of the efficiency of chirality transfer of all Au NPs as well as their free ligands.
We here report on the alignment and electro-optic properties of nematic liquid crystals (LCs) either containing nanoscale
particles as additives or featuring particles patterned on substrates. The investigated nematic LCs or LC dispersions are
doped or in contact with magic-sized semiconductor CdSe nanocrystals (MSNCs) or silane- and alkylthiol monolayercapped
gold nanoparticles. Three single-sized CdSe quantum dots capped with myristic acid exhibiting bright bandgap
photoluminescence (PL) at λmax ~ 463 nm were tested as additives. Two of the quantum dots only vary in the amount of
defects as indicated by different bandgap and deep trap PL. The third MSNC sample is compositionally different, doped
with Zn. These MSNCs with almost identical sizes were doped at different concentrations (1-5 wt%) into the nematic
phase of the 2-phenylpyrimidine-based LC1. Only the Zn-doped MSNCs showed the formation of birefringent stripes
surrounded by areas of homeotropic alignment between plain glass slides at all concentrations as observed for many
other nanoparticle-doped nematic LCs reported earlier by our group. In polyimide-coated glass slides favoring planar
orientation of the nematic director, planar alignment was observed. Similarly, siloxane-coated gold nanoparticle
additives with narrow size distribution, but larger size, show homeotropic alignment between plain glass and planar
alignment in rubbed polyimide-coated cells. Surprisingly then, we succeeded in creating alignment patterns using
smaller, ~2 nm alkylthiol-capped gold nanoparticles using a process called stenciling that allowed us to generate patterns
of homeotropic alignment in a continuum of planar alignment of the nematic LC. Finally, electro-optic investigations on
some of these samples revealed that only the Zn-doped magic-sized MSNCs significantly lower the dielectric anisotropy
as well as the splay elastic constant of the nematic host, despite identical size and surface functionality of the three used
MSNCs, which highlights the tremendous effect of the nanocrystal core composition on the electro-optic properties of
the nematic host.
It is well known that doping nematic liquid crystals with nanoparticles can alter the electrooptic response of the nematic
host as well as the alignment of the liquid crystal molecules on various substrates. In addition, nanoparticles dispersed in
a nematic matrix often induce defects and defect patterns justifying the necessity for more detailed optical and electrooptic
investigations including effects of nanoparticle size, coating, concentration and core material. We studied the local
alignment of nematic LC molecules in such dispersions by means of fluorescence confocal polarizing microscopy. The
results of two- and three-dimensional imaging indicate that frequently observed birefringent stripes, which are induced
by the presence of metal nanoparticles and semiconductor quantum dots, correspond to twist disclinations located at the
LC/substrate interface. The luminescence of dispersed quantum dots shows that the ends of these disclination threads are
pinned to conglomerates of nanoparticles that stabilize these line defects. By performing (x,z)-scans, it can be shown that
the defects are not walls extending through the entire cell gap, but lines that are located at the substrate surface. Our
experiments also confirm, as hypothesized before, that the nanoparticles preferably reside at the liquid crystal/substrate
interfaces. Finally, detailed electrooptic investigations also revealed that a contrast inversion observed earlier is initiated
by a change from parallel to homeotropic anchoring, thereby causing an instability, which in turn leads to the appearance
of convection rolls (Kapustin-Williams domains). This electrohydrodynamic instability is likely an example for the
behavior of (+, -) systems predicted by de Gennes, which was only recently experimentally observed for the first time.
To capitalize on the unique size and shape-dependent optical and electronic properties of nanoscale particles for liquid
crystal (LC) applications, detailed structure and size-property relationship studies are critical. To enhance our understanding of the thermal, optical and electro-optic effects of nanoparticles in nematic LCs we produced numerous different nematic LC mixtures containing small quantities of dispersed metal nanoparticles (i.e. gold and silver nanoclusters) or semiconductor quantum dots (i.e. CdTe nanocrystals) and studied their optical (texture, alignment, defect formation, luminescence) and electro-optic properties. Depending on several experimental parameters such as nanoparticle functionalization and concentration, as well as thermal history in combination with an applied electric field, these nanoparticle/LC mixtures with the nanoparticles differing in surface functionality, size, and core material gave rise to unique alignment effects and electro-optic responses in the two investigated nematic LC (N-LC) hosts.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.