Chiral
fluorescent materials with fluorescent nanoparticles assembled
into a chiral structure represent a grand challenge. Here, we report
self-assembled emissive needle-like nanostructures through decorating
cellulose nanocrystals (CNCs) with carbon quantum dots (CQDs). This
assembly is facilitated by the heterogeneous amphiphilic interactions
between natural and synthetic components. These emissive nanostructures
can self-organize into chiral nematic solid-state materials with enhanced
mechanical performance. The chiral CQD/CNC films demonstrate an intense
iridescent appearance superimposed with enhanced luminescence that
is significantly higher than that for CQD films and other reported
CQD/CNC films. A characteristic fluorescent fingerprint signature
is observed in the CQD/CNC film, proving the well-defined chiral organization
of fluorescent nanostructures. The chiral organization of CQDs enables
the solid CQD/CNC film to form a right-hand chiral fluorescence with
an asymmetric factor of −0.2. Additionally, we developed chemical
2D printing and soft lithography patterning techniques to fabricate
the freestanding chiral fluorescent patterns that combines
mechanical intergrity and chiral nematic structure with light diffraction
and emission.
We report novel dual-responsive plasmonic
core–shell anisotropic
nanostructures composed of gold nanorod (AuNR) and responsive polyaniline
(PANI) shells with plasmonic mode appearance reversibly modulated
through orthogonal stimuli (i.e., electrical potential and pH change).
In this system, the PANI shells provide AuNR cores with three different
refractive index environments depending on stimuli (pH and electrical
potential). Therefore, no additional secondary responsive component
is necessary to induce the dual-responsive properties of AuNR cores.
Furthermore, in this study, dual-responsive properties can be realized
for nanostructures fixed on substrates, whereas previously reported
dual-responsive plasmonic systems can only be controlled in solution.
Here, the highest localized surface plasmonic resonance (LSPR) shift
of the AuNR cores can be induced by changing both local pH and applying
electric potential. Notably, a significant plasmon band shift by 107
nm is realized with only 8 nm thick PANI shell due to the large refractive
index change at the gold–polymer interface. A maximum shift
of the longitudinal plasmon mode of 149 nm is obtained by applying
a modest electrical potential (below ±1 V), a large shift rarely
reported in the literature for metal nanostructures. Moreover, our
anisotropic core/shell nanostructures exhibit stable and reversible
dual-responsive LSPR behavior over 100 cycles without degradation.
Second-harmonic generation (SHG) has been applied to study the influence of defects in short-period (SimGen)p strained-layer superlattices. With a misfit stacking fault defect density of ∼1010 cm−2 shown by transmission electron microscopy, it is found that the SH intensity increases by about one order of magnitude from that of the defect-free samples. We propose that the inhomogeneous strain field around the fault planes in the superlattice layers is responsible for this abrupt increase of SHG. The expected symmetry and the magnitude of the nonlinear susceptibility from these stacking fault defects are shown to be in agreement with the experimental observations.
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