We suggest that silver nanocube (AgNC) aggregates within cylindrical pores (PAM-AgNC) can be employed as efficient nanostructures for highly efficient, robust, tunable, and reusable surface-enhanced Raman scattering (SERS) substrates for trace level organic vapor detection which is a challenging task in chemical detection. We demonstrate the ability to tune both the detection limit and the onset of signal saturation of the substrate by switching the adsorption behavior of AgNCs between highly aggregated and more disperse by varying the number of adsorption-mediating polyelectrolyte bilayers on the pore walls of the membrane. The different AgNC distributions show large differences in the trace vapor detection limit of the common Raman marker benzenethiol (BT) and a widely used explosive binder Nmethyl-4-nitroaniline (MNA), demonstrating the importance of the large electromagnetic field enhancement associated with AgNC coupling. The SERS substrate with highly aggregated AgNCs within the cylindrical pores allows for consistent trace detection of mid ppb ($500) for BT analyte, and a record limit of detection of low ppb ($3) for MNA vapors with an estimated achievable limit of detection of approximately 600 ppt. The dispersed AgNC aggregates do not saturate at higher ppb concentrations, providing an avenue to distinguish between higher ppb concentrations and increase the effective range of the SERS substrate design. A comparison between the AgNC substrate and an electroless deposition substrate with silver quasi-nanospheres (PAM-AgNS) also demonstrates a higher SERS activity, and better detection limit, by the nanocube aggregates. This is supported by FDTD electromagnetic simulations that suggest that the higher integrated electromagnetic field intensity of the hot spots and the large specific interfacial areas impart greatly improved SERS for the AgNCs. Moreover, we demonstrated that the AgNC substrate can be reused multiple times without significant loss of SERS activity which opens up new avenues for in-field monitoring.

We demonstrate the fabrication of highly open spherical cages with large through pores using high aspect ratio cellulose nanocrystals with "haystack" shell morphology. In contrast to traditional ultrathin shell polymer microcapsules with random porous morphology and pore sizes below 10 nm with limited molecular permeability of individual macromolecules, the resilient cage-like microcapsules show a remarkable open network morphology that facilitates across-shell transport of large solid particles with a diameter from 30 to 100 nm. Moreover, the transport properties of solid nanoparticles through these shells can be pH-triggered without disassembly of these shells. Such behavior allows for the controlled loading and unloading of solid nanoparticles with much larger dimensions than molecular objects reported for conventional polymeric microcapsules.

A facile one‐step fabrication of large‐area multicolored emissive photopatterns in mixed quantum dot‐polymer films is demonstrated. This is in sharp contrast to the current photopatterning approaches that utilize only a single quantum dot (QD) component for single‐color patterns. Strategies are presented that allow for either selective or collective modification of specific predetermined photoluminescent peaks of green and red QDs during photopattern development. These strategies yield novel patterns and allow for unprecedented control over how the color contrast of the photopattern evolves with continuous light illumination. These results clearly show that the evolution of the emission spectra of a multicolor mixed QD‐polymer film can be readily tailored during pattern development, either by careful selection of the excitation wavelength or through combinations of controllably unstable and stable QDs with different recovery rates. Notably, these strategies are simple, fast, and robust, yielding high‐resolution microscopic patterns over large areas (up to fractions of a cm2). Furthermore, the flexibility and capabilities of these strategies greatly expand the potential applications of multicolor emissive photopatterns, particularly in the areas of sensing, imaging, and lasing systems where it is important to exert delicate control over the intensity of selected colors within specific spatial regions.

Proper selection of the quantum dot ligand allows for controllable enhancement of optical gain characteristics (threshold, magnitude, and stability) in quantum dot films.

We report high optical gain from freestanding, optically stable, and mechanically robust films that are loaded with cross-linked CdSe/Cd1–x Zn x Se1–y S y core/alloyed shell quantum dots (QD). These solid films display very high net optical gain as high as 650 cm–1 combined with a low pump excitation gain threshold of 44 μJ/cm2. The functionalization of the QDs using short-chain bifunctional cross-linkers not only significantly improves the net optical gain by allowing for a nearly 2-fold increase in QD loading but also provides stable passivation of the QDs which imparts excellent thermal stability, mechanical robustness, and stability under harsh chemical environments. The gain achieved here is up to 3-fold higher than that typically reported for traditional drop-cast QD films. Moreover, stable photoluminescence over long shelf storage time is a distinguished characteristic of the films. The QD films fabricated here span large areas (several cm2), can be readily micropatterned and sustain multiple harsh chemical treatment. Furthermore, they can be readily transferred onto different substrates without compromising their structural integrity and without diminishing optical activity that opens the paths to design complex and robust gain–loss optical structures.

This work demonstrates a facile and versatile method for generating low scattering cross-linked quantum dot (QD)-polymer composite films and patterned highly emissive structures with ultrahigh QD loading, minimal phase separation, and tunable mechanical properties. Uniform QD-polymer films are fabricated using thiol-ene chemistry, in which cross-linked polymer networks are rapidly produced in ambient conditions via fast UV polymerization in bulk to suppress QD aggregation. UV-controlled thiol-ene chemistry limits phase separation through producing highly QD loaded cross-linked composites with loadings above majority of those reported in the literature (<1%) and approaching 30%. As the QD loading is increased, the thiol and ene conversion decreases, resulting in nanocomposites with widely variable and tailorable mechanical properties as a function of UV irradiation time with an elastic modulus decreasing to 1 GPa being characteristic of reinforced elastomeric materials, in contrast to usually observed stiff and brittle materials under these loading conditions. Furthermore, we demonstrate that the thiol-ene chemistry is compatible with soft-imprint lithography, making it possible to pattern highly loaded QD films while preserving the optical properties essential for high gain and low optical loss devices. The versatility of thiol-ene chemistry to produce high-dense QD-polymer films potentially makes it an important technique for polymer-based elastomeric optical metamaterials, where efficient light propagation is critical, like peculiar waveguides, sensors, and optical gain films.

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2pyridine) (PS n P2VP n ) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into the LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.

The key to utilizing quantum dots (QDs) as lasing media is to effectively reduce non-radiative processes, such as Auger recombination and surface trapping. A robust strategy to craft a set of CdSe/Cd(1-x)Zn(x)Se(1-y)S(y)/ZnS core/graded shell-shell QDs with suppressed re-absorption, reduced Auger recombination rate, and tunable Stokes shift is presented. In sharp contrast to conventional CdSe/ZnS QDs, which have a large energy level mismatch between CdSe and ZnS and thus show strong re-absorption and a constrained Stokes shift, the as-synthesized CdSe/Cd(1-x)Zn(x)Se(1-y)S(y)/ZnS QDs exhibited the suppressed re-absorption of CdSe core and tunable Stokes shift as a direct consequence of the delocalization of the electron wavefunction over the entire QD. Such Stokes shift-engineered QDs with suppressed re-absorption may represent an important class of building blocks for use in lasers, light emitting diodes, solar concentrators, and parity-time symmetry materials and devices.