No abstract

Detailed experiments designed to optimize and understand the solvent vapor annealing of cylinder-forming poly(styrene)-block-poly(lactide) thin films for nanolithographic applications are reported. By combining climate-controlled solvent vapor annealing (including in situ probes of solvent concentration) with comparative small-angle X-ray scattering studies of solvent-swollen bulk polymers of identical composition, it is concluded that a narrow window of optimal solvent concentration occurs just on the ordered side of the order-disorder transition. In this window, the lateral correlation length of the hexagonally close-packed ordering, the defect density, and the cylinder orientation are simultaneously optimized, resulting in single-crystal-like ordering over 10 μm scales. The influences of polymer synthesis method, composition, molar mass, solvent vapor pressure, evaporation rate, and film thickness have all been assessed, confirming the generality of this behavior. Analogies to thermal annealing of elemental solids, in combination with an understanding of the effects of process parameters on annealing conditions, enable qualitative understanding of many of the key results and underscore the likely generality of the main conclusions. Pattern transfer via a Damascene-type approach verified the applicability for high-fidelity nanolithography, yielding large-area metal nanodot arrays with center-to-center spacing of 38 nm (diameter 19 nm). Finally, the predictive power of our findings was demonstrated by using small-angle X-ray scattering to predict optimal solvent annealing conditions for poly(styrene)-block-poly(lactide) films of low molar mass (18 kg mol(-1)). High-quality templates with cylinder center-to-center spacing of only 18 nm (diameter of 10 nm) were obtained. These comprehensive results have clear and important implications for optimization of pattern transfer templates and significantly advance the understanding of self-assembly in block copolymer thin films.

ganic CsPbX 3 QDs possess narrow full width at half maximum (FWHM) of emission (as small as 12 nm) and excellent quantum yield (QY: 50-90%). [1,8] They have a Bohr diameter up to 12 nm, [1] exhibiting a size-tunable bandgap in the visible region. It is also notable that the exchange of halide ions (Cl − , Br − , and I − ) in as-synthesized perovskite QDs is highly effective, rendering easy and rapid access to a wide range of perovskite QDs with tunable absorption and photoluminescence (PL) spectra. [1] In spite of significant advances in perovskite research noted above, a key to the success of perovskite-based materials and devices is the stability of perovskites as they are susceptible to decomposition due to their ionic crystal nature. [7,9] Recently, several methods including coating with alumina by atomic layer deposition, [10] partial coating with SiO 2 via sol-gel process, [11] physical mixing with hydrophobic polymers, [12] and encapsulation within mesoporous silica [7] or polymer beads [13] have proven to be effective in improving stability in polar and ambient environments. However, nearly all approaches described above for stability enhancement result in nanocomposites with multiple perovskite QDs encapsulated in microscopic protective matrices. These microscale nanocomposites may be disadvantageous for biomedical applications where cellular uptake is more feasible for smaller nanoscopic particles, [14] or LEDs where the processing of nanoscopic luminescent particles often leads to low scattering loss, higher loading and packing density, and thus film uniformity. [11] Clearly, the ability to deliberately and reliably improve the stability of perovskite QDs (e.g., against humidity and polar solvents) while retaining their individual nanometer size represents a critical step that underpins future advances in optoelectronic and biological applications.Herein, we report a general and robust strategy by capitalizing on judiciously designed amphiphilic star-like diblock copolymers with well-controlled molecular weight and low polydispersity of each block as molecularly engineered nanoreactors to craft uniform perovskite QDs. Remarkably, these QDs simultaneously possess precisely tunable dimensions Instability of perovskite quantum dots (QDs) toward humidity remains one of the major obstacles for their long-term use in optoelectronic devices. Herein, a general amphiphilic star-like block copolymer nanoreactor strategy for in situ crafting a set of hairy perovskite QDs with precisely tunable size and exceptionally high water and colloidal stabilities is presented. The selective partition of precursors within the compartment occupied by inner hydrophilic blocks of star-like diblock copolymers imparts in situ formation of robust hairy perovskite QDs permanently ligated by outer hydrophobic blocks via coprecipitation in nonpolar solvent. These size-and compositiontunable perovskite QDs reveal impressive water and colloidal stabilities as the surface of QDs is intimately and permanently ligated by a layer of outer ...

The past few years have witnessed rapid advances in the synthesis of high-quality perovskite nanocrystals (PNCs). However, despite the impressive developments, the stability of PNCs remains a substantial challenge. The ability to reliably improve stability of PNCs while retaining their individual nanometer size represents a critical step that underpins future advances in optoelectronic applications. Here, we report an unconventional strategy for crafting dual-shelled PNCs (i.e., polymer-ligated perovskite/SiO2 core/shell NCs) with exquisite control over dimensions, surface chemistry, and stabilities. In stark contrast to conventional methods, our strategy relies on capitalizing on judiciously designed star-like copolymers as nanoreactors to render the growth of core/shell NCs with controlled yet tunable perovskite core diameter, SiO2 shell thickness, and surface chemistry. Consequently, the resulting polymer-tethered perovskite/SiO2 core/shell NCs display concurrently a stellar set of substantially improved stabilities (i.e., colloidal stability, chemical composition stability, photostability, water stability), while having appealing solution processability, which are unattainable by conventional methods.

We report a novel orthogonal lithography fabrication of patterned inorganic perovskite CsPbX 3 (X= Cl, Br, I) quantum dot (QD) arrays which cannot be patterned with traditional approaches. This approach involves a combination of fluorinated polymer and solvent to resolve issues of polar-non-polar solvent constraints thus enabling the fabrication of complex patterns with high optical gain and bright and multicolor emission. We utilized this approach to fabricate high-resolution large-area arrays of microdisk lasers and milticolor (binary-and ternary-emission) pixels. The optical cavity modes of CsPbBr 3 QD microdisk lasers were readily controlled by tuning the disk size, where the mode spacing decreases while the number of modes increases with increasing disk diameter. Finally, we demonstrated the versatility of our approach for the integration of environmentally-sensitive QDs with different emission signatures and composition on the same chip, while achieving high density, highresolution large-area QD arrays with multicolor pixels.