Orientation and stretching of supracolloidal chains of diblock copolymer micelles by spin-coating process.

Supracolloidal chains consisting of nano- or micro-scale particles exhibit anisotropic properties not observed in individual particles. The orientation of the chains is necessary to manifest such characteristics on a macroscopic scale. In this study, we demonstrate the orientation of supracolloidal chains composed of nano-scale micelles of a diblock copolymer through spin-coating. We observed separate chains coated on a substrate with electron microscopy, and analyzed the orientation and stretching of the chains quantitatively with image analysis software. In drop-casting, the chains were coated randomly with no preferred orientation, and the degree of stretching exhibited an intrinsic semi-flexible nature. In contrast, spin-coated chains were aligned in the radial direction, and the apparent persistence length of the chain increased, confirming the stretching of the chain quantitatively. Furthermore, by incorporating fluorophores into supracolloidal chains and confirming the oriented chains with confocal fluorescence microscopy, it is demonstrated that oriented chains can be utilized as a template to align functional materials.

Step-growth polymerization of supracolloidal chains from patchy micelles of diblock copolymers.

HYPOTHESIS: The formation of supracolloidal chains from the patchy micelles of diblock copolymers bears a close resemblance to traditional step-growth polymerization of difunctional monomers in many aspects, including chain-length evolution, size distribution, and initial-concentration dependence. Thus, understanding the colloidal polymerization based on the step-growth mechanism can offer potential control over the formation of supracolloidal chains in terms of chain structure and reaction rate. EXPERIMENTS: We analyzed the size evolution of supracolloidal chains of patchy micelles of PS-b-P4VP by investigating a large number of colloidal chains visualized in SEM images. We varied the initial concentration of patchy micelles to achieve a high degree of polymerization and a cyclic chain. To manipulate the polymerization rate, we also changed the ratio of water to DMF and adjusted the patch size by employing PS(25)-b-P4VP(7) and PS(145)-b-P4VP(40). FINDINGS: We confirmed the step-growth mechanism for the formation supracolloidal chains from patchy micelles of PS-b-P4VP. Based on this mechanism, we were able to achieve a high degree of polymerization early in the reaction by increasing the initial concentration and form cyclic chains by diluting the solution. We also accelerated colloidal polymerization by increasing the ratio of water to DMF in the solution and patch size by using PS-b-P4VP with a larger molecular weight.

High-Density, Localized Quantum Emitters in Strained 2D Semiconductors.

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect- and strain-induced single-photon emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach for creating large areas of localized emitters with high density (∼150 emitters/um2) in a WSe2 monolayer. We induce strain inside the WSe2 monolayer with high spatial density by conformally placing the WSe2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters will be applied to scalable, tunable, and versatile quantum light sources.

White-emitting film of diblock copolymer micelles with perovskite nanocrystals.

Perovskite nanocrystals are synthesized in diblock copolymer micelles to improve their processability and stability. The copolymer micelle approach allows fluorescence from a stretchable or flexible substrate by coating processes, and stable emission in water by protecting the nanocrystals in the micelles. Fluorescent films in three primary colors of blue, green, and red are also produced with the assistance of anion exchange reactions for perovskite nanocrystals in the micelles. Then, by stacking films in three primary colors, we are able to produce a white-emitting film of copolymer micelles containing only perovskite nanocrystals without the support of other kinds of emissive materials.

Patch formation on diblock copolymer micelles confined in templates for inducing patch orientation and cyclic colloidal molecules.

HYPOTHESIS: Chemically or physically distinct patches can be induced on the micelles of amphiphilic block copolymers, which facilitate directional binding for the creation of hierarchical structures. Hence, control over the direction of patches on the micelles is a crucial factor to attain the directionality on the interactions between the micelles, particularly for generating colloidal molecules mimicking the symmetry of molecular structures. We hypothesized that direction and combination of the patches could be controlled by physical confinement of the micelles. EXPERIMENTS: We first confined spherical micelles of diblock copolymers in topographic templates fabricated from nanopatterns of block copolymers by adjusting the coating conditions. Then, patch formation was conducted on the confined micelles by exposing them with a core-favorable solvent. Microscopic techniques of SEM, TEM, and AFM were employed to investigate directions of patches and structures of combined micelles in the template. FINDINGS: The orientation of the patches on the micelles was guided by the physical confinement of the micelles in linear trenches. In addition, by confining the micelles in a circular hole, we obtained a specific polygon arrangement of the micelles depending on the number of micelles in the hole, which enabled the formation of cyclic colloidal molecules consisting of micelles.

In situ conversion from crew-cut to hairy micelles by surface-initiated polymerization.

Whether spherical micelles of block copolymers have short or long coronas is intrinsically determined by the molecular weight of the corona-forming block with respect to that of the core block before the micelles are assembled. Because of the inherent conditions of packing copolymer chains into a micelle, the core diameter is altered when we assemble a micelle from a block copolymer having a long corona block, compared to that having a short corona block with the same length of the core block. However, micelles with the same core diameter but having various corona lengths can be guaranteed when the corona is extended upon surface-initiated polymerization on the micelles. Herein, we demonstrated in situ conversion from crew-cut to hairy micelles by selectively extending a corona block while maintaining the spherical shape of block copolymer micelles. We first synthesized block copolymers having a chain transfer agent (CTA) positioned at the end of the corona block and then assembled them into a crew-cut micelle. Employing this micelle as an assembly of macro-CTAs, we conducted surface-initiated polymerization on the micelle by photo-induced energy/electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Since PET-RAFT enables the polymerization at room temperature, the corona block was selectively extended with preservation of the core diameter, thereby converting a crew-cut micelle to a hairy one. In addition, by applying the same polymerization protocol to a worm-like micelle, we could selectively extend the coronas, leading to the formation of a worm-like micelle with a long corona. If such copolymer chains were assembled into a micelle, we would obtain a spherical micelle instead of a worm-like micelle having a hairy corona, which is difficult to assess because of the inherent packing problem.

Porous self-supporting film of semi-flexible supracolloidal chains of diblock copolymer micelles.

Patchy micelles of diblock copolymers can be polymerized into a linear supracolloidal chain. We measure the persistence and contour lengths of supracolloidal chains coated on a solid substrate to evaluate their flexibility. Based on the analysis, the chain is semi-flexible, and the conformation is suitably explained by the worm-like chain model. In addition, utilizing a spin-coating technique with the semi-flexible nature of the chains, we produce a self-supporting film of supracolloidal chains having nanoscale pores essentially from colloidal constituents that tend to form dense packing if there is no prior organization of them into a semi-flexible chain.

Blue emission at atomically sharp 1D heterojunctions between graphene and h-BN.

Atomically sharp heterojunctions in lateral two-dimensional heterostructures can provide the narrowest one-dimensional functionalities driven by unusual interfacial electronic states. For instance, the highly controlled growth of patchworks of graphene and hexagonal boron nitride (h-BN) would be a potential platform to explore unknown electronic, thermal, spin or optoelectronic property. However, to date, the possible emergence of physical properties and functionalities monitored by the interfaces between metallic graphene and insulating h-BN remains largely unexplored. Here, we demonstrate a blue emitting atomic-resolved heterojunction between graphene and h-BN. Such emission is tentatively attributed to localized energy states formed at the disordered boundaries of h-BN and graphene. The weak blue emission at the heterojunctions in simple in-plane heterostructures of h-BN and graphene can be enhanced by increasing the density of the interface in graphene quantum dots array embedded in the h-BN monolayer. This work suggests that the narrowest, atomically resolved heterojunctions of in-plane two-dimensional heterostructures provides a future playground for optoelectronics.

Shearing with solvent vapor annealing on block copolymer thin films for templates with macroscopically aligned nanodomains.

A template with macroscopically aligned nanopatterns can be an effective vehicle for arranging nanoscale particles or rods in a particular orientation to achieve their anisotropic properties. A room-temperature process is also desirable for nanoscale patterning of heat-sensitive functional molecules such as organic fluorophores. Here, large-area orientation of nanodomains of block copolymers is demonstrated by simultaneous shearing and solvent vapor annealing at room temperature. The shear-aligned nanodomains are applied to a chemical template for nanoscale patterning of green fluorescent molecules. In addition, the grooved nanochannels obtained from the macroscopically aligned nanodomains work as a physical template for guiding Au nanorods to end-to-end assemblies which exhibit the polarization-dependent plasmonic extinction.

Author Correction: Planar and van der Waals heterostructures for vertical tunnelling single electron transistors.

The original version of this Article contained an error in the spelling of the author Matthew Holwill, which was incorrectly given as Mathew Holwill. This has now been corrected in both the PDF and HTML versions of the Article.

Planar and van der Waals heterostructures for vertical tunnelling single electron transistors.

Despite a rich choice of two-dimensional materials, which exists these days, heterostructures, both vertical (van der Waals) and in-plane, offer an unprecedented control over the properties and functionalities of the resulted structures. Thus, planar heterostructures allow p-n junctions between different two-dimensional semiconductors and graphene nanoribbons with well-defined edges; and vertical heterostructures resulted in the observation of superconductivity in purely carbon-based systems and realisation of vertical tunnelling transistors. Here we demonstrate simultaneous use of in-plane and van der Waals heterostructures to build vertical single electron tunnelling transistors. We grow graphene quantum dots inside the matrix of hexagonal boron nitride, which allows a dramatic reduction of the number of localised states along the perimeter of the quantum dots. The use of hexagonal boron nitride tunnel barriers as contacts to the graphene quantum dots make our transistors reproducible and not dependent on the localised states, opening even larger flexibility when designing future devices.

Fluorescent Supracolloidal Chains of Patchy Micelles of Diblock Copolymers Functionalized with Fluorophores.

By selective attachment of fluorescent dyes to the core-forming block, we produced patchy micelles of diblock copolymers with fluorophores localized in the micellar cores. From these patchy micelles functionalized with dyes, fluorescent supracolloidal chains in a few micrometers were polymerized by combining the patches in neighboring micelles, indicating that selective modification of the core-forming block delivered the functionality into the supracolloidal chain without altering the polymerization of patchy micelles. Thus, with the same polymerization condition, we were able to produce red-, green-, and blue-emitting supracolloidal chains by varying the fluorescent dyes attached to the core-forming block. In addition, we directly visualized individual supracolloidal chains by fluorescence confocal microscopy as well as by transmission electron microscopy.

Supracolloidal chains of patchy micelles of diblock copolymers with in situ synthesized nanoparticles.

Supracolloidal chains of diblock copolymer micelles were functionalized with gold and silver nanoparticles (NPs). Both NPs were independently synthesized in situ in the core of spherical micelles which were then converted to patchy micelles. With these patchy micelles as colloidal monomers, supracolloidal chains were polymerized by combining the patches of neighboring micelles. Since all micelles contained NPs, NPs were incorporated in every repeat unit of chains. In addition, a single gold NP was synthesized in the micellar core in contrast to several silver NPs so that we differentiated the chains with Au NPs from those with Ag NPs by the number of NPs in the repeat unit as well as by plasmonic bands in UV-Vis spectra.

Fabrication of size-controlled nanoring arrays by selective incorporation of ionic liquids in diblock copolymer micellar cores.

We report the synthesis of arrayed nanorings with tunable physical dimensions from thin films of polystyrene-block-poly(4-vinylpyridine) (PS-P4VP) micelles. For accurate control of the inner and outer diameters of the nanorings, we added imidazolium-based ionic liquids (ILs) into the micellar solution, which were eventually incorporated into the micellar cores. We observed the structural changes of the micellar cores coated on a substrate due to the presence of ILs. The spin-coated micellar cores were treated with an acidic precursor solution and generated toroid nanostructures, of which size depended on the amount of IL loaded into the micelles. We then treated the transformed micellar films with oxygen plasma to produce arrays of various metal and oxide nanorings on a substrate. The spacings and diameters of nanorings were governed by the molecular weight of the PS-P4VP and the amount of IL used. We also demonstrated that arrayed Pt nanorings enabled the fabrication of reduced graphene oxide anti-nanoring arrays via a catalytic tailoring process.

Branched and crosslinked supracolloidal chains with diblock copolymer micelles having three well-defined patches.

We report controlled branching and eventual crosslinking in supracolloidal chains by introducing well-defined trifunctional patchy micelles. Uniform micelles having three patches were induced from core-crosslinked micelles of diblock copolymers. Three patches in the micelles served as functional groups for crosslinking as well as branching in supracolloidal polymerization.

Short-range ordered photonic structures of lamellae-forming diblock copolymers for excitation-regulated fluorescence enhancement.

Photonic crystals can be represented by periodic nanostructures with alternating refractive indices, which create artificial stop bands with the appearance of colors. In this regard, nanodomains of block copolymers and the corresponding structural colors have been intensively studied in the past. However, the practical application of photonic crystals of block copolymers has been limited to a large degree because of the presence of large defects and grain boundaries in the nanodomains of block copolymers. The present study focuses on the alternative opportunity of short-range ordered nanodomains of block copolymers for fluorescence enhancement, which also has a direct relevance to the development of fluorescence sensors or detectors. The enhancement mechanism was found to be interconnected with the excitation process rather than the alternation of the decay kinetics. In particular, we demonstrate that randomly oriented, but regular grains of lamellae of polystyrene-block-polyisoprene, PS-b-PI, diblock copolymers and their blend with PS homopolymers can behave as Bragg mirrors to induce multiple reflections of the excitation source inside the photonic structures. This process in turn significantly increases the effective absorption of the given fluorophores inside the polymeric photonic structures to amplify the fluorescence signal.

Vertically aligned nanostructured TiO2 photoelectrodes for high efficiency perovskite solar cells via a block copolymer template approach.

We fabricated perovskite solar cells with enhanced device efficiency based on vertically oriented TiO2 nanostructures using a nanoporous template of block copolymers (BCPs). The dimension and shape controllability of the nanopores of the BCP template allowed for the construction of one-dimensional (1-D) TiO2 nanorods and two-dimensional (2-D) TiO2 nanowalls. The TiO2 nanorod-based perovskite solar cells showed a more efficient charge separation and a lower charge recombination, leading to better performance compared to TiO2 nanowall-based solar cells. The best solar cells employing 1-D TiO2 nanorods showed an efficiency of 15.5% with VOC = 1.02 V, JSC = 20.0 mA cm(-2) and fill factor = 76.1%. Thus, TiO2 nanostructures fabricated from BCP nanotemplates could be applied to the preparation of electron transport layers for improving the efficiency of perovskite solar cells.

Fluorescent supracolloidal polymer chains with quantum dots.

We demonstrate the fabrication of fluorescent supracolloidal chains functionalized with quantum dots, which were polymerized from patched micelles of diblock copolymers by adjusting the polarity of the solvent. Supracolloidal random and block chains with green- and red-emitting quantum dots were also synthesized.

Transferrable superhydrophobic TiO2 nanorods on reduced graphene oxide films using block copolymer templates.

Superhydrophobic surfaces are normally fixed on the chosen materials. Here, we report transferrable superhydrophobicity which was enabled by fabricating TiO2 nanorods on a reduced graphene oxide (rGO) film. Superhydrophobic TiO2 nanorods were first synthesized from a nanoporous template of block copolymers (BCPs). The controllability over the dimension and shape of nanopores of the BCP template allowed for the adjustment of TiO2 nanostructures for superhydrophobicity. Since the rGO film provided effective transferring, TiO2 nanorods were conveyed onto a flexible polymer film and a metal substrate. Thus, the surface of the designated substrate was successfully changed to a superhydrophobic surface without alteration of its inherent characteristics.

Energy and charge transfer in nanoscale hybrid materials.

Hybrid materials composed of colloidal semiconductor quantum dots and π-conjugated organic molecules and polymers have attracted continuous interest in recent years, because they may find applications in bio-sensing, photodetection, and photovoltaics. Fundamental processes occurring in these nanohybrids are light absorption and emission as well as energy and/or charge transfer between the components. For future applications it is mandatory to understand, control, and optimize the wide parameter space with respect to chemical assembly and the desired photophysical properties. Accordingly, different approaches to tackle this issue are described here. Simple organic dye molecules (Dye)/quantum dot (QD) conjugates are studied with stationary and time-resolved spectroscopy to address the dynamics of energy and ultra-fast charge transfer. Micellar as well as lamellar nanostructures derived from diblock copolymers are employed to fine-tune the energy transfer efficiency of QD donor/dye acceptor couples. Finally, the transport of charges through organic components coupled to the quantum dot surface is discussed with an emphasis on functional devices.