June Huh

Directed Assembly of High Molecular Weight Block Copolymers: Highly Ordered Line Patterns of Perpendicularly Oriented Lamellae with Large Periods

The directed assembly of block copolymer nanostructures with large periods exceeding 100 nm remains challenging because the translational ordering of long-chained block copolymer is hindered by its very low chain mobility. Using a solvent-vapor annealing process with a neutral solvent, which was sequentially combined with a thermal annealing process, we demonstrate the rapid evolution of a perpendicularly oriented lamellar morphology in high molecular weight block copolymer films on neutral substrate. The synergy with the topographically patterned substrate facilitated unidirectionally structural development of ultrahigh molecular weight block copolymer thin films-even for the structures with a large period of 200 nm-leading to perfectly guided, parallel, and highly ordered line-arrays of perpendicularly oriented lamellae in the trenched confinement. This breakthrough strategy, which is applicable to nanolithographic pattern transfer to target substrates, can be a simple and efficient route to satisfy the demand for block copolymer assemblies with larger feature sizes on hundreds of nanometers scale.

Three-Dimensional Multilayered Nanostructures with Controlled Orientation of Microdomains from Cross-Linkable Block Copolymers

Three-dimensional (3D) nanostructures were obtained by the directed formation of multilayer block copolymer (BCP) thin films. The initial step in this strategy involves the assembly and cross-linking of cylinder-forming polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) BCP, in which 1.5 mol % of reactive azido (-N(3)) groups were randomly incorporated along the styrene backbone. Significantly, assembly of thin films of lamellar-forming BCPs on top of the underlying cross-linked cylindrical layer exhibited perpendicular orientations of microdomains between lamellae and cylinder layers. From the theoretical calculation of free energy in the multilayers, it was found that the nematic interactions between polymer chains at the interface play a critical role in the perpendicular orientation of lamellae on the cross-linked cylinder layers. Removal of the PMMA domains then affords nonsymmetrical nanostructures which illustrate the promise of this strategy for the design of well-defined 3D nanotemplates. It was also demonstrated that this structure can be effectively used to enhance the light extraction efficiency of GaN light-emitting diodes. Furthermore, we anticipate that such 3D nanotemplates can be applied to various areas, including advanced BCP nanolithography and responsive surface coating.

Nanopatterning of thin polymer films by controlled dewetting on a topographic pre-pattern

We develop a non-lithographic method for fabricating ordered micro/nanostructures of polymer thin films based on controlled dewetting of the films on topographically pre-patterned substrates with a large area. An ordered nanopattern of polystyrene (PS) is accomplished by thermal treatment of a thin PS film above its Tg spin coated on a topographically patterned substrate. We investigate the influence of pattern geometry on the final morphology of the dewetted polymer films using both mesa and indent patterned substrates. The controlled dewetting, initiated preferentially at the edges of individual pre-patterned mesas, in particular gives rise to spherical cap domains located at the center of the mesas. The domains are much smaller than the individual mesas as a consequence of the significant pattern reduction to nearly 300%. The arrays of 70 nm PS nano-sphere caps are obtained from arrays of 200 nm square pre-patterned mesas. Our method is also applicable for other polymers such as a poly(4-vinyl pyridine) (P4VP) containing Rhodamine 6G (Rh6G) dye on a pre-patterned PS substrate and successfully produced highly fluorescent stable nanopatterned films.

Efficient photocatalytic hybrid Ag/TiO2 nanodot arrays integrated into nanopatterned block copolymer thin films

Well defined, ordered arrays of hybrid Ag/TiO2 hetero nanodots were fabricated on solid substrates using amphiphilic poly(styrene-block-ethylene oxide) diblock copolymer (PS-b-PEO) micelles loaded with AgNO3 and TiO2 sol–gel precursors as templates. The inorganic precursors were selectively incorporated into PEO domains due to specific chemical affinity. The conversion of AgNO3 to metallic Ag was induced by UV irradiation and confirmed by the presence of a surface plasmon band in the UV–vis absorbance spectra. The organic matrix has been removed by deep UV irradiation, leading to arrays of Ag/TiO2 composite nanoparticles (NPs). The morphology and photocatalytic activities of the resulting hybrid nanoparticle arrays were studied. Markedly enhanced photocatalytic degradation of methylene blue has been observed for Ag/TiO2 nanodot arrays compared with pure TiO2 NP arrays.

Synthesis of Thermally Stable Organosilicate for Exfoliated Poly(ethylene terephthalate) Nanocomposite with Superior Tensile Properties

AbstractsA poly(ethylene terephthalate) (PET)/organosilicate nanocomposite, with enhanced mechanical properties, has been prepared using the melt intercalation method. For this purpose, a new organic modifier has been synthesized for the preparation of organosilicate, which is thermally stable and compatible with PET. The use of the new organosilicate yielded almost exfoliated PET nanocomposite; whereas, the PET nanocomposites prepared by use of commercial organoclays (Cloisite 15A and 30B) show only an intercalated morphology. Particularly, the use of the new organosilicate showed an enhanced tensile modulus, andwithout sacrifice of the tensile strength and elongation on breaking, while the use of commercial organoclays only exhibit a trade-off between those mechanical properties.

High-Temperature Operating Non-volatile Memory of Printable Single-Wall Carbon Nanotubes Self-Assembled with a Conjugate Block Copolymer

Printable non-volatile polymer memories are fabricated with solution-processed nanocomposite films of poly(styrene-block-paraphenylene) (PS-b-PPP) and single-wall carbon nanotubes (SWNTs). The devices show stable data retention at high temperatures of up to 100 °C without significant performance degradation due to the strong, non-destructive, and isomorphic π-π interactions between the SWNTs and PPP block.

Printable and Rewritable Full Block Copolymer Structural Color

Structural colors (SCs) of photonic crystals (PCs) arise from selective constructive interference of incident light. Here, an ink-jet printable and rewritable block copolymer (BCP) SC display is demonstrated, which can be quickly written and erased over 50 times with resolution nearly equivalent to that obtained with a commercial office ink-jet printer. Moreover, the writing process employs an easily modified printer for position- and concentration-controlled deposition of a single, colorless, water-based ink containing a reversible crosslinking agent, ammonium persulfate. Deposition of the ink onto a self-assembled BCP PC film comprising a 1D stack of alternating layers enables differential swelling of the written BCP film and produces a full-colored SC display of characters and images. Furthermore, the information can be readily erased and the system can be reset by application of hydrogen bromide. Subsequently, new information can be rewritten, resulting in a chemically rewritable BCP SC display.

Commensurability effect in diblock copolymer lamellar phase under d-dimensional nanoconfinement

We theoretically consider the commensurability problem of AB diblock lamellar phase confined between parallel plates, in cylinder, and in sphere calculating the free energy of confined lamellar phase which is generalized in terms of dimensionality of confinement (d) and conformational asymmetry (ɛ). We find that the first-order layer-addition transition of lamellar layers parallel to the confining surface (L(∥)) becomes suppressed as the dimensionality of confinement increases. For lamellae confined in curved space, the conformational asymmetry alters the location of layer-addition transition point and the stability of L(∥) against nonconcentric layers. When the surface-preferential block becomes flexible, the radius of cylindrically or spherically confined space at the layer-addition transition, where the number of A-B layers of L(∥) changes from l layers to l+1 layers, increases if l is odd and decreases otherwise due to the tendency of less flexible block filling innermost layer. The curved space also weakens the stability L(∥) competing with nonconcentric layers when the surface-preferential block becomes less flexible. The phase maps in the parameter space of conformational asymmetry and degree of confinement are constructed for different cases of the confinement dimensionality and the surface fields, demonstrating the effects of various system variables on the confined lamellar structures.

Ordered Micropatterns by Confined Dewetting of an Imprinted Polymer Thin Film and Their Microlens Application

We fabricated ordered micro/nano patterns induced by controlled dewetting on the topographically patterned PS/P4VP bilayer thin film. The method is based on utilizing microimprinting lithography to induce a topographically heterogeneous bilayer film that allows the controlled dewetting upon subsequent thermal annealing. The dewetting that was initiated strictly at the boundary of the thicker and thinner regions was guided by the presence of the topographic structure. The dewetting front velocity of the microdomains in the confined regions was linearly proportional to the measurement time, which enabled us to control the size of the dewet domain with annealing time. In particular, the submicron sized dot arrays between lines were generated with ease when the dewetting was confined into geometry with a few microns in size. The kinetically driven, non-lithographical pattern structures accompanied the pattern reduction to 400%. The pattern arrays on a transparent glass substrate were especially useful for noncircular microlens arrays where the focal length of the lens was easily tunable by controlling the thermal annealing.

Functionalized Soft Nanoporous Materials through Supramolecular Assembly of End‐Functionalized Polymer Blends

Supramolecular assembly through complementary interaction between molecular subgroups belonging to phase-separating polymer species offers a great opportunity, not only for constructing nanoscale soft templates reminiscent of conventional block copolymer morphologies, but also for tailoring surface properties by facile removal of one of the structure components by cleaving complementary interactions. Herein we report the fabrication of a novel, organic, nanoporous film through supramolecular assembly of two complementarily, end-interacting, mono-end-functionalized polymers under solvent annealing. The film of end-functionalized polymer blends under solvent annealing yielded phase-separated nanodomains that resemble nanoscopically ordered structures of block copolymers, but that are more advantageous due to easily cleavable and exchangeable links between the phase-separated domains. The removal of one of the components of the precursor structure formed from the end-functionalized polymers through cleavage of complementary interactions allowed us to fabricate mono- or multilayered nanoporous structures in which the chemically useful end-functionalities of the remnant polymers are rich on the surface of the pores. The resultant, organic, nanoporous films with tailored surface functionality offer a useful platform for various chemical and biological applications.