Block Copolymer Patterns Research Articles

Roll-to-plate 0.1-second shear-rolling process at elevated temperature for highly aligned nanopatterns

The shear-rolling process is a promising directed self-assembly method that can produce high-quality sub−10 nm block copolymer line-space patterns cost-effectively and straightforwardly over a large area. This study presents a high temperature (280 °C) and rapid (~0.1 s) shear-rolling process that can achieve a high degree of orientation in a single process while effectively preventing film delamination, that can be applied to large-area continuous processes. By minimizing adhesion, normal forces, and ultimate shear strain of the polydimethylsiloxane pad, shearing was successfully performed without peeling up to 280 °C at which the chain mobility significantly increases. This method can be utilized for various high-χ block copolymers and surface neutralization processes. It enables the creation of block copolymer patterns with a half-pitch as small as 8 nm in a unidirectional way. Moreover, the 0.1-second rapid shear-rolling was successfully performed on long, 3-inch width polyimide flexible films to validate its potential for the roll-to-roll process.

Direct Printing of Ultrathin Block Copolymer Film with Nano-in-Micro Pattern Structures.

Nanotransfer printing (nTP) is one of the most promising nanopatterning methods given that it can be used to produce nano-to-micro patterns effectively with functionalities for electronic device applications. However, the nTP process is hindered by several critical obstacles, such as sub-20nm mold technology, reliable large-area replication, and uniform transfer-printing of functional materials. Here, for the first time, a dual nanopatterning process is demonstrated that creates periodic sub-20nm structures on the eight-inch wafer by the transfer-printing of patterned ultra-thin (<50nm) block copolymer (BCP) film onto desired substrates. This study shows how to transfer self-assembled BCP patterns from the Si mold onto rigid and/or flexible substrates through a nanopatterning method of thermally assisted nTP (T-nTP) and directed self-assembly (DSA) of Si-containing BCPs. In particular, the successful microscale patternization of well-ordered sub-20nm SiOx patterns is systematically presented by controlling the self-assembly conditions of BCP and printing temperature. In addition, various complex pattern geometries of nano-in-micro structures are displayed over a large patterning area by T-nTP, such as angular line, wave line, ring, dot-in-hole, and dot-in-honeycomb structures. This advanced BCP-replicated nanopatterning technology is expected to be widely applicable to nanofabrication of nano-to-micro electronic devices with complex circuits.

Nano sized gallium oxide surface features for enhanced antimicrobial and osteo-integrative responses

Gallium oxide has known beneficial osteo-integrative properties. This may have importance for improving the osteointegration of orthopedic implants. At high concentrations gallium is cytotoxic. Therefore, integration of gallium into implant devices must be carefully controlled to limit its concentration and release. A strategy based on surface doping of gallium although challenging seems an appropriate approach to limit dose amounts to minimize cytotoxicity and maximize osteointegration benefits. In this work we develop a novel form of patterned surface doping via a block copolymer-based surface chemistry that enables very low gallium content but enhanced osteointegration as proven by comprehensive bioassays. Polystyrene-b-poly 4vinyl pyridine (PS-b-P4VP) BCP (block copolymer) films were produced on surfaces. Selective infiltration of the BCP pattern with a gallium salt precursor solution and subsequent UV-ozone treatment produced a surface pattern of gallium oxide nanodots as evidenced by atomic force and scanning electron microscopy. A comprehensive study of the bioactivity was carried out, including antimicrobial and sterility testing, gallium ion release kinetics and the interaction with human marrow mesenchymal stomal cells and mononuclear cells. Comparing the data from osteogenesis media assay tests with osteoclastogenesis tests demonstrated the potential for the gallium oxide nanodot doping to improve osteointegration properties of a surface.

Trilayered Block Copolymer Nanostructures Formed by an Iterative Layering Strategy

AbstractNanostructured block copolymer (BCP) thin films enable the formation on‐demand of a variety of periodic patterns at the nanometer scale by tuning the macromolecular BCP characteristics and annealing processes. Significant progress in the control of the self‐assembly has been witnessed over the past decade with the implementation of robust directed self‐assembly methods. However, the self‐assembled structural patterns obtained at equilibrium are limited and methods to expand the range of structural configurations are required to harness additional functionalities. Here, this work demonstrates how polystyrene‐b‐poly(methyl methacrylate) BCP thin layers can be stacked to produce a library of complex 3D hierarchical heterostructures. In this iterative assembly process based on simple building bricks (i.e., immobilized BCP patterns forming Holes, Lines and Dots), the stacking configuration (i.e., self‐assembly and registration) of a BCP thin film is directed with respect to the previous layer using confinement effects and interfacial energy tuning. This responsive layering can lead to intricate 3D Al2O3 structures and opens the way to a broad variety of structural designs toward functional applications.

Dewetting-Induced Hierarchical Self-Assembly of Block Copolymers Templated by Colloidal Crystals.

Recent advances in high-performance flexible electronic devices have increased the demand for more diverse and complex nanofabrication methods; high-resolution, high-efficiency, and low-cost patterning strategies for next-generation devices are therefore required. In this study, we demonstrate the formation of dewetting-induced hierarchical patterns using two self-assembled materials: block copolymers (BCPs) and colloidal crystals. The combination of the two self-assembly methods successfully generates multiscale hierarchical patterns because the length scales of the periodic colloidal crystal structures are suitable for templating the BCP patterns. Various concentric ring patterns were observed on the templated BCP films, and a free energy model of the polymer chain was applied to explain the formation of these patterns relative to the template width. Frequently occurring spiral-defective features were also examined and found to be promoted by Y-junction defects.

Nanostructured doping of WSe2via block copolymer patterns and its self-powered photodetector application.

Transition metal dichalcogenides (TMDs), e.g., MoS2, MoSe2, ReS2, and WSe2, are effective materials for advanced optoelectronics owing to their intriguing optical, structural, and electrical properties. Various approaches for manipulating the surface of the TMDs have been suggested to unleash the optoelectronic potential of the TMDs. Herein, we employed the self-assembly of the poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer (BCP) to prepare a nanoporous pattern and generate nanostructured charge-transfer p-doping on the WSe2 surface, maximizing the depletion region in the absorber layer. After the spin coating and thermal annealing of PS-b-PMMA, followed by the selective etching of PMMA cylindrical microdomains using oxygen reactive-ion plasma, nanopatterned WOx with high electron affinity was grown on the WSe2 surface, forming a three-dimensional homojunction. The nanopatterned WOx significantly expanded the depletion region in the WSe2 layer, thus enhancing optoelectronic performance and self-powered photodetection. The proposed approach based on the nanostructured doping of the TMDs via BCP nanolithography can help create a promising platform for highly functional optoelectrical devices.

(Invited) ALD-Based Infiltration and Growth of Inorganic Materials in Polymers

Sequential infiltration synthesis (SIS) has emerged in the past decade as a powerful technique for growth of inorganic materials within polymers through atomic layer deposition (ALD) chemistry. In SIS, ALD precursors diffuse into the polymer and interact with it, leading to inorganic materials growth within the polymer’s free volume. If desired, the polymer can later be removed, yielding polymer-templated inorganic structures. Combining SIS with self-assembled block copolymer (BCP) patterns results in selective growth of inorganic materials within the polar domains of the BCP, making it an attractive method for directed templating of inorganic nanostructures. Thus, SIS opens a pathway for exploiting ALD precision and rich materials library in new 3D morphologies, defined by the polymer.To build SIS design rules and expand SIS’ possibilities, we probed SIS growth and evolution at the atomic scale and explored the role of reversible polymer-precursor interactions in SIS growth through a plethora of methods: in-situ growth analysis (microgravimetry and FTIR), ex-situ high-resolution electron microscopy and extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations. This knowledge was then applied in fabrication by design of metal oxide fibers, porous particles, and membranes.We fabricated Al2O3 and ZnO nanofibers, nanobelts, and core-shell fibers using designed growth profiles within electrospun polymer fibers. By controlling the organometallic precursors’ diffusion time, simultaneous but spatially controlled growth of Al2O3 and ZnO within the fibers was achieved, leading to the formation of metal oxide core-shell fibers. Self-assembled BCP particles were used to template porous metal oxide particles by selective growth of Al2O3 in the major block of the self-assembled structure. The uniform BCP assembly led to uniporous pores in the metal oxide particles. Finally, we utilized SIS and ALD within and onto BCP membranes for exceptional pore size control and pores’ surface engineering, yielding highly selective filtration membranes.

Large-area patterning for broadband, quasi-omnidirectional low-reflectance glass

A method for producing large-area, broadband, quasi-omnidirectional low-reflectivity glass surfaces is presented. Using block copolymer patterning and inductively coupled plasma etching, near-periodic arrays of pillars are formed in glass. The patterned surface has reflectivity 0.5%—almost an order of magnitude smaller than plain glass—with a bandwidth of ∼300 nm. Substrates etched on both sides transmit 99.5% across the wavelength range 850–1200 nm, with 99% down to λ = 650 nm. The process is demonstrated on a 5 cm diameter fused silica wafer and high transmittance is maintained up to at least 70∘ incidence. The resulting substrates might find application as lab optics (windows, lenses, etc) display screens for televisions, computers, phones, and as encapsulants for optoelectronic devices.

Facile and Fast Interfacial Engineering Using a Frustrated Interfacial Self‐Assembly of Block Copolymers for Sub‐10‐nm Block Copolymer Nanopatterning

AbstractA requisite for successful nanopatterning is a precise interface control to meet the adequate surface energies. In block copolymer (BCP) nanopatterning, the interfaces need to be neutralized, promoting both blocks to wet the substrate, and thus realizing the perpendicular orientation of BCPs. However, conventional methods for surface neutralization are expensive and require complex multi‐step processes, which hinders the application of BCP to continuous lithography processes. In this study, the simplest method for controlling the out‐of‐plane domain orientation using frustrated interfacial self‐assembly (FISA) of BCPs is introduced. The FISA layer is a randomly segregated structure that is readily created from the air/water interface. The FISA layer can be transferred to any target substrate, neutralizing both free and substrate interfaces. Employing FISA, the highly aligned and perpendicularly oriented sub‐10‐nm BCP patterns are produced with exceptional simplicity.

Directed Self‐Assembly for Dense Vertical III–V Nanowires on Si and Implications for Gate All‐Around Deposition

AbstractFabrication of next generation transistors calls for new technological requirements, such as reduced size and increased density of structures. Development of cost‐effective processing techniques to fabricate small‐pitch vertical III–V nanowires over large areas will be an important step toward realizing dense gate all‐around transistors, having high electron mobility, and low power consumption. It is demonstrated here, how arrays of III–V nanowires with a controllable number of rows, ranging from one single row up to bands of 500 nm, can be processed by directed self‐assembly (DSA) of block copolymer (BCP). Furthermore, it is shown that the DSA‐orientation with respect to the substrate's crystal direction affects the nanowire facet configuration, and thereby the nanowire spacing and gate all‐around deposition possibilities. A high χ poly(styrene)‐block‐poly(4‐vinylpyridine) BCP pattern directed by electron beam lithography‐defined guiding lines is transferred into silicon nitride. The silicon nitride is then used as a selective area metal‐organic vapor phase epitaxy mask atop an indium arsenide (InAs) buffer layer on a silicon platform to grow vertical InAs nanowires at 44–60 nm row pitch. Finally, deposition of high‐κ oxide and titanium nitride at this high pattern density is demonstrated, to further illustrate the considerations needed for next generation transistors.

Shear-Rolling Process for Unidirectionally and Perpendicularly Oriented Sub-10-nm Block Copolymer Patterns on the 4 in Scale.

Shear alignment of the block copolymer (BCP) thin film is one of the promising directed self-assembly (DSA) methodologies for the unidirectional alignment of sub-10 nm microdomains of BCPs for next-generation nanolithography and nanowire-grid polarizers. However, because of the differences in the surface/interfacial energies at the top surface/bottom interface, the shear-induced ordering of BCP nanopatterns has been restricted to BCPs with spherical and cylindrical nanopatterns and cannot be realized for high-aspect-ratio perpendicular lamellar structures, which is essential for practical application to semiconductor pattern processes. It is still a difficult challenge to fabricate the unidirectional alignment in a short time over a large area. In this study, we propose an approach for combining the shear-rolling process with the filtered plasma treatment of BCP films for the fabrication of unidirectionally aligned and perpendicularly oriented lamellar nanostructures. This approach enables fabrication within 1 min on a 4 in scale. We treated filtered plasma on the BCP film for perpendicular orientation and executed the hot-rolling process with different roller and stage speeds. Large-scale shear was generated only at the location where the BCP film was in contact with both the roller and stage, effectively applying shear stress to a large area of the BCP film within a short time. The repeated application of this shear-rolling process can achieve a higher level of unidirectional alignment. Our aligned BCP vertical lamellae were used to fabricate a high-aspect-ratio sub-10-nm-wide metallic nanowire array via dry/wet processes. In addition, shear-rolling with chemoepitaxy patterns can achieve higher orientational order and lower defectivity.

Structural Evolution of Nanophase Separated Block Copolymer Patterns in Supercritical CO2.

Nanopatterns can readily be formed by annealing block copolymers (BCPs) in organic solvents at moderate or high temperatures. However, this approach can be challenging from an environmental and industrial point of view. Herein, we describe a simple and environmentally friendly alternative to achieve periodically ordered nanoscale phase separated BCP structures. Asymmetric polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin film patterns of different molecular weight were achieved by annealing in supercritical carbon dioxide (sc-CO2). Microphase separation of PS-b-PEO (16,000–5000) film patterns were achieved by annealing in scCO2 at a relatively low temperature was previously reported by our group. The effects of annealing temperature, time and depressurisation rates for the polymer system were also discussed. In this article, we have expanded this study to create new knowledge on the structural and dimensional evolution of nanohole and line/space surface periodicity of four other different molecular weights PS-b-PEO systems. Periodic, well defined, hexagonally ordered films of line and hole patterns were obtained at low CO2 temperatures (35–40 °C) and pressures (1200–1300 psi). Further, the changes in morphology, ordering and feature sizes for a new PS-b-PEO system (42,000–11,500) are discussed in detail upon changing the scCO2 annealing parameters (temperature, film thickness, depressurization rates, etc.). In relation to our previous reports, the broad annealing temperature and depressurisation rate were explored together for different film thicknesses. In addition, the effects of SCF annealing for three other BCP systems (PEO-b-PS, PS-b-PDMS, PS-b-PLA) is also investigated with similar processing conditions. The patterns were also generated on a graphoepitaxial substrate for device application.

Lithographically Defined Cross-Linkable Top Coats for Nanomanufacturing with High-χ Block Copolymers.

The directed self-assembly (DSA) of block copolymers (BCPs) is a powerful method for the manufacture of high-resolution features. Critical issues remain to be addressed for successful implementation of DSA, such as dewetting and controlled orientation of BCP domains through physicochemical manipulations at the BCP interfaces, and the spatial positioning and registration of the BCP features. Here, we introduce novel top-coat (TC) materials designed to undergo cross-linking reactions triggered by thermal or photoactivation processes. The cross-linked TC layer with adjusted composition induces a mechanical confinement of the BCP layer, suppressing its dewetting while promoting perpendicular orientation of BCP domains. The selection of areas of interest with perpendicular features is performed directly on the patternable TC layer via a lithography step and leverages attractive integration pathways for the generation of locally controlled BCP patterns and nanostructured BCP multilayers.

Strategy for Enhancing Ultrahigh-Molecular-Weight Block Copolymer Chain Mobility to Access Large Period Sizes (>100 nm).

Assembling ultrahigh-molecular-weight (UHMW) block copolymers (BCPs) in rapid time scales is perceived as a grand challenge in polymer science due to slow kinetics. Through surface engineering and identifying a nonvolatile solvent (propylene glycol methyl ether acetate, PGMEA), we showcase the impressive ability of a series of lamellar poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) BCPs to self-assemble directly after spin-coating. In particular, we show the formation of large-period (≈111 nm) lamellar structures from a neat UHMW PS-b-P2VP BCP. The significant influence of solvent-polymer solubility parameters are explored to enhance the polymer chain mobility. After optimization using solvent vapor annealing, increased feature order of ultralarge-period PS-b-P2VP BCP patterns in 1 h is achieved. Isolated metallic and dielectric features are also demonstrated to exemplify the promise that large BCP periods offer for functional applications. The methods described in this article center on industry-compatible patterning schemes, solvents, and deposition techniques. Thus, our straightforward UHMW BCP strategy potentially paves a viable and practical path forward for large-scale integration in various sectors, e.g., photonic band gaps, polarizers, and membranes that demand ultralarge period sizes.

Block copolymer directed self-assembly defect modes induced by localized errors in chemoepitaxial guiding underlayers: A molecular simulation study

Block copolymer (BCP) directed self-assembly (DSA) has been presented as a potential economically attractive enhancement to extend the capabilities of optical lithography for semiconductor manufacturing. One concern in DSA is the level of defectivity that can be achieved in such a process. Although entropic effects will always lead to some degree of defectivity, highly ordered structures with a low theoretical equilibrium defect density can be produced by guiding the ordering and placement of the BCP domains using a patterned underlayer. Recent experimental studies have shown that while DSA processes can significantly reduce the observed defect density, defectivity levels are generally still higher than allowable for high-volume manufacturing and higher than what would be anticipated from free energy estimates of the observed defect modes. In particular, bridge defects are one of the most commonly observed defect modes in experimental DSA studies. A number of hypotheses have been proposed to explain the origins of these defects. One hypothesis is that so-called affinity defects present in the underlayer can spawn bridge defects in the overlying BCP film. The goal of the work reported here was to investigate the extent to which bridge defects can be generated or further reinforced in lamellae-forming block copolymer films due to affinity defects in the underlayer pattern. Coarse-grained molecular dynamics simulations were used to simulate the chemoepitaxial DSA of monodisperse block copolymer films atop underlayers with varying affinity defect sizes. Affinity defects were simulated by creating circular regions of a single polymer block type (which is the opposite block type of that used to pattern the underlayer guiding stripes) in the nominally neutral background region of the underlayer. These affinity defects were positioned in regions of the underlayer where they were the incorrect type to match the overlying block copolymer pattern. It was observed that the presence of an affinity defect in the neutral region of the underlayer caused the energetically preferential polymer block to wet the affinity defect, thus creating the nucleus of what could potentially become a bridge defect—even when the affinity defects were very small. As the radius of the underlayer affinity defect (RoD) increased, the amount of block copolymer of incorrect type (with respect to a perfectly assembled copolymer pattern) that assembled above the affinity defect increased; but, in general, the thickness of the wetting layer in contact with the affinity defect was only roughly one polymer chain thick. These data suggest that an affinity defect in the underlayer alone is unlikely to be noticeably enhanced by significant bridge defect formation in a monodisperse block copolymer film.

Commensurability-Driven Orientation Control during Block Copolymer Directed Self-Assembly.

In this study, the orientation of block copolymer (BCP) patterns in topographical templates is controlled using a simple template design rule. The orientation of the pattern is selected by using a template with one commensurate dimension and one incommensurate dimension. An array of binary states of a BCP pattern can be programmed into a desired layout by tuning of the template wall thickness.

High-Fidelity, Sub-5 nm Patterns from High-χ Block Copolymer Films with Vapor-Deposited Ultrathin, Cross-Linked Surface-Modification Layers.

Despite their capability, sub-10 nm periodic nano-patterns formed by strongly segregating block copolymer (BCP) thin films cannot be easily oriented perpendicular to the substrate due to the huge surface energy differences of the constituent blocks. To produce perpendicular nano-patterns, the interfacial energies of both the substrate and free interfaces should be controlled precisely to induce non-preferential wetting. Unfortunately, high-performance surface modification layers are challenging to design, and different kinds of surface modification methods must be devised respectively for each neutral layer and top coat. Furthermore, conventional approaches, largely based on spin-coating processes, are highly prone to defect formation and may readily cause dewetting at sub-10 nm thickness. To date, these obstacles have hampered the development of high-fidelity, sub-5 nm BCP patterns. Herein, an all-vapor phase deposition approach initiated chemical vapor deposition is demonstrated to form 9-nm-thick, uniform neutral bottom layer and top coat with exquisite control of composition and thickness. These layers are employed in BCP films to produce perpendicular cylinders with a diameter of ≈4 nm that propagate throughout a BCP thickness of up to ≈60 nm, corresponding to five natural domain spacings of the BCP. Such a robust approach will serve as an advancement for the reliable generation of sub-10 nm nano-patterns.

Fabrication of Free-Standing Three-Dimensional Block Copolymer Patterns on Substrate

As the importance of three-dimensiona (3D) nano patterns and structures has recently emerged, interest in the study of 3D structures of block copolymers has increased. However, most existing studies on block copolymer 3D patterns on substrates are limited to simple 3D structures such as a multi-layered forms. In this study, we propose an experimental method for realizing free-standing 3D block copolymer patterns on substrates using an e-beam lithographic template and film transfer method. The block copolymer 3D structure formed in wide hole templates are similar to simple multi-layered structures; however, as the width of the hole template become narrower, more complex block copolymer 3D structures are formed in which the upper and lower layer structures are interconnected. Furthermore, we introduce a method to fabricate novel block copolymer structures in which the 2D planar structures are connected to 3D complex structures. Proposed 3D block copolymer fabrication method provides a framework for generation of unconventional 3D structures of block copolymer, which can be useful for next generation 3D devices.

Direct Imaging of Interfacial Fluctuations in Confined Block Copolymer with in Situ Slow-Scan-Disabled Atomic Force Microscopy.

Using environmentally controlled, high-speed atomic force microscopy (AFM), we examine dynamic fluctuations of topographically confined poly(styrene-block-methyl methacrylate) (PS-b-PMMA) cylinders. During thermal annealing, fluctuations drive perturbations of the block copolymer (BCP) interface between polymer domains, leading to pattern roughness. Whereas previous investigations have examined roughness in room-temperature and kinetically quenched samples, we directly visualize the dynamics of PS/PMMA interfaces in real space and time at in situ temperatures above the glass transition temperature, Tg. Imaging under these experimentally challenging thermal annealing conditions is critical to understanding the inherent connection between thermal fluctuations and BCP pattern assembly. Through the use of slow-scan-disabled AFM, we dramatically improve the imaging time resolution for tracking polymer dynamics. Fluctuations increase in intensity with temperature and, at high temperatures, become spatially coherent across their confining potential. Additionally, we observe that topographic confinement suppresses fluctuations and correlations in the proximity of the guiding field. In situ imaging at annealing temperatures represents a significant step in capturing the dynamics of chain mobility at BCP interfaces.

Manipulating the sequences of block copolymer patterns on corrugated substrates

This paper describes manipulating the sequences of cylinder-forming block copolymer patterns on corrugated substrates. Upon thermal annealing, the topographic corrugation of the substrate generates a spontaneous flow-field of the block copolymer and induces thickness-dependent microdomains. The corrugation gradient has some range of surface roughness characterized by its topographic parameters. When the substrate topography matches the dimensions of the intrinsic surface relief structures of the block copolymer, the surface roughening is suppressed by inverted terrace formation, and sequenced patterns of in-plane cylinders and nonbulk lamella phases are generated. As soon as the surface roughening forms on the corrugated substrate with a roughness parameter lower than that of the surface relief structures, the reverse sequences of the alternative microphase separated structures are developed. However, enhanced mobility of the block copolymer induced by solvent annealing suppresses the pattern sequencing and the in-plane cylinders with a relatively high degree of ordering generated over the entire surface of the corrugated substrate. This observation may further enable new approaches for manipulating the sequences of spatially registered hierarchical surface patterns of block copolymers.