Metal Oxide Heterostructure Array via Spatially Controlled-Growth within Block Copolymer Templates.

Nanofabrication is continuously searching for new methodologies to fabricate 3D nanostructures with 3D control over their chemical composition. A new approach for heterostructure nanorod array fabrication through spatially controlled-growth of multiple metal oxides within block copolymer (BCP) templates is presented. Selective growth of metal oxides within the cylindrical polymer domains of polystyrene-block-poly methyl methacrylate is performed using sequential infiltration synthesis (SIS). Tuning the diffusion of trimethyl aluminum and diethyl zinc organometallic precursors in the BCP film directs the growth of AlOx and ZnO to different locations within the cylindrical BCP domains, in a single SIS process. BCP removal yields an AlOx -ZnO heterostructure nanorods array, as corroborated by 3D characterization with scanning transmission electron microscopy (STEM) tomography and a combination of STEM and energy-dispersive X-ray spectroscopy tomography. The strategy presented here will open up new routes for complex 3D nanostructure fabrication.

Molecular pathways for defect annihilation in directed self-assembly.

Over the last few years, the directed self-assembly of block copolymers by surface patterns has transitioned from academic curiosity to viable contender for commercial fabrication of next-generation nanocircuits by lithography. Recently, it has become apparent that kinetics, and not only thermodynamics, plays a key role for the ability of a polymeric material to self-assemble into a perfect, defect-free ordered state. Perfection, in this context, implies not more than one defect, with characteristic dimensions on the order of 5 nm, over a sample area as large as 100 cm(2). In this work, we identify the key pathways and the corresponding free energy barriers for eliminating defects, and we demonstrate that an extraordinarily large thermodynamic driving force is not necessarily sufficient for their removal. By adopting a concerted computational and experimental approach, we explain the molecular origins of these barriers and how they depend on material characteristics, and we propose strategies designed to overcome them. The validity of our conclusions for industrially relevant patterning processes is established by relying on instruments and assembly lines that are only available at state-of-the-art fabrication facilities, and, through this confluence of fundamental and applied research, we are able to discern the evolution of morphology at the smallest relevant length scales-a handful of nanometers-and present a view of defect annihilation in directed self-assembly at an unprecedented level of detail.

The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Building Semipermeable Films One Monomer at a Time: Structural Advantages via Molecular Layer Deposition vs Interfacial Polymerization.

Molecular layer deposition (MLD) provides the opportunity to perform condensation polymerization one vaporized monomer at a time for the creation of precise, selective nanofilms for desalination membranes. Here, we compare the structure, chemistry, and morphology of two types of commercial interfacial polymerzation (IP) membranes with lab-made MLD films. M-phenylenediamine (MPD) and trimesoyl chloride (TMC) produced a cross-linked, aromatic polyamide often used in reverse osmosis membranes at MLD growth rates of 2.9 Å/cycle at 115 °C. Likewise, piperazine (PIP) and TMC formed polypiperazine amide, a common selective layer in nanofiltration membranes, with MLD growth rates of 1.5 Å/cycle at 115 °C. Ellipsometry and X-ray reflectivity results suggest that the surface of the MLD films is comprised of polymer segments roughly two monomers in length, which are connected at one end to the cross-linked bulk layer. As a result of this structure as well as the triple-functionality of TMC, MPD-TMC had a temperature window of stable growth rate from 115 to 150 °C, which is unlike any non-cross-linked MLD chemistries reported in the literature. Compared to IP films, corresponding MLD films were denser and morphologically conformal, which suggests a reduction in void volumes; this explains the high degree of salt rejection and reduced flux previously observed for exceptionally thin MPD-TMC MLD membranes. Using X-ray photoelectron spectroscopy and infrared spectroscopy, MLD PIP-TMC films evidenced a completely cross-linked internal structure, which lacked amine and carboxyl groups, pointing to a hydrophobic bulk structure, ideal for optimized water flux. Grazing-incidence wide-angle X-ray scattering showed broad features in each polyamide with d-spacings of 5.0 Å in PIP-TMC compared to that of 3.8 Å in MPD-TMC. While MLD and IP films were structurally identical to PIP-TMC, MPD-TMC IP films had a structure that may have been altered by post-treatment compared to MLD films. These results provide foundational insights into the MLD process, structure-performance relationships, and membrane fabrication.

Control over in-channel mesostructure orientation through AAM surface modification.

The synthesis of mesostructured silica from a tetrahydrofuran (THF) based sol-gel was carried out in the channels of an anodic alumina membrane (AAM) using the evaporation induced self-assembly (EISA) method. The effect of channel surface chemistry on the orientation of the in-channel hexagonal mesostructure was studied by treating the channel walls. A variety of channel-surface modifications have been performed, including oxygen plasma treatment, atomic layer deposition (ALD) of pure alumina, and deposition of a hydrophobic monolayer. The in-channel mesostructures were characterized using transmission electron microscopy (TEM) and energy filtered TEM (EFTEM). It was found that these modifications control the concentration of anions at the channel surfaces, and consequently the orientation of the hexagonal mesostructure. Namely, high anion concentration at the channel surface induces the formation of the desired vertically aligned columnar hexagonal phase. A model to understand the effect of anions at the channel wall on the competition between mesostructure phase transformation and silica condensation is proposed. Finally, this study demonstrates that by judiciously modifying the chemistry at the channel walls the formation of desired orientations can be induced.

Revealing the 3D Structure of Block Copolymers with Electron Microscopy: Current Status and Future Directions.

Block copolymers (BCPs) are considered model systems for understanding and utilizing self-assembly in soft matter. Their tunable nanometric structure and composition enable comprehensive studies of self-assembly processes as well as make them relevant materials in diverse applications. A key step in developing and controlling BCP nanostructures is a full understanding of their three-dimensional (3D) structure and how this structure is affected by the BCP chemistry, confinement, boundary conditions, and the self-assembly evolution and dynamics. Electron microscopy (EM) is a leading method in BCP 3D characterization owing to its high resolution in imaging nanosized structures. Here we discuss the two main 3D EM methods: namely, transmission EM tomography and slice and view scanning EM tomography. We present each method's principles, examine their strengths and weaknesses, and discuss ways researchers have devised to overcome some of the challenges in BCP 3D characterization with EM- from specimen preparation to imaging radiation-sensitive materials. Importantly, we review current and new cutting-edge EM methods such as direct electron detectors, energy dispersive X-ray spectroscopy of soft matter, high temporal rate imaging, and single-particle analysis that have great potential for expanding the BCP understanding through EM in the future.

Atomic layer deposition enables multi-modal three-dimensional electron microscopy of isoporous membranes.

Block copolymers (BCPs) are promising materials for water purification. They enable the fabrication of integral asymmetric isoporous membranes with high permeability and good selectivity. Commonly, the characterization of such hierarchical structures is performed by conventional electron microscopy (EM) means, namely scanning and transmission electron microscopy (SEM and TEM, respectively). However, due to the inherent lack of contrast between BCP domains, external contrast agents are required to achieve informative, high-resolution imaging. In addition, such EM techniques are typically limited to a certain cross-section or surface morphology only. In this paper, we harness the selective growth of AlOx in the pore-forming domains of BCPs to create an internal and stable contrast difference between the blocks. This in turn allowed us to perform advanced three-dimensional characterization of the membranes with focused ion beam (FIB)-SEM and TEM tomography, providing an understanding of the 3D structure and properties such as 3D geometry of the pores, 3D tortuosity, and 3D permeability. This 3D characterization also provides better correlations between the membrane structure and its performance. Such knowledge can allow better design and fine-tuning of BCP membranes and other membranes for their applications.

Mechanical Behavior of Hybrid Thin Films Fabricated by Sequential Infiltration Synthesis in Water-Rich Environment.

Sequential infiltration synthesis (SIS) is an emerging technique for fabricating hybrid organic-inorganic materials with nanoscale precision and controlled properties. Central to SIS implementation in applications such as membranes, sensors, and functional coatings is the mechanical properties of hybrid materials in water-rich environments. This work studies the nanocomposite morphology and its effect on the mechanical behavior of SIS-based hybrid thin films of AlOx-PMMA under aqueous environments. Water-supported tensile measurements reveal an unfamiliar behavior dependent on the AlOx content, where the modulus decreases after a single SIS cycle and increases with additional cycles. In contrast, the yield stress constantly decreases as the AlOx content increases. A comparison between water uptake measurements indicates that AlOx induces water uptake from the aqueous environment, implying a "nanoeffect" stemming from AlOx-water interactions. We discuss the two mechanisms that govern the modulus of the hybrid films: softening due to increased water absorption and stiffening as the AlOx volume fraction increases. The decrease in the yield stress with SIS cycles is associated with the limited mobility and extensibility of polymer chains caused by the growth of AlOx clusters. Our study highlights the significance of developing hybrid materials to withstand aqueous or humid conditions which are crucial to their performance and durability.

Mesostructured Materials with Controllable Long-Range Orientational Ordering and Anisotropic Properties.

Inorganic-organic mesophase materials provide a wide range of tunable properties, which are often highly dependent on their nano-, micro-, or meso-scale compositions and structures. Among these are macroscopic orientational order and corresponding anisotropic material properties, the adjustability of which are difficult to achieve. This is due to the complicated transient and coupled transport, chemical reaction, and surface processes that occur during material syntheses. By understanding such processes, general criteria are established and used to prepare diverse mesostructured materials with highly aligned channels with uniform nanometer dimensions and controllable directionalities over macroscopic dimensions and thicknesses. This is achieved by using a micropatterned semipermeable poly(dimethylsiloxane) stamp to manage the rates, directions, and surfaces at which self-assembling phases nucleate and the directions that they grow. This enables mesostructured surfactant-directed silica and titania composites, including with functional guest species, and mesoporous carbons to be prepared with high degrees of hexagonal order, as well as controllable orthogonal macroscopic orientational order. The resulting materials exhibit novel anisotropic properties, as demonstrated by the example of direction-dependent photocurrent generation, and are promising for enhancing the functionality of inorganic-organic nanocomposite materials in separations, catalysis, and energy conversion applications.

Mesostructured silica containing conjugated polymers formed within the channels of anodic alumina membranes from tetrahydrofuran-based solution.

The synthesis of mesostructured silica from a tetrahydrofuran (THF)-based sol gel was carried out in the channels of an anodic alumina membrane (AAM) using the evaporation-induced self-assembly (EISA) method. Two different nonionic surfactants were used as structure-directing agents, the triblock copolymer Pluronic P123 and the oligomer surfactant Brij56. The effect of the relative humidity and surfactant concentration on the type of mesophase and orientation of the in-channel mesostructures was studied using transmission electron microscopy (TEM) and grazing incidence small angel X-ray scattering (GISAXS). The in-channel structures obtained in this study were primarily of the 2D hexagonal phase with a circular orientation in which the hexagonally packed cylinders form a spiral-like shape from the channel wall inward. In addition, a columnar orientation of the hexagonal phase, in which the axes of the hexagonally packed cylinders are oriented parallel to the channel axes, was also observed. Finally, the use of the THF-based synthesis allowed the in situ incorporation of the highly hydrophobic yellow-emitting conjugated polymer poly[9,9-dioctylfluorene-co-benzothiadiazole] into the in-channel mesostructure upon its formation. The conjugated polymer was well distributed within the mesostructure and maintained its optical properties.

Atomic Layer Deposition for Gradient Surface Modification and Controlled Hydrophilization of Ultrafiltration Polymer Membranes.

In recent years, atomic layer deposition (ALD) has emerged as a powerful technique for polymeric membrane surface modification. In this research, we study Al2O3 growth via ALD on two polymeric phase-inverted membranes: polyacrylonitrile (PAN) and polyetherimide (PEI). We demonstrate that Al2O3 can easily be grown on both membranes with as little as 10 ALD cycles. We investigate the formation of Al2O3 layer gradient through the depth of the membranes using high-resolution transmission electron microscopy and elemental analysis, showing that at short exposure times, Al2O3 accumulates at the top of the membrane, reducing pore size and creating a strong growth gradient, while at long exposure time, more homogeneous growth occurs. This detailed characterization creates the knowledge necessary for controlling the deposition gradient and achieving an efficient growth with minimum pore clogging. By tuning the Al2O3 exposure time and cycles, we demonstrate control over the Al2O3 depth gradient and membranes' pore size, hydrophilicity, and permeability. The oil antifouling performance of membranes is investigated using in situ confocal imaging during flow. This characterization technique reveals that Al2O3 surface modification reduces oil droplet surface coverage.

Polymer dewetting in solvent-non-solvent environment- new insights on dynamics and lithography-free patterning.

HYPOTHESIS: We show that one may employ polymer dewetting in solvent-non-solvent environment to obtain lithography-free fabrication of well-defined nano- to micro- scale polymer droplets arrays from pre-patterned polymer films. The polymer droplet pattern may be converted to a series of hybrid organic-inorganic and inorganic well-defined nano-patterns by using sequential infiltration synthesis (SIS). In particular, we scrutinize the physical parameters which govern the dewetting of flat and striped polymer thin films, which is the key to obtaining our objective of lithography-free ordered nano-patterns. EXPERIMENTS: We immerse polystyrene (PS) and polymethyl methacrylate (PMMA) thin films in water in the presence of chloroform vapors. We study the ensuing polymer dewetting dynamics and the pattern formation of nanospheres by employing in-situ light microscopy and scanning electron microscopy. We then investigate pattern formation by dewetting of polymer stripes, fabricated by directed solvent evaporation, and SIS of AlOx from vapor phase precursors, trimethyl aluminum (TMA) and H2O, within the nanosphere patterns. FINDINGS: We find that solvent- non-solvent environments render film dewetting rates, which are an order of magnitude faster than solvent vapor dewetting, and supports the formation of small solid polymer droplets, down to sub-100 nm droplet size, of large contact angles with the solid substrate. Pre-patterned polymer film stripes support the formation of highly ordered structures of polymer droplets, which are easily transformed to hybrid polymer-AlOx nanosphere patterns and templated AlOx nanosphere via SIS.

Fabrication of Nanoscale Oxide Textured Surfaces on Polymers.

Nanoscale textured surfaces play an important role in creating antibacterial surfaces, broadband anti-reflective properties, and super-hydrophobicity in many technological systems. Creating nanoscale oxide textures on polymer substrates for applications such as ophthalmic lenses and flexible electronics imposes additional challenges over conventional nanofabrication processes since polymer substrates are typically temperature-sensitive and chemically reactive. In this study, we investigated and developed nanofabrication methodologies to create highly ordered oxide nanostructures on top of polymer substrates without any lithography process. We developed suitable block copolymer self-assembly, sequential infiltration synthesis (SIS), and reactive ion etching (RIE) for processes on polymer substrates. Importantly, to prevent damage to the temperature-sensitive polymer and polymer/oxide interface, we developed the process to be entirely performed at low temperatures, that is, below 80 °C, using a combination of UV crosslinking, solvent annealing, and modified SIS and RIE processes. In addition, we developed a substrate passivation process to overcome reactivity between the polymer substrate and the SIS precursors as well as a high precision RIE process to enable deep etching into the thermally insulated substrate. These methodologies widen the possibilities of nanofabrication on polymers.

Mesoscale Confinement Effects and Emergent Quantum Interference in Titania Antidot Thin Films.

The effect of confinement on electron and ion transport in oxide films is of interest both fundamentally and technologically for the design of next-generation electronic devices. In metal oxides with mobile ions and vacancies, it is the interplay of the different modes of charge transport and the corresponding current-voltage signatures that is of interest. We developed a patterned structure in titania films, with feature sizes of 11-20 nm, that allow us to explore confined transport. We describe how confinement changes the competing charge transport mechanisms, the patterned antidot array leads to displacement fields and confines the charge density that results in modified and emergent electron transport with an increase in conductivity. This emergent behavior can be described by considering electron interference effects. Characterization of the charge transport with electron holography and impedance spectroscopy, and through comparison with modeling, show that nanoscale confinement is a way to control quantum interference.

Hybrid Organic-Inorganic-Organic Isoporous Membranes with Tunable Pore Sizes and Functionalities for Molecular Separation.

Accomplishing on-demand molecular separation with a high selectivity and good permeability is very desirable for pollutant removal and chemical and pharmaceutical processing. The major challenge for sub-10 nm filtration of particles and molecules is the fabrication of high-performance membranes with tunable pore size and designed functionality. Here, a versatile top-down approach is demonstrated to produce such a membrane using isoporous block copolymer membranes with well-defined pore sizes combined with growth of metal oxide using sequential infiltration synthesis and atomic layer deposition (SIS and ALD). The pore size of the membranes is tuned by controlled metal oxide growth within and onto the polymer channels, enabling up to twofold pore diameter reduction. Following the growth, the distinct functionalities are readily incorporated along the membrane nanochannels with either hydrophobic, cationic, or anionic groups via straightforward and scalable gas/liquid-solid interface reactions. The hydrophilicity/hydrophobicity of the membrane nanochannel is significantly changed by the introduction of hydrophilic metal oxide and hydrophobic fluorinated groups. The functionalized membranes exhibit a superior selectivity and permeability in separating 1-2 nm organic molecules and fractionating similar-sized proteins based on size, charge, and hydrophobicity. This demonstrates the great potential of organic-inorganic-organic isoporous membranes for high-performance molecular separation in numerous applications.

Three-dimensional superlattice engineering with block copolymer epitaxy.

Three-dimensional (3D) structures at the nanometer length scale play a crucial role in modern devices, but their fabrication using traditional top-down approaches is complex and expensive. Analogous to atomic lattices, block copolymers (BCPs) spontaneously form a rich variety of 3D nanostructures and have the potential to substantially simplify 3D nanofabrication. Here, we show that the 3D superlattice formed by BCP micelles can be controlled by lithographically defined 2D templates matching a crystallographic plane in the 3D superlattice. Using scanning transmission electron microscopy tomography, we demonstrate precise control over the lattice symmetry and orientation. Excellent ordering and substrate registration can be achieved, propagating through 284-nanometer-thick films. BCP epitaxy also showed exceptional lattice tunability, with a continuous Bain transformation from a body-centered cubic to a face-centered cubic lattice. Lattice stability was mediated by molecular packing frustration, and surface-induced lattice reconstruction was observed, leading to the formation of a unique honeycomb lattice.

Toward Fast Screening of Organic Solar Cell Blends.

The ever increasing library of materials systems developed for organic solar-cells, including highly promising non-fullerene acceptors and new, high-efficiency donor polymers, demands the development of methodologies that i) allow fast screening of a large number of donor:acceptor combinations prior to device fabrication and ii) permit rapid elucidation of how processing affects the final morphology/microstructure of the device active layers. Efficient, fast screening will ensure that important materials combinations are not missed; it will accelerate the technological development of this alternative solar-cell platform toward larger-area production; and it will permit understanding of the structural changes that may occur in the active layer over time. Using the relatively high-efficiency poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PCE11):phenyl-C61-butyric acid-methyl-ester acceptor (PCBM) blend systems, it is demonstrated that by means of straight-forward thermal analysis, vapor-phase-infiltration imaging, and transient-absorption spectroscopy, various blend compositions and processing methodologies can be rapidly screened, information on promising combinations can be obtained, reliability issues with respect to reproducibility of thin-film formation can be identified, and insights into how processing aids, such as nucleating agents, affect structure formation, can be gained.

Tin oxide nanostructure fabrication via sequential infiltration synthesis in block copolymer thin films.

Tin oxide (SnO2) nanostructures are attractive for sensing, catalysis, and optoelectronic applications. Here we investigate the fabrication of SnOx nanostructures through sequential infiltration synthesis (SIS) in block copolymer (BCP) film templates. While the growth of metal and metal oxides within polymers and BCP films via SIS has been demonstrated until now using small precursors such as trimethyl aluminum and diethyl zinc, we hypothesize that SIS can be performed using larger precursors and demonstrate SnOx SIS with tetrakis(dimethylamino)tin (TDMASn) and hydrogen peroxide. Tuning the SIS reaction and BCP chemistry resulted in highly ordered, polystyrene-block-poly(2-vinyl pyridine) (P2VP)-templated porous SnOx - AlOx and SnOx nanostructures. Detailed investigation using in-situ microbalance, high resolution electron microscopy, elemental analysis and infra-red spectroscopy shows that SnOx can directly grow within P2VP homopolymer and BCP films. Simultaneously with the growth, SnOx SIS process also contributes to the polymer etch. Performing SnOx SIS with pretreatment of a single AlOx SIS cycle increases the SnOx growth and protects the BCP template from etching. This is the first report of SnOx SIS opening a pathway for additional tetrakis-based organometallic precursors to be utilized in growth processes within polymers.

Role of interparticle interactions on microstructural and rheological properties of cellulose nanocrystal stabilized emulsions.

HYPOTHESIS: Microstructural and rheological properties of particle-stabilized emulsions are highly influenced by the nanoparticle properties such as size and surface charge. Surface charge of colloidal particles not only influences the interfacial adsorption but also the interparticle network formed by the non-adsorbed particles in the continuous phase. EXPERIMENTS: We have studied oil-in-water emulsions stabilized by cellulose nanocrystals (CNCs) with two different degrees of surface charge. Surface charge was varied by means of acidic or basic desulfation. Confocal microscopy coupled with rheology as well as cryogenic scanning electron microscopy were employed to establish a precise link between the microstructure and rheological behavior of the emulsions. FINDINGS: CNCs desulfated with hydrochloric acid (a-CNCs) were highly aggregated in water and shown to adsorb faster to the oil-water interface, yielding emulsions with smaller droplet sizes and a thicker CNC interfacial layer. CNCs desulfated using sodium hydroxide (b-CNCs) stabilized larger emulsion droplets and had a higher amount of non-adsorbed CNCs in the water phase. Rheological measurements showed that emulsions stabilized by a-CNCs formed a stronger network than for b-CNC stabilized emulsions due to increased van der Waals and H-bonding interactions that were not impeded by electrostatic repulsion.

Engineering the Kinetics of Directed Self-Assembly of Block Copolymers toward Fast and Defect-Free Assembly.

Directed self-assembly (DSA) of block copolymers (BCPs) can achieve perfectly aligned structures at thermodynamic equilibrium, but the self-assembling morphology can become kinetically trapped in defective states. Understanding and optimizing the kinetic pathway toward domain alignment is crucial for enhancing process throughput and lowering defectivity to levels required for semiconductor manufacturing, but there is a dearth of experimental, three-dimensional studies of the kinetic pathways in DSA. Here, we combined arrested annealing and TEM tomography to probe the kinetics and structural evolution in the chemoepitaxy DSA of PS- b-PMMA with density multiplication. During the initial stages of annealing, BCP domains developed independently at first, with aligned structures at the template interface and randomly oriented domains at the top surface. As the grains coarsened, the assembly became cooperative throughout the film thickness, and a metastable stitch morphology was formed, representing a kinetic barrier. The stitch morphology had a three-dimensional structure consisting of both perpendicular and parallel lamellae. On the basis of the mechanistic information, we studied the effect of key design parameters on the kinetics and evolution of structures in DSA. Three types of structural evolutions were observed at different film thicknesses: (1) immediate alignment and fast assembly when thickness < L0 ( L0 = BCP natural periodicity); (2) formation of stitch morphology for 1.25-1.45 L0; (3) fingerprint formation when thickness >1.64 L0. We found that the DSA kinetics can be significantly improved by avoiding the formation of the metastable stitch morphology. Increasing template topography also enhanced the kinetics by increasing the PMMA guiding surface area. A combination of 0.75 L0 BCP thickness and 0.50 L0 template topography achieved perfect alignment over 100 times faster than the baseline process. This research demonstrates that an improved understanding of the evolution of structures during DSA can significantly improve the DSA process.