Polystyrene Brushes Research Articles

High-resolution chemical patterns from negative tone resists for the integration of extreme ultraviolet patterns of metal-oxide resists with directed self-assembly of block copolymers

Extreme ultraviolet (EUV) lithography faces significant challenges in designing suitable resist materials that can provide adequate precision, while maintaining economically viable throughput. These challenges in resist materials have led to printing failures and high roughness in EUV patterns, compromising the performance of semiconductor devices. Integrating directed self-assembly (DSA) of block copolymers (BCPs) with EUV lithography offers a promising solution because, while the BCPs register to the EUV-defined chemical guiding pattern, the thermodynamically determined structures of the BCPs automatically rectify defects and roughness in the EUV pattern. Despite the superior resolution of metal-oxide EUV resists (MORs), their application to DSA is limited by the difficulty in converting them into chemical patterns that allow effective transfer of the rectified patterns of DSA films into inorganic materials. To address this challenge, this study introduces a novel strategy for fabricating chemical patterns using hydrogen silsesquioxane (HSQ), a high-resolution negative tone inorganic resist, as a model system for MORs. Initially, a sacrificial Cr pattern is generated from HSQ patterns via reactive ion etching. The sacrificial Cr pattern is converted into a chemical pattern by first grafting a water-soluble polyethylene oxide brush onto the substrate, then wet etching the Cr, and finally grafting nonpolar polystyrene brushes. Assembling polystyrene-block-poly(methyl methacrylate) on these patterns results in structures oriented and registered with the underlying pattern, achieving 24 nm full-pitch resolutions. This approach has the potential to integrate MOR patterns into the DSA process, thereby enabling the generation of high-quality sub-10 nm patterns with high-χ BCPs.

Polystyrene Brush Evolution by Grafting to Reaction on Deglazed and Not-Deglazed Silicon Substrates.

Two model substrates for the grafting to reaction are considered: not-deglazed silicon, whose surface is coated by a thin oxide layer with reactive silanol groups on its surface; and deglazed silicon, where the oxide layer is removed by treatment with hydrofluoric acid. The reactive polymers are hydroxy-terminated polystyrenes with molecular weights ranging from 3.9 to 13.9kgmol⁻1. The grafting to reaction is carried out at different temperatures and for different periods of time on the two different substrates. The thickness and the thermal stability of the resulting brushes are evaluated. Furthermore, the grafting of a highly dispersed system is simulated by blending two polymers with different molecular weights. Although the brush thickness growth is found to be faster on deglazed silicon, the preferential grafting of short chains occurs with equal chain selection propensity on both substrates.

Self-Assembly of Hierarchical High-χ Fluorinated Block Copolymers with an Orthogonal Smectic-within-Lamellae 3 nm Sublattice and Vertical Surface Orientation.

Hierarchical structure-within-structure assemblies offer a route toward increasingly complex and multifunctional materials while pushing the limits of block copolymer self-assembly. We present a detailed study of the self-assembly of a series of fluorinated high-χ block copolymers (BCPs) prepared via postmodification of a single poly(styrene)-block-poly(glycidyl methacrylate) (S-b-G) parent polymer with the fluorinated alkylthiol pendent groups containing 1, 6, or 8 fluorinated carbons (termed trifluoro-ethanethiol (TFET), perfluoro-octylthiol (PFOT), and perfluoro-decylthiol (PFDT), respectively). Bulk X-ray scattering of thermally annealed samples demonstrates hierarchical molecular assembly with phase separation between the two blocks and within the fluorinated block. The degree of ordering within the fluorinated block is highly sensitive to synthetic variation; a lamellar sublattice was formed for S-b-GPFOT and S-b-GPFDT. Thermal analyses of S-b-GPFOT reveal that the fluorinated block exhibits liquid crystal-like ordering. The complex thin-film self-assembly behavior of an S-b-GPFOT polymer was investigated using real-space (atomic force microscopy and scanning electron microscopy) and reciprocal-space (resonant soft X-ray scattering (RSoXS), grazing incidence small- and wide-angle scattering) measurements. After thermal annealing in nitrogen or vacuum, films thicker than 1.5 times the primary lattice spacing exhibit a 90-degree grain boundary, exposing a thin layer of vertical lamellae at the free interface, while exhibiting horizontal lamellae on the preferential (polystyrene brush) substrate. RSoXS measurements reveal the near-perfect orthogonality between the primary and sublattice orientations, demonstrating hierarchical patterning at the nanoscale.

Predicting Polymer Brush Behavior in Solvents Using the Steepest-Entropy-Ascent Quantum Thermodynamic Framework.

The steepest-entropy-ascent quantum thermodynamic (SEAQT) framework is utilized to study the effects of temperature on polymer brushes. The brushes are represented by a discrete energy spectrum, and energy degeneracies obtained through the replica-exchange Wang-Landau algorithm. The SEAQT equation of motion is applied to the density of states to establish a unique kinetic path from an initial thermodynamic state to a stable equilibrium state. The kinetic path describes the brush's evolution in state space, as it interacts with a thermal reservoir. The predicted occupation probabilities along the kinetic path are used to determine the expected thermodynamic and structural properties. The polymer density profile of a polystyrene brush in cyclohexane solvent is predicted using the equation of motion, and it agrees qualitatively with the experimental density profiles. The Flory-Huggins parameter chosen to describe brush-solvent interactions affects the solvent distribution in the brush but has a minimal impact on the polymer density profile. Three types of nonequilibrium kinetic paths with differing amounts of entropy production are considered: a heating path, a cooling path, and a heating-cooling path. Properties such as tortuosity, radius of gyration, brush density, solvent density, and brush chain conformations are calculated for each path.

Tip-Induced Nanopatterning of Ultrathin Polymer Brushes.

Patterned, ultra-thin surface layers can serve as templates for positioning nanoparticlesor targeted self-assembly of molecular structures, for example, block-copolymers. This work investigates the high-resolution, atomic force microscopebased patterning of 2nm thick vinyl-terminated polystyrene brush layers and evaluates the line broadening due to tip degradation. This work compares the patterning properties with those of a silane-based fluorinated self-assembled monolayer (SAM), using molecular heteropatterns generated by modified polymer blend lithography (brush/SAM-PBL). Stable line widths of 20nm (FWHM) over lengths of over 20000µm indicate greatly reduced tip wear, compared to expectations on uncoated SiOx surfaces. The polymerbrush acts as a molecularly thin lubricating layer, thus enabling a 5000 fold increase in tip lifetime, and the brush is bonded weakly enough that it can be removed with surgical accuracy. On traditionally used SAMs, either the tip wear is very high or the molecules are not completely removed. Polymer Phase Amplified Brush Editing is presented, which uses directed self-assembly to amplify the aspect ratio of the molecular structures by a factor of 4. The structures thus amplified allow transfer into silicon/metal heterostructures, fabricating 30nm deep, all-silicon diffraction gratings that could withstand focused high-power 405nm laser irradiation.

Controlled Orientation of Silicon-Containing Diblock Copolymer Thin Films by Substrate Functionalization Under Vacuum

This work demonstrates a simple approach to control the orientation of the self-assembled nanostructured block copolymer thin films of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) by functionalization of the oxide layer (SiO2) on the Si substrate followed by thermal annealing under low-pressure environmental conditions. The substrate can be functionalized through two-step grafting of hydroxy-terminated polystyrene brush (PS–OH brush) followed by hydroxy-terminated polydimethylsiloxane brush (PDMS–OH brush) onto the wafer substrate. By controlling the grafting ratio of PS–OH and PDMS–OH brushes, the affinities of the PS and PDMS blocks with the substrates can be fine-tuned to provide a neutral substrate in order to form perpendicular cylinders from the bottom after thermal annealing. Owing to the vacuum-driven orientation [i.e., thermal annealing under low-pressure environment conditions (∼10–4 Pa)], the orientation of the cylinders can be controlled at the air/polymer interface. Interestingly, by combining the vacuum-driven approach with substrate functionalization, perpendicular cylinders from the air/polymer interface and substrate/polymer interface can be generated, respectively. Consequently, well-aligned perpendicular cylinders with long-range ordering can be fabricated by the self-alignment process.

Glass Transition of the Surface Monolayer of Polystyrene Films with Different Film Thicknesses and Supporting Surfaces

Surface glass-transition temperature (Tgsurf) and transition width (W) within 1 nm of the surface were measured by monitoring a qualitative change in the contact angle or density of end-groups (by time-of-flight secondary ion mass spectrometry) with temperature. Polystyrene (PS) films with various thicknesses (h) and molecular weights were studied. For unannealed PS supported on oxide-coated silicon or poly(dimethyl siloxane) with h > ∼60 nm, Tgsurf approached a plateau value of ∼25 K below the bulk Tg; below 60 nm, Tgsurf decreased with decreasing h. Separately, W exhibited a stepwise increase when h was decreased below the radius of gyration of the polymer. Upon thermal preannealing or deposition on a PS brush or adsorbed layer, the films ceased to exhibit Tgsurf reductions or stepwise change in W. We discuss how an out-of-equilibrium density profile with a deficit near the substrate and de Gennes’ sliding mode may explain these observations.

Effect of molecular weight distribution on the thermal adhesion of polystyrene and PMMA brushes

The effect of the molecular weight distribution (MWD) and graft density of polymer brushes on the adhesion strength of flat substrates was investigated using polystyrene (PS) and poly(methyl methacrylate) (PMMA) brushes with variations in the molecular weight, MWD, and graft density. Two silicon wafers covered with polymer brushes were bound in a 0.5 cm2 contact area using 5 μL of toluene and a pinchcock Hoffman clamp and then annealed at 408 K in a vacuum oven for 3 h. PS brushes with a MWD narrower than Mw/Mn = 1.20 yielded an adhesion strength lower than 0.1 MPa. In contrast, PS brushes having a broad MWD (Mw/Mn = 1.3–1.4) were successfully joined to afford a lap shear adhesion strength of 1.2 MPa despite high graft density due to the intermixing of longer chains of the opposite brushes. Similar results were also obtained in the case of PMMA brush.

Semi-heterogeneous asymmetric organocatalysis: Covalent immobilization of BINOL-derived chiral phosphoric acid (TRIP) to polystyrene brush grafted on SiO2 nanoparticles

Reduced mass transfer and tedious immobilization of expensive chiral organocatalyst are two bottlenecks for the large-scale synthesis of optically active molecules in heterogeneous asymmetric organocatalysis. Here, a quasi-homogeneous organocatalysis is achieved by anchoring BINOL-derived phosphoric acid (TRIP) to polystyrene (PS) brush grafted on SiO2 nanoparticles via one-pot, effectively improving mass transfer due to the open stretching of TRIP-anchored PS brush in toluene. The PS brush enables TRIP to catalyze asymmetric allylation in significantly higher yields and enantioselectivities than PS-supported TRIP, and inslightly higher yields than homogeneous TRIP. The sparser grafting density of PS brush is more conducive to the swelling of PS brush, leading to the faster mass transfer of reactants from the top to end of PS brush. Overall,the one-pot anchoring of TRIP to PS brush combines the advantages of homogeneous and heterogeneous organocatalysis, providing an ideal strategy for solving the two bottlenecks in heterogeneous asymmetric organocatalysis.

Functionalized N-Heterocyclic Carbene Monolayers on Gold for Surface-Initiated Polymerizations

Although N-heterocyclic carbenes (NHCs) are superior to thiol adsorbates in that they form remarkably stable bonds with gold, the generation of NHC-based self-assembled monolayers (SAMs) typically requires a strong base and an inert atmosphere, which limits the utility of such films in many applications. Herein, we report the development and use of bench-stable NHC adsorbates, benzimidazolium methanesulfonates, for the direct formation of NHC films on gold surfaces under an ambient atmosphere at room temperature without the need for extraordinary precautions. The generated NHC SAMs were fully characterized using ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and contact angle measurements, and they were compared to analogous SAMs generated from an NHC bicarbonate adsorbate. Based on these findings, a unique radical initiator α,ω-bidentate azo-terminated NHC adsorbate, NHC15AZO[OMs], was designed and synthesized for the preparation of SAMs on gold surfaces with both NHC headgroups bound to the surface. The adsorbate molecules in NHC15AZO SAMs can exist in a hairpin or a linear conformation depending on the concentration of the adsorbate solution used to prepare the SAM. These conformations were studied by a combination of ellipsometry, XPS, PM-IRRAS, and scanning electron microscopy using gold nanoparticles (AuNPs) as a tag material. Moreover, the potential utility of these unique radical-initiating NHC films as surface-initiated polymerization platforms was demonstrated by controlling the thickness of polystyrene brush films grown from azo-terminated NHC monolayer surfaces simply by adjusting the reaction time of the photoinitiated radical polymer growth process.

Entropy-Enhanced Mechanochemical Activation for Thermal Degrafting of Surface-Tethered Dry Polystyrene Brushes.

Dry polymer brushes have attracted great attention because of their potential utility in regulating interface properties. However, it is still unknown whether dry polymer brushes will exhibit degrafting behavior as a result of thermal annealing. Herein, a study of the conformational entropy effect on thermal degrafting of dry polystyrene (PS) brushes is presented. For PS brushes with an initial grafting density (σpini) of 0.61 nm-2, degrafting behavior was observed at 393 K, and the equilibrium σp was approximately 0.14 nm-2 at 413 K. However, for brushes with σpini ≤ 0.14 nm-2, thermal degrafting was not observed even if the temperature was increased to 453 K. Furthermore, we found that the degrafting rate was faster for PS brushes with higher σpini and higher molecular weights when σpini > 0.14 nm-2. Our findings confirmed that degrafting is a mechanochemical activation process driven by tension imposed on bonds that anchor the chains to the surface, and the process is amplified by conformational entropy.

Enhancement of thermal stability of structural color by the substituent effect in polyhedral oligomeric silsesquioxane in block copolymers

We prepared high-molecular-weight block copolymers (BCPs) composed of polystyrene (PS) brush blocks and polyhedral oligomeric silsesquioxane (POSS)-tethered polynorbornenes with variable composition ratios. By changing the substituents at the vertex of POSS from isobutyl groups to cyclopentyl ones, we evaluated the substituent effect on structural color and thermal stability against annealing. The BCPs modified with isobutyl groups showed clear structural color, while color changes were observed after annealing. By replacing to cyclopentyl groups, structural color was also presented, and improvement of thermal resistance was observed by heating. From the series of thermal analyses, it was proposed that thermal enhancement of cyclopentyl-substituted POSS domains could be responsible for the improvement of thermal stability of structural color.

Large‐Area Uniform 1‐nm‐Level Amorphous Carbon Layers from 3D Conformal Polymer Brushes. A “Next‐Generation” Cu Diffusion Barrier? (Adv. Mater. 15/2022)

Conformal Amorphous Carbon Ultrathin Cu diffusion barriers with high conformality have gained great attention for next-generation ultrahigh-density semiconductor device miniaturization. In article number 2110454, Sun Hwa Lee, Rodney S. Ruoff, Ki-Bum Kim, Sang Ouk Kim, and co-workers introduce a handy and reliable method for the preparation of conformal amorphous carbon (a-C) barrier layers with nanometer-level thickness. A polystyrene brush layer is grafted onto a 3D copper structure with self-limiting chemistry, and subsequent carbonization yields large-area uniform 1 nm-level a-C layers with excellent Cu blocking performance.

Large-Area Uniform 1-nm-Level Amorphous Carbon Layers from 3D Conformal Polymer Brushes. A "Next-Generation" Cu Diffusion Barrier?

A reliable method for preparing a conformal amorphous carbon (a-C) layer with a thickness of 1-nm-level, is tested as a possible Cu diffusion barrier layer for next-generation ultrahigh-density semiconductor device miniaturization. A polystyrene brush of uniform thickness is grafted onto 4-inch SiO2 /Si wafer substrates with "self-limiting" chemistry favoring such a uniform layer. UV crosslinking and subsequent carbonization transforms this polymer film into an ultrathin a-C layer without pinholes or hillocks. The uniform coating of nonplanar regions or surfaces is also possible. The Cu diffusion "blocking ability" is evaluated by time-dependent dielectric breakdown (TDDB) tests using a metal-oxide-semiconductor (MOS) capacitor structure. A 0.82nm-thick a-C barrier gives TDDB lifetimes 3.3× longer than that obtained using the conventional 1.0nm-thick TaNx diffusion barrier. In addition, this exceptionally uniform ultrathin polymer and a-C film layers hold promise for selective ion permeable membranes, electrically and thermally insulating films in electronics, slits of angstrom-scale thickness, and, when appropriately functionalized, as a robust ultrathin coating with many other potential applications.

Influence of spin casting solvent on the self‐assembly of silicon‐containing block copolymer thin films via high temperature thermal treatment

AbstractThe present paper focuses on the influence of different solvents (toluene, mesitylene, acetone, tetrahydrofuran, propylene glycol monomethyl ether acetate (PGMEA) and ethyl acetate) on the self‐assembly behaviour of cylinder‐forming polystyrene‐block‐poly(dimethylsiloxane‐random‐vinylmethylsiloxane) diblock copolymer films deposited on thin brush layers of polystyrene (PS) or polymethylmethacrylate (PMMA) polymers grafted to a silicon substrate. The morphology and the key metrics for all samples were determined from the analysis of the SEM images and their evolution was investigated, as a function of the annealing time at 310 °C, for each solvent and for both PS and PMMA brushes. In general, shorter correlation lengths ξ are observed on PS brushes than on PMMA brushes. In addition, SEM data analysis reveals that tetrahydrofuran, PGMEA and ethyl acetate solvents promote a morphological change from fingerprint‐like parallel cylinders to a hexagonally packed dot pattern for annealing time tA > 30 s. Finally, the line edge roughness and linewidth roughness values are weakly dependent on both the casting solvent and the nature of the grafted brush. The reported data reveal that the choice of the polymer brush nature and of the solvent employed during the spin coating of the diblock copolymer film could substantially affect the self‐assembly process and requires accurate optimization due to their subtle interplay. © 2021 Society of Industrial Chemistry.

Optical Anisotropy of Carbon Nitride Thin Films and Photografted Polystyrene Brushes

AbstractPolymer brushes on surfaces enable advanced material design. In the present contribution, transparent and flat photoactive polymeric carbon nitride (pCN) thin films are employed as a photoactive substrate and primer layer to grow polystyrene (PS) brushes. These films are then characterized by ellipsometry. For the first time herein is reported on the optical anisotropy of pCN thin films revealing a high positive birefringence up to 0.71 with an in‐plane nD of 2.54 making this material of high interest for photonic devices. Furthermore and rather surprising, the photografted polystyrene brushes exhibit an unusual high negative birefringence, too. This negative birefringence can be attributed to a practically complete stretching of the polymer chains throughout growth in the radical chain process. As the stretched PS brushes grafted from the pCN surfaces also provide unusual surface properties, the overall system can be of great interest for photonics, but also as mechanical coating and membranes for gas separation.

Ultrastable Glassy Polymer Films with an Ultradense Brush Morphology.

Glassy polymer films with extreme stability could enable major advancements in a range of fields that require the use of polymers in confined environments. Yet, from a materials design perspective, we now know that the glass transition temperature (Tg) and thermal expansion of polymer thin films can be dramatically different from those characteristics of the bulk, i.e., exhibiting confinement-induced diminished thermal stability. Here, we demonstrate that polymer brushes with an ultrahigh grafting density, i.e., an ultradense brush morphology, exhibit a significant enhancement in thermal stability, as manifested by an exceptionally high Tg and low expansivity. For instance, a 5 nm thick polystyrene brush film exhibits an ∼75 K increase in Tg and ∼90% reduction in expansivity compared to a spin-cast film of similar thickness. Our results establish how morphology can overcome confinement and interfacial effects in controlling thin-film material properties and how this can be achieved by the dense packing and molecular ordering in the amorphous state of ultradense brushes prepared by surface-initiated atom transfer radical polymerization in combination with a self-assembled monolayer of initiators.

Polymer Spherulitic Growth Kinetics Mediated by Nanoparticle Assemblies

We systematically examine the role of the self-assembly state of polymer-grafted silica nanoparticles (GNPs) on the spherulitic growth kinetics of a poly(ethylene oxide) (PEO) matrix. The nanoparticles (NPs) are functionalized with either unimodal or bimodal polymer brushes to systematically control their self-assembly within the semicrystalline polymer matrix. In the former case, we employ a poly(methyl methacrylate) (PMMA) brush (miscible with PEO), while the latter has a short dense polystyrene (PS carpet) brush, which is immiscible with the PEO matrix, and a long, sparse PMMA brush. The unimodal GNPs always yield well-dispersed NPs possibly because both the silica NP surface and the PMMA interact favorably with the PEO. The addition of the short PS carpet makes the interaction between the surface and the matrix PEO unfavorable. However, since the NPs also have grafted PMMA chains, they act akin to surfactants and provide access to a range of self-assembled structures. In all cases, the addition of NPs decreases the PEO spherulitic growth rates. Surprisingly, we find that the spatial dispersion of NPs does not change the secondary nucleation activation energy barrier of the PEO crystallization, such that the temperature dependence of spherulite growth kinetics is relatively unaffected by the NPs. Instead, the main effect of the NPs on spherulitic growth kinetics arises from variations of the melt’s viscosity. Two apparently “universal” trends are found—bare NPs and large assemblies of GNPs appear to approximately follow the same dependence for the role of additives on polymer viscosity. On the other hand, all self-assembled NP structures which have at least one nanoscale dimension (well-dispersed NPs, one-dimensional strings or two-dimensional sheets) follow another general behavior, but one where the viscosity is much larger. Such unusual viscosity increases have been previously observed in the pioneering experiments of Composto and Winey, but there is currently no available theoretical description that can capture these changes and their effects on polymer crystallization.

The effect of short polystyrene brushes grafted from graphene oxide on the behavior of miscible PMMA/SAN blends

A new concept of utilization of particle-polymer hybrids as multifunctional additives for polymer blends was introduced in this study. Graphene oxide particles with short densely grafted polystyrene brushes (GO-g-PS) were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). Melt rheology studies revealed that GO-g-PS suppressed the phase separation of miscible poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) (PMMA/SAN) blends. The studies suggested specific interactions of GO-g-PS with the PMMA phase and this was confirmed based on calculations of activation energies of segmental relaxations by broadband dielectric spectroscopy (BDS). These unusual interactions of GO-g-PS with PMMA phase were assigned to the specific and precise architecture of the GO-g-PS particles as well as chemical nature of PS polymer brushes. The short chains of PMMA and PS provide miscibility originating from UCST behavior of PMMA/PS blend of short polymer chains. Additionally, BDS also revealed improved charge transport in PMMA/SAN blend in presence of GO-g-PS hybrid.

Sulfonated polystyrene brushes grafted onto magnetic nanoparticles as recoverable catalysts for efficient synthesis of ethyl N‐phenylformimidate

AbstractIn this work, the sulfonated polystyrene brushes were grafted onto magnetic nanoparticles to obtain recoverable catalysts for efficient synthesis of ethyl N‐phenylformimidate. First, the surface modification of Fe3O4 with a particle size of about 10 nm was performed with the silane coupling agent of vinyl triethoxysilane (SG‐151) to obtain Fe3O4 with carbon–carbon double bonds on the surface (SG‐Fe3O4). Subsequently, SG‐Fe3O4, styrene (St) and chloromethyl styrene (CMSt) were polymerized to obtain the magnetic chloromethylated polystyrene sphere (SG‐Fe3O4@PS‐Cl) with core‐shell structure by solution copolymerization. Using St as monomer and SG‐Fe3O4@PS‐Cl as macromolecular initiator, the magnetic polystyrene brush of SG‐Fe3O4@PS‐PSt was obtained by activated regenerated electron transfer catalyst atom transfer radical polymerization. Finally, SG‐Fe3O4@PS‐PSt was sulfonated with sulfuric acid to form a magnetic sulfonated polystyrene brush of SG‐Fe3O4@PS‐PSH. SG‐Fe3O4@PS‐PSH was used as a recoverable acid catalyst to synthesize ethyl N‐phenylformimidate. Due to the high loading of the sulfonic acid group of this catalyst, its added amount was lower than other solid acids such as p‐toluenesulfonic acid. The results showed that the catalytic performance of SG‐Fe3O4@PS‐PSH was better than p‐toluenesulfonic acid and commercial macroporous sulfonic acid resin. The external magnetic field can directly recover SG‐Fe3O4@PS‐PSH, simplifying the recovery of catalyst and reducing the catalyst loss. After recycling, the yield of ethyl N‐phenylformimidate was not significantly decreased.