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Sample records for block copolymer thin

  1. Rapid ordering of block copolymer thin films.

    PubMed

    Majewski, Pawel W; Yager, Kevin G

    2016-10-12

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times-hours or days-required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems. PMID:27537062

  2. Solvent enhanced block copolymer ordering in thin films

    NASA Astrophysics Data System (ADS)

    Misner, Matthew J.

    Diblock copolymer self-assembly of materials is emerging as a key element in the fabrication of functional nanostructured materials. By solvent casting or solvent annealing block copolymer thin films, we have demonstrated methods to produce diblock copolymer films with highly oriented, close-packed arrays of nanoscopic cylindrical domains with a high degree of long-range lateral order with few defects. The solvent imparts a high degree of mobility in the microphase-separated copolymer that enables a rapid removal of defects and a high degree of lateral order. Though the use of a selective cosolvent during solvent casting, it was found that the microdomain size and spacing could be increased, leading to a size-tunable system. Additionally, the presence of water also led to the ability to control the microdomain orientation during solvent annealing. Ionic complexation within cylinder-forming PS- b-EO block copolymer thin films was also investigated, where added salts bind PEO block as the minor component. Small amounts of added salts, on the order a few ions per chain, show large effects on the ordering of the copolymer films during solvent annealing. By using gold or cobalt salts, well-organized patterns of nanoparticles can be generated in the copolymer microdomains. Topographically and chemically patterned surfaces were used as a route to sectorizing and controlling the lattice orientation of copolymer films. Topographically patterned surfaces allow well-defined boundaries to confine the copolymer microdomains on a surface and effectively direct the ordering and grain orientation of the copolymer microdomains. Chemically patterned surfaces provide a route to direct the block copolymer ordering on completely flat surface, which may have advantages in applications where adding additional topography may be undesirable. To generate nanoporous templates from PS-b-PEO bases materials several routs were followed. The first route was through the addition and selective

  3. Orientation Distribution for Thin Film Block Copolymers

    NASA Astrophysics Data System (ADS)

    Jones, Ronald; Zhang, Xiaohua; Kim, Sangcheol; Karim, Alamgir; Briber, Robert; Kim, Ho-Cheol

    2008-03-01

    The directed self-assembly of nanostructured films with vertically oriented morphologies is a potential solution for manufacture of next generation data storage platforms, microelectronic devices, and nanoporous membranes. In many of these applications, the distribution of orientation must be tightly controlled to enable pattern transfer. This parameter is expected to depend on factors such as the Flory-Huggins chi parameter, but little data has been reported to date. We present results from tomographic small angle scattering on a series of block copolymer films whose assembly has been directed through solvent annealing. Films of poly(styrene-b-ethylene oxide) are cast as a function of annealing time and their orientation distribution reported. The results provide significant insight into the fundamental limits of line edge roughness and defect control possible using this fabrication technique.

  4. Nanostructured anion conducting block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Arges, Christopher; Kambe, Yu; Nealey, Paul

    Lamellae forming block copolymer electrolyte (BCE) thin-films with perpendicular aligned orientation were registered with high fidelity over large areas via a self-assembly process followed by a novel chemical vapor infiltration reaction (CVIR) technique. In this scheme, poly(styrene- b-2-vinyl pyridine) (PS bP2VP) block copolymers were self-assembled with perpendicular orientations on neutral chemical brushes using solvent vapor annealing. The ionic groups were selectively introduced into the P2VP block via a Menshutkin reaction that converted the nitrogen in the pyridine to n-methylpyridinium - anion carrier groups. FTIR-ATR and XPS tools confirmed the formation of the aforementioned ionic moieties post CVIR process and structure imaging tools (e.g., SEM and AFM imaging, GI-SAXS and RSOXs) established that incorporation of the ionic groups did not alter the self-assembled nanostructured films nor did subsequent ion-exchange processes. Electrochemical impedance spectroscopy determined the in-plane ion conductivity of different counteranions in the BCE thin films and alteration to the symmetry of the block copolymer film substantially improved (or hindered) BCE ion conductivity if the P2VP block's volume fraction was slightly greater than (or less than) 0.5. U.S. Department of Energy, Office of Science under Contract No. DE-AC02-06CH11357.

  5. Self-assembled phases of block copolymer blend thin films.

    PubMed

    Yager, Kevin G; Lai, Erica; Black, Charles T

    2014-10-28

    The patterns formed by self-assembled thin films of blended cylindrical and lamellar polystyrene-b-poly(methyl methacrylate) block copolymers can be either a spatially uniform, single type of nanostructure or separate, coexisting regions of cylinders and lamellae, depending on fractional composition and molecular weight ratio of the blend constituents. In blends of block copolymers with different molecular weights, the morphology of the smaller molecular weight component more strongly dictates the resulting pattern. Although molecular scale chain mixing distorts microdomain characteristic length scales from those of the pure components, even coexisting morphologies exhibit the same domain spacing. We quantitatively account for the phase behavior of thin-film blends of cylinders and lamellae using a physical, thermodynamic model balancing the energy of chain distortions with the entropy of mixing. PMID:25285733

  6. Simple, generalizable route to highly aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan; University of Akron Team

    Macroscopic alignment of block copolymer domains in thin films is desired for many applications, such as cell responsive surfaces or optical polarizers. Alignment generally requires specialized tools that apply external fields, shear force gradient, or produce topological patterned substrates. This requirement limits the broad academic application of aligned BCPs. Here, we describe a simple modification of commonly utilized solvent vapor annealing (SVA) process for macroscopic alignment of BCPs. Adhering a flat, crosslinked elastomer pad to the BCP film leads to differential swelling between the elastomer pad and BCP to produce a shear force that aligns the ordered BCP domains. The role of elastomer properties, solvent quality, drying rate and degree of segregation of the block copolymer will be discussed to provide generalized rules for alignment with this technique. Cylindrical nanostructures formed in polystyrene-block-polydimethylsiloxane can be transformed into arrays of silica lines and increasing the thickness from a monolayer to bilayer can effectively halve the spacing of the lines. These results illustrate a generalized method for BCP alignment and a potential route for the generation of complex hierarchical assembled structures. A generalized method for block copolymer thin film alignment: solvent vapor annealing with shear.

  7. Highly-Ordered Thin Films from Photocleavable Block Copolymers

    NASA Astrophysics Data System (ADS)

    Gu, Weiyin; Zhao, Hui; Coughlin, E.; Theato, Patrick; Russell, Thomas; University of Massachusetts at Amherst Team; University of Hamburg Team

    2013-03-01

    A robust route for the preparation of nanoscopic dot/line patterns with long range lateral order from poly(styrene-block-ethylene oxide) (PS-b-PEO) with an o-nitrobenzyl ester junction (PS-h ν-PEO) is demonstrated. Solvent annealing condition is optimized to achieve the highly ordered cylindrical block copolymer (BCP) microdomains oriented normal or parallel to the silicon substrates. Following a very mild UV exposure and successive washing with methanol, PS-hv-PEO thin films were transformed into highly ordered porous or trench templates. Afterwards the pores or trenches were either filled with PDMS by spin-coating or exposed to direct metal deposition of Au. After a plasma etching or lift-off process to remove the polymer templates, highly ordered arrays of silica or Au nanopatterns were obtained. This represents the first template application example from highly ordered nanoporous thin films derived from block copolymers featuring a photocleavable junction. DOE (DE-FG02-96ER45612), NSF-MRSEC, DFG (TH 1104/4-1), CHE 0924435, R31-10013.

  8. Nanopatterning of ultrananocrystalline diamond thin films via block copolymer lithography.

    SciTech Connect

    Ramanathan, M.; Darling, S. B.; Sumant, A. V.; Auciello, O.

    2010-07-01

    Nanopatterning of diamond surfaces is critical for the development of diamond-based microelectromechanical system/nanoelectromechanical system (MEMS/NEMS), such as resonators or switches. Micro-/nanopatterning of diamond materials is typically done using photolithography or electron beam lithography combined with reactive ion etching (RIE). In this work, we demonstrate a simple process, block copolymer (BCP) lithography, for nanopatterning of ultrananocrystalline diamond (UNCD) films to produce nanostructures suitable for the fabrication of NEMS based on UNCD. In BCP lithography, nanoscale self-assembled polymeric domains serve as an etch mask for pattern transfer. The authors used thin films of a cylinder-forming organic-inorganic BCP, poly(styrene-block-ferrocenyldimethylsilane), PS-b-PFS, as an etch mask on the surface of UNCD films. Orientational control of the etch masking cylindrical PFS blocks is achieved by manipulating the polymer film thickness in concert with the annealing treatment. We have observed that the surface roughness of UNCD layers plays an important role in transferring the pattern. Oxygen RIE was used to etch the exposed areas of the UNCD film underneath the BCP. Arrays of both UNCD posts and wirelike structures have been created using the same starting polymeric materials as the etch mask.

  9. Functional Thin Films from Aligned Block Copolymers and Blends

    NASA Astrophysics Data System (ADS)

    Vogt, Bryan; Qiang, Zhe; Cavicchi, Kevin

    Block copolymer (BCP) self-assembly provides a simple, cost effective route to fabricating nanoscale patterns. Here we describe how we can modulate the alignment/orientation of BCP films using a modified solvent vapor anealing (SVA) method where the BCP is covered with an elastomer during SVA and controlled deswelling of the elastomer macroscopically produces a shear force that aligns the BCP domains. By proper selection of the BCP or BCP + functional precursors, functional nanopatterns can be obtained. Thin films of cylindrical forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) are shear aligned. High temperature calcination converts the PDMS to silica and removes the PS to yield the silica nanolines. The spacing of these features is effectively halved by the use of bilayer films. Sequential shear-alignment of two distinct layers can generate arbitrary line based nanostructured features such as a rhombic array, but the size of the features is defined by the BCP. Oligomeric phenolic resin can effectively modulate the size and morphology of amphiphilic BCPs even at high loadings (>70 wt

  10. Identification of block copolymers and determination of their purity by thin-layer chromatography.

    PubMed

    Gankina, E S; Efimova, I I; Kever, J J; Belenkii, B G

    1987-01-01

    The application of adsorption, precipitation and extraction thin-layer chromatography to the identification of block copolymers, determination of their homogeneity (mixtures of homopolymers), and evaluation of their compositional homogeneity by one- and two-dimensional, multistage and gradient methods, is described. To detect the polymers on the thin-layer plate, various methods of detection are used, including those specific for each component of the block copolymer. Examples of analysis of the following block copolymers by thin-layer chromatography are reported: PS-PMMA, PS-PB, PS-PAN, PS-PBG, PI-PMS-PI, PMMA-PBMA, PMMA-PBG, PS-PEO. PMID:18964274

  11. Defect motion and annihilation in block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Mueller, Marcus; Li, Weihua

    2015-03-01

    Using self-consistent field theory and computer simulation of a soft, coarse-grained particle model we study defect motion and annihilation in thin films of lamella-forming block copolymers on neutral and chemically patterned substrates. By virtue of the strain-field mediated interactions, dislocation defects with opposite orientation move towards each other. This motion depends both on the thermodynamic, strain-field mediated driving force and the single-chain dynamics that is required to alter the morphology and reduce the distance between the defect cores. This interplay results in a qualitative dependence of the time evolution on the topology of the defect morphology. Upon collision of the defects, they either spontaneously annihilate or form a metastable, tight defect pair. In the latter case, a free-energy barrier has to be overcome to finally produce a defect-free structure. Computing the minimum free-energy path within self-consistent field theory we investigate the dependence of the free-energy barriers of defect motion and annihilation on incompatibility, strength of the chemical surface pattern, and defect morphology. European Union FP7 / GA No. 619793 CoLiSA.MMP.

  12. Direct Immersion Annealing of Thin Block Copolymer Films.

    PubMed

    Modi, Arvind; Bhaway, Sarang M; Vogt, Bryan D; Douglas, Jack F; Al-Enizi, Abdullah; Elzatahry, Ahmed; Sharma, Ashutosh; Karim, Alamgir

    2015-10-01

    We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene-poly(methyl methacrylate) (PS-PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the "optimal long-range order" processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering. PMID:26351823

  13. Direct Immersion Annealing of Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Karim, Alamgir

    We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene -poly(methyl methacrylate) (PS -PMMA) system: rapid short range order, optimal long-range order, and a film instability regime. Kinetic studies in the ``optimal long-range order'' processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering. Inclusion of nanoparticles in these films at high concentrations and fast ordering kinetics study with neutron reflectivity and SANS will be discussed. This is (late) Contributed Talk Abstract for Dillon Medal Symposium at DPOLY - discussed with DPOLY Chair Dvora Perahia.

  14. Confinement of block copolymers

    SciTech Connect

    1995-12-31

    The following were studied: confinement of block copolymers, free surface confinement, effects of substrate interactions, random copolymers at homopolymer interfaces, phase separation in thin film polymer mixtures, buffing of polymer surfaces, and near edge x-ray absorption fine structure spectroscopy.

  15. Surface Engineering of Styrene/PEGylated-Fluoroalkyl Styrene Block Copolymer Thin Films

    SciTech Connect

    Martinelle, E.; Menghetti, S; Galli, G; Glisenti, A; Krishnan, S; Paik, M; Ober, C; Smilgies, D; Fischer, D

    2009-01-01

    A series of diblock copolymers prepared from styrenic monomers was synthesized using atom transfer radical polymerization. One block was derived from styrene, whereas the second block was prepared from a styrene modified with an amphiphilic PEGylated-fluoroalkyl side chain. The surface properties of the resulting polymer films were carefully characterized using dynamic contact angle, XPS, and NEXAFS measurements. The polymer morphology was investigated using atomic force microscope and GISAXS studies. The block copolymers possess surfaces dominated by the fluorinated unit in the dry state and a distinct phase separated microstructure in the thin film. The microstructure of these polymers is strongly influenced by the thin film structure in which it is investigated.

  16. NEXAFS Depth Profiling of Surface Segregation in Block Copolymer Thin Films

    SciTech Connect

    Krishnan, S.; Paik, M; Ober, C; Martinelli, E; Galli, G; Sohn, K; Kramer, E; Fischer, D

    2010-01-01

    NEXAFS spectroscopy was used to probe the surface composition and under-water surface reconstruction of thin films of comb-like diblock copolymers with cylindrical and spherical microphases. The polymers consisted of a polystyrene block, and a second block prepared from a styrenic monomer grafted with fluoroalkyl-tagged poly(ethylene glycol) side chains. Compositional depth profiling of the microphase separated block copolymer films, in the top 1-3 nm of the film, was performed to understand the role of block copolymer microstructure and self-assembly on surface composition. Using experimentally determined concentration profiles, the surface concentration of phenyl ring carbon atoms was quantified and compared with those of homopolymer and random copolymer controls. The carbon atoms from the relatively high surface energy phenyl groups were depleted or excluded from the surface, in favor of the low surface-energy fluoroalkyl groups. While it is expected that block copolymer surfaces will be completely covered by a wetting lamellar layer of the lower surface energy block, a significant amount of the higher surface energy polystyrene block was found to be present in the surface region of the cylinder-forming block copolymer. Evidently, the spontaneous formation of the cylindrical polystyrene microdomains in the near-surface region compensated for the lowering of the free energy that could have been achieved by completely covering the surfaces with a lamellar layer of the lower surface energy fluorinated block. All surfaces underwent molecular reconstruction after immersion in water. The experimental concentration depth profiles indicated an increased surface depletion of phenyl ring carbon atoms in the water-immersed thin films, due to the tendency of hydrophilic PEG side groups to be present at the polymer-water interface. Such a detailed characterization of the outermost layers of the block copolymer surfaces was possible because of the exceptional depth resolution

  17. Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

    SciTech Connect

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

    Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at

  18. Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

    DOE PAGESBeta

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

    Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals thatmore » in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

  19. Macroscopic vertical alignment of nanodomains in thin films of semiconductor amphiphilic block copolymers.

    PubMed

    Brendel, Johannes C; Liu, Feng; Lang, Andreas S; Russell, Thomas P; Thelakkat, Mukundan

    2013-07-23

    Though several techniques have been reported on the alignment of conventional block copolymers, the macroscopic vertical orientation of semiconductor block copolymer microdomains in thin films has still not been accomplished. Here, we report the control on the alignment of nanostructures in a semiconductor amphiphilic block copolymer comprising an amorphous triphenyldiamine hole conductor block and a hydrophilic poly(styrene sulfonate) segment. Three different compositions with a hole conductor content of 57, 72, and 79 wt % were synthesized using a combination of controlled reversible addition/fragmentation transfer polymerization and "click" chemistry. All polymers feature a narrow molecular weight distribution. Cryo-TEM reveals the formation of micelles in DMF solutions of the amphiphilic copolymer having nanoscopic dimensions. The micelle size correlates well with the X-ray analysis of dried bulk samples. Atomic force microscopy (AFM) confirms the micellar structure in the as-cast films. Thermal annealing causes an aggregation of micelles but did not lead to morphologies known for conventional block copolymers. However, annealing in saturated DMF vapor induces a morphology transition and a vertical orientation of the microdomains which was determined by grazing incidence small-angle X-ray scattering and AFM. The morphology varies from lamella to cylinders with increasing content of the hole-conductor block. The orientation arises from the controlled evaporation of the solvent, a mechanism that is similar to that observed for conventional block copolymers. Our approach demonstrates the macroscopic vertical alignment of nanodomains in semiconductor block copolymers which is a key requirement for applications in hybrid devices. PMID:23746109

  20. PS-b-PDMS Block Copolymer Thin Film: Pattern Formation and Phase Behavior

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan; Cheng, Stephen Z. D.; Department of Polymer Science, The University of Akron Team

    2011-03-01

    Recently, block copolymer thin films attract great attention due to their potential applications in surface nano-lithography. In our work, PS- b -PDMS with cylinder morphology is chosen due to extremely large χ value between two blocks. Besides, PS- b -PDMS can be transformed into silicon oxide under UV/O3 exposure and a layer of silicon oxide with the self-assembled block copolymer patterns can be made. By utilizing the PGMEA as solvent, we can easily obtain sphere morphology in cylindrical composition block copolymer by preserved block copolymer solution morphology during film formation. Furthermore, in thermal annealing process, the phase behavior of the PS- b -PDMS thin film is strongly affects by molecular weight, film thickness and annealing temperature. In larger-molecular-weight PS- b -PDMS, we only observed spherical domains rearrangement and without morphology transition between sphere and cylinder due to high energy barrier, whereas, in the case of smaller-molecular-weight polymer, depending on the film thickness and annealing temperature, its thin film morphology transits between sphere and cylinder alternatively, which is similar to what we found in solvent annealing.

  1. Patterning square and rectangular arrays using shear-aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Davis, Raleigh L.; Register, Richard A.; Gwyther, Jessica; Nunns, Adam; Manners, Ian; Chaikin, Paul M.

    2014-03-01

    Microphase separation of block copolymers in thin films can generate periodic structures: hexagonally packed arrays of dots from spherical or cylindrical phase block copolymers, or periodic stripes from cylindrical or lamellar phase block copolymers. Square or rectangular patterns, however, do not naturally form by spontaneous self-assembly of a simple diblock copolymer, and are a challenge to create. We present a simple way to create nano-square/rectangular arrays by building up a double-layer film of a cylinder-forming diblock, where each layer is sequentially deposited, shear-aligned independently, and cross-linked. Any block copolymer with at least one crosslinkable block can in principle be employed; in this study we use cylinder-forming polystyrene-b-poly(ferrocenylisopropylmethylsilane) and polystyrene-b-poly(hexylmethacrylate). The pitch of the array is tunable by varying polymer molecular weight. Oxygen reactive ion etching is used to reveal the grid structures, and these grids can in turn form nano-wells in the silicon substrate when the cylinder-forming block is very etch-resistant under the conditions used for silicon etching. Additionally, metal dots ordered in square arrays can be created using these grids as templates, via metal evaporation and lift-off.

  2. Microphase separation in thin films of lamellar forming poydisperse di-block copolymers

    DOE PAGESBeta

    Kumar, Rajeev; Kilbey, II, S Michael; Ankner, John Francis; Heller, William T; Chen, Jihua; Sides, Scott; Browning, Jim; Lokitz, Bradley S; Sumpter, Bobby G

    2015-01-01

    Microphase separation in thin films of lamellar forming polydisperse di-block copolymers is studied using self-consistent field theory (SCFT) and neutron reflectivity experiments. Diblock copolymers containing a polydisperse block (poly(glycidylmethacrylate) (PGMA)) connected to a near monodisperse block (poly(4,4-dimethyl-d6-2-vinylazlactone) (PVDMA-d6)) are considered in this work. Effects of chain length polydispersity, film thickness, substrate monomer and monomer-monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals that an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness, in comparison to a film created with monodisperse di-block copolymers.more » This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. These predictions are verified by comparison with neutron reflectity experiments done on thin films made from moderately polydisperse PGMA-b-PVDMA-d6 di-block copolymer deposited on silicon substrates. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index makes the polydisperse blocks less flexible in comparison with monodisperse blocks. It is shown that conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness descreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. Prediction of neutron reflectivity profiles using the SCFT provides a facile and robust route for model verification and leads to useful physical insights into behavior of di-block copolymers near interfaces.« less

  3. Silver based SERS substrates fabricated from block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Lee, Wonjoo; Lee, Seung Yong; Gao, Zhenghan; Rabin, Oded; Briber, R. M.

    2013-03-01

    Poly (styrene-block-4-vinyl pyridine) (PS-b-P4VP, Mw = 47-b-10 kDa, PDI =1.10) thin films were used to form large-scale long range ordered self-assembled hexagonal patterns of vertically P4VP oriented cylinders in a PS matrix on Si substrates. The P4VP cylindrical domains were crosslinked and quaternized using 1,4-dibromobutane. Negatively charged 15nm gold nanoparticles were attached to the quaternized P4VP domains through Coulombic interactions. Silver was then grown on the gold seeds to create nanometer scale gaps between the nanoparticles. The gap between the nanoparticles was fine tuned by controlling the silver growth time. The substrates showed large enhancement factors in the Raman scattering signal for a broad range of incident wavelengths. Present address: LG Chem Ltd, Information Technology & Electronic Materials R&D, Yuseong-gu Daejeon, South Korea

  4. PS-b-PDMS Block Copolymer Thin Film: Pattern Formation and Phase Behavior

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan; Cheng, Stephen Z. D.; Chen, Feng; Fu, Qiang

    2010-03-01

    Recently, block copolymer thin films are of great interest for their applications in surface patterning, and thin films of diblock copolymers with cylindrical microdomains normal to the surface are more attractive due to the tenability of large aspect ratios of the cylindrical microdomains. Within various kind of block copolymer, PS-b-PDMS is chosen due to an extremely large χ value between PS and PDMS. PS-b-PDMS can be transformed into silicon oxide under UV/O3 exposure, and a layer of silicon oxide with the self-assembled block copolymer patterns can be made. In our work, utilizing PGMEA as solvent and its vapor as spin casting atmosphere, we found an effective approach to obtain the PDMS cylinders oriented normal to the substrate. Furthermore, during benzene solvent annealing, PDMS cylinders' orientation transfers from perpendicular to parallel and then back to perpendicular again. By changing the cylinders orientation alternatively, the lateral order of cylinder packing gradually improved. By investigating this morphology evolution, the mechanism and free energy pathway for PS-b-PDMS thin film morphology transition during solvent annealing can be constructed.

  5. Microphase separated structures of block copolymer thin film with non-volatile selective solvent

    NASA Astrophysics Data System (ADS)

    Yamamoto, Katsuhiro; Umegaki, Naoya; Matsutani, Taito; Takagi, Hideaki; Ito, Eri; Sakurai, Shinichi

    2010-11-01

    Microphase separated structures of block copolymer, polystyrene-b-polyisoprene (PS-b-PI, phiPS = 14%) including non-volatile selective solvent thin films were investigated using grazing incidence small angle X-ray scattering technique. The diethyl phthalate (DEP) was used as a non-volatile selective solvent which solves PS only. The DEP swelled PS phase selectively and the microphase separated structure transited from the PS spherical domain to the lamellar domain with an increase in DEP content in the bulk state. Similarly, the phase separated structure in the thin film prepared by spin cast on a silicon wafer from the mixture of toluene/DEP and block copolymer changed according to the initial DPE concentration. However, the morphologies developed in the thin film were shifted to the structures at lower DEP concentration than that expected from the initial concentration. Moreover, the cylindrical and lamellar domains were aligned parallel and perpendicularly to the substrate, respectively.

  6. Hierarchical assembled nanostructures of hydrogen-bonded supramolecular block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Chen, Xiaofang; Cai, Yongchen

    Controlling the microdomain orientation and long-range ordering in block copolymer thin films is very important in a number of applications, such as nanotemplate, nanoporous thin film, and data storage media. The hierarchical assemblies of block copolymers PS- b-P4VP with dendronized small molecules (DM) hydrogen-bonded onto P4VP blocks were investigated in thin films after solvent vapor annealing. P4VP/DM could form lamellar or hexagonal columnar structure with the periodicity around 8 nm, depending on the stoichiometry of the complex. Hierarchical assemblies of PS- b-P4VP(DM)x, including lamellae-within-lamellae, cylinder-within-lamellae, and cylinder-within-cylinder, were simultaneously ordered and oriented in thin films, which have been studied systematically with the help of AFM, TEM and GISAXS technologies. The orientation of supramolecular assembly depends on the P4VP(DM) fraction and can be tailored by varying the DM to P4VP ratio. Structural transitions from cylinders of (P4VP/DM), lamellae, to cylinders of PS could be achieved by simply increasing the ratio of DM to 4VP units in block copolymer systems. This work was supported by the National Natural Science Foundation of China (21174003 and 21474073).

  7. Structure and Dynamics of Cylinder Forming Block Copolymers in Thin Films

    NASA Astrophysics Data System (ADS)

    Tsarkova, Larisa A.

    In this chapter, we present fundamental aspects of the phase behavior and ordering dynamics in thin films of compositionally asymmetric block copoly- mers. Cylinder-forming AB diblock and ABA triblock copolymers are used as model systems. In the introduction we briefly describe the physics which commonly governs block copolymer phase behavior both in bulk and in thin films; then we define characteristic features of thin film behavior with spe- cial emphasis on the parameters that are readily controlled in experiments. Along with the discussion of surface fields and confinement effects in Sect. 2, we focus on the issues that are seldom discussed in the literature such as molecular weight and molecular architecture effects on the phase behavior and on microdomain dynamics (Sect. 2), and the analysis of the characteristic microdomain dimensions (Sect. 3).We present measurements of the character- istic spacings and film thickness with sub-micron resolution and demonstrate confinement induced distortions of microdomain dimensions in thin films rela- tive to the respective parameters in bulk. In Sect. 4 we describe time-resolved details of structural ordering of cylinder microdomains which indicate that the dynamics of defect annihilation in block copolymer thin films is considerably more complex than anticipated so far.

  8. Shear-alignment of metal-containing block copolymer thin films for nanofabrication

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Register, Richard; Gwyther, Jessica; Manners, Ian; Chaikin, Paul

    2013-03-01

    Cylinder-forming block copolymers can be used as etch masks for the fabrication of nanowire grids, with both fine resolution and scalability. However, achieving a high aspect ratio in these nanostructures, where reactive ion etching is employed for pattern transfer, requires strong etch contrast between two blocks of the copolymer. We achieve this strong contrast by using metal-containing block copolymers: materials which either contain metal as synthesized, or which can be selectively metallized after deposition as thin films. In the first case, iron-containing polystyrene-b-poly(ferrocenylisopropylmethylsilane) (PS-PFS) forming PFS cylinders was employed, and a spin-coated film was aligned by shearing with a polydimethylsiloxane pad. In the second case, polystyrene-b-poly-2-vinylpyridine (PS-P2VP) was deposited as a film, shear-aligned, and then platinum was selectively sequestered within the P2VP cylinders by brief soaking in an aqueous solution of a Pt salt. In both cases, shear stress produced alignment over centimeter-scale areas; this alignment was retained for PS-P2VP during the selective metallization. The line pattern in these aligned block copolymer thin films is then transferred via reactive ion etching into amorphous silicon deposited onto a quartz wafer to fabricate silicon nanowire grid polarizers which can operate at deep ultraviolet wavelengths.

  9. Quantitative study of temperature-dependent order in thin films of cylindrical morphology block copolymer

    NASA Astrophysics Data System (ADS)

    Mishra, Vindhya; Kramer, Edward

    2010-03-01

    Disordering and defect generation in block copolymer systems at high temperatures is of significance to get a better understanding of the physics governing these systems, which can also direct efforts to minimize them. We have studied the smectic-nematic-isotropic transition in confined monolayers and bilayers of cylindrical morphology poly (styrene-b-2vinyl pyridine) diblock copolymer. Previous studies of melting phenomena in block copolymer thin films have relied on quantitative AFM studies alone. We have supplemented AFM studies with grazing incidence small angle X-ray diffraction lineshape analysis to quantify the decay of translational and orientational order with increasing temperature. The results have been interpreted in the context of the Toner-Nelson theory of melting for layered systems.

  10. Analysis of Order Formation in Block Copolymer Thin Films Using Resonant Soft X-Ray Scattering

    SciTech Connect

    Virgili, J.M.; Tao, Y.; Kortright, J.B.; Balsara, N.P.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley

    2007-07-13

    The lateral order of poly(styrene-block-isoprene) copolymer (PS-b-PI) thin films is characterized by the emerging technique of resonant soft X-ray scattering (RSOXS) at the carbon {pi}* resonance and compared to ordering in bulk samples of the same materials measured using conventional small-angle X-ray scattering. We show resonance using theory and experiment that the loss of scattering intensity expected with a decrease in sample volume in the case of thin films can be overcome by tuning X-rays to the {pi}* resonance of PS or PI. Using RSOXS, we study the microphase ordering of cylinder- and sphere-forming PS-b-PI thin films and compare these results to position space data obtained by atomic force microscopy. Our ability to examine large sample areas ({approx}9000 {micro}m{sup 2}) by RSOXS enables unambiguous identification of the lateral lattice structure in the thin films. In the case of the sphere-forming copolymer thin film, where the spheres are hexagonally arranged, the average sphere-to-sphere spacing is between the bulk (body-centered cubic) nearest neighbor and bulk unit cell spacings. In the case of the cylinder-forming copolymer thin film, the cylinder-to-cylinder spacing is within experimental error of that obtained in the bulk.

  11. Pattern formation and phase behavior in PS-B-Si containing block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan

    Since the top-down approaches, such as the extremely ultraviolet (EUV) technique and the high-index fluid-based immersion ArF lithography, may be cover one or two generations, these lithography technologies are getting more severe for the feature size scaling down to sub 10 nm. The directed self-assembly technology of block copolymers is one of the candidates for next generation lithography which can afford feature sizes that are dictated by the molecular weight of the block copolymer and are typically 15 to 30 nm. Directed self-assembly of block copolymers has attracted attention as a technology to extend photoresist-based lithography to smaller dimensions. It has been demonstrated that the directed self assembly of block copolymer offers a new route to perfect nanolithographic pattering at sub-50 nm length scale with molecular scale precision. For application in electronic media, it requires large-area, long-range ordered structures, which is both a kinetic and thermodynamic problem and requires subtle balance of various parameters and processing conditions. So far, block copolymer thin films have already achieved certain success, mainly with higher molecular weights and a feature size of ˜30 nm. Several challenges still remain, such as (a) the generation of long-range ordered structure with smaller feature sizes (domain size < 22 nm), (b) obtaining sharp interface between two domains with high lithographic contrast, particularly for smaller feature sizes, and (c) etch selectivity and resistance between two phases in the nanostructure. To address these challenges, several different approaches have been used in our research. First approach is using PS-b-PDMS. PDMS-containing block copolymers have emerged as next generation block copolymers for nanolithography. Their films can be processed under dry conditions using oxygen plasma to produce inorganic, silica patterns which enables their integration into existing device fabrication. Also, the large thermodynamic

  12. Morphology Development in Block Copolymer Thin Films via Direct Immersion Annealing

    NASA Astrophysics Data System (ADS)

    Modi, Arvind; Bhaway, Sarang; Vogt, Bryan; Sharma, Ashutosh; Karim, Alamgir

    2015-03-01

    Conventional methods of annealing thin block copolymer (BCP) films include Thermal Annealing and Solvent Vapor Annealing (SVA) processes. Both of the processes have demonstrated excellent control over morphologies and nanostructures. However, both have constraints including long annealing time duration and/or complicated setup requirement. We introduce Direct Immersion Annealing (DIA) of thin block copolymer (BCP) films involving immersion of polymer films directly into the solvent mixture composed of selective non-solvent and solvent for blocks. Non-solvent prevents the dissolution of films while the good solvent permeates the film and plasticizes the blocks. A fine control of swelling ratio can be achieved through an easy and robust control of solvent volume fractions. We studied cylindrical Poly(styrene-block-methyl methacrylate) system in detail and quantified the growth of correlation length (ξ) with time(t) [ ξ = Atn]. We observe a reduction in growth exponent (n) with several fold increase in pre-exponential factor (A) compared to isotropic thermal annealing. We further demonstrate the extension of this strategy to systems with diverse range of χ-parameter, molecular weight and other morphologies.

  13. Thin Isoporous Block Copolymer Membranes: It Is All about the Process.

    PubMed

    Hahn, Janina; Clodt, Juliana I; Abetz, Clarissa; Filiz, Volkan; Abetz, Volker

    2015-09-30

    The combination of the self-assembly of amphiphilic block copolymers and the nonsolvent induced phase inversion process offers an efficient way to isoporous integral-asymmetric membranes. In this context we report fast, easily upscalable and material reducing ways to thin self-assembled membranes. Therefore, we succeeded to implement a spray or dip coating step into the membrane formation process of different diblock copolymers like polystyrene-block-poly(4-vinylpyridine), poly(α-methylstyrene)-bock-poly(4-vinylpyridine), and polystyrene-block-poly(iso-propylglycidyl methacrylate). The formation of hexagonal pore structures was possible using a highly diluted one solvent system allowing the reduction of diblock copolymer consumption and therefore the production costs are minimized compared to conventional blade casting approaches. The broad applicability of the process was proven by using different flat and hollow fiber support materials. Furthermore, the membranes made by this new method showed a more than 6-fold increase in water flux compared to conventional polystyrene-block-poly(4-vinylpyridine) membranes with similar pore sizes prepared by blade casting. The membranes could be proven to be stable at transmembrane pressures of 2 bar and showed a pH responsive flux behavior over several cycles. PMID:26349610

  14. Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

    PubMed Central

    Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.; Ober, Christopher K.

    2015-01-01

    Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, we investigated solvent vapor annealing in supported thin films of poly(2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) [PHEMA-b-PMMA] by means of grazing incidence small angle X–ray scattering (GISAXS). A spin-coated thin film of lamellar block copolymer was solvent vapor annealed to induce microphase separation and improve the long-range order of the self-assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents (methanol, MeOH, and tetrahydrofuran, THF), which are chosen to be preferential for each block, enabled selective formation of ordered lamellae, gyroid, hexagonal or spherical morphologies from a single block copolymer with a fixed volume fraction. The selected microstructure was then kinetically trapped in the dry film by rapid drying. To our knowledge, this paper describes the first reported case where in-situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram. PMID:26819574

  15. The role of tortuosity on ion conduction in block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Kambe, Yu; Arges, Christopher G.; Nealey, Paul F.

    This talk discusses the role of grain tortuosity on ion conductivity in block copolymer electrolyte (BCE) thin films. In particular, we studied lamellae forming BCEs with both domains oriented perpendicular to the substrate surface and connected directly from one electrode to another - i.e., tortuosity of one. The BCE is composed of ion-conducting, poly(2-vinyl n-methylpyridinium) blocks and non-ionic polystyrene blocks. Prior to creating the BCE, the pristine block copolymer, poly(styrene- b-2-vinyl pyridine), was directly self-assembled (DSA) on topographical or chemical patterns via graphoepitaxy and chemoepitaxy. A chemical vapor infiltration reaction modified the P2VP block into positively charged, fixed quaternary ammonium groups paired with mobile counteranions. The graphoepitaxy process utilized topographical interdigitated gold nanoelectrodes (100s of nanometers spacing between electrodes) created via e-beam lithography. Alternatively, chemical patterns had gold electrodes incorporated into them with 10s to 100s of microns spacing using conventional optical lithography. The interdigitated gold electrodes enabled in-plane ion conductivity measurements of the DSA BCEs to study the role of grain tortuosity on ion conductivity. U.S. Department of Energy Office of Science: Contract No. DE-AC02-06CH11357.

  16. Directed Ordering of Block Copolymer Thin Films with Flexible Interfaces for Functional Materials

    NASA Astrophysics Data System (ADS)

    Karim, Alamgir

    2012-02-01

    Orientation control of block copolymer (BCP) films is important for advanced technological applications. We present studies on directed ordering of block copolymer thin films on rigid substrates such as quartz to elastomeric PDMS and flexible Kapton substrates for tunable orientation of microphase separated poly (styrene) -- block -poly (methylmethacrylate) (PS-PMMA) cylinder and lamellae forming BCP films. Although the crosslinked PDMS has low surface energy, its surface energy can be tuned by exposing to UV-Ozone (UVO) that presents an opportunity to change BCP-PDMS interfacial energy to control BCP orientation across full range of orientation and film wettability. On the other hand, Kapton offers a near neutral surface for PS-PMMA without surface modification. Via a modified version of a dynamic thermal processing termed cold zone annealing-sharp (CZA-S), we obtain a wide range of orientations of the block copolymer films in unfilled and nanoparticle filled systems with an interest in photovoltaic systems. With CZA-S, vertical orientation of PS-PMMA can be obtained in films as thick as 1 micron with etchable PMMA domains for membrane applications. GISAXS characterization of these etched BCP membranes reveals up to 5 orders of diffraction indicating hexagonally packed vertical nanopores that extend throughout the film. Under similar thermal gradient, but static conditions, temporally stable vertical cylinders form only within a narrow zone of maximum temperature gradient. Primary CZA-S ordering mechanism thus involves propagating this narrow vertically oriented zone of BCP cylinders created at the maximum thermal gradient section, across the film. An optimal speed is needed since the process competes with preferential surface wetting dynamics that favors parallel orientation. These results are reproduced on large area flexible films on a prototype dynamic R2R assembly platform with incorporated multi-CZA gradient for thin (100 nm) BCP films currently.

  17. Metal nanodot arrays fabricated via seed-mediated electroless plating with block copolymer thin film scaffolding

    NASA Astrophysics Data System (ADS)

    Komiyama, Hideaki; Iyoda, Tomokazu; Sanji, Takanobu

    2015-10-01

    We present an alternative approach to fabricating hexagonally arranged nanodot arrays of various metals by seed-mediated electroless plating with a cylinder-forming block copolymer thin film, PEO-b-PMA(Az), as a scaffold. Metal ions were selectively incorporated into PEO cylinders, followed by their reduction to metal and the etching of the scaffold to obtain highly ordered seed arrays of Au, Pd, and Pt. Nanodot arrays of the target metals (Au, Ag, and Ni) were selectively grown on the seed with their highly ordered arrangement by electroless plating. We studied the fabrication processes’ suitability for control of the nanodot array size, as well as the plasmonic properties thereof.

  18. Protein based Block Copolymers

    PubMed Central

    Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

    2011-01-01

    Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

  19. Synergistic templated self-assembly of cellulose nanocrystals in thin block copolymer films

    NASA Astrophysics Data System (ADS)

    Grolman, Danielle; Gilman, Jeffrey; Davis, Chelsea; Karim, Alamgir

    2015-03-01

    Nanofillers in thin polymer films offer unique advantage to potentially modify the film's thermal, optical, electrical and mechanical properties due to the high surface area to volume ratio and intrinsic property change at the nanoscale. Nanofilled polymer films have been shown to exhibit unusual film stability to dewetting with a nonmonotonic behavior with nanofiller loading, potentially arising from factors such as competitive phase behavior and filler aggregation, particularly in the high nanofiller concentration limit. In this regard, block copolymer films can act as ideal nanoscale structured templates to selectively sequester and organize nanofillers. In conjunction with incorporated cellulose nanocrystals (CNCs), we seek to understand how individual anisotropic nanofillers can provide synergistic reinforcement to inherently anisotropic nanostructured block copolymer films. A clear enhancement in the Young's Modulus was observed with increased CNC loading using strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) for thin films. To this end, we examine the nanoscale to microscale morphology of the blend film through AFM, TEM and grazing incidence small-angle x-ray scattering (GISAXS), and CNC dispersion and percolation through high-intensity grazing incidence wide-angle x-ray scattering (GIWAXS) analysis.

  20. Directed Self-Assembly of Block Copolymers in Thin Films on Polymer Nano-Stripes

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Eun; Kang, Ho-Jong; Lee, Dong Hyun; Nano Functional Materials Lab. Team

    In this study, we report directed self-assembly (DSA) of block copolymers in thin films on nano-stripes of polymers. Unique nano-stripes of poly(tetrafluoro ethylene) (PTFE) having ~20 nm of amplitude and ~200 nm of pitch were simply generated by physically rubbing a PTFE bar on various substrates like Si wafers, glass, and polyimide due to its low friction coefficient and high wear rate. The resulting nano-stripes were extremely oriented along the rubbing direction. Then, various asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (PS- b-P2VP) were directly self-assembled on the nano-stripes of PTFE by solvent-annealing in vapor of tetrahydrofuran (THF). As a result, PS- b-P2VP exhibited extremely ordered P2VP cylinders oriented normal to the surface in large area on the underlying nano-stripes of PTFE. In addition, as utilizing the BCPs as templates, hexagonal arrays of metal nanoparticles were generated in large area for further application. BCP thin films and arrays of metal nanoparticles were characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM).

  1. Process Controlled Multiscale Morphologies in Metal-containing Block Copolymer Thin Films

    SciTech Connect

    Ramanathan, Nathan Muruganathan; Kilbey, II, S Michael; Darling, Seth B.

    2014-01-01

    Poly(styrene-block-ferrocenyldimethylsilane) (PS-b-PFS) is a metal-containing block copolymer that exhibits certain advantages as a mask for lithographic applications. These advantages include compatibility with a wide range of substrates, ease of control over domain morphologies and robust stability to etch plasma, which aid in the development of high-aspect-ratio patterns. An asymmetric cylinder-forming PS-b-PFS copolymer is subjected to different processing to manipulate the morphology of the phase-separated domains. Control of film structure and domain morphology is achieved by adjusting the film thickness, mode of annealing, and/or annealing time. Changing the process from thermal or solvent annealing to hybrid annealing (thermal and then solvent annealing in sequence) leads to the formation of mesoscale spherulitic and dendritic morphologies. In this communication, we show that reversing the order of the hybrid annealing (solvent annealing first and then thermal annealing) of relatively thick films (>100 nm) on homogeneously thick substrates develops disordered lamellar structure. Furthermore, the same processing applied on a substrate with a thin, mechanically flexible window in the center leads to the formation of sub-micron scale concentric ring patterns. Enhanced material mobility in the thick film during hybrid annealing along with dynamic rippling effects that may arise from the vibration of the thin window during spin casting are likely causes for these morphologies.

  2. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns.

    PubMed

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S; Ma, Zhenqiang; Nealey, Paul F

    2016-01-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces. PMID:27528258

  3. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

    PubMed Central

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S.; Ma, Zhenqiang; Nealey, Paul F.

    2016-01-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces. PMID:27528258

  4. Structured block copolymer thin film composites for ultra-high energy density capacitors

    NASA Astrophysics Data System (ADS)

    Samant, Saumil; Hailu, Shimelis; Grabowski, Christopher; Durstock, Michael; Raghavan, Dharmaraj; Karim, Alamgir

    2014-03-01

    Development of high energy density capacitors is essential for future applications like hybrid vehicles and directed energy weaponry. Fundamentally, energy density is governed by product of dielectric permittivity ɛ and breakdown strength Vbd. Hence, improvements in energy density are greatly reliant on improving either ɛ or Vbd or a combination of both. Polymer films are widely used in capacitors due to high Vbd and low loss but they suffer from very low permittivities. Composite dielectrics offer a unique opportunity to combine the high ɛ of inorganic fillers with the high Vbd of a polymer matrix. For enhancement of dielectric properties, it is essential to improve matrix-filler interaction and control the spatial distribution of fillers for which nanostructured block copolymers BCP act as ideal templates. We use Directed Self-assembly of block copolymers to rapidly fabricate highly aligned BCP-TiO2 composite nanostructures in thin films under dynamic thermal gradient field to synergistically combine the high ɛ of functionalized TiO2 and high Vbd of BCP matrix. The results of impact of BCP morphology, processing conditions and concentration of TiO2 on capacitor performance will be reported. U.S. Air Force of Scientific Research under contract FA9550-12-1-0306

  5. Subnanometer Porous Thin Films by the Co-assembly of Nanotube Subunits and Block Copolymers

    SciTech Connect

    Xu, Ting; Zhao, Nana; Ren, Feng; Hourani, Rami; Lee, Ming Tsang; Shu, Jessica Y; Mao, Samuel; Helms, Brett A

    2011-02-22

    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation and protective coatings. While molecularly defined nanoporous inorganic and organic materials abound, generating flexible nanoporous thin films with highly aligned channels over large areas has been elusive. Here, we developed a new approach where the growth of cyclic peptide nanotubes can be directed in a structural framework set by the self-assembly of block copolymers. By conjugating polymers to cyclic peptides, the subunit of an organic nanotube can be selectively solubilized in one copolymer microdomain. The conjugated polymers also mediate the interactions between nanotube and local medium and guide the growth of nanotubes in a confined geometry. This led to subnanometer porous membranes containing high-density arrays of through channels. This new strategy takes full advantage of nanoscopic assembly of BCPs and the reversibility of organic nanotube growth and circumvents impediments associated with aligning and organizing high aspect ratio nano-objects normal to the surface. Furthermore, the hierarchical coassembly strategy described demonstrates the feasibility of synchronizing multiple self-assembly processes to achieve hierarchically structured soft materials with molecular level control.

  6. Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

    SciTech Connect

    Tung, Shih-Huang; Kalarickal, Nisha C.; Mays, Jimmy W.; Xu, Ting

    2009-09-08

    The hierarchical assemblies of supramolecules, which consisted of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) with 3-pentadecylphenol (PDP) hydrogen-bonded to the 4VP, were investigated in thin films after solvent annealing in a chloroform atmosphere. The synergistic coassembly of PS-b-P4VP and PDP was utilized to generate oriented hierarchical structures in thin films. Hierarchical assemblies, including lamellae-within-lamellae and cylinders-within-lamellae, were simultaneously ordered and oriented from a few to several tens of nanometers over macroscopic length scales. The macroscopic orientation of supramolecular assembly depends on the P4VP(PDP) fraction and can be tailored by varying the PDP to P4VP ratio without interfering with the supramolecular morphologies. The lamellar and cylindrical microdomains, with a periodicity of {approx}40 nm, could be oriented normal to the surface, while the assembly of comb blocks, P4VP(PDP), with a periodicity of {approx}4 nm, were oriented parallel to the surface. Furthermore, using one PS-b-P4VP copolymer, thin films with different hierarchical structures, i.e., lamellae-within-lamellae and cylinders-within-lamellae, were obtained by varying the ratio of PDP to 4VP units. The concepts described in these studies can be potentially applied to other BCP-based supramolecular thin films, thus creating an avenue to functional, hierarchically ordered thin films.

  7. Thin polymer films of block copolymers and blend/nanoparticle composites

    NASA Astrophysics Data System (ADS)

    Kalloudis, Michail

    In this thesis, atomic force microscopy (AFM), transmission electron microscopy (TEM) and optical microscopy techniques were used to investigate systematically the self-assembled nanostructure behaviour of two different types of spin-cast polymer thin films: poly(isoprene-b-ethylene oxide), PI-b-PEO diblock copolymers and [poly(9,9-dioctylfluorene-co-benzothiadiazole)]:poly[9,9- dioctyfluorene-co-N-(4-butylphenyl)-diphenylamine], F8BT:TFB conjugated polymer blends. In the particular case of the polymer blend thin films, the morphology of their composites with cadmium selenide (CdSe) quantum dot (QD) nanoparticles was also investigated. For the diblock copolymer thin films, the behaviour of the nanostructures formed and the wetting behaviour on mica, varying the volume fraction of the PEO block (fPEO) and the average film thickness was explored. For the polymer blend films, the effect of the F8BT/TFB blend ratio (per weight), spin-coating parameters and solution concentration on the phase-separated nanodomains was investigated. The influence of the quantum dots on the phase separation when these were embedded in the F8BT:TFB thin films was also examined. It was found that in the case of PI-b-PEO copolymer thin films, robust nanostructures, which remained unchanged after heating/annealing and/or ageing, were obtained immediately after spin coating on hydrophilic mica substrates from aqueous solutions. The competition and coupling of the PEO crystallisation and the phase separation between the PEO and PI blocks determined the ultimate morphology of the thin films. Due to the great biocompatible properties of the PEO block (protein resistance), robust PEO-based nanostructures find important applications in the development of micro/nano patterns for biological and biomedical applications. It was also found that sub-micrometre length-scale phase-separated domains were formed in F8BT:TFB spin cast thin films. The nanophase-separated domains of F8BT-rich and TFB-rich areas

  8. Role of defects on self-assembly of nanoparticles in block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Kim, Jenny; Green, Peter

    2011-03-01

    The structure of A-b-B block copolymer (BCP) thin films is often exploited as scaffolds for directing nanoparticles into various, long-range ordered geometries. Depending on the affinity between nanoparticles and block chains, nanoparticles preferentially segregate to either A or B domains. We show that dislocations may play a dominant role in the assembly of large nanoparticles in BCP thin film that order at suboptimal thicknesses. Edge dislocations are ubiquitous in lamellar BCP thin films forming a partial surface layer, i.e. holes or island structures. When the ratio of the nanoparticle diameter, d, to the domain dimension, L, d/L 0.15, the nanoparticles were distributed uniformly throughout the film. However for larger values of d/L, the nanoparticles reside primarily at the dislocation cores. In the case of films of initial film thicknesses between L h < 3L the nanoparticles self-assemble into 2-dimensional planar shapes at the boundaries of holes or islands where edge dislocations are located.

  9. Nanoporous membrane based on block copolymer thin film for protein drug delivery

    NASA Astrophysics Data System (ADS)

    Yang, Seung Yun; Yang, Jeong-A.; Kim, Eung-Sam; Jeon, Gumhye; Oh, Eun Ju; Choi, Kwan Yong; Hahn, Sei Kwang; Kim, Jin Kon

    2010-03-01

    We studied long term and controlled release of protein drugs by using nanoporous membranes with various pore sizes. Nanoporous membrane consists of the separation layer prepared by polystyrene-block-poly(methylmethacrylate) copolymer thin film and conventional microfiltration membrane as a support. We demonstrate a long-term constant in vitro release of bovine serum albumin (BSA)and human growth hormone ) (hGH) without their denaturation up to 2 months. A nearly constant serum concentration of hGH was maintained up to 3 weeks in SD rats. The long-term constant delivery based on this membrane for protein drugs within the therapeutic range can be highly appreciated for the patients with hormone- deficiency.

  10. Co-assembly of polymer covered cyclic peptide nanotubes and block copolymer in thin films

    NASA Astrophysics Data System (ADS)

    Zhang, Chen; Lazzara, Thomas; Li, Changyi; Helmes, Brett; Xu, Ting

    2013-03-01

    Nanotubular structures have gained prevalent interest for their unique hollow structures and high aspect ratio and their potential applications ranging from molecular separation to nanocomposite membranes. We used nanotube forming cyclic peptide (CP) as the structural motif and studied the self-assembly of polymer conjugated CPs in block copolymer (BCP) matrix in thin films. The co-assembly process is mainly driven by thermodynamic quantities, namely Flory-Huggins polymer-polymer interactions that governs the interaction between CP and BCP, interfacial interactions that affects polymer chain orientation, and thin film commensurability. In addition, due to the dynamic nature of the nanotube formation, the co-assembly process is also pathway-dependent. Thus, processing conditions are critical in co-assembling CP nanotubes and BCP in thin films. Our result shows that the initial aggregation state of polymer covered CP nanotubes determines the pathway the system takes and hence the final morphology of the films. The co-assembly of polymer-conjugated CPs and BCPs demonstrates the feasibility of assembling 1D nanotubes in supramolecular thin films and opens up a new avenue for the generation of novel nanotubular structures.

  11. Photocontrol over the Disorder-to-Order Transition (DOT) in Thin Film of Polystyrene-block-Poly(methyl methacrylate) Block Copolymers Containing Photodimerizable anthracene functionality

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Li, Le; Wei, Xinyu; Balazs, Anna; Matyjaszewski, Krzysztof; Russell, Thomas

    2010-03-01

    Reversible photocontrol over the disorder-to-order transition (DOT) of block copolymers can be used to fabricate defect-free, long-range ordered nanomaterials over macroscopic distances by ``photo-combing'' the microdomains. Here, we randomly copolymerized anthracene functionalities in a ``dilute'' way with 2-hydroxyethyl methacrylate as the middle block, forming deuterated polystyrene-block-poly(2-(methacryloyloxy)ethyl anthracene-9-carboxylate-random-2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) (d8-PS-b-P(9AnEMA-r-HEMA)-b-PMMA) triblock copolymers. Upon UV irradiation of a thin film of the phase-mixed triblock copolymer, photodimerization of anthracene links the junction of d8-PS and PMMA blocks and produces an artificial interface to force a phase-separation, i.e. a UV-induced DOT, as evidenced by small angle neutron scattering (SANS). Reversible photocontrol over the DOT can be achieved by taking advantage of photodimerization and photodissociation of anthracene.

  12. Lubricating effect of thin films of styrene-dimethylsiloxane block copolymers

    SciTech Connect

    Ndoni, S.; Jannasch, P.; Larsen, N.B.; Almdal, K.

    1999-05-25

    The lubricating effect of styrene-dimethylsiloxane block copolymer films spin cast on Si wafers was found to increase with increasing size of the poly(dimethylsiloxane) (PDMS) block. Friction properties of symmetrical and close-to-symmetrical block copolymers were evaluated in contact with bromobutyl rubber in a plate-on-plate configuration. X-ray photoelectron spectroscopy showed that the copolymer films were all covered by at least a 10 nm thick layer of PDMS. The lubricating effect remained constant down to a film thickness comparable to the chain dimensions of the copolymer, R{sub 0}, after which it decreased progressively. At thicknesses below R{sub 0}, the copolymer dewetted the wafer and formed discrete domains with sizes comparable to R{sub 0}. The copolymer could further be blended with up to 70 wt % polystyrene without detecting a decrease in the lubricating effect. A mechanism is proposed for the observed frictional behavior where microflakes are abraded from lamellar copolymer surfaces and stick to the contacting rubber surface, whereafter lubrication may result from sliding of PDMS brushes against each other.

  13. Manipulating block copolymer self-assemblies in bulk and thin films by thermal and solvent annealing

    NASA Astrophysics Data System (ADS)

    Gu, Weiyin

    The self--assembly of block copolymers (BCPs) into well--ordered nanoscopic arrays holds promise for new technological breakthroughs as templates and scaffolds for the fabrication of nanostructured materials. It is essential to establish convenient approaches to control the morphology of BCPs, since some applications require addressability, the BCP microdomains must be perfectly aligned and oriented. The theme of this thesis is the use of external forces, specifically thermal and solvent annealing, to guide the self--assembly of BCPs to obtain microphase separated morphologies for different applications. Three representative BCP systems, having lamellar, cylindrical and spherical microdomains are discussed. First, the self--assembly of lamella--forming brush block copolymers (BrBCPs) having polylactide (PLA) and polystyrene (PS) side chains were studied in the bulk and in thin films. The domain size increased approximately linearly with the molecular weight of the backbone, which indicated that the backbone was in an extended conformation that was confirmed theoretically. In situ small angle x--ray scattering (SAXS) measurements indicated that the self--assembly of the BrBCPs was quite rapid, due to the rigid nature of the backbone chain, Second, the directed self--assembly of cylinder--forming polystyrene--block--poly(ethylene oxide)s (PS--b--PEOs) in thin films were investigated. The polymer--surface interactions were tuned by hydroxyl end--functionalized polymers, so that the orientation of the PS--b--PEO microdomains was controlled during thermal annealing. Cylindrical PEO microdomains embedded in a PS matrix orientated normal to the silicon substrates were observed over a wide processing window when the substrates were modified by PS-- b--PEO BCPs. PS--b--PEOs with an o--nitrobenzyl ester junction point (PS--hnu --PEOs) were used to fabricate nanoscopic dot and line patterns having long--range lateral order. The cylindrical BCP microdomains were oriented

  14. Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers

    SciTech Connect

    Vu, Thai; Mahadevapuram, Nikhila; Perera, Ginusha M.; Stein, Gila E.

    2012-03-15

    Domain orientations in thin films of lamellar copolymers are evaluated as a function of copolymer architecture, film thickness, and processing conditions. Two copolymer architectures are considered: An AB diblock of poly(styrene-b-methyl methacrylate) and an ABA triblock of poly(methyl methacrylate-b-styrene-b-methyl methacrylate). All films are cast on substrates that are energetically neutral with respect to the copolymer constituents. Film structures are evaluated with optical microscopy, atomic force microscopy, and grazing-incidence small-angle X-ray scattering. For AB diblock copolymers, the domain orientations are very sensitive to film thickness, annealing temperature, and imperfections in the 'neutral' substrate coating: Diblock domains are oriented perpendicular to the substrate when annealing temperature is elevated ({>=} 220 C) and defects in the substrate coating are minimized; otherwise, parallel or mixed parallel/perpendicular domain orientations are detected for most film thicknesses. For ABA triblock copolymers, the perpendicular domain orientation is stable for all the film thicknesses and processing conditions that were studied. The orientations of diblock and triblock copolymers are consistent with recent works that consider architectural effects when calculating the copolymer surface tension (Macromolecules 2006, 39, 9346 and Macromolecules 2010, 43, 1671). Significantly, the data demonstrate that triblocks are easier to process for applications in nanopatterning - in particular, when high-aspect-ratio nanostructures are required. However, both diblock and triblock films contain a high density of 'tilted' or bent domains, and these kinetically trapped defects should be minimized for most patterning applications.

  15. Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns

    PubMed Central

    Murphy, Jeffrey N.; Harris, Kenneth D.; Buriak, Jillian M.

    2015-01-01

    Line patterns produced by lamellae- and cylinder-forming block copolymer (BCP) thin films are of widespread interest for their potential to enable nanoscale patterning over large areas. In order for such patterning methods to effectively integrate with current technologies, the resulting patterns need to have low defect densities, and be produced in a short timescale. To understand whether a given polymer or annealing method might potentially meet such challenges, it is necessary to examine the evolution of defects. Unfortunately, few tools are readily available to researchers, particularly those engaged in the synthesis and design of new polymeric systems with the potential for patterning, to measure defects in such line patterns. To this end, we present an image analysis tool, which we have developed and made available, to measure the characteristics of such patterns in an automated fashion. Additionally we apply the tool to six cylinder-forming polystyrene-block-poly(2-vinylpyridine) polymers thermally annealed to explore the relationship between the size of each polymer and measured characteristics including line period, line-width, defect density, line-edge roughness (LER), line-width roughness (LWR), and correlation length. Finally, we explore the line-edge roughness, line-width roughness, defect density, and correlation length as a function of the image area sampled to determine each in a more rigorous fashion. PMID:26207990

  16. Heterogeneous patterns on block copolymer thin film via solvent annealing: Effect on protein adsorption

    NASA Astrophysics Data System (ADS)

    Shen, Lei; Zhu, Jintao; Liang, Haojun

    2015-03-01

    Heterogeneous patterns consisting of nanometer-scaled hydrophobic/hydrophilic domains were generated by self-assembly of poly(styrene)-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) block copolymer thin film. The effect of the heterogeneity of the polymer film surface on the nonspecific adsorption of the protein human plasma fibrinogen (FBN, 5.0 × 5.0 × 47.5 nm3) was investigated. The kinetics of the FBN adsorption varies from a single-component Langmuir model on homogeneous hydrophilic PHEMA to a two-stage spreading relaxation model on homogeneous hydrophobic PS surface. On a heterogeneous PS-b-PHEMA surface with majority PS part, the initial FBN adsorption rate remains the same as that on the homogeneous PS surface. However, hydrophilic PHEMA microdomains on the heterogeneous surface slow down the second spreading stage of the FBN adsorption process, leading to a surface excess of adsorbed FBN molecules less than the presumed one simply calculated as adsorption onto multiple domains. Importantly, when the PS-b-PHEMA surface is annealed to form minority domelike PS domains (diameter: ˜50-100 nm) surrounded by a majority PHEMA matrix, such surface morphology proves to be strongly protein-repulsive. These interesting findings can be attributed to the enhancement of the spread FBN molecule in a mobile state by the heterogeneity of polymer film surface before irreversible adsorption occurs.

  17. Continuous and patterned deposition of functional block copolymer thin films using electrospray

    NASA Astrophysics Data System (ADS)

    Toth, Kristof; Hu, Hanqiong; Kim, Myungwoong; Gopalan, Padma; Loewenberg, Michael; Osuji, Chinedum

    The delivery of sub-micron droplets of dilute polymer solutions to a heated substrate by electrospray deposition (ESD) enables precisely controlled and continuous growth of block copolymer (BCP) thin films. The ESD process overcomes many shortcomings of spin coating deposition, including the batch nature of the process, loss of potentially valuable polymer, limitations of solvent choice, and large time scales of annealing. We report that high substrate temperatures led to vertically oriented cylindrical microdomains of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) at the film surface independent of the solvent composition and deposition rates utilized. Conversely, low substrate temperatures resulted in morphologies that were more sensitive to these parameters, with poorly ordered films of globular structures. We also report on the new possibility for patterned deposition of BCP films by spatially varying the electric field at the substrate using an underlying charged grid. To overcome surface charging, a novel alternating current electrospray process is proposed for deposition on non-conductive surfaces.

  18. Formation of Lamellar Heterolattices in Block Copolymer Thin Films by Sequential Electrospray Deposition

    NASA Astrophysics Data System (ADS)

    Choo, Youngwoo; Hu, Hanqiong; Toth, Kristof; Osuji, Chinedum

    Electrospray deposition (ESD) of block copolymers (BCPs) on a heated substrate provides precise control over the formation of BCP thin films. This continuous deposition process allows one to fabricate heterogeneously assembled thin films by altering the deposition materials. Here, we demonstrate such the sequential ESD of lamellae-forming poly(styrene- b-4-vinylpyridine) BCPs with differing molecular weights and explore the morphology of the composite films. The resulting structure of the heterolattice interface was a strong function of temperature. Sharp interfaces with abrupt changes in the lamellar period (L0) were observed at lower deposition temperatures (150 - 170 °C), while higher temperature (190 °C) produced a smooth variation in the lamellar period from one molecular weight to the next. Furthermore, the ordering kinetics of a secondary layer which was deposited onto the primary layer could be substantially enhanced depending on the molecular weight of the polymer present in the underlying primary layer. We elucidate these findings in the context of temperature and molecular weight dependent diffusion dynamics of the polymers in the melt which control the inter-mixing of the layers. We gratefully acknowledge funding by NSF DRM-1410568.

  19. Rapid thermal processing of self-assembling block copolymer thin films on flat surfaces and topographically defined patterns

    NASA Astrophysics Data System (ADS)

    Perego, Michele; Ferrarese Lupi, Federico; Giammaria, Tommaso J.; Seguini, Gabriele; Gianotti, Valentina; Antonioli, Diego; Sparnacci, Katia; Laus, Michele; Enrico, Emanuele; de Leo, Natascia; Boarino, Luca; Ober, Christopher K.

    2014-03-01

    Self-assembling block copolymers generate nanostructured patterns, which are potentially useful for a wide range of applications. However, their technological implementation is prevented by the very long time required to drive the process. In this contribution, we demonstrate the capability to control the morphology of the self-assembling process of cylinder forming PS-b-PMMA diblock copolymer (DBC) thin films deposited on un-patterned and topographically patterned surfaces by means of a Rapid Thermal Processing (RTP) machine. Highly ordered patterns were obtained on flat surfaces for perpendicular-oriented cylindrical PS-b-PMMA block copolymers in less than 60 s. The BCs morphology evolution within topographically defined structures was systematically investigated as well. Irrespective of the surface neutralization, an irreversible orientational flipping of the BCP microdomains inside the trenches was observed. This effect was attributed to de-swelling of the polymeric film as a consequence of a progressive desorption of the solvent retained inside the film.

  20. Surface effects on the structure of block copolymer and homopolymer thin films

    NASA Astrophysics Data System (ADS)

    Sohn, Karen E.

    One strategy for producing effective fouling release surfaces for ship hulls is to use a bilayer system with a thermoplastic elastomer with a tunable modulus as the bottom layer and a surface active block copolymer (SABC) to control the surface chemistry. SABC's with semifluorinated liquid crystal side chains are used to minimize surface adhesion by fouling agents. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to characterize the structure of the liquid side crystal side chains. A method for depth profiling using NEXAFS spectroscopy where the post-edge intensities are fit and used to measure the thickness of the perfluoroalkyl surface layer. The Auger electron escape depth was determined to be 1.61nm, and the thickness of the perfluoroalkyl surface layer of a polystyrene homopolymer functionalized with perfluorinated alkyl chains is 0.42nm. A possible thermoplastic elastomer for the underlayer is poly(styrene-b-ethylener-butylene-b-styrene) (SEBS). The modulus can be adjusted by varying the composition of the block copolymer. The SEBS studied here has a bulk order-order transition (OOT) that transforms the morphology from hexagonally packed cylinders to body centered cubic (BCC) spheres as the temperature is increased. The thin film behavior is studied with atomic force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS). In thin films annealed both above and below the OOT, the morphology is always spherical. When the film contains less than 4 layers of spheres, they are packed on a hexagonal lattice. The packing transition from hexagonal packing to face centered orthorhombic packing occurs when there are 4 layers of spheres. The morphology is always spherical over the thickness range studied here because of the free energy penalty due to looping of the midblock, which is required for the surface to be covered by the lower surface energy PEB. The percentage of midblock chains that must loop is lower for spheres

  1. Bactericidal block copolymer micelles.

    PubMed

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  2. On the self-assembly of brush block copolymers in thin films.

    PubMed

    Hong, Sung Woo; Gu, Weiyin; Huh, June; Sveinbjornsson, Benjamin R; Jeong, Gajin; Grubbs, Robert Howard; Russell, Thomas P

    2013-11-26

    We describe a simple route to fabricate two dimensionally well-ordered, periodic nanopatterns using the self-assembly of brush block copolymers (brush BCPs). Well-developed lamellar microdomains oriented perpendicular to the substrate are achieved, without modification of the underlying substrates, and structures with feature sizes greater than 200 nm are generated due to the reduced degree of chain entanglements of brush BCPs. A near-perfect linear scaling law was found for the period, L, as a function of backbone degree of polymerization (DP) for two series of brush BCPs. The exponent increases slightly from 0.99 to 1.03 as the side chain molecular weight increases from ∼2.4 to ∼4.5 kg/mol(-1) and saturated with further increase in the side chain molecular weight due to the entropic penalty associated with the packing of the side chains. Porous templates and scaffolds from brush BCP thin films are also obtained by selective etching of one component. PMID:24156297

  3. Dynamic thermal field-induced gradient soft-shear for highly oriented block copolymer thin films.

    PubMed

    Singh, Gurpreet; Yager, Kevin G; Berry, Brian; Kim, Ho-Cheol; Karim, Alamgir

    2012-11-27

    As demand for smaller, more powerful, and energy-efficient devices continues, conventional patterning technologies are pushing up against fundamental limits. Block copolymers (BCPs) are considered prime candidates for a potential solution via directed self-assembly of nanostructures. We introduce here a facile directed self-assembly method to rapidly fabricate unidirectionally aligned BCP nanopatterns at large scale, on rigid or flexible template-free substrates via a thermally induced dynamic gradient soft-shear field. A localized differential thermal expansion at the interface between a BCP film and a confining polydimethylsiloxane (PDMS) layer due to a dynamic thermal field imposes the gradient soft-shear field. PDMS undergoes directional expansion (along the annealing direction) in the heating zone and contracts back in the cooling zone, thus setting up a single cycle of oscillatory shear (maximum lateral shear stress ∼12 × 10(4) Pa) in the system. We successfully apply this process to create unidirectional alignment of BCP thin films over a wide range of thicknesses (nm to μm) and processing speeds (μm/s to mm/s) using both a flat and patterned PDMS layer. Grazing incidence small-angle X-ray scattering measurements show absolutely no sign of isotropic population and reveal ≥99% aligned orientational order with an angular spread Δθ(fwhm) ≤ 5° (full width at half-maximum). This method may pave the way to practical industrial use of hierarchically patterned BCP nanostructures. PMID:23106286

  4. Controlling Directed Self-Assembly and Sintering of Gold Nanorods in Patterned Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Lai, Fengyuan

    As the miniaturization of electronic devices continues, proper thermal management is crucial to ensure the optimum performance and reliability of such devices within their specification. Of primary interest are the so-called thermal interface materials to minimize the thermal resistance between the heat source and the heat sink. To this end, polymer nanocomposites composed of a polymer matrix and nanoscale fillers with high thermal conductivity have attracted tremendous attention. It has been demonstrated that the formation of a nanoparticle assembly inside the polymer matrix provides a continuous pathway for efficient heat transfer, and thus it is essential for achieving high thermal conductivity. In this work, we explored the ability to direct the self-assembly of gold nanorods (AuNRs) via patterned block copolymer (BCP) thin films. Selective sequestration of AuNRs with various aspect ratios in one block domain was achieved, with over 30% of the surface covered by an ordered AuNR assembly orienting parallel to the geometric confinement. The final nanostructure resulting from the directed self-assembly process is determined by the competition between thermodynamic consideration and kinetic factors. The coalescence and sintering of the AuNR assembly was accomplished by both furnace thermal annealing and rapid thermal annealing at low temperatures. The mechanism through which efficient sintering occurred is investigated with scanning electron microscopy. It is found that the sintering process initially takes place locally, resulting in small AuNR aggregates. Eventually the aggregates grow into a globally continuous, percolating network structure. In addition, the overall heat transfer coefficient was measured in an environmental scanning electron microscope by following droplet growth over time. The present study opens up new opportunities to accomplish controlled assembly of nanoparticles with high concentration for different nanorod-based applications as well as

  5. Block copolymer battery separator

    DOEpatents

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  6. Directed Assembly of Lamellae Forming Block Copolymer Thin Films near the Order-Disorder Transition

    SciTech Connect

    Kim, Sangwon; Nealey, Paul F.; Bates, Frank S.

    2014-08-07

    The impact of thin film confinement on the ordering of lamellae was investigated using symmetric poly(styrene-b-[isoprene-ran-epoxyisoprene]) diblock copolymers bound by nonpreferential wetting interfaces. The order–disorder transition temperature (TODT) and the occurrence of composition fluctuations in the disordered state are not significantly affected by two-dimensional confinement. Directed self-assembly using chemical patterning is demonstrated near TODT. These results establish the minimum feature size attainable using directed self-assembly of a given diblock copolymer system.

  7. New Poly(dimethylsiloxane)/Poly(perfluorooctylethyl acrylate) Block Copolymers: Structure and Order Across Multiple Length Scales in Thin Films

    SciTech Connect

    E Martinelli; G Galli; S Krishnan; M Paik; C Ober; D Fischer

    2011-12-31

    Three sets of a new class of low surface tension block copolymers were synthesized consisting of a poly(dimethylsiloxane) (PDMS) block and a poly(perfluorooctylethyl acrylate) (AF8) block. The polymers were prepared using a bromo-terminated PDMS macroinitiator, to which was attached an AF8 block grown using atom transfer radical polymerization (ATRP) in such a designed way that the molecular weight and composition of the two polymer blocks were regularly varied. The interplay of both the phase separated microstructure and the mesomorphic character of the fluorinated domains with their effect on surface structure was evaluated using a suite of analytical tools. Surfaces of spin-coated and thermally annealed films were assessed using a combination of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) studies. Both atomic force microscopy (AFM) measurements and grazing incidence small angle X-ray scattering (GISAXS) studies were carried out to evaluate the microstructure of the thin films. Even in block copolymers in which the PDMS block was the majority component, a significant presence of the lower surface energy AF8 block was detected at the film surface. Moreover, the perfluorooctyl helices of the AF8 repeat units were highly oriented at the surface in an ordered, tilted smectic structure, which was compared with those of the bulk powder samples using wide-angle X-ray powder diffraction (WAXD) studies.

  8. Deconvoluting the mechanism of microwave annealing of block copolymer thin films.

    PubMed

    Jin, Cong; Murphy, Jeffrey N; Harris, Kenneth D; Buriak, Jillian M

    2014-04-22

    The self-assembly of block copolymer (BCP) thin films is a versatile method for producing periodic nanoscale patterns with a variety of shapes. The key to attaining a desired pattern or structure is the annealing step undertaken to facilitate the reorganization of nanoscale phase-segregated domains of the BCP on a surface. Annealing BCPs on silicon substrates using a microwave oven has been shown to be very fast (seconds to minutes), both with and without contributions from solvent vapor. The mechanism of the microwave annealing process remains, however, unclear. This work endeavors to uncover the key steps that take place during microwave annealing, which enable the self-assembly process to proceed. Through the use of in situ temperature monitoring with a fiber optic temperature probe in direct contact with the sample, we have demonstrated that the silicon substrate on which the BCP film is cast is the dominant source of heating if the doping of the silicon wafer is sufficiently low. Surface temperatures as high as 240 °C are reached in under 1 min for lightly doped, high resistivity silicon wafers (n- or p-type). The influence of doping, sample size, and BCP composition was analyzed to rule out other possible mechanisms. In situ temperature monitoring of various polymer samples (PS, P2VP, PMMA, and the BCPs used here) showed that the polymers do not heat to any significant extent on their own with microwave irradiation of this frequency (2.45 GHz) and power (∼600 W). It was demonstrated that BCP annealing can be effectively carried out in 60 s on non-microwave-responsive substrates, such as highly doped silicon, indium tin oxide (ITO)-coated glass, glass, and Kapton, by placing a piece of high resistivity silicon wafer in contact with the sample-in this configuration, the silicon wafer is termed the heating element. Annealing and self-assembly of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly(methyl methacrylate) (PS

  9. Azobenzene photoswitching as a tool for controlling block copolymer self-assembly in dip-coated thin films

    NASA Astrophysics Data System (ADS)

    Vapaavuori, Jaana; Grosrenaud, Josué; Borozenko, Kateryna; Pellerin, Christian; Bazuin, Geraldine; Department of Chemistry, University of Montreal Team

    Understanding how to control the characteristics of microphase-separated block copolymer thin films is of crucial importance for developing nanotechnological applications, such as producing nanoscale lithography templates for the electronics industry. The supramolecular complexation of small molecules selectively to one of the blocks in suitable block copolymers enables modulating the block volume fractions and thereby controlling the type of surface morphology obtained in thin films. In this contribution, we show that the morphology of dip-coated polystyrene-b-poly(4-vinylpyridine) polymer films containing a hydrogen-bonding azobenzene guest can be further controlled using light as an external in situ stimulus during the dip-coating procedure. A change from spherical to cylindrical morphology was demonstrated when the geometry of the azobenzene units was switched by illumination at 365 nm. Film thickness measurements revealed that the thickness of the films can also be tailored by light, since films prepared under irradiation are significantly thicker than non-irradiated ones. The photochemical requirements to guide the choice of azobenzene molecule and the nature of the solvent used will be discussed in view of an optimal material combination for easily directable systems.

  10. Shear alignment and realignment of sphere-forming and cylinder-forming block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Marencic, Andrew P.; Adamson, Douglas H.; Chaikin, Paul M.; Register, Richard A.

    2010-01-01

    In common with many other structured fluids, block copolymers can be effectively oriented by shear. This susceptibility to shear alignment has previously been shown to hold even in thin films, containing as few as two layers of spherical microdomains, or even a single layer of cylindrical microdomains. A phenomenological model has been proposed [M. W. Wu, R. A. Register, and P. M. Chaikin, Phys. Rev. E 74, 040801(R) (2006)] to describe the alignment of such block-copolymer films, yielding the microdomain lattice order parameter as a function of shearing temperature, stress, and time. Here we directly test the central idea of that model, that the grains which are most misaligned with the shear direction are selectively destroyed, to reform in a direction more closely aligned with the shear. Films are first shear aligned from a polygrain state into a monodomain orientation and are then subjected to a second shear, at a variable stress (σ) and misorientation angle (δθ) relative to the monodomain director, allowing the effects of σ and δθ to be independently and systematically probed. For both cylinder-forming and sphere-forming block copolymers, these experiments confirm the basic premise of the model, as the stress required for realignment increases monotonically as δθ becomes smaller. For a cylinder-forming block copolymer, we find that the characteristic stress σc required to realign cylinders from one monodomain orientation to another is indistinguishable from that required to generate a monodomain orientation from the polygrain state. By contrast, the hexagonal lattice of spheres requires a value of σc more than 3 times as high for reorientation than for generation of the initial monodomain orientation.

  11. Analysis of Order Formation in Block Copolymer Thin Films UsingResonant Soft X-Ray Scattering

    SciTech Connect

    Virgili, Justin M.; Tao, Yuefei; Kortright, Jeffrey B.; Balsara,Nitash P.; Segalman, Rachel A.

    2006-11-27

    The lateral order of poly(styrene-block-isoprene) copolymer(PS-b-PI) thin films is characterized by the emerging technique ofresonant soft X-ray scattering (RSOXS) at the carbon K edge and comparedto ordering in bulk samples of the same materials measured usingconventional small-angle X-ray scattering. We show resonance using theoryand experiment that the loss of scattering intensity expected with adecrease in sample volume in the case of thin films can be overcome bytuning X-rays to the pi* resonance of PS or PI. Using RSOXS, we study themicrophase ordering of cylinder- and phere-forming PS-b-PI thin films andcompare these results to position space data obtained by atomic forcemicroscopy. Our ability to examine large sample areas (~;9000 mu m2) byRSOXS enables unambiguous identification of the lateral lattice structurein the thin films. In the case of the sphere-forming copolymer thin film,where the spheres are hexagonally arranged, the average sphere-to-spherespacing is between the bulk (body-centered cubic) nearest neighbor andbulk unit cell spacings. In the case of the cylinder-forming copolymerthin film, the cylinder-to-cylinder spacing is within experimental errorof that obtained in the bulk.

  12. Interfaces between Block Copolymer Domains

    NASA Astrophysics Data System (ADS)

    Kim, Jaeup; Jeong, Seong-Jun; Kim, Sang Ouk

    2011-03-01

    Block copolymers naturally form nanometer scale structures which repeat their geometry on a larger scale. Such a small scale periodic pattern can be used for various applications such as storage media, nano-circuits and optical filters. However, perfect alignment of block copolymer domains in the macroscopic scale is still a distant dream. The nanostructure formation usually occurs with spontaneously broken symmetry; hence it is easily infected by topological defects which sneak in due to entropic fluctuation and incomplete annealing. Careful annealing can gradually reduce the number of defects, but once kinetically trapped, it is extremely difficult to remove all the defects. One of the main reasons is that the defect finds a locally metastable morphology whose potential depth is large enough to prohibit further morphology evolution. In this work, the domain boundaries between differently oriented lamellar structures in thin film are studied. For the first time, it became possible to quantitatively study the block copolymer morphology in the transitional region, and it was shown that the twisted grain boundary is energetically favorable compared to the T-junction grain boundary. [Nano Letters, 9, 2300 (2010)]. This theoretical method successfully explained the experimental results.

  13. Block copolymer investigations

    NASA Astrophysics Data System (ADS)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  14. Neutral wetting brush layers for block copolymer thin films using homopolymer blends

    NASA Astrophysics Data System (ADS)

    Antonioli, Diego; Sparnacci, Katia; Laus, Michele; Lupi, Federico Ferrarese; Giammaria, Tommaso Jacopo; Seguini, Gabriele; Ceresoli, Monica; Perego, Michele; Gianotti, Valentina

    2016-05-01

    Binary homopolymer blends of two hydroxyl-terminated polystyrene (PS-OH) and polymethylmethacrylate (PMMA-OH) homopolymers (Mn ~ 16000 g mol-1) were grafted on SiO2 substrates by high-temperature (T > 150 °C), short-time (t < 600 s) thermal treatments. The resulting brush layer was tested to screen preferential interactions of the SiO2 substrate with the different symmetric and asymmetric PS-b-PMMA block copolymers deposited on top of the grafted molecules. By properly adjusting the blend composition and the processing parameters, an efficient surface neutralization path was identified, enabling the formation, in the block copolymer film, of homogeneous textures of lamellae or cylinders perpendicularly oriented with respect to the substrate. A critical interplay between the phase segregation of the homopolymer blends and their grafting process on the SiO2 was observed. In fact, the polar SiO2 is preferential for the PMMA-rich phase that forms a homogeneous layer on the substrate, while the PS-rich phase is located at the polymer-air interface. During the thermal treatment, phase segregation and grafting proceed simultaneously. Complete wetting of the PS rich phase on the PMMA rich phase leads to the formation of a PS/PMMA bilayer. In this case, the progressive diffusion of PS chains toward the polymer-SiO2 interface during the thermal treatment allows tuning of the brush layer composition

  15. Neutral wetting brush layers for block copolymer thin films using homopolymer blends processed at high temperatures

    NASA Astrophysics Data System (ADS)

    Ceresoli, M.; Palermo, M.; Ferrarese Lupi, F.; Seguini, G.; Perego, M.; Zuccheri, G.; Phadatare, S. D.; Antonioli, D.; Gianotti, V.; Sparnacci, K.; Laus, M.

    2015-10-01

    Binary homopolymer blends of two hydroxyl-terminated polystyrene (PS-OH) and polymethylmethacrylate (PMMA-OH) homopolymers (Mn ˜ 16000 g mol-1) were grafted on SiO2 substrates by high-temperature (T > 150 °C), short-time (t < 600 s) thermal treatments. The resulting brush layer was tested to screen preferential interactions of the SiO2 substrate with the different symmetric and asymmetric PS-b-PMMA block copolymers deposited on top of the grafted molecules. By properly adjusting the blend composition and the processing parameters, an efficient surface neutralization path was identified, enabling the formation, in the block copolymer film, of homogeneous textures of lamellae or cylinders perpendicularly oriented with respect to the substrate. A critical interplay between the phase segregation of the homopolymer blends and their grafting process on the SiO2 was observed. In fact, the polar SiO2 is preferential for the PMMA-rich phase that forms a homogeneous layer on the substrate, while the PS-rich phase is located at the polymer-air interface. During the thermal treatment, phase segregation and grafting proceed simultaneously. Complete wetting of the PS rich phase on the PMMA rich phase leads to the formation of a PS/PMMA bilayer. In this case, the progressive diffusion of PS chains toward the polymer-SiO2 interface during the thermal treatment allows tuning of the brush layer composition.

  16. Simulations on a swollen gyroid nanostructure in thin films relevant to systems of ionic block copolymers.

    PubMed

    Knychała, P; Banaszak, M

    2014-07-01

    Self-assembly of symmetric A/S-B copolymer melt to gyroid nanostructure, partitioning space into interpenetrating nano-labyrinths (channels), in thin films, is investigated using a minimal lattice model with short-range interactions. This model is relevant to poly(styrenesulfonate)-b -polymethylbutylene melt consisting of three types of segments, A, B and S, corresponding to styrene, methylbutylene and styrenesulfonate, respectively. A single sequence of A, B, and S is used in simulations and the fraction of S segments is fixed at p = 0.647 which corresponds to experimental data. The film thickness, L(z), is restricted to nine values (L(z) = 17 , 22, 26, 30, 34, 42, 51, 60, and 68 in units of the underlying lattice constant). The gyroid nanostructure is found to be stable if the film thickness is equal to or greater than the bulk period of the nanophase. The observed gyroid is referred to as swollen since the volume fraction of two continuous networks made of the B segments is anomalous with respect to that of conventional diblock copolymers. In contrast to bulk state, we do not directly observe the order-disorder transition to the gyroid nanophase for thin films. In this case, however, simulations indicate a direct order-disorder transition to a lamellar phase and the order-disorder transition temperature is higher than that in the bulk state, varying strongly with the film thickness. PMID:25080175

  17. Surface Morphology Diagram for Cylinder-Forming Block Copolymer Thin Films

    SciTech Connect

    Zhang, Xiaohua; Berry, Brian C.; Yager, Kevin G.; Kim, Sangcheol; Jones, Ronald L.; Satija, Sushil; Pickel, Deanna L; Douglas, Jack F> Karim, Alamgir

    2008-01-01

    We investigate the effect of annealing temperature (T), film thickness (hf) on the surface morphology of flow coated films of a cylinder forming block copolymer, poly (styrene-block-methyl methacrylate) (PS-b-PMMA). Surface morphology transitions from a perpendicular to a parallel cylinder orientation with respect to the substrate with increasing hf are observed in these model frustrated-interaction films where the substrate interaction is preferential for one of the blocks (PMMA) and nearly neutral for the other interface (polymer-air). In these films a transition occurs from cylinders oriented parallel to the substrate to a mixed or hybrid state where the two orientations coexist followed by a transition to cylinders oriented perpendicularly to the polymer-air interface for larger hf. The characteristic values of hf defining these surface morphological transitions depend on T and we construct a surface morphology diagram as a function of hf and T. The surface morphology diagram is found to depend on the method of film formation (flow coated versus spun cast films) so non-equilibrium effects evidently have a large effect on the surface pattern morphology. In particular, the residual solvent within the film (quantified by neutron reflectivity measurements) in the context of physics of glass-formation can have a large effect on the surface morphology diagram.

  18. Chemical Interactions and Their Role in the Microphase Separation of Block Copolymer Thin Films

    PubMed Central

    Farrell, Richard A.; Fitzgerald, Thomas G.; Borah, Dipu; Holmes, Justin D.; Morris, Michael A.

    2009-01-01

    The thermodynamics of self-assembling systems are discussed in terms of the chemical interactions and the intermolecular forces between species. It is clear that there are both theoretical and practical limitations on the dimensions and the structural regularity of these systems. These considerations are made with reference to the microphase separation that occurs in block copolymer (BCP) systems. BCP systems self-assemble via a thermodynamic driven process where chemical dis-affinity between the blocks driving them part is balanced by a restorative force deriving from the chemical bond between the blocks. These systems are attracting much interest because of their possible role in nanoelectronic fabrication. This form of self-assembly can obtain highly regular nanopatterns in certain circumstances where the orientation and alignment of chemically distinct blocks can be guided through molecular interactions between the polymer and the surrounding interfaces. However, for this to be possible, great care must be taken to properly engineer the interactions between the surfaces and the polymer blocks. The optimum methods of structure directing are chemical pre-patterning (defining regions on the substrate of different chemistry) and graphoepitaxy (topographical alignment) but both centre on generating alignment through favourable chemical interactions. As in all self-assembling systems, the problems of defect formation must be considered and the origin of defects in these systems is explored. It is argued that in these nanostructures equilibrium defects are relatively few and largely originate from kinetic effects arising during film growth. Many defects also arise from the confinement of the systems when they are ‘directed’ by topography. The potential applications of these materials in electronics are discussed. PMID:19865513

  19. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

    NASA Astrophysics Data System (ADS)

    Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

    2016-06-01

    In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and

  20. Processing Cyclic Peptide-polymer Conjugates in Block Copolymer Thin Films for Sub-nm Porous Membranes

    NASA Astrophysics Data System (ADS)

    Zhang, Chen; Xu, Ting

    2014-03-01

    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation. Inspired by natural protein channels, we have developed an approach using cyclic peptide nanotubes (CPNs) embedded in polymeric matrix to mimic the transport of natural channels. The co-assembly of polymer-covered CPNs in a block copolymer (BCP) thin film requires the synchronization of two self-assembly processes, namely the microphase separation of BCP and the nanotube growth of CP-polymer conjugates. We systematically investigated the co-assembly of isolated CP-poly(ethylene glycol) (CP-PEG) conjugates and polystyrene-b-poly (methyl methacrylate) (PS-b-PMMA) in thin films as a function of CP-PEG loading (fCP-PEG) and solvent-polymer interactions. We find that there is a strong dependence of the co-assembly process on fCP-PEG due to thermodynamic limit of incorporating one CPN in one PMMA microdomain, as well as the kinetic pathway in which favorable PEG-solvent interaction helps to disperse CPNs and thus lowers the activation energy barrier of the system. This study presents critical insights in guided assemblies of functional building blocks within nanoscopic frameworks. DOE-EFRC-Gas Separation, Army Research Office.

  1. Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer.

    PubMed

    Zhang, Jieqian; Clark, Michael B; Wu, Chunyi; Li, Mingqi; Trefonas, Peter; Hustad, Phillip D

    2016-01-13

    Directed self-assembly (DSA) of block copolymers (BCPs) is an attractive advanced patterning technology being considered for future integrated circuit manufacturing. By controlling interfacial interactions, self-assembled microdomains in thin films of polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, can be oriented perpendicular to surfaces to form line/space or hole patterns. However, its relatively weak Flory interaction parameter, χ, limits its capability to pattern sub-10 nm features. Many BCPs with higher interaction parameters are capable of forming smaller features, but these "high-χ" BCPs typically have an imbalance in surface energy between the respective blocks that make it difficult to achieve the required perpendicular orientation. To address this challenge, we devised a polymeric surface active additive mixed into the BCP solution, referred to as an embedded neutral layer (ENL), which segregates to the top of the BCP film during casting and annealing and balances the surface tensions at the top of the thin film. The additive comprises a second BCP with a "neutral block" designed to provide matched surface tensions with the respective polymers of the main BCP and a "surface anchoring block" with very low surface energy that drives the material to the air interface during spin-casting and annealing. The surface anchoring block allows the film to be annealed above the glass transition temperature of the two materials without intermixing of the two components. DSA was also demonstrated with this embedded neutral top layer formulation on a chemical patterned template using a single step coat and simple thermal annealing. This ENL technology holds promise to enable the use of high-χ BCPs in advanced patterning applications. PMID:26682931

  2. Block copolymer nanolithography for the fabrication of patterned media.

    SciTech Connect

    Warke, Vishal V; Bakker, Martin G; Hong, Kunlun; Mays, Jimmy; Britt, Phillip F; Li, Xuefa; Wang, Jin

    2008-01-01

    Abstract Bit patterned perpendicular media has the potential to increase the density of magnetic recording beyond what can be achieved by granular media. Self assembling diblock copolymers are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. A method to fabricate the desired pattern using cylinder forming diblock copolymers of (PS-b-PMMA) as template is reported. Upon phase separation hexagonally packed cylinders of the minority phase (PMMA) surrounded by the continuous majority phase (PS) are obtained. The processing sequence began with spin coating the block copolymer on a suitable substrate, followed by annealing the block copolymer thin film in vacuum to orient it perpendicular to the substrate. Block copolymer templates were obtained by glacial acetic acid treatment which opened the pores in the block copolymer thin film. Ni was electrodeposited in the block copolymer templates and this pattern was then transferred onto the underlying substrate by ion milling

  3. Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application.

    PubMed

    Cummins, Cian; Ghoshal, Tandra; Holmes, Justin D; Morris, Michael A

    2016-07-01

    Block copolymers (BCPs) and their directed self-assembly (DSA) has emerged as a realizable complementary tool to aid optical patterning of device elements for future integrated circuit advancements. Methods to enhance BCP etch contrast for DSA application and further potential applications of inorganic nanomaterial features (e.g., semiconductor, dielectric, metal and metal oxide) are examined. Strategies to modify, infiltrate and controllably deposit inorganic materials by utilizing neat self-assembled BCP thin films open a rich design space to fabricate functional features in the nanoscale regime. An understanding and overview on innovative ways for the selective inclusion/infiltration or deposition of inorganic moieties in microphase separated BCP nanopatterns is provided. Early initial inclusion methods in the field and exciting contemporary reports to further augment etch contrast in BCPs for pattern transfer application are described. Specifically, the use of evaporation and sputtering methods, atomic layer deposition, sequential infiltration synthesis, metal-salt inclusion and aqueous metal reduction methodologies forming isolated nanofeatures are highlighted in di-BCP systems. Functionalities and newly reported uses for electronic and non-electronic technologies based on the inherent properties of incorporated inorganic nanostructures using di-BCP templates are highlighted. We outline the potential for extension of incorporation methods to triblock copolymer features for more diverse applications. Challenges and emerging areas of interest for inorganic infiltration of BCPs are also discussed. PMID:26749571

  4. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors.

    PubMed

    Choi, Jonathan W; Li, Zhaodong; Black, Charles T; Sweat, Daniel P; Wang, Xudong; Gopalan, Padma

    2016-06-01

    In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes. PMID:27216015

  5. Crystalline Structure in Thin Films of DEH-PPV Homopolymer And PPV-B-PI Rod-Coil Block Copolymers

    SciTech Connect

    Olsen, B.D.; Alcazar, D.; Krikorian, V.; Toney, M.F.; Thomas, E.L.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley /MIT /SLAC, SSRL

    2009-04-30

    The rod orientation and crystalline packing of a model semiconducting rodlike polymer, poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV), is shown to affect the self-assembly of weakly segregated rod-coil block copolymers. The in-plane packing of DEH-PPV rods in lamellar poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene-b-isoprene) (DEH-PPV-b-PI) diblock copolymers is nearly identical to that observed in DEH-PPV homopolymers for compositions ranging from 0.42 to 0.82 vol % coil block. The crystal structure of DEH-PPV, characterized by grazing incidence X-ray diffraction and electron diffraction, consists of a tetragonal unit cell having c = 0.665 nm with a = b = 1.348 nm. The polymer chain axis is aligned along the [001] direction, and the nearest neighbor rod-rod spacing along 110 is 1.0 nm. As-cast thin films of DEH-PPV homopolymer demonstrate chain alignment primarily perpendicular to the substrate in 5100 g/mol homopolymer, while for 3500 g/mol homopolymer the chains align both perpendicular and parallel to the substrate. For the DEH-PPV-b-PI block copolymers, a sharper 001 reflection is observed due to the effect of microphase separation, improving alignment and stacking of the rods. The lamellar phases have a smectic A-like packing structure with the rods oriented parallel to the lamellar normal regardless of coil fraction; however, at coil fractions above about 0.8 the crystalline lattice of the rods becomes rapidly disordered as evidenced by loss of all but the two strongest Bragg reflections. This suggests that the constraints of packing into the unit cell outweigh the chain stretching and segment-segment repulsion energies that are predicted to lead to a transition from normal (smectic A) to tilted (smectic C) rod orientation within the lamellae at high coil fraction; increasing coil fraction breaks apart the crystalline lattice rather than distorting it into a tilted polymorph.

  6. Skin delivery by block copolymer nanoparticles (block copolymer micelles).

    PubMed

    Laredj-Bourezg, Faiza; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Valour, Jean-Pierre; Rovère, Marie-Rose; Smatti, Batoule; Chevalier, Yves

    2015-12-30

    Block copolymer nanoparticles often referred to as "block copolymer micelles" have been assessed as carriers for skin delivery of hydrophobic drugs. Such carriers are based on organic biocompatible and biodegradable materials loaded with hydrophobic drugs: poly(lactide)-block-poly(ethylene glycol) copolymer (PLA-b-PEG) nanoparticles that have a solid hydrophobic core made of glassy poly(d,l-lactide), and poly(caprolactone)-block-poly(ethylene glycol) copolymer (PCL-b-PEG) nanoparticles having a liquid core of polycaprolactone. In vitro skin absorption of all-trans retinol showed a large accumulation of retinol in stratum corneum from both block copolymer nanoparticles, higher by a factor 20 than Polysorbate 80 surfactant micelles and by a factor 80 than oil solution. Additionally, skin absorption from PLA-b-PEG nanoparticles was higher by one order of magnitude than PCL-b-PEG, although their sizes (65nm) and external surface (water-swollen PEG layer) were identical as revealed by detailed structural characterizations. Fluorescence microscopy of histological skin sections provided a non-destructive picture of the storage of Nile Red inside stratum corneum, epidermis and dermis. Though particle cores had a different physical states (solid or liquid as measured by (1)H NMR), the ability of nanoparticles for solubilization of the drug assessed from their Hildebrand solubility parameters appeared the parameter of best relevance regarding skin absorption. PMID:26602293

  7. Micrometer-Scale Ordering of Silicon-Containing Block Copolymer Thin Films via High-Temperature Thermal Treatments.

    PubMed

    Giammaria, Tommaso Jacopo; Ferrarese Lupi, Federico; Seguini, Gabriele; Perego, Michele; Vita, Francesco; Francescangeli, Oriano; Wenning, Brandon; Ober, Christopher K; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele

    2016-04-20

    Block copolymer (BCP) self-assembly is expected to complement conventional optical lithography for the fabrication of next-generation microelectronic devices. In this regard, silicon-containing BCPs with a high Flory-Huggins interaction parameter (χ) are extremely appealing because they form high-resolution nanostructures with characteristic dimensions below 10 nm. However, due to their slow self-assembly kinetics and low thermal stability, these silicon-containing high-χ BCPs are usually processed by solvent vapor annealing or in solvent-rich ambient at a low annealing temperature, significantly increasing the complexity of the facilities and of the procedures. In this work, the self-assembly of cylinder-forming polystyrene-block-poly(dimethylsiloxane-random-vinylmethylsiloxane) (PS-b-P(DMS-r-VMS)) BCP on flat substrates is promoted by means of a simple thermal treatment at high temperatures. Homogeneous PS-b-P(DMS-r-VMS) thin films covering the entire sample surface are obtained without any evidence of dewetting phenomena. The BCP arranges in a single layer of cylindrical P(DMS-r-VMS) nanostructures parallel-oriented with respect to the substrate. By properly adjusting the surface functionalization, the heating rate, the annealing temperature, and the processing time, one can obtain correlation length values larger than 1 μm in a time scale fully compatible with the stringent requirements of the microelectronic industry. PMID:27020526

  8. Effect of χN and underlayer composition on self-assembly of thin films of block copolymers with energy asymmetric block

    NASA Astrophysics Data System (ADS)

    Lawson, Richard A.; Peters, Andrew J.; Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2015-03-01

    Many high χ block copolymer (BCP) systems often have one block which shows a strong preference to wet the free interface at the top of the film. This property makes it difficult to form vertically aligned lamellae which are desired for many directed self-assembly (DSA) applications. To better understand this behavior, simulations of thin films of BCPs were carried out using a coarse-grained molecular dynamics (MD) model. The property that leads one block to preferentially wet the free interface over the other is a difference in cohesive energy density (CED) between the two blocks. Our simulation allows for the systematic variation in the CED of each block to investigate how the magnitude of these differences affects self-assembly behavior. BCPs with no CED differences between the blocks show large ranges of underlayer compositions where vertical lamellae will form that are minimally affected by changing χ of the BCP. The range where vertical lamellae will form can be thought of as a process window. Increasing the CED asymmetry of the BCP (i.e. the difference in CED between blocks) causes a reduction in the process window and also causes a shift in the underlayer composition that is the center of the window. Increasing χ increases the process window for vertical lamellae in CED asymmetric systems. This behavior is determined by the trade-off in energy due to three interfacial interactions: A-B interface, film-free surface interface, and film-underlayer interface. At the limits of very high CED asymmetry and low χ, there may be no underlayer compositions where vertical lamellae will form. A simplified model was also developed that can accurately predict these process windows for different CED asymmetry and χ values on the order of seconds and minutes compared to hours and days for the full simulation.

  9. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G.; Matzger, Adam J.; Benin, Annabelle I.; Willis, Richard R.

    2012-12-04

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  10. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  11. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2014-11-11

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  12. Solvothermal Vapor Annealing of Lamellar Poly(styrene)-block-poly(d,l-lactide) Block Copolymer Thin Films for Directed Self-Assembly Application.

    PubMed

    Cummins, Cian; Mokarian-Tabari, Parvaneh; Andreazza, Pascal; Sinturel, Christophe; Morris, Michael A

    2016-03-30

    Solvothermal vapor annealing (STVA) was employed to induce microphase separation in a lamellar forming block copolymer (BCP) thin film containing a readily degradable block. Directed self-assembly of poly(styrene)-block-poly(d,l-lactide) (PS-b-PLA) BCP films using topographically patterned silicon nitride was demonstrated with alignment over macroscopic areas. Interestingly, we observed lamellar patterns aligned parallel as well as perpendicular (perpendicular microdomains to substrate in both cases) to the topography of the graphoepitaxial guiding patterns. PS-b-PLA BCP microphase separated with a high degree of order in an atmosphere of tetrahydrofuran (THF) at an elevated vapor pressure (at approximately 40-60 °C). Grazing incidence small-angle X-ray scattering (GISAXS) measurements of PS-b-PLA films reveal the through-film uniformity of perpendicular microdomains after STVA. Perpendicular lamellar orientation was observed on both hydrophilic and relatively hydrophobic surfaces with a domain spacing (L0) of ∼32.5 nm. The rapid removal of the PLA microdomains is demonstrated using a mild basic solution for the development of a well-defined PS mask template. GISAXS data reveal the through-film uniformity is retained following wet etching. The experimental results in this article demonstrate highly oriented PS-b-PLA microdomains after a short annealing period and facile PLA removal to form porous on-chip etch masks for nanolithography application. PMID:26950246

  13. Influence of Interfacial Energy on Electric-Field-Induced Sphere-to-Cylinder Transition in Block Copolymer Thin Films

    SciTech Connect

    Wang, J.; Chen, W; Russell, T

    2008-01-01

    The effect of the interfacial energy on the electric-field-induced sphere-to-cylinder (S-to-C) transition in polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) copolymer thin films was studied as a function of the difference in the interfacial interactions of the PS and PMMA blocks with the substrate, d. It was found that the interfacial energies altered both the critical electric field strength and the time scales of kinetics. A very strong preferential interfacial interaction suppressed the electric-field-induced S-to-C transition even though such a transition occurred on a neutralized surface where the interfacial interactions were balanced. For a moderate interfacial interaction, the S-to-C transition can be induced by an applied electric field, but the time scale of the morphology change is much longer. Furthermore, the formation of ionic complexes in the BCP was found to enhance the electric-field-induced S-to-C transition even on a native Si substrate without any surface modification, providing a simple route to generate ordered arrays of high-aspect-ratio cylinders oriented normal to a film surface.

  14. An in-situ study of structure evolution in block copolymer thin films of PS-PEO during solvent vapor annealing

    NASA Astrophysics Data System (ADS)

    Mokarian-Tabari, Parvaneh; Collins, Timothy W.; Morris, Michael A.

    2010-03-01

    Thin films of block copolymers are promising candidates for producing nano scale structures in the electronic industry such as sub-30 nm templates for nanolithography [1]. To be able to produce structures with desired morphologies and minimum defects, it is important to have a deep understanding of the ordering mechanism. We have carried out a systematic study on spin cast films made of poly(styrene-b-ethylene oxide) block copolymers during solvent and thermal annealing. The swelling behavior of the films were studied by using an environmental cell to control the vapor pressure of the gas and equipped with small angle light scattering apparatus. Our results show that the swelling starts within seconds of exposure to toluene vapor and the domains form within minutes. Cyclic transition between perpendicular and horizontal arrays is observed. [1] Ruiz R, Kang H M, Detcheverry F A, Dobisz E, Kercher D S, Albrecht T R, de Pablo J J and Nealey P F, 2008, 321, 936

  15. Structure Formation of Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Abetz, Volker

    2013-03-01

    Isoporous membranes have received increasing attention during the last couple of years. The advantage of these materials is to give access to membranes with a very high number density of pores with controlled diameters, thus leading to ultrafiltration membranes with a very high permeability, and simultaneously also with a very high selectivity in terms of size exclusion. Different approaches have been reported, which typically involve the transfer of a thin block copolymer film from a solid to a porous support, eventually followed by an edging step. An alternative strategy is to form integral asymmetric membranes, where the thin top layer is continuously changing into a spongy support layer, thus avoiding the build-up of mechanical stresses. This happens by subjecting the cast polymer solution film into a precipitant, inducing the so-called phase inversion by exchange of solvent with the non-solvent. Here it is important to have a system where solvent and nonsolvent are fully miscible. This strategy also enables the direct formation of open pores without a subsequent edging step, if the solvents and nonsolvents are appropriately chosen. Different types of amphiphilic block copolymers based on styrene, 2- or 4-vinyl pyridine, and ethylene oxide with various compositions and molecular weights will be discussed. These block copolymers were dissolved at different concentrations in various solvent mixtures, and then cast on a non-woven support, which was either pretreated with a liquid, or not. Varying the time before the cast solution was subjected to phase inversion, as well as choosing the temperature of the precipitation bath, are further parameters having strong influence on the obtained membrane film structure. Membranes with pore forming blocks showing pH or temperature sensitive behaviour can be reversibly switched from an open state to a closed state. The size of the pores can be controlled by both molecular weight and composition of the block copolymers.

  16. Materials Design for Block Copolymer Lithography

    NASA Astrophysics Data System (ADS)

    Sweat, Daniel Patrick

    Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up

  17. Directed self-assembly of block copolymer thin films: From fundamentals science to applications

    NASA Astrophysics Data System (ADS)

    Teel, George Lewis

    A modern approach to satellite based experimentation has evolved from large, multi-instrumented satellites, to cheaper, smaller, almost disposable yet still reliable small spacecrafts. These small satellites are either sent to the International Space Station (ISS) to be dropped out into low earth orbit (LEO), or dropped off as a secondary payload into various orbits. While it is cheap to have small spacecraft accomplishing these missions, the lifetime expectancy is very short. Currently there are no commercialized propulsion systems that exist to keep them flying for prolonged periods of time. Recently researched at the Micro Propulsion and Nanotechnology Lab (MPNL), at the George Washington University (GWU), have been developments of a variety of Vacuum Arc Thrusters (VAT's) dubbed Micro-Cathode Vacuum Arc Thrusters (muCATs). muCAT's provide an inert electric means of propulsion for small spacecraft. The issue with these muCATs has been their efficiency levels and low amounts of thrust that they provide. The muCATs can provide muN levels of thrust per pulse. While being proficient for small spacecrafts, an increase in thrust is highly sought for, but the improvements must retain a small footprint and low power consumption. The topic of this thesis is the development and characterization of a new type of muCAT. The interest in this new design has been conceptualized based on experiments for plasma coating techniques. By utilizing the physics of evaporation, which has been used to decrease macroparticles (MP's) for thin film deposition, it has been theorized to also be applied to VAT technology. The concept is to increase levels of thrust with the muCAT, and provide higher levels of efficiency. This effect can be created without many additional components nor multiple additional loads to the thruster subsystem. Development of this new mechanic for thruster technology has been investigated through a variety of tests for fundamental proofs of concept. Running in two

  18. Block copolymer/ferroelectric nanoparticle nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-08-01

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were

  19. Use of combined chromatographic methods including thin-layer chromatography for analysis of complex polymer systems. Determination of the polydispersity of block copolymers of styrene and methyl methacrylate by gel permeation, thin-layer and pyrolysis gas chromatography.

    PubMed

    Belenkii, B G; Gankina, E S; Nefedov, P P; Lazareva, M A; Savitskaya, T S; Volchikhina, M D

    1975-05-01

    A combination of gel permeation chromatography (GPC), thin-layer chromatography (TLC) and pyrolysis gas chromatography (PGC) has been used for investigations of a polymethyl methacrylate-polystyrene-polymethyl methacrylate block copolymer. Continuous distribution of the polymer (40-mg sample) was attained according to the content of the styrene and methyl methacrylate units and of the block copolymer and according to the composition of the copolymer as functions of the hydrodynamic radius of the macromolecules. The polymer was subjected to a preliminary fractionation with an analytical gel chromatograph. The fractions were investigated by TLC, which permitted the separation of the block copolymer and the homopolymers. The composition of the fractions obtained by GPC and TLC was determined by PGC. As a result, it was possible to establish the composition of the block copolymer and its ratio to polymethyl methacrylate in each fraction. This investigation was based on a combination of highly effective fractionation by chromatographic methods with precise quantitative ratios obtained from Benoit's universal calibration graph and from determinations of the composition of the polymer fractions by PGC. The mechanism of the TLC of polymers, including the appearance of artefacts that distort the results of analysis, is also discussed. PMID:1150816

  20. On the mechanism of electrical conduction in thin films of some polysulfone-poly(alkylene oxide)-poly(dimethylsiloxane) block copolymers

    NASA Astrophysics Data System (ADS)

    Rusu, G. G.; Airinei, A.; Hamciuc, V.; Rambu, A. P.; Caplanus, I.; Rusu, G. I.

    2014-01-01

    Polysulfone poly(alkylene oxide)-poly(dimethylsiloxane) block copolymers have been prepared by the hydrosilylation reaction of allyl endcapped poly[(ethylene oxide) (propylene oxide)] oligomers with Si-H terminated polydimethylsiloxane in chlorobenzene using an isopropanol solution of hexachloroplatinic (IV) acid as catalyst for hydrosilylation. The temperature dependences of electrical conductivity and thermoelectric power (Seebeck coefficient) of copolymers were studied using thin-film samples deposited from dimethylformamide (spin coating technique) onto glass substrates. Organic films with reproducible electronic transport and optical properties can be obtained if, after deposition, they are submitted to a heat treatment consisting of several successive heating/cooling cycles within temperature range of (295-485) K. Investigated copolymers presents typical semiconducting characteristics. The values of some fundamental parameters (activation energy of electrical conduction, ratio of carrier mobilities, optical energy bandgap) have been determined. The mechanisms of electronic transport are identified in different temperature domains. Transmission and absorption spectra have been recorded and optical energy bandgaps are calculated from the absorption spectra. The thermistor effect of investigated copolymers is also discussed.

  1. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  2. Pattern transfer using block copolymers.

    PubMed

    Gu, Xiaodan; Gunkel, Ilja; Russell, Thomas P

    2013-10-13

    To meet the increasing demand for patterning smaller feature sizes, a lithography technique is required with the ability to pattern sub-20 nm features. While top-down photolithography is approaching its limit in the continued drive to meet Moore's law, the use of directed self-assembly (DSA) of block copolymers (BCPs) offers a promising route to meet this challenge in achieving nanometre feature sizes. Recent developments in BCP lithography and in the DSA of BCPs are reviewed. While tremendous advances have been made in this field, there are still hurdles that need to be overcome to realize the full potential of BCPs and their actual use. PMID:24000358

  3. Order-disorder transition in thin films of horizontally-oriented cylinder-forming block copolymers: thermal fluctuations vs. preferential wetting.

    PubMed

    Kim, Sangwon; Li, Wei; Fredrickson, Glenn H; Hawker, Craig J; Kramer, Edward J

    2016-07-01

    We present experimental and theoretical investigations of the order-disorder transition (ODT) in thin films of cylinder-forming diblock copolymers with asymmetric wetting conditions. Grazing incidence small-angle X-ray scattering (GISAXS) was implemented to determine the ODT temperatures (TODT) for poly(styrene-b-2-vinyl pyridine) (PS-P2VP) block copolymer thin films on a P2VP-preferential silicon substrate. Specifically, films consisting of multilayers of horizontally-oriented cylindrical structures (from 1- to 9-layers) were tested. We find that films with more than 2 cylindrical layers have a TODT comparable to the bulk case. However, TODT decreases as the film becomes thinner and the monolayer system has an ODT 30 °C below the bulk. Using self-consistent field theory (SCFT), we studied the ordering in corresponding thin films with asymmetric (top and bottom surface) wetting conditions. Surprisingly, SCFT is found to predict an opposite trend in TODT with film thickness than observed experimentally. Field-theoretic simulations with complex Langevin sampling were employed to resolve this discrepancy and demonstrate that thermal fluctuations in the PS-P2VP thin-film system dominate its ordering behavior in monolayer and bilayer films. PMID:27334558

  4. Block Copolymers with a Twist

    SciTech Connect

    Ho, R.; Chiang, Y; Chen, C; Wang, H; Hasegawa, H; Akasaka, S; Thomas, E; Burger, C; Hsiao, B

    2009-01-01

    Chiral block copolymers (BCPs*) comprising chiral entities were designed to fabricate helical architectures (i.e., twisted morphologies) from self-assembly. A new helical phase (H*) with P622 symmetry was discovered in the self-assembly of poly(styrene)-b-poly(l-lactide) (PS-PLLA) BCPs*. Hexagonally packed, interdigitated PLLA helical microdomains in a PS matrix were directly visualized by electron tomography. The phase diagram of the PS-PLLA BCPs* was also established. Phase transitions from the H* phase to the stable cylinder and gyroid phases were found after long-time annealing, suggesting that the H* is a long-lived metastable phase. In contrast to racemic poly(styrene)-b-poly(d,l-lactide) BCPs, chiral interaction significantly enhances the incompatibility between achiral PS and chiral PLLA blocks in the PS-PLLA BCPs* and can be estimated through the determination of the interaction parameter.

  5. Nanopatterned articles produced using surface-reconstructed block copolymer films

    DOEpatents

    Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2016-06-07

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  6. Method for making block siloxane copolymers

    DOEpatents

    Butler, N.L.; Jessop, E.S.; Kolb, J.R.

    1981-02-25

    A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  7. Method for making block siloxane copolymers

    DOEpatents

    Butler, Nora; Jessop, Edward S.; Kolb, John R.

    1982-01-01

    A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  8. Reordering transitions during annealing of block copolymer cylinder phases

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.

  9. Combining mixed titania morphologies into a complex assembly thin film by iterative block-copolymer-based sol-gel templating

    NASA Astrophysics Data System (ADS)

    Niedermeier, M. A.; Magerl, D.; Zhong, Q.; Nathan, A.; Körstgens, V.; Perlich, J.; Roth, S. V.; Müller-Buschbaum, P.

    2012-04-01

    Sol-gel templating combined with iterative spin-coating steps are used to custom-tailor hierarchically structured titania thin films. Using poly(styrene-block-ethylene oxide) P(S-b-PEO) as the structure directing agent, a foam-like structure is combined with nanogranules. Both structural elements are merged into a complex assembly in thin film geometry. The resulting morphology is pictured by SEM and probed with GISAXS. The installed mesoporous titania sandwich structure exhibits holes with a size of 45 nm which makes it promising for applications in photovoltaics or photocatalysis. An optical characterization completes the structural investigation.

  10. Log-rolling block copolymers cylinders

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Kim, Ye Chan; Kim, Dong Hyup; Kwon, Na Kyung; Register, Richard A.

    Shear has been the most effective method to create long range order of micro- or nano- structures in soft materials. When shear is applied, soft particles or polymers tend to align along the shear direction to minimize the viscous dissipation, thus transverse (so-called ``log-rolling'') alignment is unfavored. In this study, for the first time we report the transverse alignment of cylinder-forming block copolymers. Poly(styrene-b-methyl methacrylate), PS-PMMA, can form a metastable hemicylinder structure when confined in a thin film, and this hemicylinder structure can align either along the shear direction, or transverse to the shear direction (``log-rolling''), depending on the shearing temperature. This unusual ``log-rolling'' behavior is explained by the different chain mobility of the two blocks in PS-PMMA; the rigidity of core cylinder is the critical parameter determining the direction of shear alignment.

  11. Comparing Fluid and Elastic Block Copolymer Shells

    NASA Astrophysics Data System (ADS)

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Emulsions can be stabilized with the addition of an amphiphilic diblock copolymer, resulting in droplets surrounded and protected by a polymer monolayer. Such droplets show considerable promise as advanced cargo carriers in pharmaceuticals or cosmetics due to their strength and responsiveness. Diblock copolymer interfaces remain mostly fluid and may not be able to attain the mechanical performance desired by industry. To strengthen block copolymer emulsion droplets we have developed a novel method for creating thin elastic shells using polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS). Characterization of the fluid filled elastic shells is difficult with traditional means which lead us to develop a new and general method of mechanical measurement. Specifically, we use laser scanning confocal microscopy to achieve a high resolution measure of the deformation of soft spheres under the influence of gravity. To prove the resilience of the technique we examine both a polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized emulsion and the PS-PAA-PS emulsion. The mechanical measurement allows the physics of the polymer at the interface to be examined, which will ultimately lead to the rational development of these technologies.

  12. Synthesis and morphology characterization of polydimethylsiloxane-containing block copolymers

    NASA Astrophysics Data System (ADS)

    Wadley, Maurice

    The thin film morphology characteristics of polydimethylsiloxane-containing block copolymers have been investigated. For this investigation, a commercially available hydroxyl terminated PDMS was purchased from Gelest and attached to a carboxylic acid functional reversible addition-fragmentation chain transfer (RAFT) agent by Steglich esterification. This produced macro-RAFT agents to which styrene monomer was polymerized. By using this approach the generation of low polydispersity polystyrene-block-polydimethylsiloxane (PS-block-PDMS) copolymers of various molecular weights spanning a wide volume fraction range in which the PDMS block remained the same in each polymerization. Synthesized block copolymers were characterized by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Bulk and thin film characterization of PS-block-PDMS copolymers was done by small-angle x-ray scattering (SAXS), transmission electron microscopy (TEM), contact angle measurements, scanning force microscopy (SFM), and grazing incidence small-angle X-ray scattering (GISAXS). The following observations have been made. For PS-rich PS-block -PDMS copolymer thin films the low surface tension of PDMS caused it to migrate to the film surface regardless of solvent choice. The surface morphology was found to depend strongly on the solubility parameter of the solvent and exhibited SFM images consistent with parallel cylinder, perforated lamellar, and lamellar surface layers with increasing solvent solubility parameter. This behavior was due to the selective swelling of the individual blocks under slightly selective, good solvent conditions. A custom solvent annealing apparatus provided similar results in which order-order transitions in the thin films were observed with increasing solvent solubility parameter. Additionally improvements in the long-range order were observed after 1 h of solvent annealing. PS-rich PS-block-PDMS copolymer thin films also displayed PDMS

  13. Block copolymer adsorbed layers on solids

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Gowd, Bhoje; Endoh, Maya; Koga, Tadanori

    Block copolymer thin films offer a simple and effective route to fabricate highly ordered periodic microdomain structures. The fundamental, yet unsolved question is whether these highly oriented microdomain structures persist even near an impenetrable solid wall. We here report the adsorbed structures of polystyrene-block-poly (4-vinylpyridine) (PS-block-P4VP, Mw = 41,000, PS (weight fraction =0.81) formed on planar silicon substrates. Perpendicularly aligned cylindrical microdomains were created by solvent vapor annealing (Gowd et al., Soft Matter, 2014, 10, 7753), and the adsorbed layer was derived by solvent leaching with chloroform, a good solvent for the polymers and thereafter characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle x-ray scattering, and x-ray reflectivity. The results showed that both PS and P4VP chains lie flat on the substrate, forming a microphase-separated structure (MSS) without long-range order. Moreover, a spin-coated PS-block-P4VP thin film annealed under vacuum at 190 °C showed similar MSS on the substrate, indicating the generality of the interfacial polymer structure. Details will be discussed in the presentation. NSF Grant No. CMMI-1332499.

  14. Block Copolymer Membranes for Biofuel Purification

    NASA Astrophysics Data System (ADS)

    Evren Ozcam, Ali; Balsara, Nitash

    2012-02-01

    Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

  15. Block copolymer structures in nano-pores

    NASA Astrophysics Data System (ADS)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei

    2010-03-01

    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  16. Phase Behavior of Symmetric Sulfonated Block Copolymers

    SciTech Connect

    Park, Moon Jeong; Balsara, Nitash P.

    2008-08-21

    Phase behavior of poly(styrenesulfonate-methylbutylene) (PSS-PMB) block copolymers was studied by varying molecular weight, sulfonation level, and temperature. Molecular weights of the copolymers range from 2.9 to 117 kg/mol. Ordered lamellar, gyroid, hexagonally perforated lamellae, and hexagonally packed cylinder phases were observed in spite of the fact that the copolymers are nearly symmetric with PSS volume fractions between 0.45 and 0.50. The wide variety of morphologies seen in our copolymers is inconsistent with current theories on block copolymer phase behavior such as self-consistent field theory. Low molecular weight PSS-PMB copolymers (<6.2 kg/mol) show order-order and order-disorder phase transitions as a function of temperature. In contrast, the phase behavior of high molecular weight PSS-PMB copolymers (>7.7 kg/mol) is independent of temperature. Due to the large value of Flory-Huggins interaction parameter, x, between the sulfonated and non-sulfonated blocks, PSS-PMB copolymers with PSS and PMB molecular weights of 1.8 and 1.4 kg/mol, respectively, show the presence of an ordered gyroid phase with a 2.5 nm diameter PSS network. A variety of methods are used to estimate x between PSS and PMB chains as a function of sulfonation level. Some aspects of the observed phase behavior of PSS-PMB copolymers can be rationalized using x.

  17. Thermal annealing as an easy tool for the controlled arrangement of gold nanoparticles in block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Ledo-Suárez, Ana; Hoppe, Cristina Elena; Lazzari, Massimo; Lopez Quintela, M. Arturo; Zucchi, Ileana Alicia

    2013-06-01

    Thermal annealing was used for the bottom-up fabrication of morphologically controlled gold-block-copolymer (Au-BC) nanocomposites. Three different blends formed by polystyrene (PS) homopolymer and PS-coated gold nanoparticles (PSSH@Au) were used as modifiers of asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA): PS26/PS26SH@Au, PS75/PS75SH@Au and PS167/PS167SH@Au (where the subscripts refer to the number of styrene monomeric units). The results indicated that all three blends used as modifiers (PSn/PSnSH@Au) were successfully located in the PS phase during thermally induced BC self-assembly for a composition range from 5 to 43 wt% without macro-phase separation. The PSnSH@Au moiety experienced molecular desorption, nanocrystal core coalescence and partial molecular re-encapsulation processes during thermal annealing, leading to sphere-like gold NPs with a larger average size (without exceeding an interdomain distance). Ligand chain length regulated the degree of coalescence and re-encapsulation, defining ultimate core size. Furthermore, proper combination of chain length and composition enabled tuning of NP partitioning and arrangement on different length scales through thermally activated cooperative assembly processes. These results have not only significant impact for establishing thermal processing as a useful tool for the precise control of NP size and distribution, but also much broader implications for many nanoparticle-based technologies.

  18. Effect of chain topology of block copolymer on micellization: ring vs linear block copolymer

    NASA Astrophysics Data System (ADS)

    Kim, Kwang Hee; Huh, June; Jo, Won Ho

    2003-03-01

    The aggregation of amphiphilic block copolymers in solution to form micelles has attracted great interest in recent years because of its importance in industrial applications. Many studies on these systems have mainly focused on a di- or triblock copolymer and much less attention was given to other architectures such as ring block copolymer. Recent experimental work has extended those works to include ring block copolymer, made by end-linking the triblock copolymer. Although the micellization of the ring block copolymer seemed to be favored over that of the linear triblock copolymer, two block copolymers showed similar values of cmc in experiments. In the present work, micellization of ring block copolymer (ring-B9A8) was simulated by Brownian dyanmics and micellar behavior is compared with triblock copolymer (A4B9A4) to investigate more systematically the effect of molecular architecture. Critical micelle concentration (cmc), average aggregation number and micellar distribution are compared with corresponding quantities measured for linear triblock copolymers having the same chain length and composition. Simulation results show that the cmc of ring-B9A8 is smaller than that of A4B9A4. The difference is explained by simple mean-field type theory.

  19. Electrostatic control of block copolymer morphology

    NASA Astrophysics Data System (ADS)

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de La Cruz, Monica

    2014-07-01

    Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

  20. Block copolymers for enhanced oil recovery

    SciTech Connect

    Wu, M.M.; Ball, L.E.

    1987-05-19

    A water soluble block copolymer is described comprising two or more water soluble polymer blocks, wherein the water soluble polymer blocks comprise polymerized monomers. The monomers are selected from the group consisting of acrylamide, methacrylamide, vinyl methyl ether, acrylic and methacrylic acid and their water soluble salts and N-substituted acrylamides.

  1. Arbitrary lattice symmetries via block copolymer nanomeshes

    PubMed Central

    Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

    2015-01-01

    Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566

  2. Rapid self-assembly of block copolymers to photonic crystals

    DOEpatents

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  3. Field-Based Simulations of Confined Block Copolymers

    NASA Astrophysics Data System (ADS)

    Fredrickson, Glenn

    2009-03-01

    This presentation will discuss field-theoretic simulation methods that can be used to analyze the self-assembly behavior of thin block copolymer films, including films that are laterally confined on a flat substrate and curved films on a spherical manifold. Our studies of lateral confinement have revealed strategies for epitaxially templating microdomain patterns with long-range in-plane order and minimal defects (``graphoepitaxy"), and methods for diversifying the set of stable 2D lattice structures. On the sphere, we have found defective ground state block copolymer morphologies that are analogous to spherical crystalline packings in other contexts, e.g. the Thompson problem and viruses. The methods and findings have applications in block copolymer lithography and in dispersion technology of polymer-stabilized nanoparticles and colloids.

  4. Block copolymer libraries: modular versatility of the macromolecular Lego system.

    PubMed

    Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

    2004-12-21

    The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships. PMID:15599456

  5. Mixing thermodynamics of block-random copolymers

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan Scott

    Random copolymerization of A and B monomers represents a versatile method to tune interaction strengths between polymers, as ArB random copolymers will exhibit a smaller effective Flory interaction parameter chi; (or interaction energy density X) upon mixing with A or B homopolymers than upon mixing A and B homopolymers with each other, and the ArB composition can be tuned continuously. Thus, the incorporation of a random copolymer block into the classical block copolymer architecture to yield "block-random" copolymers introduces an additional tuning mechanism for the control of structure-property relationships, as the interblock interactions and physical properties can be tuned continuously through the random block's composition. However, typical living or controlled polymerizations produce compositional gradients along the "random" block, which can in turn influence the phase behavior. This dissertation demonstrates a method by which narrow-distribution copolymers of styrene and isoprene of any desired composition, with no measurable down-chain gradient, are synthesized. This synthetic method is then utilized to incorporate random copolymers of styrene and isoprene as blocks into block-random copolymers in order to examine the resulting interblock mixing thermodynamics. A series of well-defined near-symmetric block and block-random copolymers (S-I, Bd-S, I-SrI, S-SrI and Bd-S rI diblocks, where S is polystyrene, I is polyisoprene and Bd is polybutadiene), with varying molecular weight and random-block composition are synthesized and the mixing thermodynamics---via comparison of their interaction energy densities, X---of their hydrogenated derivatives is examined through measurement of the order-disorder transition (ODT) temperature. Hydrogenated derivatives of I-SrI and S-SrI block-random copolymers, both wherein the styrene aromaticity is retained and derivatives wherein the styrene units are saturated to vinylcyclohexane (VCH), are found to hew closely to the

  6. Substrate tolerant direct block copolymer nanolithography.

    PubMed

    Li, Tao; Wang, Zhongli; Schulte, Lars; Ndoni, Sokol

    2016-01-01

    Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly simplifies the main stream BC lithography process, showing a broad substrate tolerance and allowing for efficient pattern transfer over wafer scale. PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are directly applied on substrates including polymers, silicon and graphene. A single oxygen plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning. PMID:26606904

  7. Finding Optimal Templates for the Directed Self-Assembly of Thin Film Block Copolymers with Inverse Self-Consistent Field Theory Simulations

    NASA Astrophysics Data System (ADS)

    Hannon, Adam; Ding, Yi; Bai, Wubin; Ross, Caroline; Alexander-Katz, Alfredo

    2014-03-01

    Achieving sub-10 nm patterns with non-periodic features is a key goal in the development of next generation integrated circuits devices. One route to create such features at this length scale is the directed self-assembly of thin film block copolymers (BCPs). Inverse design methods are becoming a key part in developing templates needed for given target patterns where the required template is both non-intuitive and requires optimization. Here we use a self-consistent field theory based inverse design algorithm to find template solutions for target structures. Recent studies have revealed a wide parameter space with multiple solutions for given target structures. Using fidelity and topology functions, we characterize how well different template solutions yield given target structures and refine these solutions beyond simply being free energy minimum solutions. Experiments using polystyrene- b-polydimethylsiloxane BCPs templated by hydrogen silsesquioxane posts are used for verifying and refining the simulation results. Results show that key factors influencing the fidelity and topology of the samples include the effective volume fraction of the solvent annealed system, size of the posts, and areal post density. Optimization of these parameters achieves refined template solutions with better reproducibility and lower defectivity both computationally and experimentally.

  8. Thermodynamic Interactions in Organometallic Block Copolymers

    SciTech Connect

    Pople, John A

    2002-08-06

    The thermodynamic interactions in anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) copolymers were examined using birefringence, small angle X-ray and neutron scattering (SAXS and SANS). We show that birefringence detection of the order-disorder transition is possible in colored samples provided the wavelength of the incident beam is in the tail of the absorption spectrum. The location of the order-disorder transition was confirmed by SAXS. The temperature-dependence of the Flory-Huggins parameter, {chi}, of SF copolymers, determined by SAXS, is similar in magnitude to that between polystyrene and polyisoprene chains. We find that {chi} is independent of block copolymer composition (within experimental error). We also demonstrate that the neutron scattering length densities of styrene and ferrocenyldimethylsilane moieties are identical due to a surprising cancellation of factors related to density and atomic composition.

  9. Beyond Orientation: The Impact of Electric Fields on Block Copolymers

    SciTech Connect

    Liedel, Clemens; Boker, A.; Pester, Christian; Ruppel, Markus A; Urban, Volker S

    2012-01-01

    Since the first report on electric field-induced alignment of block copolymers (BCPs) in 1991, electric fields have been shown not only to direct the orientation of BCP nanostructures in bulk, solution, and thin films, but also to reversibly induce order-order transitions, affect the order-disorder transition temperature, and control morphologies' dimensions with nanometer precision. Theoretical and experimental results of the past years in this very interesting field of research are summarized and future perspectives are outlined.

  10. Reordering transitions during annealing of block copolymer cylinder phases

    DOE PAGESBeta

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontalmore » state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.« less

  11. Molecular transfer printing using block copolymers.

    PubMed

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul F

    2010-02-23

    Soft lithographic techniques augment or enhance the capabilities of traditional patterning processes and expand the diversity of materials that can be patterned. Realization of robust parallel techniques for creating chemical patterns at the nanoscale has been challenging. Here we present a method for creating and replicating chemical patterns that uses functionalized homopolymer inks that are preferentially segregated into the nanodomains of phase-separated diblock copolymer films. The inks are transferred by reaction to substrates that are brought into contact with block copolymer films, creating chemical patterns on the substrate that mirror the domain structure present at the film surface with high fidelity and resolution. In addition to printing from self-assembled domain structures, we can also direct the assembly of the block copolymer films from which transfer occurs using lithographically defined masters so as to replicate and transfer patterns of inks with controlled and well-defined geometries. The transferred patterns may be at higher resolution than the lithographically defined master, and the process can be repeated to create multiple copies of identical replicas. Transfer of one ink from one block of the copolymer is also possible, and filling the interspatial regions of the pattern with a second ink provides a pathway toward creating patterns with diverse chemical functionalities. PMID:20041629

  12. Influence of substrate interaction and confinement on electric-field-induced transition in symmetric block-copolymer thin films.

    PubMed

    Mukherjee, Arnab; Mukherjee, Rajdip; Ankit, Kumar; Bhattacharya, Avisor; Nestler, Britta

    2016-03-01

    In the present work, we study morphologies arising due to competing substrate interaction, electric field, and confinement effects on a symmetric diblock copolymer. We employ a coarse-grained nonlocal Cahn-Hilliard phenomenological model taking into account the appropriate contributions of substrate interaction and electrostatic field. The proposed model couples the Ohta-Kawasaki functional with Maxwell equation of electrostatics, thus alleviating the need for any approximate solution used in previous studies. We calculate the phase diagram in electric-field-substrate strength space for different film thicknesses. In addition to identifying the presence of parallel, perpendicular, and mixed lamellae phases similar to analytical calculations, we also find a region in the phase diagram where hybrid morphologies (combination of two phases) coexist. These hybrid morphologies arise either solely due to substrate affinity and confinement or are induced due to the applied electric field. The dependence of the critical fields for transition between the various phases on substrate strength, film thickness, and dielectric contrast is discussed. Some preliminary 3D results are also presented to corroborate the presence of hybrid morphologies. PMID:27078402

  13. Influence of substrate interaction and confinement on electric-field-induced transition in symmetric block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Mukherjee, Arnab; Mukherjee, Rajdip; Ankit, Kumar; Bhattacharya, Avisor; Nestler, Britta

    2016-03-01

    In the present work, we study morphologies arising due to competing substrate interaction, electric field, and confinement effects on a symmetric diblock copolymer. We employ a coarse-grained nonlocal Cahn-Hilliard phenomenological model taking into account the appropriate contributions of substrate interaction and electrostatic field. The proposed model couples the Ohta-Kawasaki functional with Maxwell equation of electrostatics, thus alleviating the need for any approximate solution used in previous studies. We calculate the phase diagram in electric-field-substrate strength space for different film thicknesses. In addition to identifying the presence of parallel, perpendicular, and mixed lamellae phases similar to analytical calculations, we also find a region in the phase diagram where hybrid morphologies (combination of two phases) coexist. These hybrid morphologies arise either solely due to substrate affinity and confinement or are induced due to the applied electric field. The dependence of the critical fields for transition between the various phases on substrate strength, film thickness, and dielectric contrast is discussed. Some preliminary 3D results are also presented to corroborate the presence of hybrid morphologies.

  14. Regulating block copolymer phases via selective homopolymers.

    PubMed

    Yang, Shuang; Lei, Zhen; Hu, Nan; Chen, Er-Qiang; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer. PMID:25833605

  15. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  16. Regulating block copolymer phases via selective homopolymers

    SciTech Connect

    Yang, Shuang E-mail: eqchen@pku.edu.cn; Lei, Zhen; Hu, Nan; Chen, Er-Qiang E-mail: eqchen@pku.edu.cn; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer.

  17. Diamond-Forming Block Copolymers and Diamond-like Morphologies: a New Route towards efficient Block Copolymer Membranes?

    NASA Astrophysics Data System (ADS)

    Erukhimovich, Igor; Kriksin, Yury

    2014-03-01

    Formation of ordered (microphase separated) block copolymer nanostructures is a promising route towards creating isoporous membranes suitable for technological applications. We propose a new route to achieve this target: to choose such block copolymer architectures, which would provide a practically isotropic permeability both in the bulk and in thin films. Basing both on the weak segregation theory extension into the thin films and the self-consistent field theory numerical procedure we present the results concerning the effects of the wall confinement both with neutral, selective and patterned walls on the structure and stability of the block copolymer ordered films. The diamond-like morphology is found to be the most promising one as to optimizing the permeability of thin films. A new effect of the diamond morphology stability enhancement in the presence of a properly designed lamellar-like wall pattern is discovered and the corresponding phase diagram demonstrating the effect of the pattern scale and film width on the diamond morphology stability is presented. The financial support was provided by Ministry of Science and Education of Russian Federation (State Contract No. 02.740.11.0858) and European Commission (FP7 project NMP3-SL-2009- 228652 (SELFMEM)).

  18. Block copolymer blend phase behavior: Binary diblock blends and amphiphilic block copolymer/epoxy mixtures

    NASA Astrophysics Data System (ADS)

    Lipic, Paul Martin

    The phase behavior of block copolymers and block copolymer blends has provided an extensive amount of exciting research and industrial applications for over thirty years. However, the unique nanoscale morphologies of microphase separated block copolymer systems is still not completely understood. This thesis examines the phase behavior of diblock copolymers and binary diblock copolymer blends in the strong segregation limit (SSL), and blends of an amphiphilic diblock copolymer with an epoxy resin. Studies of high molecular weight (˜84,000 g/mole) poly(ethylene)-poly(ethyl ethylene) (PE-PEE) diblock copolymers probed the ability of block copolymers to reach equilibrium in the SSL. Samples of pure diblocks or binary diblock blends prepared using different preparation techniques (solvent casting or precipitation) had different phase behaviors, as identified with transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS), confirming non-equilibrium phase behavior. This non-equilibrium behavior was metastable, and these results identify the caution that should be used when claiming equilibrium phase behavior in the SSL. Blends of an amphiphilic diblock copolymer, poly(ethylene oxide)-poly(ethylene-alt-propylene) (PEO-PEP) with a polymerizable epoxy resin selectively miscible with PEO, poly(Bisphenol-A-co-epichlorohydrin), supported theoretical calculations and increased the understanding of block copolymer/homopolymer blends. These blends formed different ordered structures (lamellae, bicontinuous cubic gyroid, hexagonally packed cylinders, cubic and hexagonally packed spheres) as well as a disordered spherical micellar structure, identified with SAXS and rheological measurements. Addition of hardener, methylene dianiline, to the system resulted in cross-linking of the epoxy resin and formation of a thermoset material. Macrophase separation between the epoxy and block copolymer did not occur, but local expulsion of the PEO from the epoxy was

  19. Rod-Coil Block Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

    2005-01-01

    This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

  20. Dynamics of Block Copolymer Nanocomposites

    SciTech Connect

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  1. Hierarchical porous polymer scaffolds from block copolymers.

    PubMed

    Sai, Hiroaki; Tan, Kwan Wee; Hur, Kahyun; Asenath-Smith, Emily; Hovden, Robert; Jiang, Yi; Riccio, Mark; Muller, David A; Elser, Veit; Estroff, Lara A; Gruner, Sol M; Wiesner, Ulrich

    2013-08-01

    Hierarchical porous polymer materials are of increasing importance because of their potential application in catalysis, separation technology, or bioengineering. Examples for their synthesis exist, but there is a need for a facile yet versatile conceptual approach to such hierarchical scaffolds and quantitative characterization of their nonperiodic pore systems. Here, we introduce a synthesis method combining well-established concepts of macroscale spinodal decomposition and nanoscale block copolymer self-assembly with porosity formation on both length scales via rinsing with protic solvents. We used scanning electron microscopy, small-angle x-ray scattering, transmission electron tomography, and nanoscale x-ray computed tomography for quantitative pore-structure characterization. The method was demonstrated for AB- and ABC-type block copolymers, and resulting materials were used as scaffolds for calcite crystal growth. PMID:23908232

  2. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film.

    PubMed

    Wang, Zhexiao; Shao, Jing; Pan, Heng; Feng, Xiaoshuang; Chen, Peng; Xia, Ru; Wu, Xiangsong; Qian, Jiasheng

    2015-02-23

    Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures. PMID:25504337

  3. Synthesis and Application of Conducting Block Copolymers in Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Boudouris, Bryan W.; Hillmyer, Marc A.; Frisbie, C. Daniel

    2007-03-01

    Recent advances in the fabrication and post-processing of polymer -- fullerene bulk heterojunction solar cells have allowed for devices with power conversion efficiencies up to 5% to be generated. An understanding of how the internal morphology of the active layer affects device performance would facilitate optimization and ultimately lead to higher efficiencies. Block copolymers have been shown to self-assemble into well-structured, microphase-separated domains on the order of the diffusion length (˜ 10 nm) of an exciton (bound electron-hole pair) in thin films. In an effort to make a nanostructured active layer morphology we have synthesized block copolymers where the conducting moiety is either poly(3-hexylthiophene) or poly(3-dodeclythiophene) and the second, etchable block is polylactide. Hydroxyl-terminated polythiophene molecules were synthesized via the McCullough method and used as macroinitiators for the ring-opening polymerization of D,L-lactide. AFM images of spin-coated block copolymer films show separation between the polythiophene and polylactide segments. After subjecting the samples to a dilute aqueous base for short periods of time, we have selectively etched the polylactide segments to create pits in the semicrystalline polythiophene matrices. In addition to these findings, preliminary device results will also be discussed.

  4. Combinatorial Block Copolymer Ordering on Tunable Rough

    SciTech Connect

    Kulkarni M. M.; Yager K.; Sharma, A.; Karim, A.

    2012-05-01

    Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period of

  5. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

    PubMed

    Fan, Yin; Tang, Shengchang; Thomas, Edwin L; Olsen, Bradley D

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins. PMID:25393374

  6. Perspective: Evolutionary design of granular media and block copolymer patterns

    NASA Astrophysics Data System (ADS)

    Jaeger, Heinrich M.; de Pablo, Juan J.

    2016-05-01

    The creation of new materials "by design" is a process that starts from desired materials properties and proceeds to identify requirements for the constituent components. Such process is challenging because it inverts the typical modeling approach, which starts from given micro-level components to predict macro-level properties. We describe how to tackle this inverse problem using concepts from evolutionary computation. These concepts have widespread applicability and open up new opportunities for design as well as discovery. Here we apply them to design tasks involving two very different classes of soft materials, shape-optimized granular media and nanopatterned block copolymer thin films.

  7. Are block copolymer worms more effective Pickering emulsifiers than block copolymer spheres?

    PubMed

    Thompson, K L; Mable, C J; Cockram, A; Warren, N J; Cunningham, V J; Jones, E R; Verber, R; Armes, S P

    2014-11-21

    RAFT-mediated polymerisation-induced self-assembly (PISA) is used to prepare six types of amphiphilic block copolymer nanoparticles which were subsequently evaluated as putative Pickering emulsifiers for the stabilisation of n-dodecane-in-water emulsions. It was found that linear poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymer spheres and worms do not survive the high shear homogenisation conditions used for emulsification. Stable emulsions are obtained, but the copolymer acts as a polymeric surfactant; individual chains rather than particles are adsorbed at the oil-water interface. Particle dissociation during emulsification is attributed to the weakly hydrophobic character of the PHPMA block. Covalent stabilisation of these copolymer spheres or worms can be readily achieved by addition of ethylene glycol dimethacrylate (EGDMA) during the PISA synthesis. TEM studies confirm that the resulting cross-linked spherical or worm-like nanoparticles survive emulsification and produce genuine Pickering emulsions. Alternatively, stabilisation can be achieved by either replacing or supplementing the PHPMA block with the more hydrophobic poly(benzyl methacrylate) (PBzMA). The resulting linear spheres or worms also survive emulsification and produce stable n-dodecane-in-water Pickering emulsions. The intrinsic advantages of anisotropic worms over isotropic spheres for the preparation of Pickering emulsions are highlighted. The former particles are more strongly adsorbed at similar efficiencies compared to spheres and also enable smaller oil droplets to be produced for a given copolymer concentration. The scalable nature of PISA formulations augurs well for potential applications of anisotropic block copolymer nanoparticles as Pickering emulsifiers. PMID:25254485

  8. Oriented Protein Nanoarrays on Block Copolymer Template.

    PubMed

    Shen, Lei; Zhu, Jintao

    2016-03-01

    Here, a simple yet robust method is developed to fabricate oriented protein nanoarrays by employing a block copolymer (BCP) template, which presents nano-scaled spot areas at high-density arrays. Unlike the conventional BCP nanolithography, the BCP platform described here resists nonspecific protein adsorption and prevents the denaturation of immobilized proteins in aqueous solution. The orderly arranged array areas are functionalized by linking chemistry which allows for the precise control of protein orientation. This approach allows us to generate potentially oriented protein nanoarrays at high-density array spots, which is useful for miniaturized nanoarrays within high-throughput proteomic applications. PMID:26785818

  9. Tunable Morphologies from Charged Block Copolymers

    SciTech Connect

    Goswami, Monojoy; Sumpter, Bobby G; Mays, Jimmy; Messman, Jamie M

    2010-01-01

    The bulk morphologies formed by a new class of charged block copolymers, 75 vol % fluorinated polyisoprene (FPI) 25 vol% sulfonated polystyrene (PSS) with 50% sulfonation, are characterized, and the fundamental underlying forces that promote the self-assembly processes are elucidated. The results show how the bulk morphologies are substantially different from their uncharged diblock counterparts (PS-PI) and also how morphology can be tuned with volume fraction of the charged block and the casting solvent. A physical understanding based on the underlying strong electrostatic interactions between the charged block and counterions is obtained using Monte Carlo (MC) and Molecular Dynamics (MD) simulations. The 75/25 FPI-PSS shows hexagonal morphologies with the minority blocks (PSS) forming the continuous phase due to charge percolation and the FPI blocks arranged in hexagonal cylinders. Some long-range order can be sustained even if lipophobicity is increased (addition of water), albeit with lower dimensional structures. However, thermal annealing provides sufficient energy to disrupt the percolated charges and promotes aggregation of ionic sites which leads to a disordered system. Diverse and atypical morphologies are readily accessible by simply changing the number distribution of the charges on PSS block.

  10. Fabrication of Complex Three-Dimensional Nanostructures from Self-Assembling Block Copolymer Materials on Patterned Surfaces: A computational Study

    NASA Astrophysics Data System (ADS)

    Ye, Xianggui; Edwards, Brian J.; Khomami, Bamin

    2010-03-01

    Chemically patterned substrates can direct the assembly of adsorbed layers or thin films of block copolymers. Here, we consider the self-assembly of a lamella-forming diblock copolymer on periodically stripe-patterned substrates. The morphology of the block copolymer follows the pattern at the substrate; however, with an increasing degree of mismatch between the width of the stripe-pattern and the periodic spacing of bulk block copolymer, novel morphologies have been found. Therefore, it is possible to adjust the morphologies in thin bock copolymer films by adjusting the mismatch between the width of the stripe-pattern and the periodic spacing of the bulk block copolymer. These results demonstrate a promising strategy for fabrication of complex interfacial nanostructures from chemically patterned templates.

  11. Interface-enforced complexation between copolymer blocks.

    PubMed

    Steinschulte, Alexander A; Xu, Weinan; Draber, Fabian; Hebbeker, Pascal; Jung, Andre; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V; Plamper, Felix A

    2015-05-14

    Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering. PMID:25807174

  12. Controlling Structure in Sulfonated Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Truong, Phuc; Stein, Gila; Strzalka, Joe

    2015-03-01

    In many ionic block copolymer systems, the strong incompatibility between ionic and non-ionic segments will trap non-equilibrium structures in the film, making it difficult to engineer the optimal domain sizes and transport pathways. The goal of this work is to establish a framework for controlling the solid-state structure of sulfonated pentablock copolymer membranes. They have ABCBA block sequence, where A is poly(t-butyl styrene), B is poly(hydrogenated isoprene), and C is poly(styrene sulfonate). To process into films, the polymer is dissolved in toluene/n-propanol solvent mixtures, where the solvent proportions and the polymer loading were both varied. Solution-state structure was measured with small angle X-ray scattering (SAXS). We detected micelles with radii that depend on the solvent composition and polymer loading. Film structure was measured with grazing-incidence SAXS, which shows (i) domain periodicity is constant throughout film thickness; (ii) domain periodicity depends on solvent composition and polymer loading, and approximately matches the micelle radii in solutions. The solid-state packing is consistent with a hard sphere structure factor. Results suggest that solid-state structure can be tuned by manipulating the solution-state self-assembly.

  13. Method of producing nanopatterned articles using surface-reconstructed block copolymer films

    SciTech Connect

    Russell, Thomas P; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2013-08-27

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  14. Theory of Chirality Transfer in Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Prasad, Ishan; Grason, Gregory

    Block copolymers assemble into a rich spectrum of ordered phases, with complexity driven by asymmetry in copolymer architecture. Despite decades of study, influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has been largely instrumental in prediction of physical properties of polymeric systems. Recently, a polar orientational self-consistent field (oSCF) theory was adopted to model chiral block copolymers having a thermodynamic preference for cholesteric ordering in chiral segments, and which confirmed the equilibrium stability of a helical cylinder morphology observed for chiral diblocks. Here, I describe a newly developed oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar interactions, and focus our study on intra-domain nematic ordering in flexible block copolymer assemblies, and in particular, mechanisms of transfer of segment chirality to mesochiral symmetries of self-assembled bicontinuous network morphologies.

  15. Piezoelectric Properties of Non-Polar Block Copolymers

    SciTech Connect

    Pester, Christian; Ruppel, Markus A; Schoberth, Heiko; Schmidt, K.; Liedel, Clemens; Van Rijn, Patrick; Littrell, Ken; Schindler, Kerstin; Hiltl, Stephanie; Czubak, Thomas; Mays, Jimmy; Urban, Volker S; Boker, Alexander

    2011-01-01

    Piezoelectric properties in non-polar block copolymers are a novelty in the field of electroactive polymers. The piezoelectric susceptibility of poly(styrene-b-isoprene) block copolymer lamellae is found to be up to an order of magnitude higher when compared to classic piezoelectric materials. The electroactive response increases with temperature and is found to be strongest in the disordered phase.

  16. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    PubMed

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation. PMID:25811763

  17. Light-emitting block copolymers composition, process and use

    DOEpatents

    Ferraris, John P.; Gutierrez, Jose J.

    2006-11-14

    Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

  18. Block Copolymer Templates for Optical Materials and Devices

    NASA Astrophysics Data System (ADS)

    Urbas, Augustine; Martin, Maldovan; Carter, W. C.; Thomas, E. L.; Fasolka, Michael; Fraser, Cassandra

    2002-03-01

    Block copolymers can act as super-lattices for creating novel optical structures. We have fabricated block copolymer photonic crystals from one, two and three dimensionally periodic systems and have enhanced their dielectric properties towards creating complete 3D band gaps. By using carefully selected blends of linear and star block copolymers, we are able to create hierarchical blends which exhibit precise molecular positioning of fluorescent molecules. We are exploring these unique patterning capabilities of block copolymer systems for the formation of ordered arrays of optically active components within a photonic crystal. Precise location of both fluorescent and nonlinear components within block copolymer photonic crystals affords new opportunities for creating low threshold, upconverting and array lasers as well as optical modulators and other photonic devices.

  19. Anomalous Micellization of Pluronic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  20. Block copolymer ion gels for gas separation

    NASA Astrophysics Data System (ADS)

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

    Carbon dioxide removal from light gases (eg. N2, CH4, and H2) is a very important technology for industrial applications such as natural gas sweetening, CO2 capture from coal-fire power plant exhausts and hydrogen production. Current CO2 separation method uses amine-absorption, which is energy-intensive and requires frequent maintenance. Membrane separation is a cost-effective solution to this problem, especially in small-scale applications. Ionic liquids have recently received increasing interest in this area because of their selective solubility for CO2 and non-volatility. However, ionic liquid itself lacks the persistent structure and mechanical integrity to withstand the high pressure for gas separation. Here, we report the development and gas separation performances of physically crosslinked ion gels based on self-assembly of ABA-triblock copolymers in ionic liquids. Three different types of polymers was used to achieve gelation in ionic liquids. Specifically, a triblock copolymer ion gel with a polymerized ionic liquid mid-block shows performances higher than the upper bound of well-known ``Robeson Plot'' for CO2/N2.

  1. Reflectivity studies on adsorbed block copolymers under shear

    SciTech Connect

    Smith, G.S.; Wages, S.; Baker, S.M.; Toprakcioglu, C.; Hadziioannou, G.

    1994-12-01

    The authors report neutron reflectivity data on (poly)styrene-(poly)ethylene oxide (PS-PEO) diblock copolymers adsorbed onto quartz from the selective solvent cyclohexane (a non-solvent for PEO and a poor solvent for PS). The PEO ``anchor block`` adsorbs strongly to form a thin layer on the quartz substrate, while the deuterated PS chains dangle into the solvent. They find that under static conditions the density profile of the PS block in a poor solvent can be well described by a Schultz function which is indicative of a polymer ``mushroom.`` Furthermore, they have studied the same system under shear at shear rates from 0--400s{sup {minus}1}. They find that there is a dramatic increase in the thickness of the PS layer under shear in cyclohexane and that the relaxation time from the shear-on profile back to the static profile is on the order of several days.

  2. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  3. Structure property relations in glassy-semicrystalline block copolymers

    NASA Astrophysics Data System (ADS)

    Khanna, Vikram

    The ability of block copolymers to segregate into nanoscale morphologies makes them a versatile class of engineering materials. This work investigates the relation between the block copolymer structure and its mechanical properties, film dynamics and diffusion kinetics. The first part investigates the influence of structure on the mechanical properties of poly(cyclohexylethylene)-poly(ethylene) (PCHE-PE) block copolymer films. For lamellar block copolymers the mechanical properties depend significantly on the chain architecture (diblock, triblock and pentablock). Diblock copolymer films show complete failure at small strains and pentablock copolymer films show the toughest, response. Moreover, the orientation of the cylinders in a cylinder forming pentablock copolymer affects the toughness of the block copolymer films. In the second part, the effect of surface energy and chain architecture on the orientation of microdomains in the same block copolymer films is investigated. Cylindrical and lamellar triblock copolymers with a PE midblock orient their microdomains normal to the surface. However, a lamellar diblock copolymer prefers a parallel orientation of the sheets with an E surface. Moreover, a cylindrical triblock copolymer with a reduced surface energy poly(ethylene-butylene) midblock orders with the cylinder domains oriented parallel to the surface. Self-consistent field theory calculations suggest that the entropic cost of forming a wetting layer comprised entirely of looping blocks for the triblock architecture, a constraint absent in diblock copolymers, stabilizes the perpendicular orientation. Thus in triblock copolymers, parallel orientations are only stabilized when the surface energy of the midblock is small enough to compensate for this conformational penalty. Finally, a study of the diffusion kinetics of cylinder forming poly(styrene)-poly(ethylene) triblock (SES) and pentablock (SESES) copolymers suggests that for similar molecular weights SESES

  4. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, Michael S.; Saunders, Randall

    1997-01-01

    Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

  5. Morphological studies on block copolymer modified PA 6 blends

    NASA Astrophysics Data System (ADS)

    Poindl, M.; Bonten, C.

    2014-05-01

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  6. Morphological studies on block copolymer modified PA 6 blends

    SciTech Connect

    Poindl, M. E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C. E-mail: christian.bonten@ikt.uni-stuttgart.de

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  7. Molecular Transfer Printing Using Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul

    2009-03-01

    We report a new parallel patterning technique, molecular transfer printing (MTP), for replicating geometrically complex patterns over macroscopic areas with sub-15 nm feature dimensions, and the ability to replicate the same pattern multiple times. In MTP, inks are mixed with block copolymers (BCPs) and deposited as films on a substrate. The inks are compatible with only one block of the BCP, and sequestered into domains of nanometer scale dimensions after microphase separation. A second substrate is then placed in contact with the surface of the film. By designing the inks to react, adsorb, or otherwise interact with the second substrate, inks are transferred to the second substrate in the exact pattern of domains present at the surface of the ``master'' BCP film. Here we demonstrate high degrees of perfection on both line and dot patterns. We also show that 1) the master template can be regenerated, 2) the resultant replica can be used to direct the assembly of BCPs and as a daughter master for MTP, and 3) the master and daughter templates can be reused tens of times.

  8. Nanopatterning of recombinant proteins and viruses using block copolymer templates

    NASA Astrophysics Data System (ADS)

    Cresce, Arthur Von Wald

    The study of interfaces is important in understanding biological interactions, including cellular signaling and virus infection. This thesis is an original effort to examine the interaction between a block copolymer and both a protein and a virus. Block copolymers intrinsically form nanometer-scale structures over large areas without expensive processing, making them ideal for the synthesis of the nanopatterned surfaces used in this study. The geometry of these nanostructures can be easily tuned for different applications by altering the block ratio and composition of the block copolymer. Block copolymers can be used for controlled uptake of metal ions, where one block selectively binds metal ions while the other does not. 5-norbornene-2,3-dicarboxylic acid is synthesized through ring-opening metathesis polymerization. It formed spherical domains with spheres approximately 30 nm in diameter, and these spheres were then subsequently loaded with nickel ion. This norbornene block copolymer was tested for its ability to bind histidine-tagged green fluorescent protein (hisGFP), and it was found that the nickel-loaded copolymer was able to retain hisGFP through chelation between the histidine tag and the metal-containing portions of the copolymer surface. Poly(styrene-b-4-vinylpyridine) (PS/P4VP) was also loaded with nickel, forming a cylindrical microstructure. The binding of Tobacco mosaic virus and Tobacco necrosis virus was tested through Tween 20 detergent washes. Electron microscopy allowed for observation of both block copolymer nanostructures and virus particles. Results showed that Tween washes could not remove bound Tobacco mosaic virus from the surface of PS/P4VP. It was also seen that the size and tunability of block copolymers and the lack of processing needed to attain different structures makes them attractive for many applications, including microfluidic devices, surfaces to influence cellular signaling and growth, and as a nanopatterning surface for

  9. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    NASA Astrophysics Data System (ADS)

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-10-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

  10. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    PubMed Central

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-01-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected. PMID:26471862

  11. Obtaining Perpendicular Block Copolymer Morphologies with Solvent Annealing

    NASA Astrophysics Data System (ADS)

    Gotrik, Kevin; Son, Jeong Gon; Hannon, Adam; Ross, Caroline

    2012-02-01

    Being able to control block copolymer (BCP) thin film morphology and orientation is of interest for lithographic applications where creation of feature sizes ranging from 10-100nm is desirable. Perpendicular oriented cylinders and lamellae are especially valuable due to their high aspect ratios but are difficult to achieve in BCP systems with a large Flory-Huggins interaction parameter (χ). We explore the morphological phase behavior that films (30-200nm) of poly(styrene-b-dimethylsiloxane) (PS-PDMS, 45kg/mol, χ=0.26) exhibit under different solvent conditions with focus on conditions that produce perpendicular microdomains. The microdomains are revealed by selectively etching the PS with an oxygen plasma (50W CF4). Variation in the solvent vapor conditions results in selective swelling of the different blocks of the copolymer depending on the relative Hildebrand solubility parameters (e.g. PS- 18.5, toluene-18.3 MPâ(1/2)), affecting the microdomain morphologies, and the solvent evaporation and deswelling process influences the orientation of the microdomains. Two different strategies are presented involving solvent vapor annealing that result in perpendicular morphologies in films of PS-PDMS and the results are compared with self-consistent field theory modeling of solvent-polymer systems.

  12. Tunable Cosolvent Annealing Affects on Block Copolymer Morphology

    NASA Astrophysics Data System (ADS)

    Gotrik, Kevin; Son, Jeong Gon; Hannon, Adam; Alexander-Katz, Alfredo; Ross, Caroline

    2011-03-01

    Being able to precisely and reproducibly control block copolymer (BCP) morphology is of interest for lithographic applications due to the techniques ability to result in feature sizes ranging from 10-100nm. We explore the morphological phase behavior that thin films (30-40nm) of poly(styrene-b-dimethylsiloxane) (PS-PDMS, 45kg/mol, ~ 0.26 segmental Flory-Huggins interaction parameter) exhibit under different cosolvent vapors of toluene and heptane. Variation in the solvent conditions results in selective swelling of the different blocks of the copolymer depending on relative Hildebrand solubility parameters (e.g. PS- 18.5, toluene-18.3 (MPa)1/2) resulting in cylinders, spheres, lamella, and perforatted lamella self-assembled features which can be revealed by selectively etching the PS with an oxygen plasma (50W CF4). Here we describe precision solvent vapor control while doing in situ spectral reflectometry (230-1500nm) to track swelling of the BCP films as a function of time to gain insight into this BCP system.

  13. Surface Structure of Thin Films of Multifunctional Ionizable Copolymers

    NASA Astrophysics Data System (ADS)

    Wickramasinghe, Anuradhi; Perahia, Dvora

    Phase segregation results in a rich variety of structures in co-polymers where interfacial forces often dominate the structure of thin films. Introduction of ionizable segments often drives the formation of compounded structures with multiple blocks residing at the interfaces. Here we probe thin films, 40-50nm, of an A-B-C-B-A co-polymer where C is a randomly sulfonated polystyrene with sulfonation fractions of 0, 26 and 52 mole %, B is poly (ethylene-r-propylene), and A is poly (t-butyl styrene) as the sulfonation level and temperature are varied using Neutron Reflectivity AFM, and surface tension measurements. As cast films form layers with both hydrophobic blocks dominating the solid and air interfaces and the ionizable block segregating to the center. Following annealing at 1700C, above Tg of styrene sulfonate, the films coarsen, with surface aggregation dominating the structure, though interfacial regions remain dominated by the hydrophobic segments. We show that in contrast to non-ionic co-polymers, formation of micelles dominated the structure of these ionic structured films. Supported in part by DOE Grant No. DE-SC007908.

  14. High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

    NASA Astrophysics Data System (ADS)

    Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

    Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

  15. Macroscopic phase decomposition in block copolymers driven by thermooxidative reactions

    NASA Astrophysics Data System (ADS)

    Fan, Shaobin

    Macroscopic phase separations have been observed in a commercial styrene- block-butadiene-block-styrene (SBS) triblock copolymer (Kraton 1102), an as-synthesized SBS triblock copolymer, an as-synthesized styrene-block-butadiene (SB) diblock copolymer and a commercial styrene-block-isoprene-block-styrene (SIS) triblock copolymer (Kraton 1107) at elevated temperatures. To the best of our knowledge, this is the first report on macroscopic phase separations in neat copolymers, including block copolymers. The temporal evolution of the structure, growth dynamics, origin and mechanism of the macroscopic phase separations have been investigated. A theoretical model has been established to describe such phase separation in SB diblock copolymer and numerical simulations have been undertaken to predict the structure evolution and growth dynamics. For styrene-butadiene block copolymers, the phase transition process consists of the first and second phase separations. The origin of such phase separations is attributed to chain scission and crosslinking reactions due to thermooxidative degradation. The formation of phase separated domains is the result of separation of polystyrene-rich domains from polybutadiene-rich domains. A mechanism, termed secondary spinodal decomposition, has been proposed to explain second phase separation. It has also demonstrated that the theoretical model and numerical simulations capture the essential features of the experimental observations. Growth rate was seen to depend on phase separation as well as reaction kinetics. The universal scaling laws have been shown to be invalid in macroscopic phase separations of styrene-butadiene block copolymers. The macroscopic phase separation process is more complex in the SIS triblock copolymer. It consists of a first phase separation, phase dissolution and a second phase separation. The origin of such phase decompositions has been shown to be a progressive chain scission reaction during thermal oxidative

  16. Computer simulations of block copolymer tethered nanoparticle self-assembly

    NASA Astrophysics Data System (ADS)

    Chan, Elaine R.; Ho, Lin C.; Glotzer, Sharon C.

    2006-08-01

    We perform molecular simulations to study the self-assembly of block copolymer tethered cubic nanoparticles. Minimal models of the tethered nanoscale building blocks (NBBs) are utilized to explore the structures arising from self-assembly. We demonstrate that attaching a rigid nanocube to a diblock copolymer affects the typical equilibrium morphologies exhibited by the pure copolymer. Lamellar and cylindrical phases are observed in both systems but not at the corresponding relative copolymer tether block fractions. The effect of nanoparticle geometry on phase behavior is investigated by comparing the self-assembled structures formed by the tethered NBBs with those of their linear ABC triblock copolymer counterparts. The tethered nanocubes exhibit the conventional triblock copolymer lamellar and cylindrical phases when the repulsive interactions between different blocks are symmetric. The rigid and bulky nature of the cube induces interfacial curvature in the tethered NBB phases compared to their linear ABC triblock copolymer counterparts. We compare our results with those structures obtained from ABC diblock copolymer tethered nanospheres to further elucidate the role of cubic nanoparticle geometry on self-assembly.

  17. Graphoepitaxy of self-assembled block copolymers on two-dimensional periodic patterned templates.

    PubMed

    Bita, Ion; Yang, Joel K W; Jung, Yeon Sik; Ross, Caroline A; Thomas, Edwin L; Berggren, Karl K

    2008-08-15

    Self-assembling materials are the building blocks of bottom-up nanofabrication processes, but they need to be templated to impose long-range order and eliminate defects. In this work, the self-assembly of a thin film of a spherical-morphology block copolymer is templated using an array of nanoscale topographical elements that act as surrogates for the minority domains of the block copolymer. The orientation and periodicity of the resulting array of spherical microdomains are governed by the commensurability between the block copolymer period and the template period and is accurately described by a free-energy model. This method, which forms high-spatial-frequency arrays using a lower-spatial-frequency template, will be useful in nanolithography applications such as the formation of high-density microelectronic structures. PMID:18703736

  18. Manipulating Ordering Transitions in Interfacially Modified Block Copolymers

    SciTech Connect

    Singh, N.; Tureau, M; Epps, T

    2009-01-01

    We report a synthetic strategy that allows us to manipulate the interfacial region between blocks and control ordering transitions in poly(isoprene-b-styrene) [P(I-S)] block copolymers. This interfacial modification is accomplished by combining a semi-batch feed with anionic polymerization techniques. Using this approach, we are able to control the segmental composition and molecular interactions in our phase-separated block copolymers, independent of molecular weight and block constituents. A library of copolymers is prepared with various interfacial modifications to examine the effect of interfacial composition on copolymer self-assembly. The morphological characteristics of the self-assembled structures are investigated using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). Normal and inverse tapered block copolymers, containing approximately 15-35 vol% tapered material, show a measurable decrease in the order-disorder transition temperature (TODT) relative to the corresponding non-tapered diblock copolymers, with the inverse tapered materials showing the greatest deviation in TODT. Additionally, TODT was inversely related to the volume fraction of the tapered region in both normal and inverse tapered copolymer materials.

  19. Synthesis of Amylose-b-P2 VP Block Copolymers.

    PubMed

    Kumar, Kamlesh; Woortman, Albert J J; Loos, Katja

    2015-12-01

    A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2 VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2 VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2 VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures. PMID:26437256

  20. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains.

    PubMed

    Pollard, Benjamin; Raschke, Markus B

    2016-01-01

    Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force-distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  1. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains

    PubMed Central

    Pollard, Benjamin

    2016-01-01

    Summary Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force–distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  2. Ionic Block Copolymers for Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  3. Orientation of Microdomains of Block Copolymers by Zone casting

    NASA Astrophysics Data System (ADS)

    Tang, Chuanbing; Matyjaszewski, Krzysztof; Kowalewski, Tomasz

    2007-03-01

    As a ``bottom up'' method, the self-assembly of block copolymers plays a vital role in the development of soft lithography for the fabrication of microelectronic devices. A variety of methods have been developed toward better and more precise controlled patterns on solid substrates. This presentation will describe a novel solution casting technique, ``zone casting'', to induce orientation of cylindrical and lamellar microphase-separated domains of various block copolymers.

  4. Self-doped microphase separated block copolymer electrolyte

    DOEpatents

    Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

    2002-01-01

    A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

  5. New adhesive systems based on functionalized block copolymers

    SciTech Connect

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  6. Preparation and Morphology of ABn Mictoarm Block Copolymers

    NASA Astrophysics Data System (ADS)

    Takano, Atsushi; Watanabe, Momoka; Asai, Yusuke; Suzuki, Jiro; Matsushita, Yushu

    A series of ABn mictoarm block copolymers (bottle brush copolymers) consisting of polystyrene (S) as a backbone and polyisoprenes (I) as grafts were precisely synthesized by an anionic polymerization, and their microphase-separated structures were investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering(SAXS). A copolymer with composition of φS =0.57 and number of grafts(n) of 10 shows characteristic cylindrical structure, where microdomains of S reveals hexagonal cross section with non-constant mean curvature interface. While a sample with composition of φS =0.37 and number of grafts(n) of 40 shows spherical structure with rather large S isolated domains and characteristic domain packing manner was found. Furthermore composition dependence of microphase-separated structures for SIn mictoarm block copolymers were investigated and compared to SI diblock copolymer system.

  7. Oligoaniline-containing supramolecular block copolymer nanodielectric materials.

    PubMed

    Hardy, Christopher G; Islam, Md Sayful; Gonzalez-Delozier, Dioni; Ploehn, Harry J; Tang, Chuanbing

    2012-05-14

    We report a new generation of nanodielectric energy storage materials based on supramolecular block copolymers. In our approach, highly polarizable, conducting nanodomains are embedded within an insulating matrix through block copolymer microphase separation. An applied electric field leads to electronic polarization of the conducting domains. The high interfacial area of microphase-separated domains amplifies the polarization, leading to high dielectric permittivity. Specifically, reversible addition fragmentation transfer (RAFT) polymerization was used to prepare block copolymers with poly(methyl acrylate) (PMA) as the insulating segment and a strongly acidic dopant moiety, poly-(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), as the basis for the conducting segment. The PAMPSA block was complexed with an oligoaniline trimer to form a dopant-conjugated moiety complex that is electronically conductive after oxidation. For the undoped neat block copolymers, the increase of the PMA block length leads to a transition in dielectric properties from ionic conductor to dielectric capacitor with polarization resulting from migration of protons within the isolated PAMPSA domains. The oligoaniline-doped copolymers show remarkably different dielectric properties. At frequencies above 200 kHz, they exhibit characteristics of dielectric capacitors with much higher permittivity and lower dielectric loss than the corresponding undoped copolymers. PMID:22331602

  8. Stress induced topographic patterning in thin diblock copolymer films

    NASA Astrophysics Data System (ADS)

    Croll, Andrew; Crosby, Alfred

    2011-03-01

    When a thin rigid polymer film is attached to a soft elastic substrate and placed in a state of compressive stress, the system wrinkles as a critical stress is surpassed. This simple deformation pattern contains information about the mechanical state of both the polymer film and substrate. Although classical mechanics can be used to relate the global deformation of the film/substrate to the local wrinkle geometry as a function of materials properties, relatively little is known about how the thin capping film material accommodates the localized bending (and therefore localized stress). Here we conduct wrinkling experiments using a model diblock copolymer/elastomer composite. Wrinkling a homogeneous, disordered block copolymer film places the film in a well-defined initial stress state. When heated above its glass transition, the wrinkled film flows, microphase separates, and relaxes from the stress imposed by local wrinkle deformations. The periodic stress relaxation leads to the emergence of a new pattern in the microphase separated surface structure, thus providing new insight into how block copolymers react to stress.

  9. Electrically conductive doped block copolymer of polyacetylene and polyisoprene

    DOEpatents

    Aldissi, Mahmoud

    1985-01-01

    An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

  10. Using Tapered Block Copolymers to Create Conducting Nanomaterials

    NASA Astrophysics Data System (ADS)

    Epps, Thomas, III

    2014-03-01

    Soft materials, such as polymers, colloids, surfactants, and liquid crystals, are a technologically important class of matter employed in a variety of applications. One sub-class of soft material, block copolymers, provides the opportunity to design materials with attractive chemical and mechanical properties based on the ability to assemble into periodic structures with nanoscale domain spacings. Several applications for block copolymers currently under investigation in my group include battery and fuel cell membranes, analytical separations membranes, nano-tool templates, precursors to electronic arrays, and drug delivery vehicles. One area of recent progress in the group focuses on the behavior of conventional block copolymer and tapered block copolymer systems for lithium battery membrane applications. We find that we can tune poly(styrene- b-ethylene oxide) diblock copolymer nanostructures by adjusting the lithium counterion and lithium salt concentration, as well as the taper volume fraction and composition. Additionally, we can estimate the effective interaction parameters (χeff) for the salt-doped copolymers to determine the overall influence of tapering on the energetics of copolymer assembly. These tapered materials allow us to design nanostructured membrane systems with increased conductivity and improved mechanical properties in ion transport devices. We gratefully acknowledge AFOSR-PECASE (FA9550-09-1-0706) and NSF-CAREER (DMR-0645586) for financial support.

  11. Morphology and Proton Transport in Porous Block Copolymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    Chen, Chelsea; Kortright, Jeffrey; Wong, David; Balsara, Nitash

    2015-03-01

    Block copolymer electrolyte membranes consisting of a proton-conducting block and an uncharged structural block are attractive due to their potential in clean energy applications. Herein we demonstrate a novel approach of fabricating block copolymer electrolyte membranes, by inducing pores in the proton-conducting phase. We examine morphology of these membranes with contrast-matched resonant soft X-ray scattering (RSoXS) and electron tomography. Proton conductivity as a function of porosity and water activity is also investigated. By tuning the porosity of the membranes, we are able to adjust the water uptake of the membranes for improved proton conductivities, in both humid air and liquid water.

  12. Fracture of Semicrystalline-Glassy Block Copolymers: Chain Architecture Effects

    NASA Astrophysics Data System (ADS)

    Ryu, C. Y.; Fredrickson, G. H.; Kramer, E. J.; Hahn, S. F.

    2000-03-01

    We investigate the influence of chain architecture on the deformation and fracture of poly(vinylcyclohexane)-poly(ethylene) (PCHE-PE) block copolymers. Ordered thin films of PCHE-PE-PCHE (CEC) triblock and CECEC pentablock copolymers are bonded to ductile copper grids and deformed in tension and then examined by optical and transmission electron microscopy. Both PCHE homopolymer (M = 283,000 g/mol) and CEC triblock (M = 107,000 g/mol; fE =3D 0.29) undergo fracture via crazing followed by breakdown of crazes to form cracks producing catastrophic failure at a strain ɛ < 6%. The mechanism of deformation and the strain for catastrophic failure changes dramatically for CECEC. Deformation of the CECEC pentablock (M = 110,000 g/mol; fE = 0.29) takes place mainly by (shear) deformation zone formation. Shear deformation and crazing compete and the shear blunting of craze tips is frequently observed. The strain for the catastrophic failure increases in CECEC to ɛ > 30%, and breakdown of the deformed film occurs only locally. We attribute this change in deformation and failure mechanisms to the bridging chains within the C domains of CECEC.

  13. Block copolymer blends with improved oil absorption resistance

    SciTech Connect

    Himes, G.R.; Sanders, A.

    1989-11-14

    This patent describes a thermoplastic blend. It comprises: about 80 to about 20 parts by weight of an elastometric block copolymer having the general configuration A-B-A, wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35w% of the elastomeric block copolymer; and each B block is a non-hydrogenated butadiene hydrocarbon block consisting of 8 to 55 mole percent condensed butadiene units in the 1,2 configuration, or a hydrogenated butadiene hydrocarbon block consisting of 35 to 55 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and about 20 to about 80 parts by weight of a block copolymer having the general configuration A-B-A wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35 w % of the block copolymer; each B block is a polymerized butadiene hydrocarbon block consisting of about 18 to 34 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and the B blocks are hydrogenated to an unsaturation that is less than about 5% of the original unsaturation.

  14. Effect of Film Thickness and Domain Spacing on Defect Densities in Directed Self-Assembly of Cylindrical Morphology Block Copolymers

    SciTech Connect

    Mishra, Vindhya; Fredrickson, Glenn H.; Kramer, Edward J.

    2012-04-30

    Directed assembly of block copolymer thin films is recognized as a high-throughput, low-cost complement to optical lithography with the ability to overcome the 32 nm natural resolution limit of conventional lithographic techniques. For bulk block copolymer systems, desired feature sizes ranging from 5 to 100 nm can be obtained by controlling the molecular weight and composition of a block copolymer, as long as the bulk order-disorder temperature (ODT) is such that the copolymer is well-segregated at the processing conditions. However, our studies on graphoepitaxially aligned cylindrical morphology block copolymer monolayer and bilayer films demonstrate that, as domain sizes are reduced, the block copolymer becomes increasingly susceptible to an unacceptably high density of thermally generated defects, resulting in a significant reduction of the ODT. Thus, in thin films, the minimum feature spacing accessible is limited by thermal defect generation and not by the bulk ODT. Our experimental studies on monolayer films of cylindrical morphology polystyrene-b-poly(2-vinyl pyridine) with microdomain spacings approaching 20 nm reveal that defect densities and the ODT are surprisingly sensitive to variations as small as 2 nm in the microdomain spacing. Additionally, the monolayer and bilayer ODT differ by nearly 100 C when the monolayer domain spacing is 20 nm, while the difference is only 20 C when the monolayer domain spacing is 22 nm. We explain this behavior using a quantitative estimation of the energetic cost of defect production in terms of the domain spacing, {chi}N, and block copolymer composition. These studies reveal unexpected consequences on the equilibrium defect densities of thin film block copolymers which must be accounted for when designing a block-copolymer-based directed-assembly process.

  15. Millisecond ordering of block-copolymer films via photo-thermal gradients

    DOE PAGESBeta

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in lessmore » than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.« less

  16. Selective Semiconductor Nanocluster Deposition on Eptaxially Patterned Semicrystalline Block Copolymer Film

    NASA Astrophysics Data System (ADS)

    Park, Cheolmin; Lee, Jinwook; Jensen, Klavs F.; Bawendi, Moungi G.; Thomas, Edwin L.

    2001-03-01

    Monodisperse ZnS encapsulated CdSe semiconductor nanoclusters are sequestered in between the crystalline polyethylene (PE) lamellae of poly (ethylene-b-ethylene-alt-propylene-b ethylene) semicrystalline triblock copolymer epitaxially crystallized on single crystal of anthracene (AN). Epitaxy between PE block and An created a cross oriented texture of the edge-on crystalline PE lamellae in the thin film. At the same time, the nanoclusters, initially dissolved in the mixture of block copolymer and AN, were rejected out of the crystalline lamellae during epitaxial crystallization and selectively deposited in the amorphous region of the block copolymer. Selective distribution of nanoclusters on the cross oriented pattern structure is clearly evidenced by selected area diffraction (SAD) and bright field transmission electron microscope (TEM).

  17. Millisecond ordering of block-copolymer films via photo-thermal gradients

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in less than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.

  18. Patterned silica films using microphase separation of a block copolymer

    NASA Astrophysics Data System (ADS)

    Kataoka, Sho; Takeuchi, Yasutaka; Endo, Akira

    2014-11-01

    Block copolymers exhibit various nanoscale ordered morphologies induced by microphase separation. Here, we present a method for providing two types of patterned silica films on Si wafer substrates simply by shifting the phase equilibrium of a block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP). In this method, siloxane is adsorbed onto poly(4-vinylpyridine) blocks of PS-P4VP whose structure varies with solvent polarity and is calcined to remove the block copolymer. Siloxane is in a dispersed phase with toluene as a solvent resulting in silica nanoparticle arrays, while siloxane is in a continuous phase with N, N-dimethylformamide (DMF) resulting in silica films with ordered mesopores. Since the pore size of silica films prepared in DMF is approximately 20 nm, the film has the ability to serve as a support for enzymes such as laccase.

  19. Fluorinated polyphenylenevinylene (PPV) block co-polymers for nanophotonics

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Nguyen, Thuong; Brooks, Jaleesa

    2013-09-01

    Polymer based optoelectronic materials and thin film devices exhibit great potential in future space applications due to their flexibility, light weight, large light absorption coefficient, and promising radiation tolerance in space environment as compared to their inorganic semiconductor counterparts. Since carbon-fluorine (C-F) chemical bonds are much stronger than the carbon-hydrogen (C-H) bonds, fluorinated polymer films offer great potential for space applications due their expected resistance to oxidation, thermal stability, excellent wear properties, and low coefficients of friction. Their use in a space environment is extremely attractive since they are expected to retain their lubricating characteristics in vacuum, unlike many solid lubricants. Current existing polymer photovoltaic materials and devices suffer low photoelectric power conversion efficiencies due to a number factors including poor morphologies at nano scale that hinder the charge separation and transport. This paper reports our recent work on a fluorinated DBfA type block copolymer system where the donor (D) block contains a donor substituted and hydrocarbon based polyphenylenevinylene (PPV), acceptor (fA) block contains a fluorinated and a sulfone acceptor substituted polyphenylenevinylene (f-PPV), and B is a non-conjugated and flexible bridge unit. Preliminary studies reveal DBfA exhibits better nano phase morphologies and over 100 times more efficient optoelectronic conversion efficiencies as compared to D/fA blend.

  20. Design of nanostructured materials from block copolymer self-assembly

    NASA Astrophysics Data System (ADS)

    Leolukman, Melvina

    We present two classes of nanostructured materials by combining the self assembly of block copolymer (BCP) with suitable small molecule chemistry, which are applicable to organic electro-optics (EO) and as etch-resistant masks for nanofabrication. The underlying principles of designing the specific interactions between BCP host and guest molecules, driving the self-assembly in bulk and thin film, and dictating domain orientation are concepts common to both of these areas. Nanostructured EO materials were created by selectively encapsulating EO chromophores by hydrogen-bonding to the pyridine groups of a linear-diblock copolymer (linear-diBCP) namely polystyrene-block-poly(4-vinyl pyridine) [PS-b-P4VP], or a linear-dendritic-BCP. With the linear-diBCP host, we discovered that poled order in confined domains depends on domain shape, chromophore concentration within the domain, and thermal history. The linear-dendritic-BCP is an excellent host as it efficiently disperses the chromophores into small domains (5-10nm), and keeps the chromophores apart within the domains due to the dendritic architecture. These morphological effects translated into excellent film processability, increased chromophore loading, and two-fold enhancements in the EO coefficient (r 33) when compared to a corresponding homopolymer system. A new class of organic-inorganic nanostructured materials based on polyhedral oligomeric silsesquioxane (POSS) was synthesized as a passive template for pattern transfer. We developed a living anionic polymerization route for methacrylate-functionalized POSS and synthesized two kinds of BCPs, namely PS-b-PMAPOSS and PMMA-b-PMAPOSS. The anionic route allows high degree of polymerization, narrow polydispersity, and tunable POSS block length. These lead to well defined spherical, cylindrical, and lamellar morphologies, as well as formation of hierarchical structures upon thermal annealing. Both POSS-containing BCPs were assembled in thin film and converted to hard

  1. Using click chemistry to modify block copolymers and their morphologies

    NASA Astrophysics Data System (ADS)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  2. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there

  3. Formation and structural properties of multi-block copolymer vesicles

    NASA Astrophysics Data System (ADS)

    Wang, Rong; Ma, Shiying

    2014-03-01

    Due to the unique structure, vesicles have attracted considerable attention for their potential applications, such as gene and drug delivery, microcapsules, nanoreactors, cell membrane mimetic, synthetic organelles, etc. By using dissipative particle dynamics, we studied the self-assembly of amphiphilic multi-block copolymer. The phase diagram was constructed by varying the interaction parameters and the composition of the block copolymers. The results show that the vesicles are stable in a large region which is different from the diblock copolymer or triblock copolymer. The structural properties of vesicles can be controlled by varying the interaction parameters and the length of the hydrophobic block. The relationship between the hydrophilic and hydrophobic block length vs the aqueous cavity size and vesicle size are revealed. The copolymers with shorter hydrophobic blocks length or the higher hydrophilicity are more likely to form vesicles with larger aqueous cavity size and vesicle size as well as thinner wall thickness. However, the increase in hydrophobic-block length results to form vesicles with smaller aqueous cavity size and larger vesicle size. Acknowledgments. This work has been supported by NNSFC (No. 21074053) and NBRPC (No. 2010CB923303).

  4. Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment

    SciTech Connect

    Liedel, Clemens; Pester, Christian; Ruppel, Markus A; Lewin, Christian; Pavan, Mariela J.; Urban, Volker S; Shenhar, Roy; Bosecke, Peter; Boker, Alexander

    2013-01-01

    We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.

  5. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, M.S.; Saunders, R.

    1997-02-18

    Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

  6. Morphology of Novel Semicrystalline Ethylene-α-Olefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Register, Richard; Landes, Brian

    2009-03-01

    In semicrystalline block copolymers, the solid-state structure can be set either by block incompatibility or by crystallization of one or more blocks. Depending on the block interaction strength, a wide array of solid-state morphologies may be observed, ranging from spherulitic to confined crystallization within preexisting microphase-separated domains. Dow Chemical has recently developed a novel chain shuttling polymerization process to produce olefin block copolymers with alternating amorphous and semicrystalline chain segments, where each block exhibits the most-probable distribution. We examined the melt and solid-state morphologies of these novel olefin block copolymers, having a high octene content in the amorphous block, using two- dimensional synchrotron small-angle and wide-angle x-ray scattering on specimens oriented by channel die compression. Multiblock and diblock copolymers with near-symmetric compositions showed well-ordered lamellar structures at room temperature with long periods exceeding 100 nm, with little dependence on thermal history, indicating the presence of a mesophase-separated melt which templates crystallization.

  7. Ion and temperature sensitive polypeptide block copolymer.

    PubMed

    Joo, Jae Hee; Ko, Du Young; Moon, Hyo Jung; Shinde, Usha Pramod; Park, Min Hee; Jeong, Byeongmoon

    2014-10-13

    A poly(ethylene glycol)/poly(L-alanine) multiblock copolymer incorporating ethylene diamine tetraacetic acid ([PA-PEG-PA-EDTA(m)) was synthesized as an ion/temperature dual stimuli-sensitive polymer, where the effect of different metal ions (Cu(2+), Zn(2+), and Ca(2+)) on the thermogelation of the polymer aqueous solution was investigated. The dissociation constants between the metal ions and the multiblock copolymer were calculated to be 1.2 × 10(-7), 6.6 × 10(-6), and 1.2 × 10(-4) M for Cu(2+), Zn(2+), and Ca(2+), respectively, implying that the binding affinity of the multiblock copolymer for Cu(2+) is much greater than that for Zn(2+) or Ca(2+). Atomic force microscopy and dynamic light scattering of the multiblock copolymer containing metal ions suggested micelle formation at low temperature, which aggregated as the temperature increased. Circular dichroism spectra suggested that changes in the α-helical secondary structure of the multiblock copolymer were more pronounced by adding Cu(2+) than other metal ions. The thermogelation of the multiblock copolymer aqueous solution containing Cu(2+) was observed at a lower temperature, and the modulus of the gel was significantly higher than that of the system containing Ca(2+) or Zn(2+), in spite of the same concentration of the metal ions and their same ionic valence of +2. The above results suggested that strong ionic complexes between Cu(2+) and the multiblock copolymer not only affected the secondary structure of the polymer but also facilitated the thermogelation of the polymer aqueous solution through effective salt-bridge formation even in a millimolar range of the metal ion concentration. Therefore, binding affinity of metal ions for polymers should be considered first in designing an effective ion/temperature dual stimuli-sensitive polymer. PMID:25178662

  8. Highly conductive side chain block copolymer anion exchange membranes.

    PubMed

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days. PMID:27216558

  9. Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

    SciTech Connect

    Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

    2015-10-13

    A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

  10. Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

    NASA Astrophysics Data System (ADS)

    Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

    We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

  11. Radical-cured block copolymer-modified thermosets

    SciTech Connect

    Redline, Erica M.; Francis, Lorraine F.; Bates, Frank S.

    2013-01-10

    Poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP-PEO) diblock copolymers were synthesized and added at 4 wt % to 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA), a monomer that cures using free radical chemistry. In separate experiments, poly(ethylene glycol) dimethacrylate (PEGDMA) was combined as a secondary monomer with BisGMA and the monomers were loaded with 4 wt % PEP-PEO. The diblock copolymers self-assembled into well-dispersed spherical micelles with PEP cores and PEO coronas. No appreciable change in the final extent of cure of the thermosets was caused by the addition of diblock copolymer, except in the case of BisGMA, where the addition of the block copolymer increased extent of cure by 12%. Furthermore, the extent of cure was increased by 29% and 37% with the addition of 25 and 50 wt % PEGDMA, respectively. Elastic modulus and fracture resistance were also determined, and the values indicate that the addition of block copolymers does not significantly toughen the thermoset materials. This finding is surprising when compared with the large increase in fracture resistance seen in block copolymer-modified epoxies, and an explanation is proposed.

  12. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer

    SciTech Connect

    Lokitz, Bradley S; Wei, Jifeng; Hinestrosa Salazar, Juan P; Ivanov, Ilia N; Browning, James B; Ankner, John Francis; Kilbey, II, S Michael; Messman, Jamie M

    2012-01-01

    The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.

  13. Host-guest self-assembly in block copolymer blends.

    PubMed

    Park, Woon Ik; Kim, Yongjoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  14. Host-Guest Self-assembly in Block Copolymer Blends

    PubMed Central

    Park, Woon Ik; Kim, YongJoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L.; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  15. Dynamic response of block copolymer wormlike micelles to shear flow

    NASA Astrophysics Data System (ADS)

    Lonetti, B.; Kohlbrecher, J.; Willner, L.; Dhont, J. K. G.; Lettinga, M. P.

    2008-10-01

    The linear and nonlinear dynamic response to an oscillatory shear flow of giant wormlike micelles consisting of Pb-Peo block copolymers is studied by means of Fourier transform rheology. Experiments are performed in the vicinity of the isotropic-nematic phase transition concentration, where the location of isotropic-nematic phase transition lines is determined independently. Strong shear-thinning behaviour is observed due to critical slowing down of orientational diffusion as a result of the vicinity of the isotropic-nematic spinodal. This severe shear-thinning behaviour is shown to result in gradient shear banding. Time-resolved small-angle neutron scattering experiments are used to obtain an insight into the microscopic phenomena that underlie the observed rheological response. An equation of motion for the order parameter tensor and an expression of the stress tensor in terms of the order parameter tensor are used to interpret the experimental data, both in the linear and nonlinear regimes. Scaling of the dynamic behaviour of the orientational order parameter and the stress is found when critical slowing down due to the vicinity of the isotropic-nematic spinodal is accounted for.

  16. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration.

    PubMed

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor Manuel; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2015-11-16

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux. PMID:26388216

  17. Liquid-crystalline ordering helps block copolymer self-assembly.

    PubMed

    Yu, Haifeng; Kobayashi, Takaomi; Yang, Huai

    2011-08-01

    Interaction between liquid-crystalline elastic deformation and microphase separation in liquid-crystalline block copolymers enables them to supramolecularly assemble into ordered nanostructures with high regularity. With the help of liquid-crystalline alignment, parallel and perpendicular patterning of nanostructures is fabricated with excellent reproducibility and mass production, which provides nanotemplates and nanofabrication processes for preparing varieties of nanomaterials. Furthermore, nanoscale microphase separation improves the optical performance of block-copolymer fi lms by eliminating the scattering of visible light, leading to advanced applications in optical devices and actuators. Recent progress in liquid-crystalline block copolymers, including their phase diagram, structure-property relationship, nanostructure control and nanotemplate applications, is reviewed. PMID:21910267

  18. Characterization of Lithium Polysulfide Salts in Homopolymers and Block Copolymers

    NASA Astrophysics Data System (ADS)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

    Ion-conducting polymers are important for solid-state batteries due to the promise of better safety and the potential to produce higher energy density batteries. Nanostructured block copolymer electrolytes can provide high ionic conductivity and mechanical strength through microphase separation. One of the potential use of block copolymer electrolytes is in lithium-sulfur batteries, a system that has high theoretical energy density wherein the reduction of sulfur leads to the formation of lithium polysulfide intermediates. In this study we investigate the effect of block copolymer morphology on the speciation and transport properties of the polysulfides. The morphology and conductivities of polystyrene-b-poly(ethylene oxide) (SEO) containing lithium polysulfides were studies using small-angle X-ray scattering and ac impedance spectroscopy. UV-vis spectroscopy is being used to determine nature of the polysulfide species in poly(ethylene oxide) and SEO. Department of Energy, Soft Matter Electron Microscopy Program and Battery Materials Research Program.

  19. Controlling block copolymer phase behavior using ionic surfactant

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  20. Amphiphilic block copolymer nanocontainers as bioreactors

    NASA Astrophysics Data System (ADS)

    Nardin, C.; Widmer, J.; Winterhalter, M.; Meier, W.

    2001-04-01

    Self-assembly of an amphiphilic triblock copolymer carrying polymerizable end-groups is used to prepare nanometer-sized vesicular structures in aqueous solution. The triblock copolymer shells of the vesicles can be regarded as a mimetic of biological membranes although they are 2 to 3 times thicker than a conventional lipid bilayer. Nevertheless, they can serve as a matrix for membrane-spanning proteins. Surprisingly, the proteins remain functional despite the extreme thickness of the membranes and that even after polymerization of the reactive triblock copolymers. This opens a new field to create mechanically stable protein/polymer hybrid membranes. As a representative example we functionalize (polymerized) triblock copolymer vesicles by reconstituting a channel-forming protein from the outer cell wall of Gram-negative bacteria. The protein used (OmpF) acts as a size-selective filter, which allows only for passage of molecules with a molecular weight below 400 g mol^{-1}. Therefore substrates may still have access to enzymes encapsulated in such protein/polymer hybrid nanocontainers. We demonstrate this using the enzyme β -lactamase which is able to hydrolyze the antibiotic ampicillin. In addition, a transmembrane voltage above a given threshold causes a reversible gating transition of OmpF. This can be used to reversibly activate or deactivate the resulting nanoreactors.

  1. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

    PubMed

    Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

    2016-07-11

    Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials. PMID:27276387

  2. Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

    DOE PAGESBeta

    Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

    2015-11-03

    All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show thatmore » the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

  3. Self-Assembly of a Selectively Modified Fluorinated Block Copolymer

    NASA Astrophysics Data System (ADS)

    Davidock, Drew; Hillmyer, Marc; Lodge, Timothy

    2002-03-01

    Selective modification can be used to systematically tune the strength of the thermodynamic interaction between the two segments of a block copolymer. It also offers an effective method for the preparation of model fluorinated block copolymers, which are difficult to synthesize directly. In this study, the effect of controlled difluorocarbene (CF_2) addition to the polyisoprene block on the self-assembly of a series of poly(ethylethylene)-b-polyisoprene (PEE-b-PI) copolymers was investigated. Equilibrium morphologies were determined by small-angle X-ray scattering (SAXS). An effective interaction parameter (\\chi_eff) between the PEE and FPI-s-PI was calculated from the domain spacing, and is found to increase by a factor of ~400 upon complete CF2 modification. The resulting materials also offer an opportunity to examine the phase behavior all the way from weak to strong segregation with one parent copolymer. Using a binary interaction model originally developed for homopolymer/copolymer blends, we were able to model the dependence of \\chi_eff on the extent of fluorination in a quantitative manner and obtain values for the three pairwise interaction parameters.

  4. Block and Graft Copolymers of Polyhydroxyalkanoates

    NASA Astrophysics Data System (ADS)

    Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

    2004-03-01

    Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

  5. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  6. Chain exchange kinetics of block copolymer micelles in ionic liquids

    NASA Astrophysics Data System (ADS)

    Ma, Yuanchi; Lodge, Timothy

    The chain exchange kinetics of block copolymer micelles has been studied using time-resolved small-angle neutron scattering (TR-SANS), a key tool in determining the average micelle composition in contrast-matched solvents. In this work, PMMA-block-PnBMA was selected as the model block copolymer, which has a LCST behavior in the common ionic liquids, [EMIM][TFSI] and [BMIM][TFSI]. We examined the chain exchange kinetics of three PMMA-block-PnBMA copolymers, with identical PMMA block length (MPMMA = 25000) and different PnBMA block lengths (MPnBMA = 24000, 35000 and 53000); the Flory-Huggins interaction parameter (χ) between the core (PnBMA) and the solvent were varied by mixing [EMIM][TFSI] and [BMIM][TFSI] in different ratios. We found that the relaxation of the initial segregation of h- and d- micelles followed the same form with the time as previously developed by our group. Assuming that single chain expulsion is the rate limiting step, the thermal barrier was found to depend linearly on the core block length (Ncore) . Furthermore, the effect of χ on the chain exchange kinetics will also be discussed.

  7. Modeling Line Edge Roughness in Lamellar Block Copolymer Systems

    NASA Astrophysics Data System (ADS)

    Patrone, Paul; Gallatin, Gregg

    2012-02-01

    Block copolymers offer an appealing alternative to current lithographic techniques with regard to fabrication of the next generation microprocessors. However, if copolymers are to be useful on an industrial manufacturing scale, they must meet or exceed lithography specifications for placement and line edge roughness (LER) of resist features. Here we discuss a field theoretic approach to modeling the LER in the lamellar phase of a strongly segregated block copolymer system. Our model is based on the Leibler-Ohta-Kawasaki free energy functional, which takes the Flory-Huggins parameter and index of polymerization as inputs. We consider a domain with a finite number of phase separated microdomains; at the system boundary, we apply conditions akin to a chemical pinning field. Using a path integral formalism, we determine how fluctuations of the microdomain boundaries depend on distance from the system boundary, number of microdomains, the Flory-Huggins parameter, and index of polymerization.

  8. Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug

    PubMed Central

    2016-01-01

    We introduce the use of block copolymer membranes for an emerging application, “drug capture”. The polymer is incorporated in a new class of biomedical devices, referred to as ChemoFilter, which is an image-guided temporarily deployable endovascular device designed to increase the efficacy of chemotherapy-based cancer treatment. We show that block copolymer membranes consisting of functional sulfonated polystyrene end blocks and a structural polyethylene middle block (S-SES) are capable of capturing doxorubicin, a chemotherapy drug. We focus on the relationship between morphology of the membrane in the ChemoFilter device and efficacy of doxorubicin capture measured in vitro. Using small-angle X-ray scattering and cryogenic scanning transmission electron microscopy, we discovered that rapid doxorubicin capture is associated with the presence of water-rich channels in the lamellar-forming S-SES membranes in aqueous environment. PMID:27547493

  9. Development of block co-polymers as self-assembling templates for patterned media.

    SciTech Connect

    Warke, V.; Bakker, M. G.; Hong, K.; Mays, J.; Britt, P.; Li, X.; Wang, J.; X-Ray Science Division; Univ. of Alabama; ORNL

    2006-01-01

    Block copolymers that self-organize are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. Poly(styrene)-Poly(methylmethacrylate) block co-polymers (PS-b-PMMA) of appropriate block length and PS to PMMA ratio self-assemble into a 2-D hexagonal phase in which the PS majority phase is continuous and surrounds cylinders of the minority, PMMA phase. For application of this phase to patterned media it is necessary that the cylinders of the minority phase be oriented perpendicular to the substrate surface. This can be achieved by a number of methods, including appropriate choice of substrate and use of a random co-polymer underlayer. Appropriate substrates include H-terminated silicon, some carbon coatings and some ITO glasses. Use of an acetic acid wash causes the minority PMMA component can be induced to be rearranged, giving rise to pores perpendicular to the substrate. Electrodeposition of a metal into the pores produces a hardmask which can be used with ion-milling to transfer the block co-polymer pattern onto a magnetic thin film.

  10. Direct Immersion Solvent Annealing of Nano-filled Block Copolymer Films

    NASA Astrophysics Data System (ADS)

    Longanecker, Melanie; Modi, Arvind; Yuan, Guangcui; Satija, Sushil; Bang, Joona; Karim, Alamgir; University of Akron Team; National Institute of Technology Collaboration; Korea University Collaboration

    The addition of nanoparticles to polymer films is a strategic approach to enhance film properties such as optical, thermal, hardness, conductivity, permeability etc. with inorganic components while maintaining an easily processable polymer matrix. To this end, the ``annealing'' of block copolymers while immersed directly in a chamber of solvent is examined to determine its efficacy in ordering nano-filled block copolymer films. Previously we have shown that it is possible to order neat block copolymer films in a mixture of solvents, and this research follows up that work. Specifically, we observe and utilize the effects of direct immersion solvent annealing (DIA) on lamellar poly(styrene-b-methyl methacrylate) thin films with loadings of gold nanoparticles as high as 25 percent by mass. Neutron reflection confirms that DIA is a viable technique applicable to ordering these highly loaded, nano-filled block copolymer systems. Some notable differences exist with respect to results on conservation of domain spacing that may be beneficial to film barrier properties, accomplished with minimal disruption of order and fast kinetics that is compatible with roll-to-roll techniques.

  11. Hierarchical pattern formation through photo-induced disorder in block copolymer/additive composite films

    NASA Astrophysics Data System (ADS)

    Yao, Li; Watkins, James

    2013-03-01

    Segregation strength in hybrid materials can be increased through selective hydrogen bonding between organic or nanoparticle additives and one block of weakly segregated block copolymers to generate well ordered hybrid materials. Here, we report the use of enantiopure tartaric acid as the additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Phase behavior and morphologies within both bulk and thin films were studied by TEM, AFM and X-ray scattering. Suppression of PEO crystallization by the interaction between tartaric acid and the PEO block enables the formation of well ordered smooth thin films. With the addition of a photo acid generator, photo-induced disorder in PEO-b-PtBA/tartaric acid composite system can be achieved upon UV exposure to deprotect PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Due to the strong interaction of tartaric acid with both blocks, the system undergoes a disordering transition within seconds during a post-exposure baking. With the assistance of trace-amounts of base quencher, high resolution, hierarchical patterns of sub-micron regions of ordered and disordered domains were achieved in thin films through area-selective UV exposure using a photo-mask. Funding from Center for Hierarchical Manufacturing (CHM); Facility support from Materials Research Science and Engineering Center at UMass Amherst and Cornell High Energy Synchrotron Source

  12. Fast assembly of ordered block copolymer nanostructures through microwave annealing.

    PubMed

    Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

    2010-11-23

    Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy. PMID:20964379

  13. Linear-dendritic block copolymer for drug and gene delivery.

    PubMed

    Fan, Xiaohui; Zhao, Yanli; Xu, Wei; Li, Lingbing

    2016-05-01

    Dendrimers as a new class of polymeric materials have a highly ordered branched structure, exact molecular weight, multivalency and available internal cavities, which make them extensively used in biology and drug-delivery. Concurrent with the development of dendrimers, much more attention is drawn to a novel block copolymer which combines linear chains with dendritic macromolecules, the linear-dendritic block copolymer (LDBC). Because of the different solubility of the contrasting regions, the amphiphilic LDBCs could self-assemble to form aggregates with special core-shell structures which exhibit excellent properties different from traditional micelles, such as lower critical micelle concentration, prolonged circulation in the bloodstream, better biocompatibility, and lower toxicity. The present review briefly describes the type of LDBC, the self-assembly behavior in solution, and the application in delivery system including the application as drug carriers and gene vectors. The interactions between block copolymers and drugs are also summarized to better understand the release mechanism of drugs from the linear-dendritic block copolymers. PMID:26952501

  14. Order and Disorder in Polydisperse Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Lynd, Nathaniel; Hillmyer, Marc

    2007-03-01

    Utilizing creative strategies for the synthesis of model controlled-polydispersity poly(ethylene-alt-propylene)-b-poly(d,l-lactide)(PEP-PLA) and polystyrene-b-polyisoprene(PS-PI) block copolymers, the effects of increased breadth in the molecular weight distribution on block copolymer self-assembly were investigated. Small-angle x-ray scattering and rheological measurements were carried out to characterize the morphological details of these self-assembled materials as a function of their polydispersity, interaction strengths, and compositions. A number of surprising consequences of increased breadth in the molecular weight distribution emerged; the domain spacing of the ordered structures increased, changes in morphology occurred, and the degree of segregation at the order-disorder transitions changed as well, particularly for asymmetric block copolymers. The change in the degree of segregation at the order-disorder transition as the polydispersity was increased was found to be dependent on the block copolymer composition, e.g., for PEP-PLA and PS-PI at asymmetric compositions, when the polydispersity was increased in the minority component, the degree of segregation at the order-disorder transition decreased, whereas when the polydispersity was increased in the majority component, the degree of segregation at the order-disorder transition increased.

  15. Electrical biomolecule detection using nanopatterned silicon via block copolymer lithography.

    PubMed

    Jeong, Chang Kyu; Jin, Hyeong Min; Ahn, Jae-Hyuk; Park, Tae Jung; Yoo, Hyeon Gyun; Koo, Min; Choi, Yang-Kyu; Kim, Sang Ouk; Lee, Keon Jae

    2014-01-29

    An electrical biosensor exploiting a nanostructured semiconductor is a promising technology for the highly sensitive, label-free detection of biomolecules via a straightforward electronic signal. The facile and scalable production of a nanopatterned electrical silicon biosensor by block copolymer (BCP) nano-lithography is reported. A cost-effective and large-area nanofabrication, based on BCP self-assembly and single-step dry etching, is developed for the hexagonal nanohole patterning of thin silicon films. The resultant nanopatterned electrical channel modified with biotin molecules successfully detects the two proteins, streptavidin and avidin, down to nanoscale molarities (≈1 nm). The nanoscale pattern comparable to the Debye screening length and the large surface area of the three-dimensional silicon nanochannel enable excellent sensitivity and stability. A device simulation confirms that the nanopatterned structure used in this work is effective for biomolecule detection. This approach relying on the scalable self-assembly principle offers a high-throughput manufacturing process for clinical lab-on-a-chip diagnoses and relevant biomolecular studies. PMID:23881835

  16. Square Grains in Asymmetric Rod-Coil Block Copolymers

    SciTech Connect

    Olsen, B.D.; Toney, M.F.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley /SLAC, SSRL

    2009-04-30

    Unlike the rounded grains that are well known to form in most soft materials, square grains of microphase-separated lamellae are observed in thin films of a rod-coil block copolymer because of hierarchical structuring originating from the molecular packing of the rods. The square grains are oriented with lamellar layers parallel to the film interface and result from growth along orthogonal low-surface-energy directions as a result of the effects of the tetragonal crystalline lattice that forms within the rod-rich lamellar nanodomains of poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylene vinylene)-b-polyisoprene (PPV-b-PI). These grain shapes form only for a narrow range of coil volume fractions around 72% as a result of kinetic barriers at lower coil fractions and disordering of the lattice at higher coil fractions, and the polydisperse grain size suggests that growth is nucleation-limited. The grains form in both weakly and moderately segregated polymers at all annealing temperatures below the order-disorder transition, and they are observed for all thicknesses at which parallel-oriented grains are grown.

  17. Fluctuation Dynamics of Block Copolymer Vesicles

    SciTech Connect

    Falus, P.; Borthwick, M.A.; Mochrie, S.G.J.

    2010-07-13

    X-ray photon correlation spectroscopy was used to characterize the wave-vector- and temperature-dependent dynamics of spontaneous thermal fluctuations in a vesicle (L4) phase that occurs in a blend of a symmetric poly(styrene-ethylene/butylene-styrene) triblock copolymer with a polystyrene homopolymer. Measurements of the intermediate scattering function reveal stretched-exponential behavior versus time, with a stretching exponent slightly larger than 2/3. The corresponding relaxation rates show an approximate q{sup 3} dependence versus wave vector. Overall, the experimental measurements are well described by theories that treat the dynamics of independent membrane plaquettes.

  18. A route to nanoscopic materials via seeded sequential infiltration synthesis on block copolymer templates.

    SciTech Connect

    Peng, Q.; Tseng, Y.-C.; Darling, S. B.; Elam, J. W.

    2011-06-01

    Sequential infiltration synthesis (SIS), combining stepwise molecular assembly reactions with self-assembled block copolymer (BCP) substrates, provides a new strategy to pattern nanoscopic materials in a controllable way. The selective reaction of a metal precursor with one of the pristine BCP domains is the key step in the SIS process. Here we present a straightforward strategy to selectively modify self-assembled polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP thin films to enable the SIS of a variety of materials including SiO{sub 2}, ZnO, and W. The selective and controlled interaction of trimethyl aluminum with carbonyl groups in the PMMA polymer domains generates Al-CH{sub 3}/Al-OH sites inside the BCP scaffold which can seed the subsequent growth of a diverse range of materials without requiring complex block copolymer design and synthesis.

  19. Nanostructured Amphiphilic Star-Hyperbranched Block Copolymers for Drug Delivery.

    PubMed

    Seleci, Muharrem; Seleci, Didem Ag; Ciftci, Mustafa; Demirkol, Dilek Odaci; Stahl, Frank; Timur, Suna; Scheper, Thomas; Yagci, Yusuf

    2015-04-21

    A robust drug delivery system based on nanosized amphiphilic star-hyperbranched block copolymer, namely, poly(methyl methacrylate-block-poly(hydroxylethyl methacrylate) (PMMA-b-PHEMA) is described. PMMA-b-PHEMA was prepared by sequential visible light induced self-condensing vinyl polymerization (SCVP) and conventional vinyl polymerization. All of the synthesis and characterization details of the conjugates are reported. To accomplish tumor cell targeting property, initially cell-targeting (arginylglycylaspactic acid; RGD) and penetrating peptides (Cys-TAT) were binding to each other via the well-known EDC/NHS chemistry. Then, the resulting peptide was further incorporated to the surface of the amphiphilic hyperbranched copolymer via a coupling reaction between the thiol (-SH) group of the peptide and the hydroxyl group of copolymer by using N-(p-maleinimidophenyl) isocyanate as a heterolinker. The drug release property and targeting effect of the anticancer drug (doxorobucin; DOX) loaded nanostructures to two different cell lines were evaluated in vitro. U87 and MCF-7 were chosen as integrin αvβ3 receptor positive and negative cells for the comparison of the targeting efficiency, respectively. The data showed that drug-loaded copolymers exhibited enhanced cell inhibition toward U87 cells in compared to MCF-7 cells because targeting increased the cytotoxicity of drug-loaded copolymers against integrin αvβ3 receptor expressing tumor cells. PMID:25816726

  20. Facile Synthesis and Characterization of Well-Defined Rod-Coil Block Copolymers Composed of Regioregular Poly(3-hexyl thiophene)

    NASA Astrophysics Data System (ADS)

    Moon, Hong Chul; Kim, Jin Kon

    2011-03-01

    We synthesized rod-coil block copolymers composed of regioregular poly(3-hexyl thiopene) (P3HT) block via anionic coupling reaction. Three different coil blocks (poly(2-vinyl pyridine) (P2VP) and polyisoprene (PI)) and poly(methyl methacrylate) (PMMA)) were selected. For the synthesis of P2VP- b -P3HT- b -P2VP and P2VP- b -P3HT- b -P2VP, the chain ends of the P3HT were capped by the aldehyde group. On the other hand, phenyl acrylate (PA)-capped P3HT was prepared for coupling reaction with living PMMA anions. When the excess amount of the used living anions was removed by column chromatography, all of the neat block copolymers showed lower PDI without leaving any homopolymers. We also investigated the optical property and thin film morphology of synthesized various block copolymers.

  1. Intriguing transmission electron microscopy images observed for perpendicularly oriented cylindrical microdomains of block copolymers

    NASA Astrophysics Data System (ADS)

    Ohnogi, Hiroshi; Isshiki, Toshiyuki; Sasaki, Sono; Sakurai, Shinichi

    2014-08-01

    Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods.Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods. Electronic supplementary information (ESI) available. See DOI: 10.1039/c

  2. Structure-Property Relationships in Polyolefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mansour, Ameara Salah

    Poly(cyclohexylethylene) (PCHE for a homopolymer or C in a block copolymer) is created by hydrogenating polystyrene, and this polymer exhibits interesting properties, such as a high glass transition temperature (147 °C), high flexural modulus (2.8 GPa), low stress optical coefficient (-0.2 * 10-9 Pa-1), and low cost. However, the inherently brittle nature of PCHE prevents it from being used in applications that simultaneously require high modulus, ductility, thermal stability, and optical clarity. Previous research has shown that incorporating PCHE into a block copolymer with rubbery poly(ethylene-alt-propylene) (P) or poly(ethylethylene) (EE) or semicrystalline polyethylene (E) results in a tough material. In some cases, applications also require specific mechanical or optical properties. In order to tune these properties, this research examined tuning crystallinity using two methods: (1) by controlling the microstructure of the soft block by synthesizing a random copolymer of E and EE, and (2) by blending high C content pentablock copolymers with semicrystalline and rubbery minority components. In the first study, diblock copolymers of C(EcoEE) also were used to understand how the microstructure of the random copolymer affects the thermodynamics of the system. In the second study, CECEC and CPCPC, designed to form the same morphology (hexagonally packed cylinders with glassy C matrices), and have similar order-to-disorder transition temperatures and domain spacings, were blended together. Isothermal crystallization experiments were used to determine how the confining E and P in one domain affects the crystallization process. The effect of architecture, the state of the minority component, and the percent crystallinity on the mechanical properties of high glass content materials was also examined. These results were compared to the mechanical properties of homopolymer PCHE, polystyrene, and polycarbonate. The processing conditions needed to create smooth films of

  3. Directed Self-assembly of Block Copolymer with Sub-15 nm Domain Spacing Using Nanoimprinted Photoresist Templates

    NASA Astrophysics Data System (ADS)

    Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Coughlin, E. Bryan; Xiao, Shuaigang; Russell, Thomas

    There has been increasing interest in preparing block copolymer thin films with ultra-small domain spacings for use as etching masks for ultra-high resolution nanolithography. One method to prepare block copolymer materials with small feature sizes is salt doping, increasing the Flory-Huggins interaction and allowing microphase separation to be maintained at lower molecular weights. Lamellae-forming P2VP- b-PS- b-P2VP block copolymer with various molecular weight was synthesized using RAFT polymerization with a dual functional chain transfer agent. Copper (II) Chloride or Gold (III) chloride was found to be selectively associated with P2VP block and increase the unfavorable interactions between PS and P2VP blocks, driving the disordered block copolymer into the ordered state. A 14 nm lamellar spacing of P2VP- b-PS- b-P2VP thin film was prepared using copper (II) Chloride doping after acetone vapor annealing on neutral brushes. Metallic nano-wire arrays were prepared after selective infiltration of platinum salt into the P2VP domain and oxygen plasma treatment. The directed self-assembly of salt doped P2VP- b-PS- b-P2VP triblock copolymer having long-rang lateral order on nanoimprinted photoresist templates with shallow trenches was also studied.

  4. Polythiophene-block-Polyfluorene and Polythiophene-block-Poly(fluorene-co-benzothiadiazole): insights into the self-assembly of all-conjugated block copolymers

    SciTech Connect

    Verduzco, Rafael; Botiz, Ioan; Dimasi, Elaine; Pickel, Deanna L; Hong, Kunlun; Kilbey, II, S Michael; Darling, Seth B.

    2011-01-01

    Block copolymers made by covalently linking two or more conjugated polymers have significant potential for organic optoelectronic applications, particularly those requiring a p/n junction. Herein, we report the structure of all-conjugated diblock copolymers poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene) and poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene-co-benzothiadiazole) in thin films and in the bulk. The diblock copolymers are prepared using a combination of Grignard metathesis polymerization and Suzuki polycondensation and purified using solvent extraction and column chromatography. 1H NMR, SEC, and UV/Visible absorbance measurements are used to characterize the materials and quantify the amount of homopolymer impurities. Thin films and bulk structure are characterized using a combination of differential scanning calorimetry, x-ray diffraction, small-angle x-ray scattering, and atomic force microscopy. Atomic force microscopy images reveal nanoscale lamellar domains in solvent-annealed diblock copolymer thin films, and peaks in x-ray diffraction data correspond to poly(3-hexylthiophene) crystallites. On cooling from temperatures above the crystallization temperature to below the crystallization temperature, two peaks appear in temperature-dependent small-angle x-ray scattering traces - one associated with poly(3-hexylthiophene) crystallites and a second low-angle peak indicative of a self-assembled nanostructured. These measurements show all-conjugated diblock copolymers self-assemble into nanoscale crystalline domains present throughout the bulk samples which may be useful for improving the performance of organic photovoltaics and organic light-emitting diodes.

  5. Block-copolymer-induced structure formation in microemulsions

    SciTech Connect

    Hilfiker, R.; Eicke, H.F.; Steeb, C.; Hofmeier, U. )

    1991-02-07

    Transient electric birefringence measurements were performed on water/AOT (sodium bis(2-ethylhexyl) sulfosuccinate)/isooctane microemulsions with various amounts of block-copoly(oxyethylene/isoprene/oxyethylene) added. The authors could show that addition of the copolymer leads to a formation of nanodroplet (ND)-copolymer-aggregates. The contributions of NDs and aggregates to the induced birefringence could easily be separated because the NDs exhibited a negative and the aggregates a positive induced birefringence and because the time scales corresponding to the two processes were different.

  6. Beyond Spherical Micelles in Styrene-Isoprene Block Copolymer Solutions

    NASA Astrophysics Data System (ADS)

    Bang, Joona; Lodge, Timothy P.

    2004-03-01

    As macromolecular surfactants, block copolymers have been shown to self-assemble into various microstructures. Many studies have focused on aqueous systems, in which the strongly amphiphilic characteristics of the polymers lead to various micellar shapes (worms, vesicles, compound micelles, etc). However, such micellar shape changes are apparently very rare in organic systems. We report systematic shape changes of the micelles in styrene-isoprene block copolymer solutions. Remarkably, such changes could be accomplished in a single block copolymer by varying the solvent selectivity. We studied two asymmetric poly(styrene-b-isoprene) diblock copolymers with the styrene volume fractions of approximately 0.15 in a series of solvents with varying styrene selectivity, dibuthyl phthalate, diethyl phthalate, and dimethyl phthalate. The degree of the solvent selectivity was adjusted by mixing two solvents. With increasing solvent selectivity, the micellar shape changes from cylindrical micelles to bilayer vesicles, and then phase-separates, reflecting the changing interfacial curvature induced by solvent selectivity. The detailed micellar morphologies were characterized by dynamic light scattering, rheology, electron microscopy, and small angle x-ray scattering.

  7. Gas Permeation through Polystyrene-Poly(ethylene oxide) Block Copolymers

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel, Jr.; Minelli, Matteo; Giacinti-Baschetti, Marco; Balsara, Nitash

    2013-03-01

    Lithium air batteries are a potential technology for affordable energy storage. They consist of a lithium metal anode and a porous air cathode separated by a solid polymer electrolyte membrane, such as PEO/LiTFSI (PEO = poly(ethylene oxide), LiTFSI = lithium bis-trifluoromethane sulfonimide). For extended operation of such a battery, the polymer electrolyte must conduct lithium ions while blocking electrons and gases present in air. In order to maintain a pressure difference the membrane must be mechanically robust, which can be achieved by incorporating the PEO into a block copolymer with a glassy block such as PS (PS = polystyrene). To protect the lithium electrode, the membrane must have low permeability to gases in air such as CO2, N2, and O2. We have therefore studied the permeation of pure gases through a PS-PEO block copolymer. A high molecular weight, symmetric block copolymer with a lamellar morphology was used to cast free-standing membranes. Gas permeability was measured through these membranes with a standard, pressure-based technique. A model was developed to account for transport through the polymer membrane consisting of semi-crystalline PEO lamellae and amorphous PS lamellae. PEO crystallinity was extracted from the permeation model and compares well with values from differential scanning calorimetry measurements.

  8. Formation and Characterization of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  9. Grain Rotation in Ion-Complexed Symmetric Diblock Copolymer Thin Films under an Electric Field

    SciTech Connect

    Wang,J.; Leiston-Belanger, J.; Sievert, J.; Russell, T.

    2006-01-01

    In symmetric polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer thin films, lithium-PMMA complexes were formed with the addition of lithium chloride (LiCl), significantly increasing both {chi} and dielectric constant. These led to a transition in the kinetic pathway of the orientation of lamellar microdomains under an applied electric field from a disruption and re-formation of the microdomains to a grain rotation mediated by movement of defects. By controlling the number of lithium-PMMA complexes, the microdomain alignment is possibly regulated in PS-b-PMMA copolymer thin films.

  10. Synthesis and interactions with blood of polyetherurethaneurea/polypeptide block copolymers.

    PubMed

    Ito, Y; Miyashita, K; Kashiwagi, T; Imanishi, Y

    1993-01-01

    Polyurethane/polypeptide block copolymers were synthesized. Infrared spectroscopy and differential scanning calorimetry revealed that in the block copolymers both segments undergo phase-mixing, while in polyurethane/polypeptide blend both components undergo phase-separation. Contact angle measurement showed that in the block copolymers polyurethane segments tended to appear on the membrane surface, whereas in polyurethane/polypeptide blend polypeptide components appeared on the membrane surface. In vitro nonthrombogenicity of the block copolymers was similar to that of homopolymers or polymer blends, though adhesion and deformation of platelets were suppressed on the block copolymer membranes. PMID:8260582