Characteristics of the surface-induced orientation for symmetric diblock PS/PMMA copolymers

Russell, Thomas P.; Coulon, G.; Deline, V. R.; Miller, Dolores C.

doi:10.1021/ma00202a036

Cited by 310 publications

(339 citation statements)

References 4 publications

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“…A difference in block interfacial energies will attract one of the blocks to the substrate, inducing a layering effect on the remainder of the film [132][133][134][135][136][137]. Lamellar films possess a natural repeat spacing of the domain structure, L 0 , and pay a free energy penalty due to chain stretching or compression when the film thickness is not commensurate with this spacing.…”

Section: Film Thicknessmentioning

confidence: 99%

Patterning with block copolymer thin films

Segalman

2005

Materials Science and Engineering: R: Reports

931

921

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The nanometer-scale architectures in thin films of self-assembling block copolymers have inspired a variety of new applications. For example, the uniformly sized and shaped nanodomains formed in the films have been used for nanolithography, nanoparticle synthesis, and high-density information storage media. Imperative to all of these applications, however, is a high degree of control over orientation of the nanodomains relative to the surface of the film as well as control over order in the plane of the film. Induced fields including electric, shear, and surface fields have been demonstrated to influence orientation. Both heteroepitaxy and graphoepitaxy can induce positional order on the nanodomains in the plane of the film. This article will briefly review a variety of mechanisms for gaining control over block copolymer order as well as many of the applications of these materials. Particular attention is paid to the potential of perfecting long-range two-dimensional order over a broader range of length scales and the extension of these concepts to functional materials and more complex architectures. #

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Section: Film Thicknessmentioning

confidence: 99%

Patterning with block copolymer thin films

Segalman

2005

Materials Science and Engineering: R: Reports

931

921

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“…[ 8 , 11 , 18-21 ] In the case of poly(styrene-b -methyl methacrylate) (PS-b -PMMA), the PMMA blocks preferentially interact with silicon substrates and results in a disadvantageous parallel orientation of the microstructure. [22][23][24] To achieve vertical orientation, one of the most successful strategies for large-area applications has been to neutralize the substrate with a random copolymer of poly(styrene-methyl methacrylate) [P(S-r -MMA)].…”

Section: Introductionmentioning

confidence: 99%

Efficient Surface Neutralization and Enhanced Substrate Adhesion through Ketene Mediated Crosslinking and Functionalization

Jung

Leibfarth

Woo

et al. 2012

Adv Funct Materials

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Balancing the interfacial interactions between a polymer and substrate is one of the most commonly employed methods to ensure the vertical orientation of nanodomains in block copolymer lithography. Although a number of technologies have been developed to meet this challenge, there remains a need for a universal solution for surface neutralization that combines simple synthesis, fast processing times, generality toward substrate, low density of film defects, and good surface adhesion. The chemistry of ketenes, which combines highly efficient polymer crosslinking through dimerization and surface adhesion through reaction with the substrate, is shown to be well suited to the challenge. The versatile chemistry of ketenes are accessed through the post‐polymerization of Meldrum's acid, which can be easily incorporated into copolymers through controlled radical polymerization processes. Further, the Meldrum's acid monomer is synthesized on a large scale in one step without the need for chromatography. Processing times of seconds, low defect density, simple synthetic procedures, and good substrate adhesion make these materials attractive as robust block copolymer neutralization layers.

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“…3,4 Indeed, effective control over the spatial location and/or orientation of the nanofiller particles in PNCs offers great possibilities for dramatically improved composite properties. 1 In the block copolymer field, great strides have been made in developing techniques to globally orient the BCP microdomains using external fields 5 (e.g., shear 6 or electric fields 7 ) or surfaces, [8][9][10][11] even further enhancing the possibility for the creation of nanocomposites with precisely defined morphology.In this Communication, we present a general method for creation of aligned block copolymer/nanoparticle (BCP/NP) composites, although via something of an inverse approach: an external (magnetic) field is used to define the spatial orientation of rodshaped magnetic NPs, which then serve as structure-directing agents for neighboring BCP domains. Specifically, the oriented NPs, which are incorporated at a concentration of only a few percent, present templating surfaces for the alignment of cylindrical block copolymer nanodomains.…”

mentioning

confidence: 99%

Mutual Alignment of Block Copolymer−Magnetic Nanoparticle Composites in a Magnetic Field

et al. 2010

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For the past ∼30 years, polymer nanocomposites (PNCs) 1 and block copolymers (BCPs) 2 have represented two extremely active areas of research within the polymer science community. It was inevitable, then, that the two topics should overlap; block copolymer/nanoparticle composites represent a relatively new and exciting field in materials research. A large portion of such work has, to date, sought to employ the well-ordered microphaseseparated structures available in block copolymers as scaffolds to direct the spatial arrangement of the nanofiller. 3,4 Indeed, effective control over the spatial location and/or orientation of the nanofiller particles in PNCs offers great possibilities for dramatically improved composite properties. 1 In the block copolymer field, great strides have been made in developing techniques to globally orient the BCP microdomains using external fields 5 (e.g., shear 6 or electric fields 7 ) or surfaces, [8][9][10][11] even further enhancing the possibility for the creation of nanocomposites with precisely defined morphology.In this Communication, we present a general method for creation of aligned block copolymer/nanoparticle (BCP/NP) composites, although via something of an inverse approach: an external (magnetic) field is used to define the spatial orientation of rodshaped magnetic NPs, which then serve as structure-directing agents for neighboring BCP domains. Specifically, the oriented NPs, which are incorporated at a concentration of only a few percent, present templating surfaces for the alignment of cylindrical block copolymer nanodomains. In a sense, our approach is an extrapolation of the graphoepitaxy technique, which can be used to template BCP cylinder orientation in thin films, 10,11 to thicker films, and eventually into the bulk. The ability of rod-shaped NPs to nucleate coaxially oriented BCP cylinders has recently been established. 12,13 There has also been a fair amount of work using magnetic fields to orient block copolymers, although it is necessary to use copolymers which contain moieties or semicrystalline domains with appreciable magnetic susceptibility. 5,[14][15][16][17] In the absence of such a condition, we introduced the rod-shaped nanoparticles, which are capable of being magnetically aligned. Using this kind of scheme to induce reorientation in lyotropic liquid crystal/nanomagnet composites has also been demonstrated. 18,19 The composite under study consisted of a polystyrene-blockpoly(2-vinylpyridine) (PS-P2VP) diblock copolymer, which forms cylindrical microdomains of P2VP in a PS matrix, 20 and spindletype hematite (R-Fe 2 O 3 ) particles, which were synthesized by the forced hydrolysis of Fe(ClO 4 ) 3 , according to procedures previously described by Ocaña et al. 21 The particles, an example of which is shown in the transmission electron microscopy (TEM) image in Figure 1a, had an average diameter of 55 ( 6 nm and an average long axis length of 330 ( 38 nm (see the Supporting Information, Figure S1). Such hematite particles are weakly ferromagnetic and hav...

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Characteristics of the surface-induced orientation for symmetric diblock PS/PMMA copolymers

Cited by 310 publications

References 4 publications

Patterning with block copolymer thin films

Patterning with block copolymer thin films

Efficient Surface Neutralization and Enhanced Substrate Adhesion through Ketene Mediated Crosslinking and Functionalization

Mutual Alignment of Block Copolymer−Magnetic Nanoparticle Composites in a Magnetic Field

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