Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Cui, Guihua; Fujikawa, Masamichi; Nagano, Shusaku; Sano, Masami; Takase, Hiroshi; Miyazaki, Tsukasa; Sakurai, Shinichi; Yamamoto, Katsuhiro

doi:10.1016/j.polymer.2014.01.060

Cited by 8 publications

(4 citation statements)

References 52 publications

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“…12 The morphologies formed in these thin films can be varied by controlling the vapor pressures and ratio of selective solvents, and often differ qualitatively from the bulk morphology. 24,33,61,[67][68][69] The morphology can even be changed reversibly upon further annealing in solvents with different selectivity. 24,32,70 The solvent plasticizes the film [71][72][73][74] raising its diffusivity and allowing ordering to occur even at ambient temperature.…”

Section: A Experimental Basismentioning

confidence: 99%

Simulation methods for solvent vapor annealing of block copolymer thin films

et al. 2015

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Recent progress in modelling the solvent vapor annealing of thin film block copolymers is examined in the context of a self-consistent field theory framework. Key control variables in determining the final microdomain morphologies include swelling ratio or swollen film solvent volume fraction, swollen film thickness, substrate and vapor atmosphere surface energies, effective volume fraction, and effective Flory-Huggins interaction parameter. The regime of solvent vapor annealing studied is where the block copolymer has a high enough Flory-Huggins parameter that ordered structures form during swelling and are then trapped in the system through quenching. Both implicit and explicit consideration of the solvent vapor is considered to distinguish the cases in which solvent vapor leads to a non-bulk morphology. Block-selective solvents are considered based on the experimental systems of polystyrene-b-polydimethylsiloxane annealed with toluene and heptane. The results of these simulations are compared with these experiments.

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Section: A Experimental Basismentioning

confidence: 99%

Simulation methods for solvent vapor annealing of block copolymer thin films

et al. 2015

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“…The capability to achieve a perpendicular orientation of the nanodomains is essential for their utilization as templates for subsequent additive or subtractive nanofabrication processes . Among the different strategies, surface neutralization through the grafting of a random copolymers (RCP) is the base option to balance the surface interactions. − Specifically, the quite similar surface energies of all-organic polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) BCPs are easily neutralized by grafting to the surface the appropriate poly(styrene- random -methyl methacrylate) P(S- r -MMA) RCP. − This benefit along with the good selective etching of the PMMA component with respect to the PS matrix and the chemical similarity with the standard photoresist materials lead to evaluate the integration of the PS–PMMA based copolymers in nanolithographic pilot lines for the manufacturing of structures with minimum dimensions around 10 nm. − …”

Section: Introductionmentioning

confidence: 99%

Enhanced Lateral Ordering in Cylinder Forming PS-b-PMMA Block Copolymers Exploiting the Entrapped Solvent

Seguini¹,

Zanenga²,

Giammaria

et al. 2016

ACS Appl. Mater. Interfaces

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The self-assembly of block copolymer (BCP) thin films produces dense and ordered nanostructures. Their exploitation as templates for nanolithography requires the capability to control the lateral order of the nanodomains. Among a multiplicity of polymers, the widely studied all-organic polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP can easily form nanodomains perpendicularly oriented with respect to the substrate, since the weakly unbalanced surface interactions are effectively neutralized by grafting to the substrate an appropriate poly(styrene-random-methyl methacrylate) P(S-r-MMA) random copolymer (RCP). This benefit along with the selective etching of the PMMA component and the chemical similarity with the standard photoresist materials deserved for PS-b-PMMA the role of BCP of choice for the technological implementation in nanolithography. This work demonstrates that the synergic effect of thermal annealing with the initial solvent naturally trapped in the basic RCP + BCP system after the deposition process can be exploited to enhance the lateral order. The solvent content embedded in the total RCP + BCP system can be tuned by changing the molecular weight and thus the thickness of the grafted RCP brush layer, without introducing external reservoirs or dedicated setup and/or systems. The appropriate supply of solvent supports a grain coarsening kinetics following a power law with a 1/3 growth exponent for standing hexagonally ordered cylinders.

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“…Previous SVA studies have reported that BCP nanostructures with various orientations can be obtained by controlling solvent selectivity, − ,,, swelling ratio (SR) of BCP films, , annealing time, ,, and/or initial spin-coating state (film thickness and solvent removal rate). While many successful orientation controls have been reported, they have not considered the aforementioned factors comprehensively, and sometimes seemingly conflicting results have been reported. − , …”

Section: Introductionmentioning

confidence: 99%

Orientation of Microphase in Polystyrene-b-polyisoprene Thin Film under Solvent Vapor Annealing

Lee

Park

et al. 2020

Macromolecules

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We investigated the microphase in thin films of polystyrene-b-polyisoprene showing cylinder morphology to elucidate the orientation mechanism of the cylinder phase during solvent vapor annealing (SVA). For the purpose, we examined the effects of swelling ratio of the film, annealing time, and selectivity of the solvent as well as molecular weight and composition of the block copolymers on the orientation of the nanostructure using grazing incidence small-angle X-ray scattering and transmission electron microscopy. In general, the orientation of the cylinders proceeds from disordered state in a spin-coated film to horizontally oriented cylinder phase via vertically oriented cylinder phase. The rate of the orientation change is strongly affected by the SVA condition as well as the nature of the block copolymers. The orientation change rate is slower for higher molecular weight block copolymers under a more selective solvent and at a lower swelling ratio seemingly due to the low mobility of polymer chains. Therefore, the vertically oriented cylinder morphology is more favorably observed at these SVA conditions while the general orientation behavior is the same regardless of the SVA condition and the nature of the block copolymers.

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Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Cited by 8 publications

References 52 publications

Simulation methods for solvent vapor annealing of block copolymer thin films

Simulation methods for solvent vapor annealing of block copolymer thin films

Enhanced Lateral Ordering in Cylinder Forming PS-b-PMMA Block Copolymers Exploiting the Entrapped Solvent

Orientation of Microphase in Polystyrene-b-polyisoprene Thin Film under Solvent Vapor Annealing

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