An <i>in situ</i> GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in‐plane sphere order upon deswelling

Gunkel, Ilja; Gu, Xiaodan; Sun, Zhiwei; Schaible, Eric; Hexemer, Alexander; Russell, Thomas P.

doi:10.1002/polb.23933

Cited by 43 publications

(63 citation statements)

References 41 publications

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“…Solvent vapor annealing (SVA) is a widely used method to obtain highly ordered nanostructured BCP thin films, which also has been applied to modify the BCP thin film morphology . In recent years, the efficiency of this approach was improved by the so‐called warm or solvothermal vapor annealing (STVA) .…”

Section: Introductionmentioning

confidence: 99%

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures

Berezkin

Jung

Posselt

et al. 2018

Adv Funct Materials

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Solvothermal vapor annealing at elevated temperature is applied to a thin film from a cylinder-forming polystyrene-block-poly(dimethyl siloxane) (PS-b-PDMS) diblock copolymer. At this, the film is swollen in the vapor of n-heptane (highly selective for PDMS). This vapor is stepwise replaced by the vapor of toluene (weakly selective for PS). The morphologies are investigated using in situ, real-time grazing-incidence small-angle X-ray scattering (GISAXS). The initial cylindrical morphology is transformed into, among others, the lamellar one. This novel type of experiments allows probing a trajectory in the state diagram of the PS-b-PDMS/n-heptane/toluene mixture. To corroborate the morphologies, they are generated by molecular simulations, and the 2D GISAXS maps are calculated using the distorted-wave Born approximation. To relate the morphologies to the solvent distribution in the two types of nanodomains, the latter is estimated from the intensities of the Bragg reflections in the 2D GISAXS maps along with the swelling ratio of the film. Comparison with the results from a similar experiment carried out at room temperature results in the same sequence of morphologies; however, at elevated temperature, more well-ordered structures are obtained. This new approach proves to be efficient to achieve a block copolymer thin film having a desired morphology and orientation.

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Section: Introductionmentioning

confidence: 99%

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures

Berezkin

Jung

Posselt

et al. 2018

Adv Funct Materials

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“…In a recent study, Gunkel et al [197] found an in-plane restructuring of the P4VP spheres in a PS matrix. Swelling in THF (which is selective for the PS matrix) leads to hexagonally packed microdomains.…”

Section: Figure 16mentioning

confidence: 95%

“…SVA in combination with in-situ GISAXS has been shown to be able to alter the morphology of BCP thin films [144,193,194,197]. Using the same PMS-b-PHOST DBCP as described in (Figure 15, Table 3).…”

Section: Studies Aiming At Altering the Morphologymentioning

confidence: 99%

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Posselt

Zhang

Smilgies

et al. 2017

Progress in Polymer Science

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Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications, such as nanolithography and as nanotemplates, nanoporous membranes and sensors. Solvent vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of BCP thin films, e.g.,, by healing defects, by altering the orientation of the microdomains and by changing the morphology. Due to high time resolution and compatibility with SVA environments, grazing-incidence small-angle X-ray scattering (GISAXS) is an indispensable technique for studying the SVA process, providing information of the BCP thin film structure both laterally and along the film normal. Especially, state-of-the-art combined GISAXS/SVA setups at synchrotron sources have facilitated in-situ and real-time studies of the SVA process with a time resolution of a few seconds, giving important insight into the pathways and mechanisms of SVA induced restructuring. We give a short introduction to the GISAXS method and review recent theoretical studies, experimental techniques such as sample preparation and in-situ chambers together with SVA protocols, and we review and discuss experimental results. We conclude by giving an outlook on emerging developments of the in-situ real-time GISAXS scattering technique in combination with new approaches to control BCP thin film structures using SVA.

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“…GISAXS is a useful technique and it has been applied to many polymeric functional materials in the form of thin films . Especially for block copolymer thin films, it is a powerful method for analyzing nanostructure and its orientation . It should also be noted that time‐resolved GISAXS measurements have been conducted for analyzing nanostructure formation process during the spin‐cast process, during the slot‐die coating process and during the solvent vapor annealing process .…”

Section: Grazing‐incidence Saxsmentioning

confidence: 99%

“…Especially for block copolymer thin films, it is a powerful method for analyzing nanostructure and its orientation . It should also be noted that time‐resolved GISAXS measurements have been conducted for analyzing nanostructure formation process during the spin‐cast process, during the slot‐die coating process and during the solvent vapor annealing process . Future perspectives of this method enhanced using XFEL femtosecond pulses and full coherence have been presented in the review by Ree .…”

Section: Grazing‐incidence Saxsmentioning

confidence: 99%

Recent developments in polymer applications of synchrotron small‐angle X‐ray scattering

Sakurai

2016

Polymer International

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Synchrotron radiation facilities have been established and become very familiar in the polymer community not only from academic but also industrial viewpoints. It is not so unusual now to conduct simultaneous measurements of small-angle X-ray scattering (SAXS) with other techniques such as wide-angle X-ray scattering, stress-strain, light scattering, and so forth. New techniques have also been established and have become more familiar in recent years. In this review, recent developments in polymer applications of synchrotron SAXS are summarized. Instrumental developments and progress in data analyses are reviewed from the following aspects: ultra-small-angle X-ray scattering, anomalous SAXS, X-ray photon correlation spectroscopy, new types of simultaneous measurements, grazing-incidence SAXS, new trends in nanoparticle analyses and industrial applications.

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An in situ GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in‐plane sphere order upon deswelling

Cited by 43 publications

References 41 publications

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures

Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing

Recent developments in polymer applications of synchrotron small‐angle X‐ray scattering

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