Dewetting of Thin Diblock Copolymer Films:  Spinodal Dewetting Kinetics

Müller‐Buschbaum, Peter; Gutmann, Jochen S.; Lorenz-Haas, C.; Wunnicke, Odo; Stamm, Manfred; Petry, W.

doi:10.1021/ma010192y

Cited by 42 publications

(52 citation statements)

References 54 publications

(134 reference statements)

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“…To investigate the correlation of the dewetted holes along the film surface, fast Fourier transition (FFT) was performed by taking There is a peak at q = 0.0044 nm −1 , corresponding to the periodic structures with size of 1400 nm. The result makes it clear that the holes are correlated with each other, which is a typical symbol of spinodal dewetting or dewetting by means of composition fluctuation [27][28][29].…”

Section: Resultsmentioning

confidence: 92%

Stability and structure evolution in PMMA/SAN bilayer films upon solvent annealing

et al. 2016

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The stability of bilayer polymer films upon solvent annealing has been investigated with the help of atomic force microscopy (AFM) by taking PMMA [poly(methyl methacrylate), the upper layer] and SAN [poly(styrene-ran-acrylonitrile), the bottom layer] system as an example. Our results indicate that the stability and structure evolution depend crucially on the selectivity of the adopted annealing solvents. In the vapor of acetic acid (HAc, the selective solvent for PMMA), the upper PMMA layer dewets on the stable bottom SAN layer; upon annealing in 1, 2-dichlorobenzene (OBD, the selective solvent for SAN) vapor, the bilayer film remains stable because it is very hard for OBD molecules to penetrate and cross the upper PMMA layer. When dimethylformamide (exhibiting much higher solubility for SAN than PMMA) is used to anneal the specimen, the solvent molecules swell and cross the upper PMMA layer and enrich in the bottom SAN layer. As a result, SAN layer dewets the substrate, producing some SAN droplets while the upper PMMA is Bcarried^by the movement of SAN. This is the reason for the rupture of the upper film and the formation of BSAN droplets covered by PMMA islands.K eywords Dewetting . Bilayer . Solvent annealing . AFM . PMMA/SAN

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Section: Resultsmentioning

confidence: 92%

Stability and structure evolution in PMMA/SAN bilayer films upon solvent annealing

et al. 2016

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“…In many previous studies, the film instability of diblock copolymers has been investigated in disordered state above the ODT temperature . Recently, several studies reported hierarchical patterns formed as a result of dewetting and microphase separation in diblock copolymer thin films.…”

Section: Discussionmentioning

confidence: 99%

Dewetting and microphase separation in symmetric polystyrene‐block‐polyisoprene diblock copolymer ultrathin films

Cheng

Perahia

2015

Polymer International

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The kinetics of surface structure evolution in ultrathin films of low‐molecular‐weight polystyrene‐block‐polyisoprene (Mw: 7300 g mol−1–7300 g mol−1) diblock copolymer at temperatures below the bulk order‐to‐disorder transition temperature are presented. Films with two different thicknesses were studied as a function of annealing temperature using atomic force microscopy. These film thicknesses enabled the investigation of the competition between microphase separation and dewetting that resulted in two different morphologies: long‐range bicontinuous structures and random holes. Three distinctive stages of structure evolution were observed in bicontinuous structure, with the underlying mechanism compared with spinodal dewetting. Thicker films presented holes on their surfaces upon annealing at elevated temperatures, and kinetics of formation of the holes were discussed. We found that the molecular mobility determined the rates of dewetting, while the microphase separation hardly affected the dewetting process. © 2015 Society of Chemical Industry

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“…Little is understood about the film instability and dewetting of copolymer liquids . Despite experiments and theories on these instabilities, there remain discrepancies in the morphology and dynamics of dewetting between BCP liquids and simple polymer liquids.…”

Section: Introductionmentioning

confidence: 99%

Film Instability of Amphiphilic Block Copolymer Thin Films Driven by Solvent Annealing and Drying

Sun

Chen

Liou

et al. 2015

Macro Chemistry & Physics

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This paper investigates the film instability and structural evolution of solvent‐annealed polystyrene‐block‐poly(4‐vinylpyridine), P(S‐b‐4VP), as thin films of initially monolayer thickness on bare substrates (SiOx/Si) and substrates coated with end‐grafting PS (PS–SiOx/Si) under tetrahydrofuran vapor. At an early stage of solvent annealing, merging of nanospheres to form nanocylinders produces film rupture, creating small holes within a continuous layer. Because of the connectivity, the coalescence of incipient holes is driven by 2D pressure relaxation. Upon further iterative solvent annealing and drying, flat islands progressively grow outward at the expense of expanding holes until they contact with the edges of holes to form a network‐like cellular structure, and then decay into hemispherical droplets. The capillary driving forces associated with the negative excess interfacial entropy are responsible for the film instability of micelles on PS–SiOx/Si. In contrast, thin P(S‐b‐4VP) films on SiOx/Si reveal only small holes during iterative swelling and drying. The presence of these small holes is ascribed to an incomplete coverage during the merging of nanospheres and the anchoring of P(S‐b‐4VP) chains on SiOx/Si. Adsorption in micellar films has three important effects—retarding the motion of micelles, increasing the film stability, and favoring complete wetting.

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Dewetting of Thin Diblock Copolymer Films: Spinodal Dewetting Kinetics

Cited by 42 publications

References 54 publications

Stability and structure evolution in PMMA/SAN bilayer films upon solvent annealing

Stability and structure evolution in PMMA/SAN bilayer films upon solvent annealing

Dewetting and microphase separation in symmetric polystyrene‐block‐polyisoprene diblock copolymer ultrathin films

Film Instability of Amphiphilic Block Copolymer Thin Films Driven by Solvent Annealing and Drying

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