Simulation methods for solvent vapor annealing of block copolymer thin films

Hannon, Adam F.; Bai, Wubin; Alexander‐Katz, Alfredo; Ross, Caroline A.

doi:10.1039/c5sm00324e

Cited by 38 publications

(61 citation statements)

References 88 publications

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“…It has been shown theoretically [27] and experimentally [28,29] that amphiphilic micelles can undergo surface reorganization in response to different environmental conditions. Intriguingly, when the hierarchically assembled rings composed of pure PS bP4VP micelles or PSbP4VP/HAuCl 4 ·xH 2 O micelles were exposed to ethanol or acidic water, corecorona inversion of micelles within the rings occurred in pure PSbP4VP micelles, in which the brighter PS cores were surrounded by the darker P4VP coronas (Figure 3a,c), while such corecorona inver sion was suppressed in PSbP4VP/HAuCl 4 ·xH 2 O micelles (Figure 4a,d).…”

Section: Doi: 101002/marc201900525mentioning

confidence: 99%

A Simple Route to Hierarchical Rings of Diblock Copolymer Micelles

Yin

Peng

2019

Macromol. Rapid Commun.

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for use in catalysis and optoelectronic materials, etc. [7] As the fabrication of litho graphic templates usually invokes costly and multistep procedures, it is highly desirable to employ nonlithographic tem plates for creating hierarchically assem bled micelles."Breath figure" method has been widely recognized as an extremely simple and nonlithographic route to yield intriguing 2D or 3D honeycomb structures. [8][9][10] This approach involves evaporating a layer of solution that spreads on a flat support under a flow of moist gas. When solvent and water droplets evaporate completely, an ordered honeycomb array of macro porous films is formed. Notably, this is a onestep selfassembly process, which can be readily extended to a diversity of mate rials. [11][12][13][14][15][16][17] It is interesting to note that when decreasing the concentration of sol utes, the honeycomb films can transform into a set of isolated rings. [18,19] However, hierarchically assem bled rings composed of block copolymer micelles in breath figure method have not yet been largely explored.Herein, we report on a simple route to crafting hierar chically necklacelike structures of an amphiphilic diblock copoly mer (i.e., polystyreneblockpoly(4vinylpyridine) (PS bP4VP)) micelles by combining two concurrent selfassembling processes at different scales, namely, the breath figure strategy of the PSbP4VP solution evaporating in humid air to form rings at the microscopic scale and a spontaneous selfassembly of PSbP4VP micelles within individual ring at the nanometer scale. Remarkably, hierarchical gold necklacelike assemblies or lightemitting assemblies can be also produced by evapo rating the PSbP4VP/gold precursor solution or PSbP4VP/ fluorescent dyes solution in humid air. Quite intriguingly, corecorona inversion of micelles within the rings occurred in response to P4VPselective solvents, while such corecorona inversion was prohibited when the PSbP4VP micelles were loaded with gold precursors. A model is proposed to rationalize the occurrence or inhibition of corecorona inversion within the micelles. This simple and facile strategy may be potentially applicable to assemble a set of functional block copolymer micelles and inorganic nanocrystals into hierarchical organicinorganic nanohybrid rings for a wide range of applications in optics, electronics, optoelectronics, sensory devices, etc.As toluene is a selective solvent for the PS block while a poor solvent for the P4VP block, spherical micelles with an average diameter of ≈52 nm were formed in toluene, consisting of A hierarchically assembled necklace composed of amphiphilic diblock copoly mer micelles is exquisitely produced by capitalizing on two concurrent self-assembly processes at different scales (i.e., "breath figure" strategy of diblock copolymer micelles solution evaporating in humid air to yield rings at the microscopic scale in conjunction with self-assembly of diblock copolymer micelles within individual ring at the nanometer scale). Intriguingly, hierarchical rings of diblock copolym...

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Section: Doi: 101002/marc201900525mentioning

confidence: 99%

A Simple Route to Hierarchical Rings of Diblock Copolymer Micelles

Yin

Peng

2019

Macromol. Rapid Commun.

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“…asymmetric DBCPs, was intensively studied [62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79]. Most of the confined copolymer films have been investigated in the weak segregation regime using SCFT [70,72,73,75,79,80] and DDFT [62,63,65,67,76,77]. The strong segregation regime was considered in computer simulations with the bond fluctuation model [66,78] as well as using thermodynamic scaling theories [68,69,74].…”

Section: Equilibrium Structure Of Dbcp Films In a Slitmentioning

confidence: 99%

“…Theoretical approaches to describe the role of the solvent in BCP thin films during SVA has only recently been attempted. A number of different approaches was used to understand the effect of a solvent in equilibrium [90][91][92][93][94][95] and at different stages of SVA [94,[96][97][98][99][100][101][102][103] on the structure and microdomain orientation in BCP thin films, using MD simulations [96,98,[100][101][102], MC simulations [90,91,95], the Flory-Huggins Cahn-Hilliard model [97], SCFT [80,92], DFT [93,103], DPD [94,102,104], and analytical theory [99,105]. Most of these studies consider the case of fast solvent evaporation resulting in a large gradient of the solvent concentration in the BCP film.…”

Section: Effect Of Solvent On the Structure Of Bcp Filmsmentioning

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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“…Despite the widespread use of SVA, a quantitative understanding of its effect in defect removal has not yet been established 1,3,17,21,22,[27][28][29][30][31] . The two principal problems are lack of standardized SVA processes and no rigorous understanding of the evolution of the nanostructure of the final dried film from its solvent-swollen state.…”

Section: Introductionmentioning

confidence: 99%

“…Most previous theoretical and computational studies use either self-consistent field theory or particle-based simulation methods that include a large number of molecular parameters [27][28][29][30][31] . Here, we propose an alternative continuum two-fluid model for SVA processes in BCP (b) A sketch of the temporal evolution of solvent volume fraction.…”

Section: Introductionmentioning

confidence: 99%

Defect Removal by Solvent Vapor Annealing in Thin Films of Lamellar Diblock Copolymers

Man

Doi

et al. 2019

Macromolecules

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Aviv University, Ramat Aviv 69978, Tel Aviv, Israel Solvent vapor annealing (SVA) is known to be a simple, low-cost and highly efficient technique to produce defect-free diblock copolymer (BCP) thin films. Not only can the solvent weaken the BCP segmental interactions, but it can vary the characteristic spacing of the BCP microstructures. We carry out systematic theoretical studies on the effect of adding solvent into lamellar BCP thin films on the defect removal close to the BCP order-disorder transition. We find that the increase of the lamellar spacing, as is induced by addition of solvent, facilitates more efficient removal of defects. The stability of a particular defect in a lamellar BCP thin film is given in terms of two key controllable parameters: the amount of BCP swelling and solvent evaporation rate. Our results highlight the SVA mechanism for obtaining defect-free BCP thin films, as is highly desired in nanolithography and other industrial applications.arXiv:1902.04753v3 [cond-mat.soft]

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Simulation methods for solvent vapor annealing of block copolymer thin films

Cited by 38 publications

References 88 publications

A Simple Route to Hierarchical Rings of Diblock Copolymer Micelles

A Simple Route to Hierarchical Rings of Diblock Copolymer Micelles

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

Defect Removal by Solvent Vapor Annealing in Thin Films of Lamellar Diblock Copolymers

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