Phase Behavior of Solvent Vapor Annealed Thin Films of PS-<i>b</i>-P4VP(PDP) Supramolecules

Zoelen, Wendy van; Asumaa, Terhi; Ruokolainen, Janne; Ikkala, OlliI; Brinke, G. ten

doi:10.1021/ma702780c

Cited by 122 publications

(158 citation statements)

References 57 publications

(142 reference statements)

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“…It was observed that the P4VP(PDP) was present at the SiO 2 interface as well as the air interface, implying symmetric boundary conditions, and the morphologies depended on the chloroform vapor pressure as well as on the formation of terraces. 33 However, there have been limited reports on controlling the supramolecular assemblies over multiple length scales, in particular the assembly of small molecules within the microdomains, thereby achieving hierarchically ordered structures. Moeller et al investigated the thin film morphologies of wedgeshaped liquid crystalline amphiphilic molecules complexed with poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP-b-PEO) diblock copolymer via proton transfer.…”

Section: Introductionmentioning

confidence: 99%

Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

et al. 2008

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The hierarchical assemblies of supramolecules, which consisted of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) with 3-pentadecylphenol (PDP) hydrogen-bonded to the 4VP, were investigated in thin films after solvent annealing in a chloroform atmosphere. The synergistic coassembly of PS-b-P4VP and PDP was utilized to generate oriented hierarchical structures in thin films. Hierarchical assemblies, including lamellae-within-lamellae and cylinders-within-lamellae, were simultaneously ordered and oriented from a few to several tens of nanometers over macroscopic length scales. The macroscopic orientation of supramolecular assembly depends on the P4VP(PDP) fraction and can be tailored by varying the PDP to P4VP ratio without interfering with the supramolecular morphologies. The lamellar and cylindrical microdomains, with a periodicity of ∼40 nm, could be oriented normal to the surface, while the assembly of comb blocks, P4VP(PDP), with a periodicity of ∼4 nm, were oriented parallel to the surface. Furthermore, using one PS-b-P4VP copolymer, thin films with different hierarchical structures, i.e., lamellae-withinlamellae and cylinders-within-lamellae, were obtained by varying the ratio of PDP to 4VP units. The concepts described in these studies can be potentially applied to other BCP-based supramolecular thin films, thus creating an avenue to functional, hierarchically ordered thin films.

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Section: Introductionmentioning

confidence: 99%

Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

et al. 2008

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“…Because of the selectivity of chloroform towards PS, the morphology of the large length scale could be changed by annealing at different vapor pressures, which, for a specific strongly segregated system that was on the boundary between lamellar and cylindrical, resulted in terraces of metastable perpendicular lamellae. 138 The morphology of the short length scale was however not observed. In a different study, which focused on low molecular weight systems with a large P4VP(PDP) fraction, the short length scale was observed in the form of hierarchical terrace formation.…”

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confidence: 97%

“…Thin films of PS-b-P4VP(PDP) supramolecules have been investigated by van Zoelen et al and Tung et al [138][139][140] In a study on solvent annealed systems of high molecular weight asymmetric comb copolymers with a small P4VP(PDP) block on silicon, the presence of PDP induced enough mobility to induce structure formation in the high molecular weight ($320 000 g mol À1 ) block copolymer. Furthermore, it was found that as opposed to pure PS-b-P4VP diblock copolymers, which exhibit asymmetric wetting conditions (PS wets the surface and P4VP the substrate), the P4VP(PDP) comb wetted both the substrate and the air interface due to the low surface energy of PDP, which shielded P4VP from the surface.…”

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confidence: 99%

Thin films of complexed block copolymers

2009

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Due to their ability to microphase separate into well ordered structures with periodicities on the nanometre scale, block copolymers have received widespread attention as building blocks for the fabrication of nanomaterials. In particular, thin films of block copolymers promise new technological breakthroughs in e.g. computer memory applications. This Review gives a short overview of progress that has been made in preparing suitable thin films of conventional coil-coil diblock copolymer systems, while the advantages as well as the complexities of using more unconventional systems such as triblock copolymers and supramolecular systems are emphasized. Gerrit tenBrinke obtained his PhD in Statistical Physics from the University of Groningen, The Netherlands. He spent two years as a postdoctoral fellow at the University of Massachusetts at Amherst. In 1985 he became Associate Professor in the Polymer Department of the University of Groningen and in 1996 Professor. During 1994-1999 he was also part time Professor at the Helsinki University of Technology working closely together with Olli Ikkala. His research interests are self-assembly in complex polymer systems.

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“…The most commonly reported small molecules for such supramolecular complexes are 2-(4′-hydroxybenzeneazo)benzoic acid (HABA) and 3-pentadecylphenol (PDP). Tung et al [21,31] and ten Brinke et al [32,33] have investigated the structure-within-structure morphologies in thin films involving the interaction of PDP with P4VP. Tung et al have demonstrated the correlation between the morphology orientation in thin films and the volume fraction of P4VP/PDP block [21].…”

Section: Introductionmentioning

confidence: 99%

“…Tung et al have demonstrated the correlation between the morphology orientation in thin films and the volume fraction of P4VP/PDP block [21]. Ten Brinke and coworkers have reported the terrace formation in thin films comprising P4VP/PDP supramolecular assemblies [32]. Stamm and coworkers realized homogeneous thin films from the supramolecular assembly of PS-b-P4VP and HABA [17,18,[34][35][36].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Assemblies from Poly(styrene)-block-poly(4-vinylpyridine) Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

2013

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Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA), with poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine) (P4VP) blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS) corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

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Phase Behavior of Solvent Vapor Annealed Thin Films of PS-b-P4VP(PDP) Supramolecules

Cited by 122 publications

References 57 publications

Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

Thin films of complexed block copolymers

Supramolecular Assemblies from Poly(styrene)-block-poly(4-vinylpyridine) Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

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