Bridging the gap between the mesoscopic 2D order–order transition and molecular-level reorganization in dot-patterned block copolymer monolayers
dc.contributor.author | Richard-Lacroix, Marie | |
dc.contributor.author | Borozenko, Kateryna | |
dc.contributor.author | Pellerin, Christian | |
dc.contributor.author | Bazuin, Geraldine | |
dc.date.accessioned | 2021-07-07T19:37:20Z | |
dc.date.available | NO_RESTRICTION | fr |
dc.date.available | 2021-07-07T19:37:20Z | |
dc.date.issued | 2016-11-21 | |
dc.identifier.uri | http://hdl.handle.net/1866/25336 | |
dc.publisher | American Chemical Society | fr |
dc.subject | Block copolymers | fr |
dc.subject | Langmuir-Blodgett monolayers | fr |
dc.subject | Supramolecular complexes | fr |
dc.subject | Order-order transition | fr |
dc.subject | Infrared spectroscopy | fr |
dc.title | Bridging the gap between the mesoscopic 2D order–order transition and molecular-level reorganization in dot-patterned block copolymer monolayers | fr |
dc.type | Article | fr |
dc.contributor.affiliation | Université de Montréal. Faculté des arts et des sciences. Département de chimie | fr |
dc.identifier.doi | 10.1021/acs.macromol.6b01980 | |
dcterms.abstract | Langmuir–Blodgett (LB) films of amphiphilic block copolymers (BCs) form well-defined nanostructures with long-range order useful, for instance, for nanolithography applications. Nanostructures with a 2D circular micelle (“dot”) morphology are known to present a constant pressure plateau in their Langmuir isotherm (surface pressure vs molecular area curve at the air/water interface), indicative of a first-order transition. We have previously shown, with LB films of polystyrene-b-poly(4-vinylpyridine) (PS-P4VP) and its supramolecular complex with 3-n-pentadecylphenol (PDP), that there is an order–order transition of the dots from hexagonal to square at the plateau. However, various literature results indicate that the molecular-level understanding of the transition is poorly understood. Here, using polarized infrared spectroscopy on the PS-P4VP/PDP system, we identify what molecular changes occur at the plateau. The only changes found are an edge-on to isotropic orientation of the pyridine rings and an increase in the level of P4VP hydrogen bonding with PDP; no changes are found in alkyl chain conformation or orientation. On the basis of these results and AFM observations of the film morphologies, we propose a new mechanism involving 2D to 3D folding of the P4VP chains on the water surface at the plateau pressure that connects the molecular changes with the hexagonal-square reorganization of the dot array. We further show how the model can be generalized to dot-forming LB films of pure PS-P4VP and other BC systems and even to BC monolayers obtained by spin-coating from dilute solutions. This study thus lays the foundation for a generalized fundamental understanding of dot-forming LB block copolymer films and enables predicting their behavior in order to precisely control their organization and, ultimately, their properties at different length scales. | fr |
dcterms.isPartOf | urn:ISSN:0024-9297 | fr |
dcterms.isPartOf | urn:ISSN:1520-5835 | fr |
dcterms.language | eng | fr |
UdeM.ReferenceFournieParDeposant | 10.1021/acs.macromol.6b01980 | fr |
UdeM.VersionRioxx | Version acceptée / Accepted Manuscript | fr |
oaire.citationTitle | Macromolecules | fr |
oaire.citationVolume | 49 | fr |
oaire.citationIssue | 23 | fr |
oaire.citationStartPage | 9089 | fr |
oaire.citationEndPage | 9099 | fr |
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