Crystallization of molecular layers produced under confinement onto a surface

resumo

It is well known that molecules confined very close to a surface arrange into molecular layers. Because solid-liquid interfaces are ubiquitous in the chemical, biological and physical sciences, it is crucial to develop methods to easily access molecular layers and exploit their distinct properties by producing molecular layered crystals. Here we report a method based on crystallization in ultra-thin puddles enabled by gas blowing, which allows to produce molecular layered crystals with thickness down to the monolayer onto a surface, making them directly accessible for characterization and further processing. By selecting four molecules with different types of polymorphs, we observed exclusive crystallization of polymorphs with Van der Waals interlayer interactions, which have not been observed with traditional confinement methods. In conclusion, the gas blowing approach unveils the opportunity to perform materials chemistry under confinement onto a surface, enabling the formation of distinct crystals with selected polymorphism. Molecules arranged in close proximity to a surface form molecular layers, exhibiting distinct properties. However, the creation of these layers is challenging. Here, the authors present a technique for generating molecular layers through crystallization induced by gas blowing onto a surface.

palavras-chave

LIQUID-METAL; THIN-FILMS; POLYMORPHISM; TRANSITIONS; NUCLEATION; TRANSPORT; CRYSTALS; GLYCINE; FORCES; GROWTH

categoria

Science & Technology - Other Topics

autores

Tong, JC; de Bruyn, N; Alieva, A; Legge, EJ; Boyes, M; Song, XJ; Walisinghe, AJ; Pollard, AJ; Anderson, MW; Vetter, T; Melle-Franco, M; Casiraghi, C

Grupos

G6 - Materiais Virtuais e Inteligência Artificial

Projectos

Projeto de Investigação Exploratória: Manuel Melle (IF Manuel Melle)

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

Engineered Conductive Proteins for Bioelectronics (E-PROT)

agradecimentos

J.T. thanks Michael L. Turner, Amadou Doumbia and Jingzhen Du for useful discussion. A.J.P. acknowledges Keith Paton for discussions on the manuscript. C.C. acknowledges useful discussions with Kostya Novoselov, Paolo Samori and Laura Fumagalli on the manuscript. This work is supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme under grants agreement No 648417 and by the UKRI (Grant EP/X028844/1). J.T. acknowledges the University of Manchester for the President Scholarship Award (PDSA). N.d.B acknowledges support from the ESPRC (i-Case Award). E.J.L and A.J.P. acknowledge funding from the National Measurement System of the Department of Business, Energy and Industrial Strategy (BEIS), U.K, from Grant 124089. E.J.L. acknowledges funding the EPSRC for funding a DOCCAT collaboration and support from Grants EP/R025304/1 and EP/L02263X/1. T.V. thanks the Royal Academy of Engineering for the support through an Engineering for Development research fellowship (Grant No. RF1516/15/22). M.M-F. acknowledges support from the project IF/00894/2015 and within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC) and from the European Union's Horizon 2020 Research and Innovation Programme under Grant Agreement No. 964593.