Homogeneously Mixed Monolayers: Emergence of Compositionally Conflicted Interfaces

• Published in: Langmuir Vol. 33; no. 36; pp. 8839 - 8855
• Main Authors: Marquez, Maria D, Zenasni, Oussama, Jamison, Andrew C, Lee, T. Randall
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.09.2017
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/acs.langmuir.7b00755

The ability to manipulate interfaces at the nanoscale via a variety of thin-film technologies offers a plethora of avenues for advancing surface applications. These include surfaces with remarkable antibiofouling properties as well as those with tunable physical and electronic properties. Molecular self-assembly is one notably attractive method used to decorate and modify surfaces. Of particular interest to surface scientists has been the thiolate–gold system, which serves as a reliable method for generating model thin-film monolayers that transform the interfacial properties of gold surfaces. Despite widespread interest, efforts to tune the interfacial properties using mixed adsorbate systems have frequently led to phase-separated domains of molecules on the surface with random sizes and shapes depending on the structure and chemical composition of the adsorbates. This feature article highlights newly emerging methods for generating mixed thin-film interfaces, not only to enhance the aforementioned properties of organic thin films, but also to give rise to interfacial compositions never before observed in nature. An example would be the development of monolayers formed from bidentate adsorbates and other unique headgroup architectures that provide the surface bonding stability necessary to allow the assembly of interfaces that expose mixtures of chains that are fundamentally different in character (i.e., either phase-incompatible or structurally dissimilar), producing compositionally “conflicted” interfaces. By also exploring the prior efforts to produce such homogeneously blended interfaces, this feature article seeks to convey the relationships between the methods of film formation and the overall properties of the resulting interfaces.