Plenty of Room at the Top: A Multi-Scale Understanding of nm-Resolution Polymer Patterning on 2D Materials.

Lamellar phases of alkyldiacetylenes in which the alkyl chains lie parallel to the substrate represent a straightforward means for scalable 1-nm-resolution interfacial patterning. This capability has the potential for substantial impacts in nanoscale electronics, energy conversion, and biomaterials design. Polymerization is required to set the 1-nm functional patterns embedded in the monolayer, making it important to understand structure-function relationships for these on-surface reactions. Polymerization can be observed for certain monomers at the single-polymer scale using scanning probe microscopy. However, substantial restrictions on the systems that can be effectively characterized have limited utility. Here, using a new multi-scale approach, we identify a large, previously unreported difference in polymerization efficiency between the two most widely used commercial diynoic acids. We further identify a core design principle for maximizing polymerization efficiency in these on-surface reactions, generating a new monomer that also exhibits enhanced polymerization efficiency.

Oleylamine Impurities Regulate Temperature-Dependent Hierarchical Assembly of Ultranarrow Gold Nanowires on Biotemplated Interfaces.

Nanocrystals are often synthesized using technical grade reagents such as oleylamine (OLAm), which contains a blend of 9-cis-octadeceneamine with trans-unsaturated and saturated amines. Here, we show that gold nanowires (AuNWs) synthesized with OLAm ligands undergo thermal transitions in interfacial assembly (ribbon vs. nematic); transition temperatures vary widely with the batch of OLAm used for synthesis. Mass spectra reveal that higher-temperature AuNW assembly transitions are correlated with an increased abundance of trans and saturated chains in certain blends. DSC thermograms show that both pure (synthesized) and technical-grade OLAm have primary melting transitions near -5 °C (20-30 °C lower than the literature melting temperature range of OLAm). A second, broader melting transition (in the previous reported melting range) appears in technical grade blends; its temperature varies with the abundance of trans and saturated chains. Our findings illustrate that, similar to biological membranes, blends of alkyl chains can be used to generate mesoscopic hierarchical nanocrystal assembly, particularly at interfaces that further modulate transition temperatures.

Large-Scale Noncovalent Functionalization of 2D Materials through Thermally Controlled Rotary Langmuir-Schaefer Conversion.

As two-dimensional (2D) materials are more broadly utilized as components of hybrid materials, controlling their surface chemistry over large areas through noncovalent functionalization becomes increasingly important. Here, we demonstrate a thermally controlled rotary transfer stage that allows areas of a 2D material to be continuously cycled into contact with a Langmuir film. This approach enables functionalization of large areas of the 2D material and simultaneously improves long-range ordering, achieving ordered domain areas up to nearly 10 000 µm2. To highlight the layer-by-layer processing capability of the rotary transfer stage, large-area noncovalently adsorbed monolayer films from an initial rotary cycle were used as templates to assemble ultranarrow gold nanowires from solution. The process we demonstrate would be readily extensible to roll-to-roll processing, addressing a longstanding challenge in scaling Langmuir-Schaefer transfer for practical applications.

Hierarchically patterned striped phases of polymerized lipids: toward controlled carbohydrate presentation at interfaces.

Complex biomolecules, including carbohydrates, frequently have molecular surface footprints larger than those in broadly utilized standing phase alkanethiol self-assembled monolayers, yet would benefit from structured orientation and clustering interactions promoted by ordered monolayer lattices. Striped phase monolayers, in which alkyl chains extend across the substrate, have larger, more complex lattices: nm-wide stripes of headgroups with 0.5 or 1 nm lateral periodicity along the row, separated by wider (∼5 nm) stripes of exposed alkyl chains. These anisotropic interfacial patterns provide a potential route to controlled clustering of complex functional groups such as carbohydrates. Although the monolayers are not covalently bound to the substrate, assembly of functional alkanes containing an internal diyne allows such monolayers to be photopolymerized, increasing robustness. Here, we demonstrate that, with appropriate modifications, microcontact printing can be used to generate well-defined microscopic areas of striped phases of both single-chain and dual-chain amphiphiles (phospholipids), including one (phosphoinositol) with a carbohydrate in the headgroup. This approach generates hierarchical molecular-scale and microscale interfacial clustering of functional ligands, prototyping a strategy of potential relevance for glycobiology.

Spatially Controlled Noncovalent Functionalization of 2D Materials Based on Molecular Architecture.

Polymerizable amphiphiles can be assembled into lying-down phases on 2D materials such as graphite and graphene to create chemically orthogonal surface patterns at 5-10 nm scales, locally modulating functionality of the 2D basal plane. Functionalization can be carried out through Langmuir-Schaefer conversion, in which a subset of molecules is transferred out of a standing phase film on water onto the 2D substrate. Here, we leverage differences in molecular structure to spatially control transfer at both nanoscopic and microscopic scales. We compare transfer properties of five different single- and dual-chain amphiphiles, demonstrating that those with strong lateral interactions (e.g., hydrogen-bonding networks) exhibit the lowest transfer efficiencies. Since molecular structures also influence microscopic domain morphologies in Langmuir films, we show that it is possible to transfer such microscale patterns, taking advantage of variations in the local transfer rates based on the structural heterogeneity in Langmuir films. Nanoscale domain morphologies also vary in ways that are consistent with predicted relative transfer and diffusion rates. These results suggest strategies to tailor noncovalent functionalization of 2D substrates through controlled LS transfer.

Multimicrometer Noncovalent Monolayer Domains on Layered Materials through Thermally Controlled Langmuir-Schaefer Conversion for Noncovalent 2D Functionalization.

As functionalized 2D materials are incorporated into hybrid materials, ensuring large-area structural control in noncovalently adsorbed films becomes increasingly important. Noncovalent functionalization avoids disrupting electronic structure in 2D materials; however, relatively weak molecular interactions in such monolayers typically reduce stability toward solution processing and other common material handling conditions. Here, we find that controlling substrate temperature during Langmuir-Schaefer conversion of a standing phase monolayer of diynoic amphiphiles on water to a horizontally oriented monolayer on a 2D substrate routinely produces multimicrometer domains, at least an order of magnitude larger than those typically achieved through drop-casting. Following polymerization, these highly ordered monolayers retain their structures during vigorous washing with solvents including water, ethanol, tetrahydrofuran, and toluene. These findings point to a convenient and broadly applicable strategy for noncovalent functionalization of 2D materials in applications that require large-area structural control, for instance, to minimize desorption at defects during subsequent solution processing.