Building two-dimensional materials one row at a time: Avoiding the nucleation barrier

• Published in: Science (American Association for the Advancement of Science) Vol. 362; no. 6419; pp. 1135 - 1139
• Main Authors: Chen, Jiajun, Zhu, Enbo, Liu, Juan, Zhang, Shuai, Lin, Zhaoyang, Duan, Xiangfeng, Heinz, Hendrik, Huang, Yu, De Yoreo, James J.
• Format: Journal Article
• Language: English
• Published: United States The American Association for the Advancement of Science 07.12.2018; AAAS
• Subjects: Arrays; Assembly; Atomic force microscopy; Construction materials; Dimers; Free energy; Molecular dynamics; Molybdenum; Molybdenum disulfide; Nucleation; Nuclei; Peptides; Phage display; Phages; Two dimensional materials
• ISSN: 0036-8075; 1095-9203; 1095-9203
• DOI: 10.1126/science.aau4146

Classical nucleation theory predicts that two-dimensional islands on a surface must reach a critical size before they continue to grow; below that size, they dissolve. Chen et al. used phage display to select for short peptides that would bind to molybdenum disulfide (MoS 2 ) (see the Perspective by Kahr and Ward). Hexagonal arrays of these peptides grew epitaxially as dimers but without a size barrier—the critical nuclei size was zero. Although two-dimensional arrays formed, growth occurred one row at time. Classical nucleation theory indeed predicts the absence of a barrier for such one-dimensional growth. Science , this issue p. 1135 ; see also p. 1111 The barrier-free, row-by-row assembly of peptides on a MoS 2 surface confirms a prediction of classical nucleation theory. Assembly of two-dimensional (2D) molecular arrays on surfaces produces a wide range of architectural motifs exhibiting unique properties, but little attention has been given to the mechanism by which they nucleate. Using peptides selected for their binding affinity to molybdenum disulfide, we investigated nucleation of 2D arrays by molecularly resolved in situ atomic force microscopy and compared our results to molecular dynamics simulations. The arrays assembled one row at a time, and the nuclei were ordered from the earliest stages and formed without a free energy barrier or a critical size. The results verify long-standing but unproven predictions of classical nucleation theory in one dimension while revealing key interactions underlying 2D assembly.