title: Spontaneous phase transformation and exfoliation of rectangular single-crystal zinc hydroxy dodecylsulfate nanomembranes.
abstract: Free-standing two-dimensional (2D) nanostructures, exemplified by graphene and semiconductor nanomembranes, exhibit exotic electrical and mechanical properties and have great potential in electronic applications where devices need to be flexible or conformal to nonplanar surfaces. Based on our previous development of a substrate-free synthesis of large-area, free-standing zinc hydroxy dodecylsulfate (ZHDS) hexagonal nanomembranes, herein, we report a spontaneous phase transformation of ZHDS nanomembranes under extended reaction time. The hexagonal ZHDS sheets transformed into rectangular single crystal nanomembranes with sizes of hundreds of micrometers. They contain long-range-ordered zinc vacancies that can be fitted into an orthorhombic superlattice. A surplus of dodecylsulfate ions and a deficit of Zn(2+) diffusion near the water surface are believed to be the factors that drive the phase transformation. The phase transformation starts with the formation of zinc vacancies at the topmost layer of the hexagonal hillock, and propagates along the spiral growth path of the initial hexagonal sheets, which bears a great resemblance to the classic "periodic slip process". Mechanical property characterization of ZHDS nanomembranes by nanoindentation shows they behave much like structural polymers mechanically due to the incorporation of surfactant molecules. We also developed a one-step exfoliation and dehydration method that converts ZHDS nanomembranes to ZnO nanosheets using n-butylamine. This work provides a further understanding of the growth and stability of ZnO-based nanomembranes, as well as advisory insight for the further development on solution-based synthesis of free-standing, single-crystalline 2D nanostructures.
authors.affiliation: Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
authors.forename: Fei
authors.initials: F
authors.lastname: Wang
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Jakes
authors.forename: Dalong
authors.initials: D
authors.lastname: Geng
authors.forename: Xudong
authors.initials: X
authors.lastname: Wang
mesh_terms: D055119:Elastic Modulus; D006244:Hardness; D008422:Materials Testing; D008567:Membranes, Artificial; D053768:Metal Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size; D044367:Phase Transition; D013499:Surface Properties; D014867:Water / Q000737:chemistry*; D017967:Zinc Compounds / Q000737:chemistry*
chemical_list: D008567:Membranes, Artificial; D017967:Zinc Compounds; D014867:Water