Inverted Wedding Cake Growth Operated by the Ehrlich-Schwoebel Barrier in Two-Dimensional Nanocrystal Evolution.

Wedding cake growth is a layer-by-layer growth model commonly observed in epitaxial growth of metal films, featured by repeated nucleation of new atomic layers on the topmost surface owing to the confinement of the Ehrlich-Schwoebel (ES) barrier. Herein, we report an inverted wedding cake growth phenomenon observed in two-dimensional nanostructure evolution. Through a dynamically controlled vapor-solid deposition process of ZnO, a unique basin-shaped crown was formed on the tip of each nanowire, featured with concentric steps. The atomic steps were nucleated along the edge and propagated toward the center. This is an opposite growth behavior compared to the conventional wedding cake growth, and is thus denoted as inverted wedding cake growth. Through the relation between the crown expansion rate and the temperature, the ES barrier of ZnO was determined to be 0.88 eV. The discovery of inverted wedding cake growth provided insight into the developing nanostructure growth mechanisms.

Nanometre-thick single-crystalline nanosheets grown at the water-air interface.

To date, the preparation of free-standing 2D nanomaterials has been largely limited to the exfoliation of van der Waals solids. The lack of a robust mechanism for the bottom-up synthesis of 2D nanomaterials from non-layered materials has become an obstacle to further explore the physical properties and advanced applications of 2D nanomaterials. Here we demonstrate that surfactant monolayers can serve as soft templates guiding the nucleation and growth of 2D nanomaterials in large area beyond the limitation of van der Waals solids. One- to 2-nm-thick, single-crystalline free-standing ZnO nanosheets with sizes up to tens of micrometres are synthesized at the water-air interface. In this process, the packing density of surfactant monolayers adapts to the sub-phase metal ions and guides the epitaxial growth of nanosheets. It is thus named adaptive ionic layer epitaxy (AILE). The electronic properties of ZnO nanosheets and AILE of other materials are also investigated.

Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns.

Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.

Development of lead iodide perovskite solar cells using three-dimensional titanium dioxide nanowire architectures.

Three-dimensional (3D) nanowire (NW) architectures are considered as superior electrode design for photovoltaic devices compared to NWs or nanoparticle systems in terms of improved large surface area and charge transport properties. In this paper, we report development of lead iodide perovskite solar cells based on a novel 3D TiO2 NW architectures. The 3D TiO2 nanostructure was synthesized via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) technique that also implemented the Kirkendall effect for complete ZnO NW template conversion. It was found that the film thickness of 3D TiO2 can significantly influence the photovoltaic performance. Short-circuit current increased with the TiO2 length, while open-circuit voltage and fill factor decreased with the length. The highest power conversion efficiency (PCE) of 9.0% was achieved with ∼ 600 nm long 3D TiO2 NW structures. Compared to other 1D nanostructure arrays (TiO2 nanotubes, TiO2-coated ZnO NWs and ZnO NWs), 3D TiO2 NW architecture was able to achieve larger amounts of perovskite loading, enhanced light harvesting efficiency, and increased electron-transport property. Therefore, its PCE is 1.5, 2.3, and 2.8 times higher than those of TiO2 nanotubes, TiO2-coated ZnO NWs, and ZnO NWs, respectively. The unique morphological advantages, together with the largely suppressed hysteresis effect, make 3D hierarchical TiO2 a promising electrode selection in designing high-performance perovskite solar cells.

Spontaneous phase transformation and exfoliation of rectangular single-crystal zinc hydroxy dodecylsulfate nanomembranes.

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.