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Nanosheets and Stacked Nanodisks
“Supramolecular precursors for the synthesis of anisotropic nanocrystals“ Whitney Bryks, Melissa Wette, Nathan Velez, Su-Wen Hsu and Andrea R. Tao. J. Am. Chem. Soc., 2014, 136 (17), pp 6175
In the past, copper sulfide nanomaterials have been used in photovoltaics, battery electrodes and electrochemical sensors. Recently, colloidal chalcocite (Cu2S) nanocrystals have drawn attention for their ability to support the excitation of localized surface plasmon resonance. However, a large barrier in the application of Cu2S as a plasmonic material stems from the difficulty of assembling Cu2S anisotropic structures consisting of either shells, rods, wires or disks. Andrea R. Tao and her team at University of California, San Diego have developed a method to create nanosheets and stacked nanodisks of Cu2S via solventless thermolysis, which they hope can be applied to work as plasmonic materials.
To control the shape that was formed with the Cu2S nanocrystals, Cu thiolates that adopt lamellar, micellar and isotropic phases in various thermolysis reactions were used to template the nucleation and growth of solid-state Cu2S nanocrystals. Cu2S was formed by melting various copper alkanethiolates, CuSC12H25, CuSC4H9 and CuSC16H33. The copper alkanethiolates entered a mesogenic phase due to their hydrophobic interactions between neighboring alkane chains and strong metal-sulfur coordination resulting in the Cu2S. Afterwards, thermolysis occurred at temperatures much higher than the melting points. It was found that each Cu2S precursor resulted in a different Cu2S nanocrystal structure. The initial phase of the alkanethiolates determined the final anisotropic structure of the nanocrystals into either nanosheets or stacked nanodisks, as seen in Fig 1.
The chain length of the copper alkanethiolates directly affected the Cu2S nanocrystal template. The longer chained alkanethiolates CuSC12H25 and CuSC16H25 formed nanodisks due to micellar columns forming at 140C. The short-chained alkanethiolates CuSC4H9 formed the nanosheets during a smectic-like lamellar phase carried out at 160C. Both morphologies can be seen in Fig 1. These findings can lead to synthetically generated nanocrystal morphologies that can be applied to plasmonic nanoelectronic and optoelectric devices.
The full article can be found here: http://pubs.acs.org/doi/ipdf/10.1021/ja500786p
Smalykuh, Ivan I, Angel Martinez, Miha Ravnik, Bruce Lucero, Rayshan Visvanathan and Slobodan Zumer. Nature Materials, 2014
Designing and assembling three-dimensional (3D) structures of low-symmetry colloidal particles is challenged by the lack of systems and techniques that allow for controlling their spatial arrangements. When considering the nanoscale confinement and mesoscale self-assembly of nanoparticles in liquid crystal, the types and the arrangements of the spatial defects are both important to keep in mind upon the construction of 3D patterns. Ivan I. Smalyukh and his team in the University of Colorado, Boulder have developed a system that enables the generation and control of 3D patterns found in knotted nematic colloids. This work can be used to predict configurations of looped line defects and the interplay of topologies of knotted surfaces, fields and defects.
Rigid particles were obtained by using a two-photon photopolymerization with spatially patterned pulsed femtosecond laser light. This method allowed the team to construct particles with the topology of colloidal knots. Consisting of polymeric tubes, the particles are looped p times with q revolutions, T(p,q), about the colloidal rotational symmetry axis. Examples of colloidal knots can be seen in Fig. 2. Various configurations of knots even became mutually tangled when constructed in large quantities. The particles’ molecular orientations and points of incompatibility with the nematic liquid crystal resulted in point defects called “boojums”.
The team found that boojums around different knots could be specifically characterized both by the number of times the director rotates as one circumnavigates the defect core and by the bulk topological charge. The overall interplay of these particle topologies with the liquid crystal was controlled by the varying surface boundary conditions. This approach to a predictable way of experimenting with knotted colloids can lead to uses involving self-assembly of metal and semiconductor nanoparticles possibly applied to information displays, metamaterials and data storage.
Daniel A. Beller, Mohamed A. Gharbi, Apiradee Honglawan, Kathleen J. Stebe, Shu Yang, and Randall D. Kamien. Phys. Rev. x 3, 041026 (2013).
Focal conic domains (FCDs) in smectic-A liquid crystals have the ability to direct the assembly of micro- and nanomaterials. FCDs can arrange themselves in a fan-like texture comprised of focal curve pairs, the hyperbolae of which intersect at a single point, and can be used to form things like microlens arrays. In contrast to the fan-like texture, the patterns studied by the authors take on a flower-like appearance, created by using curved interfaces to confine smectic LCs into the desired pattern.
The researchers, working at the University of Pennsylvania, present two systems exhibiting this flower-like pattern. In system A, a large colloidal inclusion was placed in the LC, causing the FCDs to arrange themselves radially around the particle (Fig 1). In system B, patches of SiO2 nanoparticles on the surface were used to promote degenerate planar anchoring of the smectic layers, causing the layers to bend (Fig 2). In both systems, the flower texture was observed, with thickness decreasing as distance from the center increased. In system A, the researchers show that it’s not the LC anchoring to the colloid that causes the flower texture, but the colloid’s wetting chemistry that deforms the LC-air interface. In system B, the flower texture was produced by the same geometry present in system A, but due to the bend of the LC layers, the geometry is upside down. The researchers found the flower texture in both systems to be the result of the outward tilt of the normal vector of the homeotropic interface.
These patterns of self-organization could be controlled by manipulating the eccentricity of the FCDs, which varied with the curvature of the homeotropic interface. The resulting orientation mismatch between the hybrid aligning surfaces of a smectic thin film produced changes in the overall texture of the system. The authors suggest future research can focus on self assembly and using arrangements of smectic-a liquid crystals to guide the assembly of other materials, including colloids and nanoparticles.