Nanopatterning self-assembled nanoparticle superlattices by moulding microdroplets

Highly ordered arrays of nanoparticles exhibit many properties that are not found in their disordered counterparts. However, these nanoparticle superlattices usually form in a far-from-equilibrium dewetting process, which precludes the use of conventional patterning methods owing to a lack of control over the local dewetting dynamics. Here, we report a simple yet efficient approach for patterning such superlattices that involves moulding microdroplets containing the nanoparticles and spatially regulating their dewetting process. This approach can provide rational control over the local nucleation and growth of the nanoparticle superlattices. Using DNA-capped gold nanoparticles as a model system, we have patterned nanoparticle superlattices over large areas into a number of versatile structures with high degrees of internal order, including single-particle-width corrals, single-particle-thickness microdiscs and submicrometre-sized 'supra-crystals'. Remarkably, these features could be addressed by micropatterned electrode arrays, suggesting potential applications in bottom-up nanodevices.     

Synergism in binary nanocrystal superlattices leads to enhanced p-type conductivity in self-assembled PbTe/Ag2 Te thin films

The ordered cocrystallization of nanoparticles into binary superlattices enables close contact of nanocrystals with distinct physical properties, providing a route to 'metamaterials' design. Here we present the first electronic measurements of multicomponent nanocrystal solids composed of PbTe and Ag(2)Te, demonstrating synergistic effects leading to enhanced p-type conductivity. First, syntheses of size-tuneable PbTe and Ag(2)Te nanocrystals are presented, along with deposition as thin-film nanocrystal solids, whose electronic transport properties are characterized. Next, assembly of PbTe and Ag(2)Te nanocrystals into AB binary nanocrystal superlattices is demonstrated. Furthermore, binary composites of varying PbTe-Ag(2)Te stoichiometry (1:1 and 5:1) are prepared and electronically characterized. These composites show strongly enhanced (conductance approximately 100-fold increased in 1:1 composites over the sum of individual conductances of single-component PbTe and Ag(2)Te films) p-type electronic conductivity. This observation, consistent with the role of Ag(2)Te as a p-type dopant in bulk PbTe, demonstrates that nanocrystals can behave as dopants in nanostructured assemblies.     

Diffusion and filtration properties of self-assembled gold nanocrystal membranes

Close-packed nanoparticle monolayers have recently been shown to form mechanically robust, free-standing membranes. We report the first measurements of molecular transport through such ultrathin sheets, self-assembled from dodecanethiol-ligated gold nanocrystals. For aqueous solutions we find filtration coefficients 2 orders of magnitude larger than those observed in polymer-based filters, sieving of large solutes, and for smaller solutes a pronounced dependence of rejection on being charged. These results open up new possibilities for controlled delivery and separation of nano-objects.     

Impact of nanocrystallinity segregation on the growth and morphology of nanocrystal superlattices

A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtained. On increasing the amount of materials and the evaporation time, nanocrystal films with irregular outlines are produced together with close-packed 3D superlattices exhibiting a truncated-tetrahedral shape. Using low-frequency micro-Raman scattering spectroscopy and electron microscopy the building block nanocrystallinity is characterized. Spontaneous nanocrystallinity segregation is revealed： the truncated-tetrahedral supracrystals are shown to mainly contain single domain building blocks while the supracrystalline films are composed of a mixture of single domain and polycrystalline nanocrystals. This observation points out the correlation between the nanocrystallinity segregation involved in the growth of the nanocrystal superlattices and their morphology.     

Optical properties of self-assembled lateral superlattices in AlInAs epitaxial layers and AlAs/InAs short-period superlattices

Characterization of self-assembled lateral superlattices in AlInAs epitaxial layers and AlAs/InAs short-period superlattices is presented. These structures are spontaneously generated during the epitaxial growth by metal–organic chemical vapor deposition and molecular beam epitaxy. Transmission electron microscopy reveals the structural details and electro-modulated reflectance is used to characterize the energy and anisotropy of the optical transitions in the lateral superlattices. We demonstrate several properties of these self-assembled structures: (a) the band gap energy can be changed by as much as 350 meV, (b) the polarization anisotropy of the lowest energy transition exceeds 90%, (c) the superlattice axis and the direction of the optical anisotropy can be oriented along two non-equivalent directions in the plane of the substrate, and (d) the valence band splitting between heavy- and light-hole transitions is significant. We discuss the difference between the samples from the two growth techniques. Finally, we theoretically model the electronic states in these lateral superlattices and we demonstrate that the difference in average InAs composition between the well and barrier can be as high as 35%.     

Two-dimensional binary and ternary nanocrystal superlattices: the case of monolayers and bilayers

The modular assembly of multicomponent nanocrystal (NC) superlattices enables new metamaterials with programmable properties. While self-assembly of three-dimensional (3D) binary NC superlattices (BNSLs) has advanced significantly in the past decade, limited progress has been made to grow 2D BNSLs such as monolayers and bilayers over extended areas. Here, we report the growth of large-area (～ 1 cm(2)), transferable BNSL monolayers using the liquid-air interfacial assembly approach. The BNSL monolayers are formed by an entropy-driven assembly process with structures tunable by varying the NC size ratio. We further demonstrate the liquid-air interfacial assembly of BNSL bilayers which exhibit unique superlattice structures that have not been observed in the 3D BNSLs. As a further extension, bilayered ternary NC superlattices (TNSLs) are obtained by the cocrystallization of three types of NCs at the liquid-air interface.     

Pd grating obtained by direct micromolding for use in high resolution optical diffraction based sensing

Pd grating patterns have been fabricated using the process of micromolding in capillary employing a Pd alkanethiolate precursor, which could be converted to metal in situ by thermolysis. Thus generated Pd grating were uniform in width (~950?nm) and spacing (~450?nm) over millimeter square areas on glass substrates. Importantly, the pattern when used as an optical grating produced a diffraction pattern with a high resolution (>2000); the intensities of widely separated (diffraction angle, ~26·8°) diffracted spots could be measured using a simple photodiode. By varying the concentration of Pd precursor (2?mM to 25?mM), thickness of the resulting gratings could be adjusted in the range of ~15?C115?nm. By adjusting the grating parameters optimally, a maximum diffraction efficiency of 36% has been achieved. Thus fabricated Pd grating was used as seed catalyst to deposit Cu by electroless plating. The Cu deposition process has also been monitored by employing AFM, SEM and EDS analysis. The diffraction efficiency values corroborate well with the changes in the grating thickness due to Cu deposition. The grating structures presented can be reproducibly fabricated for rapidly emerging optical diffraction based sensing applications. This has been demonstrated in the case of aqueous Cu^2?+? by depositing the latter electrolessly on Pd.     

Tunable subpicosecond optoelectronic transduction in superlattices of self-assembled ErAs nanoislands

In applications as diverse as fibre-optic communications and time-domain or terahertz spectroscopy, researchers are keen on ultrafast optoelectronic transducers that can be tailored to specific needs. The molecular beam epitaxy of photoconductors composed of equidistant layers of self-assembled ErAs-islands in a III-V semiconductor matrix, which act as efficient non-radiative carrier capture sites, enables this flexibility. Here, photocurrent autocorrelation techniques are applied to metal-semiconductor-metal photodetectors patterned on ErAs:GaAs superlattices. The experiments demonstrate that the electrical response speed can be conveniently tuned over at least two orders of magnitude starting from 190 fs by increasing the thickness of the GaAs spacer separating adjacent ErAs layers. The same concept is applied to the narrower bandgap InGaAs matrix. We demonstrate an electron lifetime of approximately 1 ps for this material. This brings closer the prospect of implementing terahertz technology at the important optical communication wavelengths of 1.3 and 1.55 microm.     

Controlling self-assembled structure of Au nanoparticles by convective self-assembly with liquid-level manipulation

Microwire networks composed of noble metal particles are promising for the use of transparent conductive films. Bottom-up approaches can offer a route to establishing a fabrication technique that is robust and cost-effective, and template-assisted self-assembly techniques are widely used. However, they require additional processes to prepare templates and generally suffer from the difficulty in a large-scale fabrication. A template-free technique thus waits to be developed.In the present study, we explore a template free technique to fabricate colloidal networks of Au nanoparticles. We combine the convective self-assembly method with a liquid-level manipulation scheme in which the suspension is periodically pumped out. By using the technique, we successfully fabricate stripe, grid, and triangle patterns with controlled periodicity and examine the relationship between operation parameters and the resultant structures. We then measure the transparency and conductivity of a grid pattern to demonstrate the property as the transparent conductive film.     

Reduction of ordering temperature of self-assembled FePt nanoparticles by addition of Au and Ag

The [FePt]94Au6 and [FePt]90Ag10 nanoparticle arrays were synthesized on Si substrates by a reverse micellar method, combined with plasma treatment and in-situ deposition of a SiO2 overlayer, and the post annealing step was performed to drive the face-centered cubic to tetragonal phase transition. These FePt nanoparticles exhibit a quasi-hexagonal order with tailored inter-particle spacing and particle size. The effects of the Ag and Au on the structural and magnetic properties of FePt were investigated. The results indicate that both Au and Ag additives can remarkably enhance the coercivity and reduce the ordering temperature, however, the optimum composition is different for them. The optimum composition is determined to be [FePt]94Au6 and [FePt]90Ag10, respectively, for which the ordering temperature of FePt nanoparticles is reduced by -100 degrees C. After 600 degrees C annealing, the [FePt]94Au6 and [FePt]90Ag10 nanoparticles are totally ferromagnetic with apparent larger coercivities of -7.0 kOe, which is about 3.8 kOe larger than that of the pure FePt nanoparticles. The mechanism of the chemical ordering acceleration may be attributed to the defects and strains caused by the Au/Ag additives.     

Electronic properties of single Au nanocrystals and synthesis of 1-dimensional nanocrystal arrays

The current-voltage characteristics of citrate- and octanethiol-capped Au nanocrystals assembled on planar Au substrates under ambient conditions in air and in solution are reported. We have found that single electron tunneling (SET) behavior is observed for citrate-capped Au crystals in air. In high dielectric media, however, SET is only seen for nanocrystals protected by the hydrophobic alkane ligands and not for the relatively bare citrate-capped nanocrystals. In addition, we report a new strategy for assembling these nanocrystals into spatially well-organized 1-dimensional (1D) arrays. The method involves trapping the crystals inside 20 nm diameter pores of porous filtration membranes. The 1D linked nanocrystals confined inside the membrane pores were characterized by ultraviolet-visible spectroscopy. “Shrinkwrapping” the nanocrystals with the organic conductive polymer polypyrrole or covalently linking the particles with alkyldithiols and subsequent dissolution of the membrane provided a suspension suitable for characterization by transmission electron microscopy. These studies are important in determining the role of spatial arrangement and chemical environment on the electronic properties of this important class of crystalline material     

Photonic crystal waveguides by direct writing of e-beam on self-assembled photonic crystals

Direct electron beam lithography technique is used for writing a variety of waveguide structures on thin films of polymethyl methacrylate (PMMA) and self-assembled three-dimensionally ordered photonic crystals made up of PMMA colloidal spheres. The waveguide structures fabricated on both these type of samples are characterized by scanning electron microscope and optical microscope images.     

Denaturation and renaturation of self-assembled yeast iso-1-cytochrome c on Au

We have made surface plasmon resonance (SPR) measurements of yeast iso-1-cytochrome c (Cyt c) on a gold surface. Angle-resolved SPR curves are recorded as a function of urea concentration before and after self-assembly of the Cyt c. Exposure to a urea solution causes denaturation of Cyt c, which shifts the minimum in the SPR curve to a larger angle and decreases the signal amplitude. The Gibbs free energy change for denaturation of the protein on Au is calculated from the change of the SPR signal amplitude with urea concentration. We find that (1) Cyt c can be reversibly denatured and renatured, depending on the urea concentration, and (2) the Gibbs free energy change for denaturation of Cyt c on Au surface in water, DeltaG degrees (water), is 1.5 kcal/mol, which is approximately 4 times less than that in bulk solution.     

Stacks of functional oxide thin films patterned by micromolding

Stacks of up to five relief patterned functional oxide thin films were obtained by a low-cost and low-tech soft-lithographic patterning technique. Micromolding was used to pattern a film of a metal-organic precursor solution for Y-stabilized ZrO(2) (YSZO). Subsequent drying and pyrolysis yielded a line-patterned YSZO film. The process was repeated up to four times with a precursor solution for BaTiO(3) on top of the YSZO film, resulting in stacks of YSZO and BaTiO(3) lines with well-defined edges. This approach presents a step forward on the way to a versatile additive micropatterning technique with which simple multi-material device structures can be fabricated in a reliable, fast, and cost-effective manner.     

Emission wavelength trimming of self-assembled InGaAs/GaAs quantum dots with GaAs/AlGaAs superlattices by rapid thermal annealing

The effects of rapid thermal annealing on InGaAs quantum dots grown by atomic layer molecular beam epitaxy to the structural transformation and optical properties are investigated. No misfit dislocation was observed from either the as-grown or annealed dots. The size and composition of the quantum dots become more uniform upon annealing mainly from the height fluctuation as predicted by the theoretical model. Large bandgap blue shifts, resulted from the In and Ga interdiffusion, were observed with the preservation of three-dimensional carrier confinement. The GaAs/AlGaAs superlattice was found to minimize the defect diffusion and dot interdiffusion during the high-temperature epitaxial overgrowth.     

Unique ordered domains of biphenylthiol self-assembled monolayers on Au(111)

The surface structure and adsorption conditions of biphenylthiol (BPT) self-assembled monolayers (SAMs) on Au(111) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). STM imaging revealed that the structural order of BPT SAMs formed in a 0.01 mM ethanol solution at 60 degrees C decreases with increasing immersion time. Interestingly, BPT SAMs formed after 30 min have unique ordered domains containing well-ordered (square root of 3 x square root of 3)R30 degrees structures and bright rows that are connected by small aggregated domains with a periodicity of approximately 10 angstroms, results that have never been observed for other thiol SAM systems. Distances between the bright rows were 20-35 angstroms. The bright small domains contained five or six BPT molecules each, which may have originated from differences in the adsorption orientations of biphenyl groups that were induced by localized interactions between them. XPS measurements for BPT SAMs on Au(111) showed the two sulfur peaks at 161.2 and 162.2 eV, implying the formation of chemisorbed monolayers. Our results are anticipated to be useful for understanding the formation and structure of BPT SAMs on gold surfaces.