Ordered Particle Arrays via a Langmuir Transfer Process: Access to Any Two-Dimensional Bravais Lattice.

We demonstrate how to directly transform a close-packed hexagonal colloidal monolayer into nonclose-packed particle arrays of any two-dimensional symmetry at the air/water interface. This major advancement in the field of nanoparticle self-assembly is based on a simple one-dimensional stretching step in combination with the particle array orientation. Our method goes far beyond existing strategies and allows access to all possible two-dimensional Bravais lattices. A key element of our work is the possibility to macroscopically stretch a particle array in a truly one-dimensional manner, which has not been possible up to now. We achieve this by stretching the nanoparticle array at an air/water interface during the transfer process. The degree of stretching is simply controlled by the wettability of the transfer substrate. To retain the symmetry of the transferred structure, the capillary forces upon drying have to be circumvented. We demonstrate two concepts based on thermal fixation for this. It allows for the first time to fabricate nonclose-packed, nonhexagonal colloidal monolayers on a macroscopic length scale.

Surface plasmon modes of nanomesh-on-mirror nanocavities prepared by nanosphere lithography.

Metal-insulator-metal (MIM) structures show great potential for numerous photonic applications due to their ability to confine light energy to volumes with deeply sub-wavelength dimensions. Here, MIM structures comprising hexagonal gold nanohole arrays were prepared by nanosphere lithography. Angle-resolved UV-vis-NIR spectroscopy revealed a series of narrow, dispersive and non-dispersive modes, which were attributed to the excitation of surface plasmon polariton (SPP) modes. Applying finite-difference time-domain (FDTD) simulations and analytical diffraction phase-matching theory all resonances can be ascribed to only two SPP modes traveling at the outer gold surface and in the gap layer sandwiched between two metal films. Metamaterial resonances, as reported in the literature for similar structures, are not needed to fully explain the reflectance spectra. Bragg scattering of the symmetric gap SPP mode results in a gap resonance, which is insensitive to the angle of incidence over a broad angular range. The spectral position of this flat band can be controlled by tuning the grating period of the nanohole array as well as the thickness and the refractive index of the dielectric gap.

Plasmonic nanomeshes: their ambivalent role as transparent electrodes in organic solar cells.

In this contribution, the optical losses and gains attributed to periodic nanohole array electrodes in polymer solar cells are systematically studied. For this, thin gold nanomeshes with hexagonally ordered holes and periodicities (P) ranging from 202 nm to 2560 nm are prepared by colloidal lithography. In combination with two different active layer materials (P3HT:PC61BM and PTB7:PC71BM), the optical properties are correlated with the power conversion efficiency (PCE) of the solar cells. A cavity mode is identified at the absorption edge of the active layer material. The resonance wavelength of this cavity mode is hardly defined by the nanomesh periodicity but rather by the absorption of the photoactive layer. This constitutes a fundamental dilemma when using nanomeshes as ITO replacement. The highest plasmonic enhancement requires small periodicities. This is accompanied by an overall low transmittance and high parasitic absorption losses. Consequently, larger periodicities with a less efficient cavity mode, yet lower absorptive losses were found to yield the highest PCE. Nevertheless, ITO-free solar cells reaching ~77% PCE compared to ITO reference devices are fabricated. Concomitantly, the benefits and drawbacks of this transparent nanomesh electrode are identified, which is of high relevance for future ITO replacement strategies.

Atomic force microscopy with nanoelectrode tips for high resolution electrochemical, nanoadhesion and nanoelectrical imaging.

Multimodal nano-imaging in electrochemical environments is important across many areas of science and technology. Here, scanning electrochemical microscopy (SECM) using an atomic force microscope (AFM) platform with a nanoelectrode probe is reported. In combination with PeakForce tapping AFM mode, the simultaneous characterization of surface topography, quantitative nanomechanics, nanoelectronic properties, and electrochemical activity is demonstrated. The nanoelectrode probe is coated with dielectric materials and has an exposed conical Pt tip apex of ∼200 nm in height and of ∼25 nm in end-tip radius. These characteristic dimensions permit sub-100 nm spatial resolution for electrochemical imaging. With this nanoelectrode probe we have extended AFM-based nanoelectrical measurements to liquid environments. Experimental data and numerical simulations are used to understand the response of the nanoelectrode probe. With PeakForce SECM, we successfully characterized a surface defect on a highly-oriented pyrolytic graphite electrode showing correlated topographical, electrochemical and nanomechanical information at the highest AFM-SECM resolution. The SECM nanoelectrode also enabled the measurement of heterogeneous electrical conductivity of electrode surfaces in liquid. These studies extend the basic understanding of heterogeneity on graphite/graphene surfaces for electrochemical applications.

Showing particles their place: deterministic colloid immobilization by gold nanomeshes.

The defined immobilization of colloidal particles on a non-close packed lattice on solid substrates is a challenging task in the field of directed colloidal self-assembly. In this contribution the controlled self-assembly of polystyrene beads into chemically modified nanomeshes with a high particle surface coverage is demonstrated. For this, solely electrostatic interaction forces were exploited by the use of topographically shallow gold nanomeshes. Employing orthogonal functionalization, an electrostatic contrast between the glass surface and the gold nanomesh was introduced on a sub-micron scale. This surface charge contrast promotes a highly site-selective trapping of the negatively charged polystyrene particles from the liquid phase. AFM force spectroscopy with a polystyrene colloidal probe was used to rationalize this electrostatic focusing effect. It provides quantitative access to the occurring interaction forces between the particle and substrate surface and clarifies the role of the pH during the immobilization process. Furthermore, the structure of the non-close packed colloidal monolayers can be finely tuned by varying the ionic strength and geometric parameters between colloidal particles and nanomesh. Therefore one is able to specifically and selectively adsorb one or several particles into one individual nanohole.