Three-dimensional Thin Films Research Articles

The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers.

Conjugated polymers with glycol-based chains, are emerging as a material class with promising applications as organic mixed ionic-electronic conductors, particularly in bioelectronics and thermoelectrics. However, little is still known about their microstructure and the role of the side chains in determining intermolecular interactions and polymer packing. Here, we use the combination of electrospray deposition and scanning tunneling microscopy to determine the microstructure of prototypical glycolated conjugated polymers (pgBTTT and p(g2T-TT)) with submonomer resolution. Molecular dynamics simulations of the same surface-adsorbed polymers exhibit an excellent agreement with the experimental images, allowing us to extend the characterization of the polymers to the atomic scale. Our results prove that, similarly to their alkylated counterparts, glycolated polymers assemble through interdigitation of their side chains, although significant differences are found in their conformation and interaction patterns. A model is proposed that identifies the driving force for the polymer assembly in the tendency of the side chains to adopt the conformation of their free analogues, i.e., polyethylene and polyethylene glycol, for alkyl or ethylene glycol side chains, respectively. For both classes of polymers, it is also demonstrated that the backbone conformation is determined to a higher degree by the interaction between the side chains rather than by the backbone torsional potential energy. The generalization of these findings from two-dimensional (2D) monolayers to three-dimensional thin films is discussed, together with the opportunity to use this type of 2D study to gain so far inaccessible, subnm-scale information on the microstructure of conjugated polymers.

Evolution of the Ionization Energy in Two- and Three-Dimensional Thin Films of Pentacene Grown on Silicon Oxide Surfaces.

The ionization energy (IE) of pentacene in two- and three-dimensional (2D and 3D) thin films and its evolution with coverage were studied via photoelectron yield spectroscopy in ambient conditions. In the 2D thin films, the IE of pentacene was found to be nearly constant at 4.91 eV, irrespective of its island size, for an average island size exceeding 1.6 × 104 nm2. In the 3D thin films, however, a reduction in IE by 0.04 eV was clearly observed upon stacking an additional molecular layer on top of the monolayer film, and the IE decreased to 4.73 eV at 20 monolayers. These experimental findings demonstrate the IE evolution in the buried layers of the 3D thin films and the significant impact of the neighboring molecular layers on the IE in layered systems with molecular aggregation.

Physics-Based Device Models and Progress Review for Active Piezoelectric Semiconductor Devices.

Piezoelectric devices transduce mechanical energy to electrical energy by elastic deformation, which distorts local dipoles in crystalline materials. Amongst electromechanical sensors, piezoelectric devices are advantageous because of their scalability, light weight, low power consumption, and readily built-in amplification and ability for multiplexing, which are essential for wearables, medical devices, and robotics. This paper reviews recent progress in active piezoelectric devices. We classify these piezoelectric devices according to the material dimensionality and present physics-based device models to describe and quantify the piezoelectric response for one-dimensional nanowires, emerging two-dimensional materials, and three-dimensional thin films. Different transduction mechanisms and state-of-the-art devices for each type of material are reviewed. Perspectives on the future applications of active piezoelectric devices are discussed.

Nano-beam X-ray microscopy of dried colloidal films.

We report on a nano-beam small angle X-ray scattering study on densely-packed, dried binary films made out of spherical silica particles with radii of 11.2 and 19.3 nm. For these three-dimensional thin films prepared by drop casting, only a finite number of colloidal particles contributes to the scattering signal due to the small beam size of 400 × 400 nm(2). By scanning the samples, the structure and composition of the silica particle films are determined spatially resolved revealing spatial heterogeneities in the films. Three different types of domains were identified: regions containing mainly large particles, regions containing mainly small particles, and regions where both particle species are mixed. Using the new angular X-ray cross-correlations analysis (XCCA) approach, spatial maps of the local type and degree of orientational order within the silica particle films are obtained. Whereas the mixed regions have dominant two-fold order, weaker four-fold and marginal six-fold order, regions made out of large particles are characterized by an overall reduced orientational order. Regions of small particles are highly ordered showing actually crystalline order. Distinct differences in the local particle order are observed by analyzing sections through the intensity and XCCA maps. The different degree of order can be understood by the different particle size polydispersities. Moreover, we show that preferential orientations of the particle domains can be studied by cross-correlation analysis yielding information on particle film formation. We find patches of preferential order with an average size of 8-10 μm. Thus, by this combined X-ray cross-correlation microscopy (XCCM) approach the structure and orientational order of films made out of nanometer sized colloids can be determined. This method will allow to reveal the local structure and order of self-assembled structures with different degree of order in general.

Three-dimensional periodic chiral sculptured thin films

Sculptured thin films (STFs) are nano-engineered materials that have controllable porosity, structural chirality, and periodicity in one, two, or three dimensions. They have been exploited in developing optical elements such as thin-film filters, polarizers, sensors, and waveguides for integrated optics. A grating theory-based modeling approach for STFs as fully three-dimensional (3-D) periodic structures is developed. Input for this model consists of a structural parameter set that is easily accessible experimentally. This parameter set is common to evaluating STFs from a fabrication as well as modeling perspective and thus furnishes a basis for developing appropriate process monitoring and control methods necessary for successful commercial production. Using the proposed model, a quantitative understanding of the limits of applicability of traditional modeling methods for STFs and guidelines for robust design of STF-based devices are developed. This knowledge gained is applied to explore STFs in two illustrative examples: (1) as a notch filter and (2) as a 3-D photonic crystal.

Self-biased Dual-phase Energy Harvesting System

ABSTRACTIn this study, we report the design and fabrication of a dual-phase energy harvester which can synchronously harvest both mechanical and magnetic energy in the absence of DC magnetic field. The harvester consists of a magnetostrictive cantilever beam and a magnetostrictive/ piezoelectric (M/P) self-biased laminate composite structure. This structure allows us to utilize piezoelectric and self-biased magnetoelectric effect simultaneously. By combining these mechanisms together, a sum effect for harvesting both magnetic and vibration energy was realized under DC magnetic field free condition. The bilayer structure provides a simplified geometry that can be easily incorporated into MEMS devices. We demonstrate a hybrid synthesis method for fabrication of complex three-dimensional thin films using a cost-effective and mask-less aerosol jet deposition process. The combination of the hybrid aerosol jet process with dual phase harvester design provides the opportunity to fabricate small scale power sources required for structural health monitoring applications.

Isophthalic acid-functionalised multiwalled carbon nanotubes as an alternative nanolayer for the layer-by-layer assembly with poly(xylylviologen)

Multiwalled carbon nanotubes (MWNTs) have been functionalised with 5-aminoisophthalic acid in an aqueous solution through an environmentally friendly diazonium-based process. The as-prepared isophthalic acid (IPA)-modified MWNT (IPA-MWNT) hybrids became more easily suspended or dissolved in water. The relative content of the covalently attached IPA substituents was about 7–9% (w/w) in the hybrids. Field emission transmission electron microscopic images revealed that the thickness of the IPA layer was about 1–2nm. These IPA-MWNT hybrids were used as an alternative layer to construct three-dimensional thin films with a positively charged poly(p-xylylviologen) (PXV) derivative by the layer-by-layer (LBL) method. The assembling process was monitored by using UV–vis absorption spectra and cyclic voltammograms, which indicated an increase of the absorption intensity or redox current intensity after each assembly of the polyelectrolyte. X-ray photoelectronic spectra indicated that the IPA-MWNTs/PXV multilayer was composed of the elements of C(1s), N(1s), and O(1s), which were from either the functionalised IPA-MWNTs or PXV. Finally, it was revealed that the IPA-MWNT hybrids randomly arranged on the substrate surface; the film thickness increased with layer numbers of the LBL films.

Dynamics of Gravity Driven Three-Dimensional Thin Films on Hydrophilic−Hydrophobic Patterned Substrates

We investigate numerically the dynamics of unstable gravity driven three-dimensional thin liquid films on hydrophilic-hydrophobic patterned substrates. We explore longitudinally striped and checkerboard arrangements. Simulations show that for longitudinal stripes, the thin film can be guided preferentially on the hydrophilic stripes, while fingers develop on adjacent hydrophobic stripes if the width of the stripes is large enough. On checkerboard patterns, the film develops as a finger on hydrophobic domains, while it spreads laterally to cover the hydrophilic domains, providing a mechanism to tune the growth rate of the film. By means of kinematical arguments, we quantitatively predict the growth rate of the contact line on checkerboard arrangements, providing a first step toward potential techniques that control thin film growth in experimental setups.

Dynamics of driven three-dimensional thin films: From hydrophilic to superhydrophobic regimes

We study the forced displacement of a thin film of fluid in contact with vertical and inclined substrates of different wetting properties, that range from hydrophilic to hydrophobic, using the lattice-Boltzmann method. We study the stability and pattern formation of the contact line in the hydrophilic and superhydrophobic regimes, which correspond to wedge-shaped and nose-shaped fronts, respectively. We find that contact lines are considerably more stable for hydrophilic substrates and small inclination angles. The qualitative behavior of the front in the linear regime remains independent of the wetting properties of the substrate as a single dispersion relation describes the stability of both wedges and noses. Nonlinear patterns show a clear dependence on wetting properties and substrate inclination angle. The effect is quantified in terms of the pattern growth rate, which vanishes for the sawtooth pattern and is finite for the finger pattern. Sawtooth shaped patterns are observed for hydrophilic substrates and low inclination angles, while finger-shaped patterns arise for hydrophobic substrates and large inclination angles. Finger dynamics show a transient in which neighboring fingers interact, followed by a steady state where each finger grows independently.

Fabrication of DNA microarrays on nanoengineered polymeric ultrathin film prepared by self-assembly of polyelectrolyte multilayers.

Microarray-based technology is in need of flexible and cost-effective chemistry for fabrication of oligonucleotide microarrays. We have developed a novel method for the fabrication of oligonucleotide microarrays with unmodified oligonucleotide probes on nanoengineered three-dimensional thin films that are deposited on glass slides by consecutive layer-to-layer adsorption of polyelectrolytes. Unmodified oligonucleotide probes were spotted and immobilized on these multilayered polyelectrolyte thin films (PET) by electrostatic adsorption and entrapment on the porous structure of the PET film. The PET provides higher probe binding capacity and thus higher hybridization signal than that of the traditional two-dimensional aminosilane and poly-L-lysine coated slides. Immobilized probe densities of 3.4 x 10(12)/cm2 were observed for microarray spots on PET with unmodified 50-mer oligonucleotide probes, which is comparable to the immobilized probe densities of alkyamine-modified 50-mer probes end-tethered on an aldehyde-functionalized slide. The study of hybridization efficiency showed that 90% of immobilized probes on PET film are accessible to target DNA to form duplex format in hybridization. The DNA microarray fabricated on PET film has wider dynamic range (about 3 orders of magnitude) and lower detection limit (0.5 nM) than the conventional amino- and aldehyde-functionalized slides. Oligonucleotide microarrays fabricated on these PET-coated slides also had consistent spot morphology. In addition, discrimination of single nucleotide polymorphism of 16S rRNA genes was achieved with the PET-based oligonucleotide microarrays. The PET microarrays constructed by our self-assembly process is cost-effective, versatile, and well suited for immobilizing many types of biological active molecules so that a wide variety of microarray formats can be developed.

Inhomogeneity-induced anomalous critical fields in metastable three-dimensional alloys.

With low current densities (\ensuremath{\sim}2 A /${\mathrm{cm}}^{2}$), measurements of upper critical fields ${H}_{c2}$(T) in amorphous thorium-based alloys exhibit narrow transitions (\ensuremath{\lesssim}3 kG). The shape of ${H}_{c2}$(T) deviates significantly above from the Maki curve (theoretical limit) and resembles those observed in some three-dimensional amorphous thin films. Increase in the current density by an order of magnitude, however, reveals increasingly broadened transitions (up to \ensuremath{\sim}10 kG) and an additional transition but only at lower temperatures. Similar deviations, but to a lesser degree, are also observed in the coexistence region of the \ensuremath{\alpha} and \ensuremath{\beta} phases in Hf and Zr alloys. Our results are explained in terms of inhomogeneous regions in metastable alloys. The present findings have important implications on the interpretation of superconducting properties in thin films.