Sub-surface laser nanostructuring in stratified metal/dielectric media: a versatile platform towards flexible, durable and large-scale plasmonic writing

Laser nanostructuring of pure ultrathin metal layers or ceramic/metal composite thin films has emerged as a promising route for the fabrication of plasmonic patterns with applications in information storage, cryptography, and security tagging. However, the environmental sensitivity of pure Ag layers and the complexity of ceramic/metal composite film growth hinder the implementation of this technology to large-scale production, as well as its combination with flexible substrates. In the present work we investigate an alternative pathway, namely, starting from non-plasmonic multilayer metal/dielectric layers, whose growth is compatible with large scale production such as in-line sputtering and roll-to-roll deposition, which are then transformed into plasmonic templates by single-shot UV-laser annealing (LA). This entirely cold, large-scale process leads to a subsurface nanoconstruction involving plasmonic Ag nanoparticles (NPs) embedded in a hard and inert dielectric matrix on top of both rigid and flexible substrates. The subsurface encapsulation of Ag NPs provides durability and long-term stability, while the cold character of LA suits the use of sensitive flexible substrates. The morphology of the final composite film depends primarily on the nanocrystalline character of the dielectric host and its thermal conductivity. We demonstrate the emergence of a localized surface plasmon resonance, and its tunability depending on the applied fluence and environmental pressure. The results are well explained by theoretical photothermal modeling. Overall, our findings qualify the proposed process as an excellent candidate for versatile, large-scale optical encoding applications. Keywords : Ceramic materials; Composite films; Environmental technology; Film growth; Film preparation; Multilayer films; Multilayers; Nanocrystals; Optical data processing; Plasmons; Silver; Substrates; Surface plasmon resonance; Thin films; Ultrathin films, Laser annealing; Localised surface plasmon resonance; Multi-layer thin film; Nano-structuring; Plasmonics, Nanocomposite film

Auxetic cardiac patches with tunable mechanical and conductive properties toward treating myocardial infarction

An auxetic conductive cardiac patch (AuxCP) for the treatment of myocardial infarction (MI) is introduced. The auxetic design gives the patch a negative Poisson's ratio, providing it with the ability to conform to the demanding mechanics of the heart. The conductivity allows the patch to interface with electroresponsive tissues such as the heart. Excimer laser microablation is used to micropattern a re-entrant honeycomb (bow-tie) design into a chitosan-polyaniline composite. It is shown that the bow-tie design can produce patches with a wide range in mechanical strength and anisotropy, which can be tuned to match native heart tissue. Further, the auxetic patches are conductive and cytocompatible with murine neonatal cardiomyocytes in vitro. Ex vivo studies demonstrate that the auxetic patches have no detrimental effect on the electrophysiology of both healthy and MI rat hearts and conform better to native heart movements than unpatterned patches of the same material. Finally, the AuxCP applied in a rat MI model results in no detrimental effect on cardiac function and negligible fibrotic response after two weeks in vivo. This approach represents a versatile and robust platform for cardiac biomaterial design and could therefore lead to a promising treatment for MI

Laser-matter interactions, phase changes and diffusion phenomena during laser annealing of plasmonic AlN:Ag templates and their applications in optical encoding

Nanocomposite thin films incorporating silver nanoparticles are emerging as photosensitive templates for optical encoding applications. However, a deep understanding of the fundamental physicochemical mechanisms occurring during laser-matter interactions is still lacking. In this work, the photosensitivity of AlN:Ag plasmonic nanocomposites is thoroughly examined and a series of UV laser annealing parameters, such as wavelength, fluence and the number of pulses are investigated. We report and study effects such as the selective crystallization of the AlN matrix, the enlargement of the Ag nanoparticle inclusions by diffusion of laser-heated Ag and the outdiffusion of Ag to the film's surface. Detailed optical calculations contribute to the identification and understanding of the aforementioned physical mechanisms and of their dependency on the laser processing parameters. We are then able to predetermine the plasmonic response of processed AlN:Ag nanocomposites and demonstrate its potential by means of optically encoding an overt or covert cryptographic pattern

A new reactive sputtering technique for the low temperature deposition of transparent light emitting ZnS:Mn thin films

The temperature sensitive nature of the substrates used in the flexible displays market necessitates a low temperature deposition technique for processing them. ZnS:Mn exhibiting high intensity photoluminescence and good crystallinity has been deposited onto Si wafers, glass microscope slides and polymeric substrates using a new reactive sputtering technology referred to as HiTUS. This technique enables very high deposition rates and requires no substrate heating. When incorporated as part of a complete EL device, as-deposited ZnS:Mn films are seen to exhibit stable electroluminescence on Si, glass and planarised PET substrate materials. Post annealing of the devices on Si and glass at temperatures of up to 600 °C show that the HiTUS films perform better than equivalent ZnS:Mn films deposited using RF magnetron sputtering

Intrinsic photoluminescence from low temperature deposited zinc oxide thin films as a function of laser and thermal annealing

An investigation into the modification of low temperature deposited ZnO thin films by different annealing processes has been undertaken using laser, thermal and rapid thermal annealing of 60 nm ZnO films deposited by high-target-utilization sputtering. Single-pulse laser annealing using a KrF excimer laser (λ = 248 nm) over a range of fluences up to 318 mJ cm−2 demonstrates controlled in-depth modification of internal film microstructure and luminescence properties without the film degradation produced by high temperature thermal and RTA processes. Photoluminescence (PL) properties show that the ratio of defect related deep level emission (DLE, 450–750 nm, 2.76–1.65 eV) to excitonic near band-edge emission (NBE at 381 nm, 3.26 eV) is directly correlated to processing parameters. Thermal and rapid thermal processing results in the evolution of a strong visible orange/red DLE PL (with peaks at 590 nm, 2.10 eV and 670 nm, 1.85 eV) dominated by defects related to excess oxygen. At higher temperatures, the appearance of a green/yellow emission (530 nm, 2.34 eV) indicates a transition of the dominant radiative transfer mechanism. In contrast, laser processing removes defect related DLE and produces films with intense NBE luminescence, correlated to the observed formation of large grains (25–40 nm)