Conductive nitrides: growth principles, optical and electronic properties, and their perspectives in photonics and plasmonics

The nitrides of most of the group IVb-Vb-VIb transition metals (TiN, ZrN, HfN, VN, NbN, TaN, MoN, WN) constitute the unique category of conductive ceramics. Having substantial electronic conductivity, exceptionally high melting points and covering a wide range of work function values, they were considered for a variety of electronic applications, which include diffusion barriers in metallizations of integrated circuits, Ohmic contacts on compound semiconductors, and thin film resistors, since early eighties. Among them, TiN and ZrN are recently emerging as significant candidates for plasmonic applications. So the possible plasmonic activity of the rest of transition metal nitrides (TMN) emerges as an important open question. In this work, we exhaustively review the experimental and computational (mostly ab initio) works in the literature dealing with the optical properties and electronic structure of TMN spanning over three decades of time and employing all the available growth techniques. We critically evaluate the optical properties of all TMN and we model their predicted plasmonic response. Hence, we provide a solid understanding of the intrinsic (e.g. the valence electron configuration of the constituent metal) and extrinsic (e.g. point defects and microstructure) factors that dictate the plasmonic performance. Based on the reported optical spectra, we evaluate the quality factors for surface plasmon polariton and localized surface plasmon for various TMN and critically compare them to each other. We demonstrate that, indeed TiN and ZrN along with HfN are the most well-performing plasmonic materials in the visible range, while VN and NbN may be viable alternatives for plasmonic devices in the blue, violet and near UV ranges, albeit in expense of increased electronic loss. Furthermore, we consider the alloyed ternary TMN and by critical evaluation and comparison of the reported experimental and computational works, we identify the emerging optimal tunable plasmonic conductors among the immense number of alloying combinations

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

Parametric localized modes in quadratic nonlinear photonic structures

We analyze two-color spatially localized modes formed by parametrically coupled fundamental and second-harmonic fields excited at quadratic (or chi-2) nonlinear interfaces embedded into a linear layered structure --- a quasi-one-dimensional quadratic nonlinear photonic crystal. For a periodic lattice of nonlinear interfaces, we derive an effective discrete model for the amplitudes of the fundamental and second-harmonic waves at the interfaces (the so-called discrete chi-2 equations), and find, numerically and analytically, the spatially localized solutions --- discrete gap solitons. For a single nonlinear interface in a linear superlattice, we study the properties of two-color localized modes, and describe both similarities and differences with quadratic solitons in homogeneous media.Comment: 9 pages, 8 figure

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

Nonlinearity and disorder: Classification and stability of nonlinear impurity modes

We study the effects produced by competition of two physical mechanisms of energy localization in inhomogeneous nonlinear systems. As an example, we analyze spatially localized modes supported by a nonlinear impurity in the generalized nonlinear Schr\"odinger equation and describe three types of nonlinear impurity modes --- one- and two-hump symmetric localized modes and asymmetric localized modes --- for both focusing and defocusing nonlinearity and two different (attractive or repulsive) types of impurity. We obtain an analytical stability criterion for the nonlinear localized modes and consider the case of a power-law nonlinearity in detail. We discuss several scenarios of the instability-induced dynamics of the nonlinear impurity modes, including the mode decay or switching to a new stable state, and collapse at the impurity site.Comment: 18 pages, 22 figure

Optical Encoding by Plasmon-Based Patterning: Hard and Inorganic Materials Become Photosensitive

The photosensitivity of nanocomposite AlN films with embedded silver nanospheres is reported. It stems from localized surface plasmon resonances (LSPR) whose modulation is photoinduced by laser annealing that induces a combined effect of metallic nanoparticle enlargement and dielectric matrix recrystallization; the photoindunced changes of the refractive index of the matrix result in strong spectral shift of LSPR. We demonstrate the utilization of this process for spectrally selective optical encoding into hard, durable, and chemically inert films