Gururaj V. Naik

Alternative Plasmonic Materials: Beyond Gold and Silver

Materials research plays a vital role in transforming breakthrough scientific ideas into next-generation technology. Similar to the way silicon revolutionized the microelectronics industry, the proper materials can greatly impact the field of plasmonics and metamaterials. Currently, research in plasmonics and metamaterials lacks good material building blocks in order to realize useful devices. Such devices suffer from many drawbacks arising from the undesirable properties of their material building blocks, especially metals. There are many materials, other than conventional metallic components such as gold and silver, that exhibit metallic properties and provide advantages in device performance, design flexibility, fabrication, integration, and tunability. This review explores different material classes for plasmonic and metamaterial applications, such as conventional semiconductors, transparent conducting oxides, perovskite oxides, metal nitrides, silicides, germanides, and 2D materials such as graphene. This review provides a summary of the recent developments in the search for better plasmonic materials and an outlook of further research directions.

Oxides and nitrides as alternative plasmonic materials in the optical range [Invited]

As alternatives to conventional metals, new plasmonic materials offer many advantages in the rapidly growing fields of plasmonics and metamaterials. These advantages include low intrinsic loss, semiconductor-based design, compatibility with standard nanofabrication processes, tunability, and others. Transparent conducting oxides such as Al:ZnO, Ga:ZnO and indium-tin-oxide (ITO) enable many high-performance metamaterial devices operating in the near-IR. Transition-metal nitrides such as TiN or ZrN can be substitutes for conventional metals in the visible frequencies. In this paper we provide the details of fabrication and characterization of these new materials and discuss their suitability for a number of metamaterial and plasmonic applications.

Engineering photonic density of states using metamaterials

The photonic density of states (PDOS), like its electronic counterpart, is one of the key physical quantities governing a variety of phenomena and hence PDOS manipulation is the route to new photonic devices. The PDOS is conventionally altered by exploiting the resonance within a device such as a microcavity or a bandgap structure like a photonic crystal. Here we show that nanostructured metamaterials with hyperbolic dispersion can dramatically enhance the photonic density of states paving the way for metamaterial-based PDOS engineering.

Demonstration of Al:ZnO as a plasmonic component for near-infrared metamaterials

Noble metals such as gold and silver are the primary metallic building blocks of metamaterial devices. Making subwavelength-sized structural elements from these metals seriously limits the optical performance of a device, however, and complicates the manufacturing process of nearly all metamaterial devices in the optical wavelength range. As an alternative to noble metals, we propose to use heavily-doped oxide semiconductors that offer both functional and fabrication advantages in the near-infrared. In this letter, we report an experimental demonstration of negative refraction in a near-infrared metamaterial device that is designed and fabricated using aluminum-doped zinc oxide.Noble metals such as gold and silver are conventionally used as the primary plasmonic building blocks of optical metamaterials. Making subwavelength-scale structural elements from these metals not only seriously limits the optical performance of a device due to high absorption, it also substantially complicates the manufacturing process of nearly all metamaterial devices in the optical wavelength range. As an alternative to noble metals, we propose to use heavily doped oxide semiconductors that offer both functional and fabrication advantages in the near-infrared wavelength range. In this letter, we replace a metal with aluminum-doped zinc oxide as a new plasmonic material and experimentally demonstrate negative refraction in an Al:ZnO/ZnO metamaterial in the near-infrared range.

Refractory Plasmonics with Titanium Nitride: Broadband Metamaterial Absorber

A high-temperature stable broadband plasmonic absorber is designed, fabricated, and optically characterized. A broadband absorber with an average high absorption of 95% and a total thickness of 240 nm is fabricated, using a refractory plasmonic material, titanium nitride. This absorber integrates both the plasmonic resonances and the dielectric-like loss. It opens a path for the interesting applications such as solar thermophotovoltaics and optical circuits.

Titanium nitride as a plasmonic material for visible and near-infrared wavelengths

The search for alternative plasmonic materials with improved optical properties, easier fabrication and integration capabilities over those of the traditional materials such as silver and gold could ultimately lead to real-life applications for plasmonics and metamaterials. In this work, we show that titanium nitride could perform as an alternative plasmonic material in the visible and near-infrared regions. We demonstrate the excitation of surface-plasmon-polaritons on titanium nitride thin films and discuss the performance of various plasmonic and metamaterial structures with titanium nitride as the plasmonic component. We also show that titanium nitride could provide performance that is comparable to that of gold for plasmonic applications and can significantly outperform gold and silver for transformation-optics and some metamaterial applications in the visible and near-infrared regions.

Shape-Dependent Plasmonic Response and Directed Self-Assembly in a New Semiconductor Building Block, Indium-Doped Cadmium Oxide (ICO)

The influence of particle shape on plasmonic response and local electric field strength is well-documented in metallic nanoparticles. Morphologies such as rods, plates, and octahedra are readily synthesized and exhibit drastically different extinction spectra than spherical particles. Despite this fact, the influence of composition and shape on the optical properties of plasmonic semiconductor nanocrystals, in which free electrons result from heavy doping, has not been well-studied. Here, we report the first observation of plasmonic resonance in indium-doped cadmium oxide (ICO) nanocrystals, which exhibit the highest quality factors reported for semiconductor nanocrystals. Furthermore, we are able to independently control the shape and free electron concentration in ICO nanocrystals, allowing for the influence of shape on the optical response of a plasmonic semiconductor to be conclusively demonstrated. The highly uniform particles may be self-assembled into ordered single component and binary nanocrystal superlattices, and in thin films, exhibit negative permittivity in the near infrared (NIR) region, validating their use as a new class of tunable low-loss plasmonic building blocks for 3-D optical metamaterials.

Improving the radiative decay rate for dye molecules with hyperbolic metamaterials

We directly demonstrate an improvement in the radiative decay rate of dye molecules near multilayer hyperbolic metamaterials (HMMs). Our comprehensive study shows a radiative decay rate for rhodamine 800 (Rh800) that is several times higher due to the use of HMM samples as compared to dielectric substrates. This is also the first experimental demonstration that multilayer hyperbolic metamaterials provide an increase in the radiative decay rate relative to those from either thin or thick gold films.

Local Heating with Lithographically Fabricated Plasmonic Titanium Nitride Nanoparticles

Titanium nitride is considered a promising alternative plasmonic material and is known to exhibit localized surface plasmon resonances within the near-infrared biological transparency window. Here, local heating efficiencies of disk-shaped nanoparticles made of titanium nitride and gold are compared in the visible and near-infrared regions numerically and experimentally with samples fabricated using e-beam lithography. Results show that plasmonic titanium nitride nanodisks are efficient local heat sources and outperform gold nanodisks in the biological transparency window, dispensing the need for complex particle geometries.

Epitaxial superlattices with titanium nitride as a plasmonic component for optical hyperbolic metamaterials

Significance Plasmonic and metamaterial devices require high-performance material building blocks, both plasmonic and dielectric, to be useful in any real-world application. Here, we develop both plasmonic and dielectric materials that can be grown epitaxially into ultrathin and ultrasmooth layers with sharp interfaces. We show that a superlattice consisting of titanium nitride as a plasmonic component behaves as an optical hyperbolic metamaterial and exhibits extremely high photonic density of states. Titanium nitride (TiN) is a plasmonic material having optical properties resembling gold. Unlike gold, however, TiN is complementary metal oxide semiconductor-compatible, mechanically strong, and thermally stable at higher temperatures. Additionally, TiN exhibits low-index surfaces with surface energies that are lower than those of the noble metals which facilitates the growth of smooth, ultrathin crystalline films. Such films are crucial in constructing low-loss, high-performance plasmonic and metamaterial devices including hyperbolic metamaterials (HMMs). HMMs have been shown to exhibit exotic optical properties, including extremely high broadband photonic densities of states (PDOS), which are useful in quantum plasmonic applications. However, the extent to which the exotic properties of HMMs can be realized has been seriously limited by fabrication constraints and material properties. Here, we address these issues by realizing an epitaxial superlattice as an HMM. The superlattice consists of ultrasmooth layers as thin as 5 nm and exhibits sharp interfaces which are essential for high-quality HMM devices. Our study reveals that such a TiN-based superlattice HMM provides a higher PDOS enhancement than gold- or silver-based HMMs.