Since 2000, there has been an explosion of activity in the field of plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In this Review, we explore the mechanism of PERS and discuss PERS hotspots — nanoscale regions with a strongly enhanced local electromagnetic field — that allow trace-molecule detection, biomolecule analysis and surface characterization of various materials. In particular, we discuss a new generation of hotspots that are generated from hybrid structures combining PERS-active nanostructures and probe materials, which feature a strong local electromagnetic field on the surface of the probe material. Enhancement of surface Raman signals up to five orders of magnitude can be obtained from materials that are weakly SERS active or SERS inactive. We provide a detailed overview of future research directions in the field of PERS, focusing on new PERS-active nanomaterials and nanostructures and the broad application prospect for materials science and technology. Assisted by rationally designed novel plasmonic nanostructures, surface-enhanced Raman spectroscopy has presented a new generation of analytical tools (that is, tip-enhanced Raman spectroscopy and shell-isolated nanoparticle-enhanced Raman spectroscopy) with an extremely high surface sensitivity, spatial resolution and broad application for materials science and technology.

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials

Infrared spectroscopy is the technique of choice for chemical identification of biomolecules through their vibrational fingerprints. However, infrared light interacts poorly with nanometric-size molecules. We exploit the unique electro-optical properties of graphene to demonstrate a high-sensitivity tunable plasmonic biosensor for chemically specific label-free detection of protein monolayers. The plasmon resonance of nanostructured graphene is dynamically tuned to selectively probe the protein at different frequencies and extract its complex refractive index. Additionally, the extreme spatial light confinement in graphene—up to two orders of magnitude higher than in metals—produces an unprecedentedly high overlap with nanometric biomolecules, enabling superior sensitivity in the detection of their refractive index and vibrational fingerprints. The combination of tunable spectral selectivity and enhanced sensitivity of graphene opens exciting prospects for biosensing.

Mid-infrared plasmonic biosensing with graphene

Core–shell nanoparticles are at the leading edge of the hot research topics and offer a wide range of applications in optics, biomedicine, environmental science, materials, catalysis, energy, and so forth, due to their excellent properties such as versatility, tunability, and stability. They have attracted enormous interest attributed to their dramatically tunable physicochemical features. Plasmonic core–shell nanomaterials are extensively used in surface-enhanced vibrational spectroscopies, in particular, surface-enhanced Raman spectroscopy (SERS), due to the unique localized surface plasmon resonance (LSPR) property. This review provides a comprehensive overview of core–shell nanoparticles in the context of fundamental and application aspects of SERS and discusses numerous classes of core–shell nanoparticles with their unique strategies and functions. Further, herein we also introduce the concept of shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) in detail because it overcomes the long...

Core–Shell Nanoparticle-Enhanced Raman Spectroscopy

Graphene plasmons were predicted to possess ultra-strong field confinement and very low damping at the same time, enabling new classes of devices for deep subwavelength metamaterials, single-photon nonlinearities, extraordinarily strong light-matter interactions and nano-optoelectronic switches. While all of these great prospects require low damping, thus far strong plasmon damping was observed, with both impurity scattering and many-body effects in graphene proposed as possible explanations. With the advent of van der Waals heterostructures, new methods have been developed to integrate graphene with other atomically flat materials. In this letter we exploit near-field microscopy to image propagating plasmons in high quality graphene encapsulated between two films of hexagonal boron nitride (h-BN). We determine dispersion and particularly plasmon damping in real space. We find unprecedented low plasmon damping combined with strong field confinement, and identify the main damping channels as intrinsic thermal phonons in the graphene and dielectric losses in the h-BN. The observation and in-depth understanding of low plasmon damping is the key for the development of graphene nano-photonic and nano-optoelectronic devices.

Highly confined low-loss plasmons in graphene-boron nitride heterostructures

The underlying principles and unique optical applications of structures exhibiting near-zero dielectric permittivity and/or magnetic permeability are reviewed. The timely relevance to nonlinear, non-reciprocal and non-local effects is highlighted. Structures with near-zero parameters (for example, media with near-zero relative permittivity and/or relative permeability, and thus a near-zero refractive index) exhibit a number of unique features, such as the decoupling of spatial and temporal field variations, which enable the exploration of qualitatively different wave dynamics. This Review summarizes the underlying principles and salient features, physical realizations and technological potential of these structures. In doing so, we revisit their distinctive impact on multiple optical processes, including scattering, guiding, trapping and emission of light. Their role in emphasizing secondary responses of matter such as nonlinear, non-reciprocal and non-local effects is also discussed.

Near-zero refractive index photonics

The field of plasmonics has the potential to enable unique applications in the mid-infrared (IR) wavelength range. However, as is the case regardless of wavelength, the choice of plasmonic material has significant implications for the ultimate utility of any plasmonic device or structure. In this manuscript, we review the wide range of available plasmonic and phononic materials for mid-IR wavelengths, looking in particular at transition metal nitrides, transparent conducting oxides, silicides, doped semiconductors, and even newer plasmonic materials such as graphene. We also include in our survey materials with strong mid-IR phonon resonances, such as GaN, GaP, SiC, and the perovskite SrTiO 3 , all of which can support plasmon-like modes over limited wavelength ranges. We will discuss the suitability of each of these plasmonic and phononic materials, as well as the more traditional noble metals for a range of structures and applications and will discuss the potential and limitations of alternative plasmonic materials at these IR wavelengths.

https://www.spiedigitallibrary.org/journals/journal-of-nanophotonics/volume-9/issue-1/093791/Review-of-mid-infrared-plasmonic-materials/10.1117/1.JNP.9.093791.pdf

Review of mid-infrared plasmonic materials

In0.53Ga0.47BixAs1−x films were grown on InP:Fe substrates by molecular beam epitaxy, with Bi concentrations up to x = 3.60%. Bi content in the epilayers was determined by Rutherford backscattering spectroscopy, and channeling measurements show Bi incorporating substitutionally. Unlike previous work, electrical and optical data are obtained for all samples. A redshift in peak wavelength of about 56 meV/%Bi was observed using spectrophotometry. The valence band anti-crossing model is applied, showing InyGa1−yBixAs1−x lattice-matched to InP is possible by varying the composition, with a theoretical cutoff wavelength of about 6 μm.

/pdf/optical-and-electrical-characterization-of-ingabias-for-use-17jpkwuqm3.pdf

Optical and electrical characterization of InGaBiAs for use as a mid-infrared optoelectronic material

We present a review of existing and potential next-generation far-infrared (20-60 μm) optical materials and devices. The far-infrared is currently one of the few remaining frontiers on the optical spectrum, a space underdeveloped and lacking in many of the optical and optoelectronic materials and devices taken for granted in other, more technologically mature wavelength ranges. The challenges associated with developing optical materials, structures, and devices at these wavelengths are in part a result of the strong phonon absorption in the Reststrahlen bands of III-V semiconductors that collectively span the far-infrared. More than just an underexplored spectral band, the far-IR may also be of potential importance for a range of sensing applications in astrochemistry, biology, and industrial and geological processes. Additionally, with a suitable far-IR optical infrastructure, it is conceivable that even more applications could emerge. In this review, we will present recent progress on far-infrared materials and phenomena such as phononic surface modes, engineered composite materials, and optoelectronic devices that have the potential to serve as the next generation of components in a far-infrared optical tool-kit.

Photonic materials, structures and devices for Reststrahlen optics

Replacing small amounts of As with Bi in InGaBiAs/InP induces large decreases and increases in the bandgap, Eg, and spin-orbit splitting, ΔSO, respectively. The possibility of achieving ΔSO > Eg and a reduced temperature (T) dependence for Eg are significant for suppressing recombination losses and improving performance in mid-infrared photonic devices. We measure Eg(x, T) and ΔSO (x, T) in In0.53Ga0.47BixAs1−x/InP samples for 0 ≤ x ≤ 0.039 by various complementary optical spectroscopic techniques. While we find no clear evidence of a decreased dEg/dT (≈0.34 ± 0.06 meV/K in all samples) we find ΔSO > Eg for x > 3.3–4.3%. The predictions of a valence band anti-crossing model agree well with the measurements.

Temperature and Bi-concentration dependence of the bandgap and spin-orbit splitting in InGaBiAs/InP semiconductors for mid-infrared applications

We describe the growth conditions of InxGa1−xBiyAs1−y (lattice-mismatched and matched) on InP substrates by molecular beam epitaxy and the resulting properties. Due to their anomalously narrow bandgaps and the presence of bismuth, these materials are promising for optoelectronics and thermoelectrics. Low growth temperature and moderate As/Bi beam equivalent pressure ratios are beneficial for Bi incorporation, in good qualitative agreement with GaBiyAs1−y on GaAs. Up to 6.75% bismuth is incorporated. High resolution x-ray diffraction and reciprocal space mapping show that InxGa1−xBiyAs1−y samples exhibit good crystalline quality and zero relaxation. The band gap is reduced in agreement with theoretical predictions. Lattice-matched samples have been produced with lattice mismatch ≤0.21%.

Y. Zhong

Papers

Review of mid-infrared plasmonic materials

Optical and electrical characterization of InGaBiAs for use as a mid-infrared optoelectronic material

Photonic materials, structures and devices for Reststrahlen optics

Temperature and Bi-concentration dependence of the bandgap and spin-orbit splitting in InGaBiAs/InP semiconductors for mid-infrared applications

Effects of molecular beam epitaxy growth conditions on composition and optical properties of InxGa1−xBiyAs1−y