High-Quality All-Inorganic Perovskite CsPbBr3 Microsheet Crystals as Low-Loss Subwavelength Exciton-Polariton Waveguides.

Nanostructured all-inorganic metal halide perovskites have attracted considerable attention due to their outstanding photonic and optoelectronic properties. Particularly, they can exhibit room-temperature exciton-polaritons (EPs) capable of confining electromagnetic fields down to the subwavelength scale, enabling efficient light harvesting and guiding. However, a real-space nanoimaging study of the EPs in perovskite crystals is still absent. Additionally, few studies focused on the ambient-pressure and reliable fabrication of large-area CsPbBr3 microsheets. Here, CsPbBr3 orthorhombic microsheet single crystals were successfully synthesized under ambient pressure. Their EPs were examined using a real-space nanoimaging technique, which reveal EP waveguide modes spanning the visible to near-infrared spectral region. The EPs exhibit a sufficient long propagation length of over 16 µm and a very low propagation loss of less than 0.072 dB·µm-1. These results demonstrate the potential applications of CsPbBr3 microsheets as subwavelength waveguides in integrated optics.

Phonon Polaritons in Twisted Double-Layers of Hyperbolic van der Waals Crystals.

Controlling the twist angle between two stacked van der Waals (vdW) crystals is a powerful approach for tuning their electronic and photonic properties. Hyperbolic media have recently attracted much attention due to their ability to tailor electromagnetic waves at the subwavelength-scale which, however, usually requires complex patterning procedures. Here, we demonstrate a lithography-free approach for manipulating the hyperbolicity by harnessing the twist-dependent coupling of phonon polaritons in double-layers of vdW α-MoO3, a naturally biaxial hyperbolic crystal. The polariton isofrequency contours can be modified due to this interlayer coupling, allowing for controlling the polaritonic characteristics by adjusting the orientation angles between the two layers. Our findings provide opportunities for control of nanoscale light flow with twisted stacks of vdW crystals.

Tetragonal Single-Crystalline Boron Nanowires with Strong Anisotropic Light Scattering Behaviors and Photocurrent Response in Visible-Light Regime.

Boron is a narrow-bandgap (1.56 eV) semiconductor with high melting-point, low-density, large Young's modulus and very high refractive index (3.03) close to silicon. Therefore, boron nanostructures is expected to possess strong visible-light scattering properties. However, photonic and optoelectronic properties of the boron nanostructures are seldom studied until now. In this paper, we have successfully prepared single-crystalline boron nanowire (BNW) arrays with high-density on Si substrate. All the BNWs are found to possess strong light-scattering behaviors in the visible regime. Most of all, the scattered light is found to polarize along the longitudinal direction of the nanowire. They also have excellent second-harmonic generation (SHG) properties under ultrafast laser irradiation. Further optoelectronic measurements show that an individual BNW device exhibits notable photocurrent responses in the visible-light range at ambient conditions, which can be attributed to the strong coupling effect between individual BNW and the visible light. The maximum photoresponsivity of an individual BNW can reach up to 12.12 A W-1 at a voltage of 10 V, and the response time is only 18 ms. Therefore, it unveils that the BNWs have a promising future in visible-light communications and detections.

Resonance Coupling in Silicon Nanosphere-J-Aggregate Heterostructures.

Due to their optical magnetic and electric resonances associated with the high refractive index, dielectric silicon nanoparticles have been explored as novel nanocavities that are excellent candidates for enhancing various light-matter interactions at the nanoscale. Here, from both of theoretical and experimental aspects, we explored resonance coupling between excitons and magnetic/electric resonances in heterostructures composed of the silicon nanoparticle coated with a molecular J-aggregate shell. The resonance coupling was originated from coherent energy transfer between the exciton and magnetic/electric modes, which was manifested by quenching dips on the scattering spectrum due to formation of hybrid modes. The influences of various parameters, including the molecular oscillation strength, molecular absorption line width, molecular shell thickness, refractive index of the surrounding environment, and separation between the core and shell, on the resonance coupling behaviors were scrutinized. In particular, the resonance coupling can approach the strong coupling regime by choosing appropriate molecular parameters, where an anticrossing behavior with a mode splitting of 100 meV was observed on the energy diagram. Most interestingly, the hybrid modes in such dielectric heterostructure can exhibit unidirectional light scattering behaviors, which cannot be achieved by those in plexcitonic nanoparticle composed of a metal nanoparticle core and a molecular shell.

Néel-type optical target skyrmions inherited from evanescent electromagnetic fields with rotational symmetry.

Optical skyrmions have recently attracted growing interest due to their potential applications in deep-subwavelength imaging and nanometrology. While optical skyrmions have been successfully demonstrated using different field vectors, the study of their generation and control, as well as their general correlation with electromagnetic (EM) fields, is still in its infancy. Here, we theoretically propose that evanescent transverse-magnetic-polarized (TM-polarized) EM fields with rotational symmetry are actually Néel-type optical target skyrmions of the electric field vectors. Such optical target skyrmions are independent of the operation frequency and medium. Our proposal was verified by numerical simulations and real-space nano-imaging experiments performed on a graphene monolayer, where the target skyrmions could be as small as ∼100 nm in diameter. The results can therefore not only further our understanding of the formation mechanisms of EM topological textures, but also provide guidelines for the facile construction of EM skyrmions that may impact future information technologies.

In-plane hyperbolic polariton tuners in terahertz and long-wave infrared regimes.

One of the main bottlenecks in the development of terahertz (THz) and long-wave infrared (LWIR) technologies is the limited intrinsic response of traditional materials. Hyperbolic phonon polaritons (HPhPs) of van der Waals semiconductors couple strongly with THz and LWIR radiation. However, the mismatch of photon - polariton momentum makes far-field excitation of HPhPs challenging. Here, we propose an In-Plane Hyperbolic Polariton Tuner that is based on patterning van der Waals semiconductors, here α-MoO3, into ribbon arrays. We demonstrate that such tuners respond directly to far-field excitation and give rise to LWIR and THz resonances with high quality factors up to 300, which are strongly dependent on in-plane hyperbolic polariton of the patterned α-MoO3. We further show that with this tuner, intensity regulation of reflected and transmitted electromagnetic waves, as well as their wavelength and polarization selection can be achieved. Our results can help the development of THz and LWIR miniaturized devices.

Controlling and Focusing In-Plane Hyperbolic Phonon Polaritons in α-MoO3 with a Curved Plasmonic Antenna.

Hyperbolic phonon polaritons (HPhPs) sustained in polar van der Waals (vdW) crystals exhibit extraordinary confinement of long-wave electromagnetic fields to the deep subwavelength scale. In stark contrast to uniaxial vdW hyperbolic materials, recently emerged biaxial hyperbolic materials, such as α-MoO3 and α-V2 O5 , offer new degrees of freedom for controlling light in two-dimensions due to their distinctive in-plane hyperbolic dispersions. However, the control and focusing of these in-plane HPhPs remain elusive. Here, a versatile technique is proposed for launching, controlling, and focusing in-plane HPhPs in α-MoO3 with geometrically designed curved gold plasmonic antennas. It is found that the subwavelength manipulation and focusing behaviors are strongly dependent on the curvature of the antenna extremity. This strategy operates effectively in a broadband spectral region. These findings not only provide fundamental insights into the manipulation of light by biaxial hyperbolic crystals at the nanoscale but also open up new opportunities for planar nanophotonic applications.

Engineering Graphene Grain Boundaries for Plasmonic Multi-Excitation and Hotspots.

Surface plasmons, merging photonics and electronics in nanoscale dimensions, have been the cornerstones in integrated informatics, precision detection, high-resolution imaging, and energy conversion. Arising from the exceptional Fermi-Dirac tunability, ultrafast carrier mobility, and high-field confinement, graphene offers excellent advantages for plasmon technologies and enables a variety of state-of-the-art optoelectronic applications ranging from tight-field-enhanced light sources, modulators, and photodetectors to biochemical sensors. However, it is challenging to co-excite multiple graphene plasmons on one single graphene sheet with high density, a key step toward plasmonic wavelength-division multiplexing and next-generation dynamical optoelectronics. Here, we report the heteroepitaxial growth of a polycrystalline graphene monolayer with patterned gradient grain boundary density, which is synthesized by creating diverse nanosized local growth environments on a centimeter-scale substrate with a polycrystalline graphene ring seed in chemical vapor deposition. Such geometry enables plasmonic co-excitation with varied wavelength diversification in the nanoscale. Via using high-resolution scanning near-field optical microscopy, we demonstrate rich plasmon standing waves, even bright plasmonic hotspots with a size up to 3 µm. Moreover, by changing the grain boundary density and annealing, we find the local plasmonic wavelengths are widely tunable, from 70 to 300 nm. Theoretical modeling supports that such plasmonic versatility is due to the grain boundary-induced plasmon-phonon interactions through random phase approximation. The seed-induced heteroepitaxial growth provides a promising way for the grain boundary engineering of two-dimensional materials, and the controllable grain boundary-based plasmon co-generation and manipulation in one single graphene monolayer will facilitate the applications of graphene for plasmonics and nanophotonics.

Polariton waveguide modes in two-dimensional van der Waals crystals: an analytical model and correlative nano-imaging.

Two-dimensional van der Waals (vdW) crystals can sustain various types of polaritons with strong electromagnetic confinements, making them highly attractive for nanoscale photonic and optoelectronic applications. While extensive experimental and numerical studies have been devoted to the polaritons of the vdW crystals, analytical models are sparse. Particularly, applying the model to describe polariton behaviors that are visualized by state of the art near-field optical microscopy requires further investigations. In this study, we develop an analytical waveguide model to describe polariton propagations in vdW crystals. The dispersion contours, dispersion relations, and localized electromagnetic field distributions of polariton waveguide modes are derived. The model is verified by real-space optical nano-imaging and numerical simulation of phonon polaritons in α-MoO3, which is a vdW biaxial crystal. Although we focus on α-MoO3, the proposed model is valid for other polaritonic crystals within the vdW family given the corresponding dielectric substitutions. Our model therefore provides an analytical rationale for describing and understanding the localized electromagnetic fields in vdW crystals that are associated with polaritons.

A mid-infrared biaxial hyperbolic van der Waals crystal.

Hyperbolic media have attracted much attention in the photonics community due to their ability to confine light to arbitrarily small volumes and their potential applications to super-resolution technologies. The two-dimensional counterparts of these media can be achieved with hyperbolic metasurfaces that support in-plane hyperbolic guided modes upon nanopatterning, which, however, poses notable fabrication challenges and limits the achievable confinement. We show that thin flakes of a van der Waals crystal, α-MoO3, can support naturally in-plane hyperbolic polariton guided modes at mid-infrared frequencies without the need for patterning. This is possible because α-MoO3 is a biaxial hyperbolic crystal with three different Reststrahlen bands, each corresponding to a different crystalline axis. These findings can pave the way toward a new paradigm to manipulate and confine light in planar photonic devices.

Highly Confined and Tunable Hyperbolic Phonon Polaritons in Van Der Waals Semiconducting Transition Metal Oxides.

2D van der Waals (vdW) layered polar crystals sustaining phonon polaritons (PhPs) have opened up new avenues for fundamental research and optoelectronic applications in the mid-infrared to terahertz ranges. To date, 2D vdW crystals with PhPs are only experimentally demonstrated in hexagonal boron nitride (hBN) slabs. For optoelectronic and active photonic applications, semiconductors with tunable charges, finite conductivity, and moderate bandgaps are preferred. Here, PhPs are demonstrated with low loss and ultrahigh electromagnetic field confinements in semiconducting vdW α-MoO3 . The α-MoO3 supports strong hyperbolic PhPs in the mid-infrared range, with a damping rate as low as 0.08. The electromagnetic confinements can reach ≈λ0 /120, which can be tailored by altering the thicknesses of the α-MoO3 2D flakes. Furthermore, spatial control over the PhPs is achieved with a metal-ion-intercalation strategy. The results demonstrate α-MoO3 as a new platform for studying hyperbolic PhPs with tunability, which enable switchable mid-infrared nanophotonic devices.

Molybdenum Nanoscrews: A Novel Non-coinage-Metal Substrate for Surface-Enhanced Raman Scattering.

ABSTRACT: For the first time, Mo nanoscrew was cultivated as a novel non-coinage-metal substrate for surface-enhanced Raman scattering (SERS). It was found that the nanoscrew is composed of many small screw threads stacking along its length direction with small separations. Under external light excitation, strong electromagnetic coupling was initiated within the gaps, and many hot-spots formed on the surface of the nanoscrew, which was confirmed by high-resolution scanning near-field optical microscope measurements and numerical simulations using finite element method. These hot-spots are responsible for the observed SERS activity of the nanoscrews. Raman mapping characterizations further revealed the excellent reproducibility of the SERS activity. Our findings may pave the way for design of low-cost and stable SERS substrates. GRAPHICAL ABSTRACT: Mo nanoscrews are for the first time cultivated as a novel type of SERS substrate. The SERS activity is originated from the electromagnetic field enhancements on the individual Mo nanoscrew, which is corroborated by single-particle optical characterizations.

A Simple Method for Synthesis of High-Quality Millimeter-Scale 1T' Transition-Metal Telluride and Near-Field Nanooptical Properties.

The controlled synthesis of MoTe2 and WTe2 is crucial for their fundamental research and potential electronic applications. Here, a simplified ambient-pressure chemical vapor deposition (CVD) strategy is developed to synthesize high-quality and large-scale monolayer and few-layer 1T'-phase MoTe2 (length ≈ 1 mm) and WTe2 (length ≈ 350 µm) crystals by using ordinary salts (KCl or NaCl) as the growth promoter combining with low-cost (NH4 )6 Mo7 O24 ·4H2 O and hydrate (NH4 )10 W12 O41 ·xH2 O as the Mo and W sources, respectively. Atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and transmission electron microscopy confirm the high-quality nature and the atomic structure of the as-grown 1T' MoTe2 and WTe2 flakes. Variable-temperature transport measurements exhibit their semimetal properties. Furthermore, near-field nanooptical imaging studies are performed on the 1T' MoTe2 and WTe2 flakes for the first time. The sub-wavelength effects of 1T'-phase MoTe2 (λp ≈ 140 nm) and WTe2 (λp ≈ 100 nm) are obtained. This approach paves the way for the growth of special transition-metal dichalcogenides materials and boosts the future polaritonic research of 2D telluride compounds.

Tailoring of electromagnetic field localizations by two-dimensional graphene nanostructures.

Graphene has great potential for enhancing light-matter interactions in a two-dimensional regime due to surface plasmons with low loss and strong light confinement. Further utilization of graphene in nanophotonics relies on the precise control of light localization properties. Here, we demonstrate the tailoring of electromagnetic field localizations in the mid-infrared region by precisely shaping the graphene into nanostructures with different geometries. We generalize the phenomenological cavity model and employ nanoimaging techniques to quantitatively calculate and experimentally visualize the two-dimensional electromagnetic field distributions within the nanostructures, which indicate that the electromagnetic field can be shaped into specific patterns depending on the shapes and sizes of the nanostructures. Furthermore, we show that the light localization performance can be further improved by reducing the sizes of the nanostructures, where a lateral confinement of λ0/180 of the incidence light can be achieved. The electromagnetic field localizations within a nanostructure with a specific geometry can also be modulated by chemical doping. Our strategies can, in principle, be generalized to other two-dimensional materials, therefore providing new degrees of freedom for designing nanophotonic components capable of tailoring two-dimensional light confinement over a broad wavelength range.

Nanoscale Insights into the Hydrogenation Process of Layered α-MoO3.

The hydrogenation process of the layered α-MoO3 crystal was investigated on a nanoscale. At low hydrogen concentration, the hydrogenation can lead to formation of HxMoO3 without breaking the MoO3 atomic flat surface. For hydrogenation with high hydrogen concentration, hydrogen atoms accumulated along the <101> direction on the MoO3, which induced the formation of oxygen vacancy line defects. The injected hydrogen atoms acted as electron donors to increase electrical conductivity of the MoO3. Near-field optical measurements indicated that both of the HxMoO3 and oxygen vacancies were responsible for the coloration of the hydrogenated MoO3, with the latter contributing dominantly. On the other hand, diffusion of hydrogen atoms from the surface into the body of the MoO3 will encounter a surface diffusion energy barrier, which was for the first time measured to be around 80 meV. The energy barrier also sets an upper limit for the amount of hydrogen atoms that can be bound locally inside the MoO3 via hydrogenation. We believe that our findings has provided a clear picture of the hydrogenation mechanisms in layered transition-metal oxides, which will be helpful for control of their optoelectronic properties via hydrogenation.

Chemically-doped graphene with improved surface plasmon characteristics: an optical near-field study.

One of the most fascinating and important merits of graphene plasmonics is their tunability over a wide range. While chemical doping has proven to be a facile and effective way to create graphene plasmons, most of the previous studies focused on the macroscopic behaviors of the plasmons in chemically-doped graphene and little was known about their nanoscale responses and related mechanisms. Here, to the best of our knowledge, we present the first experimental near-field optical study on chemically-doped graphene with improved surface plasmon characteristics. By using a scattering-type scanning near-field optical microscope (s-SNOM), we managed to show that the graphene plasmons can be tuned and improved using a facile chemical doping method. Specifically, the plasmon interference patterns near the edge of the monolayer graphene were substantially enhanced via nitric acid (HNO3) exposure. The plasmon-related characteristics can be deduced by analyzing such plasmonic fringes, which exhibited a longer plasmon wavelength and reduced plasmon damping rate. In addition, the local carrier density and therefore the Fermi energy level (EF) of graphene can be obtained from the plasmonic nano-imaging, which indicated that the enhanced plasmon oscillation originated from the injection of free holes into graphene by HNO3. These findings were further corroborated by theoretical calculations using density functional theory (DFT). We believe that our findings provide a clear nanoscale picture on improving graphene plasmonics by chemical doping, which will be helpful for optimizing graphene plasmonics and for elucidating the mechanisms of two-dimensional light confinement by atomically thick materials.

A centimeter-scale sub-10 nm gap plasmonic nanorod array film as a versatile platform for enhancing light-matter interactions.

Strongly coupled plasmonic nanostructures with sub-10 nm gaps can enable intense electric field enhancements which greatly benefit the various light-matter interactions. From the point view of practical applications, such nanostructures should be of low-cost, facile fabrication and processing, large-scale with high-yield of the ultrasmall gaps, and easy for integration with other functional components. However, nowadays techniques for reliable fabrication of these nanostructures usually involve complex, time-consuming, and expensive lithography procedures, which are limited either by their low-throughput or the small areas obtained. On the other hand, so far most of the studies on the sub-10 nm gap nanostructures mainly focused on the surface-enhanced Raman scattering and high-harmonic generations, while leaving other nonlinear optical properties unexplored. In this work, using a scalable process without any lithography procedures, we demonstrated a centimeter-scale ordered plasmonic nanorod array film (PNRAF) with well-defined sub-10 nm interparticle gaps as a versatile platform for strongly enhanced light-matter interactions. Specifically, we showed that due to its plasmon-induced localized electromagnetic field enhancements, the Au PNRAF could exhibit extraordinary intrinsic multi-photon avalanche luminescence (MAPL) and nonlinear saturable absorption (SA). Furthermore, the PNRAF can be easily integrated with semiconductor quantum dots (SQDs) as well as wide bandgap semiconductors to strongly enhance their fluorescence and photocurrent response, respectively. Our method can be easily generalized to nanorod array films consisting of other plasmonic metals and even semiconductor materials, which can have multiple functionalities derived from different materials. Overall, the findings in our study have offered a potential strategy for design and fabrication of nanostructures with ultrasmall gaps for future photonic and optoelectronic applications.

The effects of structural variations of thiophene-containing Ru(II) complexes on the acid-base and DNA binding properties.

A phenylthiophenyl-bearing Ru(II) complex of [Ru(bpy)2(Hbptip)](PF6)2 {bpy = 2,2'-bipyridine, Hbptip = 2-(4-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline} was synthesized and characterized by elemental analysis, ¹H NMR spectroscopy, and electrospray ionization mass spectrometry. The ground- and excited-state acid-base properties of the complex were studied by UV-visible absorption and photoluminescence spectrophotometric pH titrations and the negative logarithm values of the ground-state acid ionization constants were derived to be pK(a1) = 1.31 ± 0.09 and pK(a2) = 5.71 ± 0.11 with the pK(a2) associated deprotonation/protonation process occurring over 3 pK(a) units more acidic than thiophenyl-free parent complex of [Ru(bpy)2(Hpip)]²âº {Hpip = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline}. The calf thymus DNA-binding properties of [Ru(bpy)2(Hbptip)]²âº in Tris-HCl buffer (pH 7.1 and 50 mM NaCl) were investigated by DNA viscosities and density functional theoretical calculations as well as UV-visible and emission spectroscopy techniques of UV-visible and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4⁻, DNA competitive binding with ethidium bromide, DNA melting experiments, and reverse salt effects. The complex was evidenced to bind to the DNA intercalatively with binding affinity being greater than those for previously reported analogs of [Ru(bpy)2(Hip)]²âº, [Ru(bpy)2(Htip)]²âº, and [Ru(bpy)2(Haptip)]²âº {Hip = 1H-imidazo[4,5-f][1,10]phenanthroline, Htip = 2-thiophenimidazo[4,5-f][1,10]phenanthroline, Haptip = 2-(5-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline}.