Two-dimensional-lattice-confined single-molecule-like aggregates.

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes1,2, lasers3-5 and quantum technologies6,7, among others8-10. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. This two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

Purcell-Induced Bright Single Photon Emitters in Hexagonal Boron Nitride.

Single photon emitters (SPEs) in hexagonal boron nitride (hBN) are elementary building blocks for room-temperature on-chip quantum photonic technologies. However, fundamental challenges, such as slow radiative decay and nondeterministic placement of the emitters, limit their full potential. Here, we demonstrate large-area arrays of plasmonic nanoresonators (PNRs) for Purcell-induced room-temperature SPEs by engineering emitter-cavity coupling and enhancing radiative emission. Gold-coated silicon pillars with an alumina spacer enable a 10-fold local-field enhancement in the emission band of native hBN defects. We observe bright SPEs with an average saturated emission rate surpassing 5 million counts per second, an average lifetime of <0.5 ns, and 29% yield. Density functional theory reveals the beneficial role of an alumina spacer between hBN and gold, mitigating the electronic broadening of emission from defects proximal to the metal. Our results offer arrays of bright, heterogeneously integrated single-photon sources, paving the way for robust and scalable quantum information systems.

Low-loss plasmon-assisted electro-optic modulator.

For nearly two decades, researchers in the field of plasmonics 1 -which studies the coupling of electromagnetic waves to the motion of free electrons near the surface of a metal 2 -have sought to realize subwavelength optical devices for information technology3-6, sensing7,8, nonlinear optics9,10, optical nanotweezers 11 and biomedical applications 12 . However, the electron motion generates heat through ohmic losses. Although this heat is desirable for some applications such as photo-thermal therapy, it is a disadvantage in plasmonic devices for sensing and information technology 13 and has led to a widespread view that plasmonics is too lossy to be practical. Here we demonstrate that the ohmic losses can be bypassed by using 'resonant switching'. In the proposed approach, light is coupled to the lossy surface plasmon polaritons only in the device's off state (in resonance) in which attenuation is desired, to ensure large extinction ratios between the on and off states and allow subpicosecond switching. In the on state (out of resonance), destructive interference prevents the light from coupling to the lossy plasmonic section of a device. To validate the approach, we fabricated a plasmonic electro-optic ring modulator. The experiments confirm that low on-chip optical losses, operation at over 100 gigahertz, good energy efficiency, low thermal drift and a compact footprint can be combined in a single device. Our result illustrates that plasmonics has the potential to enable fast, compact on-chip sensing and communications technologies.

Greatly Enhanced Emission from Spin Defects in Hexagonal Boron Nitride Enabled by a Low-Loss Plasmonic Nanocavity.

The negatively charged boron vacancy (VB-) defect in hexagonal boron nitride (hBN) with optically addressable spin states has emerged due to its potential use in quantum sensing. Remarkably, VB- preserves its spin coherence when it is implanted at nanometer-scale distances from the hBN surface, potentially enabling ultrathin quantum sensors. However, its low quantum efficiency hinders its practical applications. Studies have reported improving the overall quantum efficiency of VB- defects with plasmonics; however, the overall enhancements of up to 17 times reported to date are relatively modest. Here, we demonstrate much higher emission enhancements of VB- with low-loss nanopatch antennas (NPAs). An overall intensity enhancement of up to 250 times is observed, corresponding to an actual emission enhancement of ∼1685 times by the NPA, along with preserved optically detected magnetic resonance contrast. Our results establish NPA-coupled VB- defects as high-resolution magnetic field sensors and provide a promising approach to obtaining single VB- defects.

Photonic time crystals: a materials perspective [Invited].

Recent advances in ultrafast, large-modulation photonic materials have opened the door to many new areas of research. One specific example is the exciting prospect of photonic time crystals. In this perspective, we outline the most recent material advances that are promising candidates for photonic time crystals. We discuss their merit in terms of modulation speed and depth. We also investigate the challenges yet to be faced and provide our estimation on possible roads to success.

Photonic time-crystals - fundamental concepts [Invited].

Photonic Time-Crystals (PTCs) are materials in which the refractive index varies periodically and abruptly in time. This medium exhibits unusual properties such as momentum bands separated by gaps within which waves can be amplified exponentially, extracting energy from the modulation. This article provides a brief review on the concepts underlying PTCs, formulates the vision and discusses the challenges.

Thickness-Dependent Drude Plasma Frequency in Transdimensional Plasmonic TiN.

Plasmonic transdimensional materials (TDMs), which are atomically thin metals of precisely controlled thickness, are expected to exhibit large tailorability and dynamic tunability of their optical response as well as strong light confinement and nonlocal effects. Using spectroscopic ellipsometry, we characterize the complex permittivity of ultrathin films of passivated plasmonic titanium nitride with thicknesses ranging from 1 to 10 nm. By measuring passivated TiN, we experimentally distinguish between the contributions of an oxide layer and thickness to the optical properties. A decrease in the Drude plasma frequency and increase in the damping in thinner films is observed due to spatial confinement. We explain the experimental trends using a nonlocal Drude dielectric response theory based on the Keldysh-Rytova (KR) potential that predicts the thickness-dependent optical properties caused by electron confinement in plasmonic TDMs. Our experimental findings are consistent with the KR model and demonstrate quantum-confinement-induced optical properties in plasmonic transdimensional TiN.

Creating Quantum Emitters in Hexagonal Boron Nitride Deterministically on Chip-Compatible Substrates.

Two-dimensional hexagonal boron nitride (hBN) that hosts room-temperature single-photon emitters (SPEs) is promising for quantum information applications. An important step toward the practical application of hBN is the on-demand, position-controlled generation of SPEs. Strategies reported for deterministic creation of hBN SPEs either rely on substrate nanopatterning that is not compatible with integrated photonics or utilize radiation sources that might introduce unpredictable damage or contamination to hBN. Here, we report a radiation- and lithography-free route to deterministically activate hBN SPEs by nanoindentation with atomic force microscopy (AFM). The method applies to hBN flakes on flat silicon dioxide-silicon substrates that can be readily integrated into on-chip photonic devices. The achieved SPE yields are above 30% for multiple indent sizes, and a maximum yield of 36% is demonstrated for indents around 400 nm. Our results mark an important step toward the deterministic creation and integration of hBN SPEs with photonic and plasmonic devices.

Visible photon generation via four-wave mixing in near-infrared near-zero-index thin films.

Optical nonlinearities can be strongly enhanced by operating in the so-called near-zero-index (NZI) regime, where the real part of the refractive index of the system under investigation approaches zero. Here we experimentally demonstrate semi-degenerate four-wave mixing (FWM) in aluminum zinc oxide thin films generating radiation tunable in the visible spectral region, where the material is highly transparent. To this end, we employed an intense pump (787 nm) and a seed tunable in the NIR window (1100-1500 nm) to generate a visible idler wave (530-620 nm). Experiments show enhancement of the frequency conversion efficiency with a maximum of 2% and a signal-to-pump detuning of 360 nm. Effective idler wavelength tuning has also been demonstrated by operating on the temporal delay between the pump and signal.

Solar Thermoplasmonic Nanofurnace for High-Temperature Heterogeneous Catalysis.

Most of existing solar thermal technologies require highly concentrated solar power to operate in the temperature range 300-600 °C. Here, thin films of refractory plasmonic TiN cylindrical nanocavities manufactured via flexible and scalable process are presented. The fabricated TiN films show polarization-insensitive 95% broadband absorption in the visible and near-infrared spectral ranges and act as plasmonic "nanofurnaces" capable of reaching temperatures above 600 °C under moderately concentrated solar irradiation (∼20 Suns). The demonstrated structures can be used to control nanometer-scale chemistry with zeptoliter (10-21 L) volumetric precision, catalyzing C-C bond formation and melting inorganic deposits. Also shown is the possibility to perform solar thermal CO oxidation at rates of 16 mol h-1 m-2 and with a solar-to-heat thermoplasmonic efficiency of 63%. Access to scalable, cost-effective refractory plasmonic nanofurnaces opens the way to the development of modular solar thermal devices for sustainable catalytic processes.

Spatial and Temporal Nanoscale Plasmonic Heating Quantified by Thermoreflectance.

The field of thermoplasmonics has thrived in the past decades because it uniquely provides remotely controllable nanometer-scale heat sources that have augmented numerous technologies. Despite the extensive studies on steady-state plasmonic heating, the dynamic behavior of the plasmonic heaters in the nanosecond regime has remained largely unexplored, yet such a time scale is indeed essential for a broad range of applications such as photocatalysis, optical modulators, and detectors. Here, we use two distinct techniques based on the temperature-dependent surface reflectivity of materials, optical thermoreflectance imaging (OTI) and time-domain thermoreflectance (TDTR), to comprehensively investigate plasmonic heating in both spatial and temporal domains. Specifically, OTI enables the rapid visualization of plasmonic heating with sub-micron resolution, outperforming a standard thermal camera, and allows us to establish the connection between the optical absorptance and heating efficiency as well as to analyze plasmonic heating dynamics on the millisecond scale. Using the TDTR technique, we, for the first time, study the optical resonance-dependent heat-transfer dynamics of a nanometer-scale plasmonic structure in the nanosecond regime and use a detailed computational model to extract the impulse response and thermal interface conductance of a multilayer plasmonic structure. The study reveals a quantitative relationship between the dimensions of the nanopatterned structure and its spatiotemporal thermal response to the light pulse excitation, a thermoplasmonic effect resulting from the spatial distribution of the absorbed electromagnetic energy. We also conclude that the two thermoreflectance techniques provide necessary feedback to nanoscale thermoplasmonic heat management, for which optimization in either heating power or temperature decay speed is needed.

Gap-plasmon enhanced water splitting with ultrathin hematite films: the role of plasmonic-based light trapping and hot electrons.

Hydrogen is a promising alternative renewable fuel for meeting the growing energy demands of the world. Over the past few decades, photoelectrochemical water splitting has been widely studied as a viable technology for the production of hydrogen utilizing solar energy. A solar-to-hydrogen (STH) efficiency of 10% is considered to be sufficient for practical applications. Amongst the wide class of semiconductors that have been studied for their application in solar water splitting, iron oxide (α-Fe2O3), or hematite, is one of the more promising candidate materials, with a theoretical STH efficiency of 15%. In this work, we show experimentally that by utilizing gold nanostructures that support gap-plasmon resonances together with a hematite layer, we can increase the water oxidation photocurrent by two times over that demonstrated by a bare hematite film at wavelengths above the hematite bandgap. Moreover, we achieve a six-fold increase in the oxidation photocurrent at near-infrared wavelengths, which is attributed to hot electron generation and decay in the gap-plasmon nanostructures. Theoretical simulations confirmed that the metamaterial geometry with gap plasmons that was used allows us to confine electromagnetic fields inside the hematite semiconductor and to enhance the surface photochemistry.

Dynamic Control of Nanocavities with Tunable Metal Oxides.

Fabry-Pérot metal-insulator-metal (MIM) nanocavities are widely used in nanophotonic applications due to their extraordinary electromagnetic properties and deeply subwavelength dimensions. However, the spectral response of nanocavities is usually controlled by the spatial separation between the two reflecting mirrors and the spacer's refractive index. Here, we demonstrate static and dynamic control of Fabry-Pérot nanocavities by inserting a plasmonic metasurface, as a passive element, and a gallium doped-zinc oxide (Ga:ZnO) layer as a dynamically tunable component within the nanocavities' spacer. Specifically, by changing the design of the silver (Ag) metasurface one can "statically" tailor the nanocavity response, tuning the resonance up to 200 nm. To achieve the dynamic tuning, we utilize the large nonlinear response of the Ga:ZnO layer near the epsilon near zero wavelength to enable effective subpicosecond (<400 fs) optical modulation (80%) at reasonably low pump fluence levels (9 mJ/cm2). We demonstrate a 15 nm red shift of a near-infrared Fabry-Pérot resonance (λ ≅ 1.16 µm) by using a degenerate pump probe technique. We also study the carrier dynamics of Ga:ZnO under intraband photoexcitation via the electronic band structure calculated from first-principles density functional method. This work provides a versatile approach to design metal nanocavities by utilizing both the phase variation with plasmonic metasurfaces and the strong nonlinear response of metal oxides. Tailorable and dynamically controlled nanocavities could pave the way to the development of the next generation of ultrafast nanophotonic devices.

Ultrabright Room-Temperature Sub-Nanosecond Emission from Single Nitrogen-Vacancy Centers Coupled to Nanopatch Antennas.

Solid-state quantum emitters are in high demand for emerging technologies such as advanced sensing and quantum information processing. Generally, these emitters are not sufficiently bright for practical applications, and a promising solution consists in coupling them to plasmonic nanostructures. Plasmonic nanostructures support broadband modes, making it possible to speed up the fluorescence emission in room-temperature emitters by several orders of magnitude. However, one has not yet achieved such a fluorescence lifetime shortening without a substantial loss in emission efficiency, largely because of strong absorption in metals and emitter bleaching. Here, we demonstrate ultrabright single-photon emission from photostable nitrogen-vacancy (NV) centers in nanodiamonds coupled to plasmonic nanocavities made of low-loss single-crystalline silver. We observe a 70-fold difference between the average fluorescence lifetimes and a 90-fold increase in the average detected saturated intensity. The nanocavity-coupled NVs produce up to 35 million photon counts per second, several times more than the previously reported rates from room-temperature quantum emitters.

Formation of Bound States in the Continuum in Hybrid Plasmonic-Photonic Systems.

A bound state in the continuum (BIC) is a localized state of an open structure with access to radiation channels, yet it remains highly confined with, in theory, an infinite lifetime and quality factor. There have been many realizations of such exceptional states in dielectric systems without loss. However, realizing BICs in lossy systems such as those in plasmonics remains a challenge. In this Letter, we explore the possibility of realizing BICs in a hybrid plasmonic-photonic structure consisting of a plasmonic grating coupled to a dielectric optical waveguide with diverging radiative quality factors. The plasmonic-photonic system supports two distinct groups of BICs: symmetry-protected BICs at the Γ point and off-Γ Friedrich-Wintgen BICs. The photonic waveguide modes are strongly coupled to the gap plasmons in the grating, leading to an avoided crossing behavior with a high value of Rabi splitting of 150 meV. Moreover, we show that the strong coupling significantly alters the band diagram of the hybrid system, revealing opportunities for supporting stopped light at an off-Γ wide angular span.

Optical Time Reversal from Time-Dependent Epsilon-Near-Zero Media.

Materials with a spatially uniform but temporally varying optical response have applications ranging from magnetic field-free optical isolators to fundamental studies of quantum field theories. However, these effects typically become relevant only for time variations oscillating at optical frequencies, thus presenting a significant hurdle that severely limits the realization of such conditions. Here we present a thin-film material with a permittivity that pulsates (uniformly in space) at optical frequencies and realizes a time-reversing medium of the form originally proposed by Pendry [Science 322, 71 (2008)SCIEAS0036-807510.1126/science.1162087]. We use an optically pumped, 500 nm thick film of epsilon-near-zero (ENZ) material based on Al-doped zinc oxide. An incident probe beam is both negatively refracted and time reversed through a reflected phase-conjugated beam. As a result of the high nonlinearity and the refractive index that is close to zero, the ENZ film leads to time reversed beams (simultaneous negative refraction and phase conjugation) with near-unit efficiency and greater-than-unit internal conversion efficiency. The ENZ platform therefore presents the time-reversal features required, e.g., for efficient subwavelength imaging, all-optical isolators and fundamental quantum field theory studies.

Enhanced Graphene Photodetector with Fractal Metasurface.

Graphene has been demonstrated to be a promising photodetection material because of its ultrabroadband optical absorption, compatibility with CMOS technology, and dynamic tunability in optical and electrical properties. However, being a single atomic layer thick, graphene has intrinsically small optical absorption, which hinders its incorporation with modern photodetecting systems. In this work, we propose a gold snowflake-like fractal metasurface design to realize broadband and polarization-insensitive plasmonic enhancement in graphene photodetector. We experimentally obtain an enhanced photovoltage from the fractal metasurface that is an order of magnitude greater than that generated at a plain gold-graphene edge and such an enhancement in the photovoltage sustains over the entire visible spectrum. We also observed a relatively constant photoresponse with respect to polarization angles of incident light, as a result of the combination of two orthogonally oriented concentric hexagonal fractal geometries in one metasurface.

Hybrid plasmonic waveguides formed by metal coating of dielectric ridges.

Bound hybrid plasmon-polariton modes supported by waveguides, which are formed by gold coating of ridges etched into a silica substrate, are analyzed using numerical simulations and investigated experimentally using near-field microscopy at telecom wavelengths (1425-1625 nm). Drastic modifications of the fundamental mode profile along with changes in the mode confinement and propagation loss are found when varying the ridge height. The main mode characteristics (effective mode index, propagation length, and mode profile) are determined from the experimental amplitude- and phase-resolved near-field images and compared with the simulations. The possibility of strongly influencing the mode properties along with subwavelength confinement found simultaneously with relatively long propagation can further be exploited in mode shaping and sensing applications.

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

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.

Controlling Random Lasing with Three-Dimensional Plasmonic Nanorod Metamaterials.

Plasmonics has brought revolutionary advances to laser science by enabling deeply subwavelength nanolasers through surface plasmon amplification. However, the impact of plasmonics on other promising laser systems has so far remained elusive. Here, we present a class of random lasers enabled by three-dimensional plasmonic nanorod metamaterials. While dense metallic nanostructures are usually detrimental to laser performance due to absorption losses, here the lasing threshold keeps decreasing as the volume fraction of metal is increased up to ∼0.07. This is ∼460 times higher than the optimal volume fraction reported thus far. The laser supports spatially confined lasing modes and allows for efficient modulation of spectral profiles by simply tuning the polarization of the pump light. Full-field speckle-free imaging at micron-scales has been achieved by using plasmonic random lasers as the illumination sources. Our findings show that plasmonic metamaterials hold potential to enable intriguing coherent optical sources.