Temperature-Dependent Excitonic Light Manipulation with Atomically Thin Optical Elements.

Monolayer 2D semiconductors, such as WS2, exhibit uniquely strong light-matter interactions due to exciton resonances that enable atomically thin optical elements. Similar to geometry-dependent plasmon and Mie resonances, these intrinsic material resonances offer coherent and tunable light scattering. Thus far, the impact of the excitons' temporal dynamics on the performance of such excitonic metasurfaces remains unexplored. Here, we show how the excitonic decay rates dictate the focusing efficiency of an atomically thin lens carved directly out of exfoliated monolayer WS2. By isolating the coherent exciton radiation from the incoherent background in the focus of the lens, we obtain a direct measure of the role of exciton radiation in wavefront shaping. Furthermore, we investigate the influence of exciton-phonon scattering by characterizing the focusing efficiency as a function of temperature, demonstrating an increased optical efficiency at cryogenic temperatures. Our results provide valuable insights into the role of excitonic light scattering in 2D nanophotonic devices.

Stacking-Order-Dependent Excitonic Properties Reveal Interlayer Interactions in Bulk ReS2.

Rhenium disulfide, a member of the transition metal dichalcogenide family of semiconducting materials, is unique among 2D van der Waals materials due to its anisotropy and, albeit weak, interlayer interactions, confining excitons within single atomic layers and leading to monolayer-like excitonic properties even in bulk crystals. While recent work has established the existence of two stacking modes in bulk, AA and AB, the influence of the different interlayer coupling on the excitonic properties has been poorly explored. Here, we use polarization-dependent optical measurements to elucidate the nature of excitons in AA and AB-stacked rhenium disulfide to obtain insight into the effect of interlayer interactions. We combine polarization-dependent Raman with low-temperature photoluminescence and reflection spectroscopy to show that, while the similar polarization dependence of both stacking orders indicates similar excitonic alignments within the crystal planes, differences in peak width, position, and degree of anisotropy reveal a different degree of interlayer coupling. DFT calculations confirm the very similar band structure of the two stacking orders while revealing a change of the spin-split states at the top of the valence band to possibly underlie their different exciton binding energies. These results suggest that the excitonic properties are largely determined by in-plane interactions, however, strongly modified by the interlayer coupling. These modifications are stronger than those in other 2D semiconductors, making ReS2 an excellent platform for investigating stacking as a tuning parameter for 2D materials. Furthermore, the optical anisotropy makes this material an interesting candidate for polarization-sensitive applications such as photodetectors and polarimetry.

Multi-Resonant Mie Resonator Arrays for Broadband Light Trapping in Ultrathin c-Si Solar Cells.

Effective photon management is critical to realize high power conversion efficiencies for thin crystalline silicon (c-Si) solar cells. Standard few-100-µm-thick bulk cells achieve light trapping with macroscopic surface textures covered by thin, continuous antireflection coatings. Such sizeable textures are challenging to implement on ultrathin cells. Here, it is illustrated how nanoscale Mie-resonator-arrays with a bimodal size distribution support multiple resonances that can work in concert to achieve simultaneous antireflection and light-trapping across the broad solar spectrum. The effectiveness of these light-trapping antireflection coatings is experimentally demonstrated on a 2.8 µm-thick c-Si solar cell. The measured short-circuit current and corresponding power conversion efficiency are notably improved, achieving efficiencies as high as 11.2%. Measurements of the saturation current density on completed cells indicate that thermal oxides can effectively limit surface recombination. The presented design principles are applicable to a wide range of solar cells.

Passive Radiative Cooling of Silicon Solar Modules with Photonic Silica Microcylinders.

Passive radiative cooling is a method to dissipate excess heat from a material by the spontaneous emission of infrared thermal radiation. For a solar cell, the challenge is to enhance PRC while retaining transparency for sunlight above the bandgap. Here, we design a hexagonal array of cylinders etched into the top surface of silica solar module glass to enhance passive radiative cooling. Multipolar Mie-like resonances in the cylinders are shown to cause antireflection effects in the infrared, which results in enhanced infrared emissivity. Using Fourier transform infrared spectrometry we measure the hemispherical reflectance of the fabricated structures and find the emissivity of the silica cylinder array in good correspondence with the simulated results. The microcylinder array increases the average emissivity between λ = 7.5-16 µm from 84.3% to 97.7%, without reducing visible light transmission.

Metasurface optofluidics for dynamic control of light fields.

The ability to manipulate light and liquids on integrated optofluidics chips has spurred a myriad of important developments in biology, medicine, chemistry and display technologies. Here we show how the convergence of optofluidics and metasurface optics can lead to conceptually new platforms for the dynamic control of light fields. We first demonstrate metasurface building blocks that display an extreme sensitivity in their scattering properties to their dielectric environment. These blocks are then used to create metasurface-based flat optics inside microfluidic channels where liquids with different refractive indices can be directed to manipulate their optical behaviour. We demonstrate the intensity and spectral tuning of metasurface colour pixels as well as on-demand optical elements. We finally demonstrate automated control in an integrated meta-optofluidic platform to open up new display functions. Combined with large-scale microfluidic integration, our dynamic-metasurface flat-optics platform could open up the possibility of dynamic display, imaging, holography and sensing applications.

Microscopic Proof of Photoluminescence from Mechanochemically Synthesized 1-Octene-Capped Quantum-Confined Silicon Nanoparticles: Implications for Light-Emission Applications.

Silicon nanoparticles (SiNPs) have been explored intensively for their use in applications requiring efficient fluorescence for LEDs, lasers, displays, photovoltaic spectral-shifting filters, and biomedical applications. High radiative rates are essential for such applications, and theoretically these could be achieved via quantum confinement and/or straining. Wet-chemical methods used to synthesize SiNPs are under scrutiny because of reported contamination by fluorescent carbon species. To develop a cleaner method, we utilize a specially designed attritor type high-energy ball-mill and use a high-purity (99.999%) Si microparticle precursor. The mechanochemical process is used under a continuous nitrogen gas atmosphere to avoid oxidation of the particles. We confirm the presence of quantum-confined NPs (<5 nm) using atomic force microscopy (AFM). Microphotoluminescence (PL) spectroscopy coupled to AFM confirms quantum-confined tunable red/near-infrared PL emission in SiNPs capped with an organic ligand (1-octene). Using micro-Raman-PL spectroscopy, we confirm SiNPs as the origin of the emission. These results demonstrate a facile and potentially scalable mechanochemical method of synthesis for contamination-free SiNPs.

Directional quantum dot emission by soft-stamping on silicon Mie resonators.

We present a soft-stamping method to selectively print a homogenous layer of CdSeTe/ZnS core-shell quantum dots (QDs) on top of an array of Si nanocylinders with Mie-type resonant modes. Using this new method, we gain accurate control of the quantum dot's angular emission through engineered coupling of the QDs to these resonant modes. Using numerical simulations we show that the emission into or away from the Si substrate can be precisely controlled by the QD position on the nanocylinder. QDs centered on a 400 nm diameter nanocylinder surface show 98% emission directionality into the Si substrate. Alternatively, for homogenous ensembles placed over the nanocylinder top-surface, the upward emission is enhanced 10-fold for 150 nm diameter cylinders. Experimental PL intensity measurements corroborate the simulated trends with cylinder diameter. PL lifetime measurements reflect well the variations of the local density of states at the QD position due to coupling to the resonant cylinders. These results demonstrate that the soft imprint technique provides a unique manner to directly integrate optical emitters with a wide range of nanophotonic geometries, with potential applications in LEDs, luminescent solar concentrators, and up- and down-conversion schemes for improved photovoltaics.

Non-local metasurfaces for spectrally decoupled wavefront manipulation and eye tracking.

Metasurface-based optical elements typically manipulate light waves by imparting space-variant changes in the amplitude and phase with a dense array of scattering nanostructures. The highly localized and low optical-quality-factor (Q) modes of nanostructures are beneficial for wavefront shaping as they afford quasi-local control over the electromagnetic fields. However, many emerging imaging, sensing, communication, display and nonlinear optics applications instead require flat, high-Q optical elements that provide substantial energy storage and a much higher degree of spectral control over the wavefront. Here, we demonstrate high-Q, non-local metasurfaces with atomically thin metasurface elements that offer notably enhanced light-matter interaction and fully decoupled optical functions at different wavelengths. We illustrate a possible use of such a flat optic in eye tracking for eyewear. Here, a metasurface patterned on a regular pair of eye glasses provides an unperturbed view of the world across the visible spectrum and redirects near-infrared light to a camera to allow imaging of the eye.

High-Performance p-n Junction Transition Metal Dichalcogenide Photovoltaic Cells Enabled by MoOx Doping and Passivation.

Layered semiconducting transition metal dichalcogenides (TMDs) are promising materials for high-specific-power photovoltaics due to their excellent optoelectronic properties. However, in practice, contacts to TMDs have poor charge carrier selectivity, while imperfect surfaces cause recombination, leading to a low open-circuit voltage (VOC) and therefore limited power conversion efficiency (PCE) in TMD photovoltaics. Here, we simultaneously address these fundamental issues with a simple MoOx (x ≈ 3) surface charge-transfer doping and passivation method, applying it to multilayer tungsten disulfide (WS2) Schottky-junction solar cells with initially near-zero VOC. Doping and passivation turn these into lateral p-n junction photovoltaic cells with a record VOC of 681 mV under AM 1.5G illumination, the highest among all p-n junction TMD solar cells with a practical design. The enhanced VOC also leads to record PCE in ultrathin (<90 nm) WS2 photovoltaics. This easily scalable doping and passivation scheme is expected to enable further advances in TMD electronics and optoelectronics.

Band-Gap Tunability in Partially Amorphous Silicon Nanoparticles Using Single-Dot Correlative Microscopy.

Silicon nanoparticles (Si-NPs) represent one of many types of nanomaterials, where the origin of emission is difficult to assess due to a complex interplay between the core and surface chemistry. Band-gap tunability in Si-NPs is predicted to span from the infrared to the ultraviolet spectral range, which is rarely observed in practice. In this work, we directly assess the size dependence of the optical band gap using a single-dot correlative microscopy tool, where the size of the individual NPs is measured using atomic force microscopy (AFM) and the optical band gap is evaluated from single-dot photoluminescence measured on the very same NPs. We analyze 2-8 nm alkyl-capped Si-NPs prepared by a sol-gel method, followed by annealing at 1300 °C. Surprisingly, we find that the optical band gap is given by the amorphous shell, as evidenced by the convergence of the optical band gap size dependence toward the amorphous Si band gap of ∼1.56 eV. We propose that the structural disorder might be the reason behind the often reported limited emission tunability from various Si-NPs in the literature. We believe that our message points toward a pressing need for development and broader use of such direct correlative single-dot microscopy methods to avoid possible misinterpretations that could arise from attempts to recover size-band gap relation from ensemble methods, as practiced nowadays.

Nanoelectromechanical modulation of a strongly-coupled plasmonic dimer.

The ability of two nearly-touching plasmonic nanoparticles to squeeze light into a nanometer gap has provided a myriad of fundamental insights into light-matter interaction. In this work, we construct a nanoelectromechanical system (NEMS) that capitalizes on the unique, singular behavior that arises at sub-nanometer particle-spacings to create an electro-optical modulator. Using in situ electron energy loss spectroscopy in a transmission electron microscope, we map the spectral and spatial changes in the plasmonic modes as they hybridize and evolve from a weak to a strong coupling regime. In the strongly-coupled regime, we observe a very large mechanical tunability (~250 meV/nm) of the bonding-dipole plasmon resonance of the dimer at ~1 nm gap spacing, right before detrimental quantum effects set in. We leverage our findings to realize a prototype NEMS light-intensity modulator operating at ~10 MHz and with a power consumption of only 4 fJ/bit.

Direct laser writing of volumetric gradient index lenses and waveguides.

Direct laser writing (DLW) has been shown to render 3D polymeric optical components, including lenses, beam expanders, and mirrors, with submicrometer precision. However, these printed structures are limited to the refractive index and dispersive properties of the photopolymer. Here, we present the subsurface controllable refractive index via beam exposure (SCRIBE) method, a lithographic approach that enables the tuning of the refractive index over a range of greater than 0.3 by performing DLW inside photoresist-filled nanoporous silicon and silica scaffolds. Adjusting the laser exposure during printing enables 3D submicron control of the polymer infilling and thus the refractive index and chromatic dispersion. Combining SCRIBE's unprecedented index range and 3D writing accuracy has realized the world's smallest (15 µm diameter) spherical Luneburg lens operating at visible wavelengths. SCRIBE's ability to tune the chromatic dispersion alongside the refractive index was leveraged to render achromatic doublets in a single printing step, eliminating the need for multiple photoresins and writing sequences. SCRIBE also has the potential to form multicomponent optics by cascading optical elements within a scaffold. As a demonstration, stacked focusing structures that generate photonic nanojets were fabricated inside porous silicon. Finally, an all-pass ring resonator was coupled to a subsurface 3D waveguide. The measured quality factor of 4600 at 1550 nm suggests the possibility of compact photonic systems with optical interconnects that traverse multiple planes. SCRIBE is uniquely suited for constructing such photonic integrated circuits due to its ability to integrate multiple optical components, including lenses and waveguides, without additional printed supports.

High quality factor phase gradient metasurfaces.

Dielectric microcavities with quality factors (Q-factors) in the thousands to billions markedly enhance light-matter interactions, with applications spanning high-efficiency on-chip lasing, frequency comb generation and modulation and sensitive molecular detection. However, as the dimensions of dielectric cavities are reduced to subwavelength scales, their resonant modes begin to scatter light into many spatial channels. Such enhanced scattering is a powerful tool for light manipulation, but also leads to high radiative loss rates and commensurately low Q-factors, generally of order ten. Here, we describe and experimentally demonstrate a strategy for the generation of high Q-factor resonances in subwavelength-thick phase gradient metasurfaces. By including subtle structural perturbations in individual metasurface elements, resonances are created that weakly couple free-space light into otherwise bound and spatially localized modes. Our metasurface can achieve Q-factors >2,500 while beam steering light to particular directions. High-Q beam splitters are also demonstrated. With high-Q metasurfaces, the optical transfer function, near-field intensity and resonant line shape can all be rationally designed, providing a foundation for efficient, free-space-reconfigurable and nonlinear nanophotonics.

Transparent multispectral photodetectors mimicking the human visual system.

Compact and lightweight photodetection elements play a critical role in the newly emerging augmented reality, wearable and sensing technologies. In these technologies, devices are preferred to be transparent to form an optical interface between a viewer and the outside world. For this reason, it is of great value to create detection platforms that are imperceptible to the human eye directly onto transparent substrates. Semiconductor nanowires (NWs) make ideal photodetectors as their optical resonances enable parsing of the multi-dimensional information carried by light. Unfortunately, these optical resonances also give rise to strong, undesired light scattering. In this work, we illustrate how a new optical resonance arising from the radiative coupling between arrayed silicon NWs can be harnessed to remove reflections from dielectric interfaces while affording spectro-polarimetric detection. The demonstrated transparent photodetector concept opens up promising platforms for transparent substrates as the base for opto-electronic devices and in situ optical measurement systems.

Dynamic Tuning of Gap Plasmon Resonances Using a Solid-State Electrochromic Device.

Plasmonic antennas and metasurfaces can effectively control light-matter interactions, and this facilitates a deterministic design of optical materials properties, including structural color. However, these optical properties are generally fixed after synthesis and fabrication, while many modern-day optics applications require active, low-power, and nonvolatile tuning. These needs have spurred broad research activities aimed at identifying materials and resonant structures capable of achieving large, dynamic changes in optical properties, especially in the challenging visible spectral range. In this work, we demonstrate dynamic tuning of polarization-dependent gap plasmon resonators that contain the electrochromic oxide WO3. Its refractive index in the visible changes continuously from n = 2.1 to 1.9 upon electrochemical lithium insertion and removal in a solid-state device. By incorporating WO3 into a gap plasmon resonator, the resonant wavelength can be shifted continuously and reversibly by up to 58 nm with less than 2 V electrochemical bias voltage. The resonator can remain in a tuned state for tens of minutes under open circuit conditions.

Spatiotemporal light control with frequency-gradient metasurfaces.

The capability of on-chip wavefront modulation has the potential to revolutionize many optical device technologies. However, the realization of power-efficient phase-gradient metasurfaces that offer full-phase modulation (0 to 2π) and high operation speeds remains elusive. We present an approach to continuously steer light that is based on creating a virtual frequency-gradient metasurface by combining a passive metasurface with an advanced frequency-comb source. Spatiotemporal redirection of light naturally occurs as optical phase-fronts reorient at a speed controlled by the frequency gradient across the virtual metasurface. An experimental realization of laser beam steering with a continuously changing steering angle is demonstrated with a single metasurface over an angle of 25° in just 8 picoseconds. This work can support integrated-on-chip solutions for spatiotemporal optical control, directly affecting emerging applications such as solid-state light detection and ranging (LIDAR), three-dimensional imaging, and augmented or virtual systems.

Probing the Band Structure of Topological Silicon Photonic Lattices in the Visible Spectrum.

We study two-dimensional hexagonal photonic lattices of silicon Mie resonators with a topological optical band structure in the visible spectral range. We use 30 keV electrons focused to nanoscale spots to map the local optical density of states in topological photonic lattices with deeply subwavelength resolution. By slightly shrinking or expanding the unit cell, we form hexagonal superstructures and observe the opening of a band gap and a splitting of the double-degenerate Dirac cones, which correspond to topologically trivial and nontrivial phases. Optical transmission spectroscopy shows evidence of topological edge states at the domain walls between topological and trivial lattices.

Reversible and selective ion intercalation through the top surface of few-layer MoS2.

Electrochemical intercalation of ions into the van der Waals gap of two-dimensional (2D) layered materials is a promising low-temperature synthesis strategy to tune their physical and chemical properties. It is widely believed that ions prefer intercalation into the van der Waals gap through the edges of the 2D flake, which generally causes wrinkling and distortion. Here we demonstrate that the ions can also intercalate through the top surface of few-layer MoS2 and this type of intercalation is more reversible and stable compared to the intercalation through the edges. Density functional theory calculations show that this intercalation is enabled by the existence of natural defects in exfoliated MoS2 flakes. Furthermore, we reveal that sealed-edge MoS2 allows intercalation of small alkali metal ions (e.g., Li+ and Na+) and rejects large ions (e.g., K+). These findings imply potential applications in developing functional 2D-material-based devices with high tunability and ion selectivity.

Metasurface Mirrors for External Control of Mie Resonances.

The ability to control and structurally tune the optical resonances of semiconductor nanostructures has far-reaching implications for a wide range of optical applications, including photodetectors, (bio)sensors, and photovoltaics. Such control is commonly obtained by tailoring the nanostructure's geometry, material, or dielectric environment. Here, we combine insights from the field of coherent optics and metasurface mirrors to effectively turn Mie resonances on and off with high spatial control and in a polarization-dependent fashion. We illustrate this in an integrated device by manipulating the photocurrent spectra of a single-nanowire photodetector placed on a metasurface mirror. This approach can be generalized to control spectral, angle-dependent, absorption, and scattering properties of semiconductor nanostructures with an engineered metasurface and without a need to alter their geometric or materials properties.

Spatially controlled doping of two-dimensional SnS2 through intercalation for electronics.

Doped semiconductors are the most important building elements for modern electronic devices 1 . In silicon-based integrated circuits, facile and controllable fabrication and integration of these materials can be realized without introducing a high-resistance interface2,3. Besides, the emergence of two-dimensional (2D) materials enables the realization of atomically thin integrated circuits4-9. However, the 2D nature of these materials precludes the use of traditional ion implantation techniques for carrier doping and further hinders device development 10 . Here, we demonstrate a solvent-based intercalation method to achieve p-type, n-type and degenerately doped semiconductors in the same parent material at the atomically thin limit. In contrast to naturally grown n-type S-vacancy SnS2, Cu intercalated bilayer SnS2 obtained by this technique displays a hole field-effect mobility of ~40 cm2 V-1 s-1, and the obtained Co-SnS2 exhibits a metal-like behaviour with sheet resistance comparable to that of few-layer graphene 5 . Combining this intercalation technique with lithography, an atomically seamless p-n-metal junction could be further realized with precise size and spatial control, which makes in-plane heterostructures practically applicable for integrated devices and other 2D materials. Therefore, the presented intercalation method can open a new avenue connecting the previously disparate worlds of integrated circuits and atomically thin materials.