Near-Unity Light-Matter Interaction in Mid-Infrared van der Waals Metasurfaces.

Accessing mid-infrared radiation is of great importance for a range of applications, including thermal imaging, sensing, and radiative cooling. Here, we study light interaction with hexagonal boron nitride (hBN) nanocavities and reveal strong and tunable resonances across its hyperbolic transition. In addition to conventional phonon-polariton excitations, we demonstrate that the high refractive index of hexagonal boron nitride outside the Reststrahlen band allows enhanced light-matter interactions in deep subwavelength (<λ/15) nanostructures across a broad 7-8 µm range. Emergence and interplay of Fabry-Perot and Mie-like resonances are examined experimentally and theoretically. Near-unity absorption and high quality (Q ≥ 80) resonance interaction in the vicinity of the hBN transverse optical phonon is further observed. Our study provides avenues to design highly efficient and ultracompact structures for controlling mid-infrared radiation and accessing strong light-matter interactions with hBN.

Enhanced Infrared Photodiodes Based on PbS/PbClx Core/Shell Nanocrystals.

Improved passivation strategies to address the more complex surface structure of large-diameter nanocrystals are critical to the advancement of infrared photodetectors based on colloidal PbS. In this contribution, the performance of short-wave infrared (SWIR) photodiodes fabricated with PbS/PbClx (core/shell) nanocrystals vs their PbS-only (core) counterparts are directly compared. Devices using PbS cores suffer from shunting and inefficient charge extraction, while core/shell-based devices exhibit greater external quantum efficiencies and lower dark current densities. To elucidate the implications of the shell chemistry on device performance, thickness-dependent energy level offsets and interfacial chemistry of nanocrystal films with the zinc oxide electron-transport layer are evaluated. The disparate device performance between the two synthetic methods is attributed to unfavorable interface dipole formation and surface defect states, associated with inadequate removal of native organic ligands in core-only films. The core/shell system offers a promising route to manage the additional nonpolar (100) surface facets of larger nanocrystals that conventional halide ligand treatments fail to sufficiently passivate.

Plasmonic nanoarcs: a versatile platform with tunable localized surface plasmon resonances in octave intervals.

The tunability of the longitudinal localized surface plasmon resonances (LSPRs) of metallic nanoarcs is demonstrated with key relationships identified between geometric parameters of the arcs and their resonances in the infrared. The wavelength of the LSPRs is tuned by the mid-arc length of the nanoarc. The ratio between the attenuation of the fundamental and second order LSPRs is governed by the nanoarc central angle. Beneficial for plasmonic enhancement of harmonic generation, these two resonances can be tuned independently to obtain octave intervals through the design of a non-uniform arc-width profile. Because the character of the fundamental LSPR mode in nanoarcs combines an electric and a magnetic dipole, plasmonic nanoarcs with tunable resonances can serve as versatile building blocks for chiroptical and nonlinear optical devices.

Binary Superlattices of Infrared Plasmonic and Excitonic Nanocrystals.

Self-assembled superlattices of nanocrystals offer exceptional control over the coupling between nanocrystals, similar to how solid-state crystals tailor the bonding between atoms. By assembling nanocrystals of different properties (e.g., plasmonic, excitonic, dielectric, or magnetic), we can form a wealth of binary superlattice metamaterials with new functionalities. Here, we introduce infrared plasmonic Cu2-xS nanocrystals to the limited library of materials that have been successfully incorporated into binary superlattices. We are the first to create a variety of binary superlattices with large excitonic (PbS) nanocrystals and small plasmonic (Cu2-xS) nanocrystals, both resonant in the infrared. Then, by controlling the surface chemistry of large Cu2-xS nanocrystals, we produced structurally analogous superlattices of large Cu2-xS and small PbS nanocrystals. Transmission electron microscopy (TEM) and grazing-incidence small-angle X-ray scattering (GISAXS) were used to characterize both types of superlattices. Furthermore, our unique surface modification of the large Cu2-xS nanocrystals also prevented them from chemically quenching the photoluminescence of the PbS nanocrystals, which occurred when the PbS nanocrystals were mixed with unmodified Cu2-xS nanocrystals. These synthetic achievements create a set of binary superlattices that can be used to understand how infrared plasmonic and excitonic nanocrystals couple in a variety of symmetries and stoichiometries.

Author Correction: Ultralow-loss polaritons in isotopically pure boron nitride.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Controlling dissolution of PbTe nanoparticles in organic solvents during liquid cell transmission electron microscopy.

We present direct visualization of the dynamics of oleic-acid-capped PbTe nanoparticles suspended in different organic solvents using liquid cell transmission electron microscopy. Liquid cell transmission electron microscopy is a powerful tool to directly observe the behavior of a variety of nanoparticles in liquids, but requires careful consideration and quantification of how the electron beam affects the systems being investigated. We find that etching and dissolution of PbTe nanoparticles occurs with a strong dependence on electron dose rate ranging from no perceivable effect on the nanoparticles with lower dose rates (50 e- Å-2 s-1) to complete dissolution within seconds or minutes at higher dose rates (100 and 200 e- Å-2 s-1). We propose that oxidative etching, resulting from the radiolysis of small amounts of water, causes the PbTe nanoparticles to dissolve after exposure to a threshold electron dose rate of 50 e- Å-2 s-1.

Controlling the Infrared Dielectric Function through Atomic-Scale Heterostructures.

Surface phonon polaritons (SPhPs), the surface-bound electromagnetic modes of a polar material resulting from the coupling of light with optic phonons, offer immense technological opportunities for nanophotonics in the infrared (IR) spectral region. However, once a particular material is chosen, the SPhP characteristics are fixed by the spectral positions of the optic phonon frequencies. Here, we provide a demonstration of how the frequency of these optic phonons can be altered by employing atomic-scale superlattices (SLs) of polar semiconductors using AlN/GaN SLs as an example. Using second harmonic generation (SHG) spectroscopy, we show that the optic phonon frequencies of the SLs exhibit a strong dependence on the layer thicknesses of the constituent materials. Furthermore, new vibrational modes emerge that are confined to the layers, while others are centered at the AlN/GaN interfaces. As the IR dielectric function is governed by the optic phonon behavior in polar materials, controlling the optic phonons provides a means to induce and potentially design a dielectric function distinct from the constituent materials and from the effective-medium approximation of the SL. We show that atomic-scale AlN/GaN SLs instead have multiple Reststrahlen bands featuring spectral regions that exhibit either normal or extreme hyperbolic dispersion with both positive and negative permittivities dispersing rapidly with frequency. Apart from the ability to engineer the SPhP properties, SL structures may also lead to multifunctional devices that combine the mechanical, electrical, thermal, or optoelectronic functionality of the constituent layers. We propose that this effort is another step toward realizing user-defined, actively tunable IR optics and sources.

Hybrid longitudinal-transverse phonon polaritons.

Phonon polaritons, hybrid light-matter quasiparticles resulting from strong coupling of the electromagnetic field with the lattice vibrations of polar crystals are a promising platform for mid-infrared photonics but for the moment there has been no proposal allowing for their electrical pumping. Electrical currents in fact mainly generate longitudinal optical phonons, while only transverse ones participate in the creation of phonon polaritons. We demonstrate how to exploit long-cell polytypes of silicon carbide to achieve strong coupling between transverse phonon polaritons and zone-folded longitudinal optical phonons. We develop a microscopic theory predicting the existence of the resulting hybrid longitudinal-transverse excitations. We then provide an experimental observation by tuning the resonance of a nanopillar array through the folded longitudinal optical mode, obtaining a clear spectral anti-crossing. The hybridisation of phonon polaritons with longitudinal phonons could represent an important step toward the development of phonon polariton-based electrically pumped mid-infrared emitters.

Effects of a Lead Chloride Shell on Lead Sulfide Quantum Dots.

The size of a quantum-confined nanocrystal determines the energies of its excitonic transitions. Previous work has correlated the diameters of PbS nanocrystals to their excitonic absorption; however, we observe that PbS quantum dots synthesized in saturated dispersions of PbCl2 can deviate from the previous 1Sh-1Se energy vs diameter curve by 0.8 nm. In addition, their surface differs chemically from that of PbS quantum dots produced via other syntheses. We find that these nanocrystals are coated in a shell that is measurable in transmission electron micrographs and contains lead and chlorine, beyond the monatomic chlorine termination previously proposed. This finding has implications for understanding the growth mechanism of this reaction, the line width of these quantum dots' photoluminescence, and electronic transport within films of these nanocrystals. Such fundamental knowledge is critical to applications of PbS quantum dots such as single-photon sources, photodetectors, solar cells, light-emitting diodes, lasers, and biological labels.

Energy Level Alignment of Molybdenum Oxide on Colloidal Lead Sulfide (PbS) Thin Films for Optoelectronic Devices.

Interfacial charge transport in optoelectronic devices is dependent on energetic alignment that occurs via a number of physical and chemical mechanisms. Herein, we directly connect device performance with measured thickness-dependent energy-level offsets and interfacial chemistry of 1,2-ethanedithiol-treated lead sulfide (PbS) quantum dots and molybdenum oxide. We show that interfacial energetic alignment results from partial charge transfer, quantified via the chemical ratios of Mo5+ relative to Mo6+. The combined effect mitigates leakage current in both the dark and the light, relative to a metal contact, with an overall improvement in open circuit voltage, fill factor, and short circuit current.

Ultralow-loss polaritons in isotopically pure boron nitride.

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called 'flat' optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitride (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.

Aspect-ratio driven evolution of high-order resonant modes and near-field distributions in localized surface phonon polariton nanostructures.

Polar dielectrics have garnered much attention as an alternative to plasmonic metals in the mid- to long-wave infrared spectral regime due to their low optical losses. As such, nanoscale resonators composed of these materials demonstrate figures of merit beyond those achievable in plasmonic equivalents. However, until now, only low-order, phonon-mediated, localized polariton resonances, known as surface phonon polaritons (SPhPs), have been observed in polar dielectric optical resonators. In the present work, we investigate the excitation of 16 distinct high-order, multipolar, localized surface phonon polariton resonances that are optically excited in rectangular pillars etched into a semi-insulating silicon carbide substrate. By elongating a single pillar axis we are able to significantly modify the far- and near-field properties of localized SPhP resonances, opening the door to realizing narrow-band infrared sources with tailored radiation patterns. Such control of the near-field behavior of resonances can also impact surface enhanced infrared optical sensing, which is mediated by polarization selection rules, as well as the morphology and strength of resonator hot spots. Furthermore, through the careful choice of polar dielectric material, these results can also serve as the guiding principles for the generalized design of optical devices that operate from the mid- to far-infrared.

Fabrication of Fully Solution Processed Inorganic Nanocrystal Photovoltaic Devices.

We demonstrate a method for the preparation of fully solution processed inorganic solar cells from a spin and spray coating deposition of nanocrystal inks. For the photoactive absorber layer, colloidal CdTe and CdSe nanocrystals (3-5 nm) are synthesized using an inert hot injection technique and cleaned with precipitations to remove excess starting reagents. Similarly, gold nanocrystals (3-5 nm) are synthesized under ambient conditions and dissolved in organic solvents. In addition, precursor solutions for transparent conductive indium tin oxide (ITO) films are prepared from solutions of indium and tin salts paired with a reactive oxidizer. Layer-by-layer, these solutions are deposited onto a glass substrate following annealing (200-400 °C) to build the nanocrystal solar cell (glass/ITO/CdSe/CdTe/Au). Pre-annealing ligand exchange is required for CdSe and CdTe nanocrystals where films are dipped in NH4Cl:methanol to replace long-chain native ligands with small inorganic Cl(-) anions. NH4Cl(s) was found to act as a catalyst for the sintering reaction (as a non-toxic alternative to the conventional CdCl2(s) treatment) leading to grain growth (136±39 nm) during heating. The thickness and roughness of the prepared films are characterized with SEM and optical profilometry. FTIR is used to determine the degree of ligand exchange prior to sintering, and XRD is used to verify the crystallinity and phase of each material. UV/Vis spectra show high visible light transmission through the ITO layer and a red shift in the absorbance of the cadmium chalcogenide nanocrystals after thermal annealing. Current-voltage curves of completed devices are measured under simulated one sun illumination. Small differences in deposition techniques and reagents employed during ligand exchange have been shown to have a profound influence on the device properties. Here, we examine the effects of chemical (sintering and ligand exchange agents) and physical treatments (solution concentration, spray-pressure, annealing time and annealing temperature) on photovoltaic device performance.

Imaging of Anomalous Internal Reflections of Hyperbolic Phonon-Polaritons in Hexagonal Boron Nitride.

We use scanning near-field optical microscopy to study the response of hexagonal boron nitride nanocones at infrared frequencies, where this material behaves as a hyperbolic medium. The obtained images are dominated by a series of "hot" rings that occur on the sloped sidewalls of the nanocones. The ring positions depend on the incident laser frequency and the nanocone shape. Both dependences are consistent with directional propagation of hyperbolic phonon-polariton rays that are launched at the edges and zigzag through the interior of the nanocones, sustaining multiple internal reflections off the sidewalls. Additionally, we observe a strong overall enhancement of the near-field signal at discrete resonance frequencies. These resonances attest to low dielectric losses that permit coherent standing waves of the subdiffractional polaritons to form. We comment on potential applications of such shape-dependent resonances and the field concentration at the hot rings.

Atomic-scale photonic hybrids for mid-infrared and terahertz nanophotonics.

The field of nanophotonics focuses on the ability to confine light to nanoscale dimensions, typically much smaller than the wavelength of light. The goal is to develop light-based technologies that are impossible with traditional optics. Subdiffractional confinement can be achieved using either surface plasmon polaritons (SPPs) or surface phonon polaritons (SPhPs). SPPs can provide a gate-tunable, broad-bandwidth response, but suffer from high optical losses; whereas SPhPs offer a relatively low-loss, crystal-dependent optical response, but only over a narrow spectral range, with limited opportunities for active tunability. Here, motivated by the recent results from monolayer graphene and multilayer hexagonal boron nitride heterostructures, we discuss the potential of electromagnetic hybrids--materials incorporating mixtures of SPPs and SPhPs--for overcoming the limitations of the individual polaritons. Furthermore, we also propose a new type of atomic-scale hybrid--the crystalline hybrid--where mixtures of two or more atomic-scale (∼3 nm or less) polar dielectric materials lead to the creation of a new material resulting from hybridized optic phonon behaviour of the constituents, potentially allowing direct control over the dielectric function. These atomic-scale hybrids expand the toolkit of materials for mid-infrared to terahertz nanophotonics and could enable the creation of novel actively tunable, yet low-loss optics at the nanoscale.

Synthesis and Optical Properties of PbSe Nanorods with Controlled Diameter and Length.

The synthesis of PbSe nanorods with low branching (<1%), high aspect ratios (up to ∼16), and controlled lengths and diameters was demonstrated via the removal of water and oleic acid from the synthesis precursors. It was determined that the proper combination of reaction time and temperature allows for the control of PbSe nanorod length and diameter and therefore control over their electronic states, as probed through absorbance and photoluminescence measurements. Similar to PbSe nanowires, nanorods display higher Stokes shifts than for spherical nanocrystals due to intrananorod diameter fluctuations.

Sub-diffractional volume-confined polaritons in the natural hyperbolic material hexagonal boron nitride.

Strongly anisotropic media, where the principal components of the dielectric tensor have opposite signs, are called hyperbolic. Such materials exhibit unique nanophotonic properties enabled by the highly directional propagation of slow-light modes localized at deeply sub-diffractional length scales. While artificial hyperbolic metamaterials have been demonstrated, they suffer from high plasmonic losses and require complex nanofabrication, which in turn induces size-dependent limitations on optical confinement. The low-loss, mid-infrared, natural hyperbolic material hexagonal boron nitride is an attractive alternative. Here we report on three-dimensionally confined 'hyperbolic polaritons' in boron nitride nanocones that support four series (up to the seventh order) modes in two spectral bands. The resonant modes obey the predicted aspect ratio dependence and exhibit high-quality factors (Q up to 283) in the strong confinement regime (up to λ/86). These observations assert hexagonal boron nitride as a promising platform for studying novel regimes of light-matter interactions and nanophotonic device engineering.

Impact of nanocrystal spray deposition on inorganic solar cells.

Solution-synthesized inorganic cadmium telluride nanocrystals (∼4 nm; 1.45 eV band gap) are attractive elements for the fabrication of thin-film-based low-cost photovoltaic (PV) devices. Their encapsulating organic ligand shell enables them to be easily dissolved in organic solvents, and the resulting solutions can be spray-cast onto indium-tin oxide (ITO)-coated glass under ambient conditions to produce photoactive thin films of CdTe. Following annealing at 380 °C in the presence of CdCl2(s) and evaporation of metal electrode contacts (glass/ITO/CdTe/Ca/Al), Schottky-junction PV devices were tested under simulated 1 sun conditions. An improved PV performance was found to be directly tied to control over the film morphology obtained by the adjustment of spray parameters such as the solution concentration, delivery pressure, substrate distance, and surface temperature. Higher spray pressures produced thinner layers (<60 nm) with lower surface roughness (<200 nm), leading to devices with improved open-circuit voltages (Voc) due to decreased surface roughness and higher short-circuit current (Jsc) as a result of enhanced annealing conditions. After process optimization, spray-cast Schottky devices rivaled those prepared by conventional spin-coating, showing Jsc = 14.6 ± 2.7 mA cm(-2), Voc = 428 ± 11 mV, FF = 42.8 ± 1.4%, and Eff. = 2.7 ± 0.5% under 1 sun illumination. This optimized condition of CdTe spray deposition was then applied to heterojunction devices (ITO/CdTe/ZnO/Al) to reach 3.0% efficiency after light soaking under forward bias. The film thickness, surface morphology, and light absorption were examined with scanning electron microscopy, optical profilometry, and UV/vis spectroscopy.

Anisotropic absorption in PbSe nanorods.

We present absorption anisotropy measurements in PbSe nanostructures. This is accomplished via a new means of measuring absorption anisotropy in randomly oriented solution ensembles of nanostructures via pump-probe spectroscopy, which exploits the polarization memory effect. We observe isotropic absorption in nanocrystals and anisotropic absorption in nanorods, which increases upon elongation from aspect ratio 1 to 4 and is constant for longer nanorods. The measured volume-normalized absorption cross section is 1.8 ± 0.3 times larger for parallel pump and probe polarizations in randomly oriented nanorods as compared to nanocrystals. We show that this enhancement would be larger than an order of magnitude for aligned nanorods. Despite being in the strong quantum confinement regime, the aspect ratio dependence of the absorption anisotropy in PbSe nanorods is described classically by the effects of dielectric contrast on an anisotropic nanostructure. These results imply that the dielectric constant of the surrounding medium can be used to influence the optoelectronic properties of nanorods, including polarized absorption and emission, phonon modes, multiple exciton generation efficiency, and Auger recombination rate.

Magneto-optical fingerprints of distinct graphene multilayers using the giant infrared Kerr effect.

The remarkable electronic properties of graphene strongly depend on the thickness and geometry of graphene stacks. This wide range of electronic tunability is of fundamental interest and has many applications in newly proposed devices. Using the mid-infrared, magneto-optical Kerr effect, we detect and identify over 18 interband cyclotron resonances (CR) that are associated with ABA and ABC stacked multilayers as well as monolayers that coexist in graphene that is epitaxially grown on 4H-SiC. Moreover, the magnetic field and photon energy dependence of these features enable us to explore the band structure, electron-hole band asymmetries, and mechanisms that activate a CR response in the Kerr effect for various multilayers that coexist in a single sample. Surprisingly, we find that the magnitude of monolayer Kerr effect CRs is not temperature dependent. This unexpected result reveals new questions about the underlying physics that makes such an effect possible.