Directive giant upconversion by supercritical bound states in the continuum.

Photonic bound states in the continuum (BICs), embedded in the spectrum of free-space waves1,2 with diverging radiative quality factor, are topologically non-trivial dark modes in open-cavity resonators that have enabled important advances in photonics3,4. However, it is particularly challenging to achieve maximum near-field enhancement, as this requires matching radiative and non-radiative losses. Here we propose the concept of supercritical coupling, drawing inspiration from electromagnetically induced transparency in near-field coupled resonances close to the Friedrich-Wintgen condition2. Supercritical coupling occurs when the near-field coupling between dark and bright modes compensates for the negligible direct far-field coupling with the dark mode. This enables a quasi-BIC field to reach maximum enhancement imposed by non-radiative loss, even when the radiative quality factor is divergent. Our experimental design consists of a photonic-crystal nanoslab covered with upconversion nanoparticles. Near-field coupling is finely tuned at the nanostructure edge, in which a coherent upconversion luminescence enhanced by eight orders of magnitude is observed. The emission shows negligible divergence, narrow width at the microscale and controllable directivity through input focusing and polarization. This approach is relevant to various physical processes, with potential applications for light-source development, energy harvesting and photochemical catalysis.

Scalable single-mode surface-emitting laser via open-Dirac singularities.

Single-aperture cavities are a key component of lasers that are instrumental for the amplification and emission of a single light mode. However, the appearance of high-order transverse modes as the size of the cavities increases has frustrated efforts to scale-up cavities while preserving single-mode operation since the invention of the laser six decades ago1-8. A suitable physical mechanism that allows single-mode lasing irrespective of the cavity size-a 'scale invariant' cavity or laser-has not been identified yet. Here we propose and demonstrate experimentally that open-Dirac electromagnetic cavities with linear dispersion-which in our devices are realized by a truncated photonic crystal arranged in a hexagonal pattern-exhibit unconventional scaling of losses in reciprocal space, leading to single-mode lasing that is maintained as the cavity is scaled up in size. The physical origin of this phenomenon lies in the convergence of the complex part of the free spectral range in open-Dirac cavities towards a constant governed by the loss rates of distinct Bloch bands, whereas for common cavities it converges to zero as the size grows, leading to inevitable multimode emission. An unconventional flat-envelope fundamental mode locks all unit cells in the cavity in phase, leading to single-mode lasing. We name such sources Berkeley surface-emitting lasers (BerkSELs) and demonstrate that their far-field corresponds to a topological singularity of charge two, in agreement with our theory. Open-Dirac cavities unlock avenues for light-matter interaction and cavity quantum electrodynamics.

Vibrational relaxation dynamics in layered perovskite quantum wells.

Organic-inorganic layered perovskites, or Ruddlesden-Popper perovskites, are two-dimensional quantum wells with layers of lead-halide octahedra stacked between organic ligand barriers. The combination of their dielectric confinement and ionic sublattice results in excitonic excitations with substantial binding energies that are strongly coupled to the surrounding soft, polar lattice. However, the ligand environment in layered perovskites can significantly alter their optical properties due to the complex dynamic disorder of the soft perovskite lattice. Here, we infer dynamic disorder through phonon dephasing lifetimes initiated by resonant impulsive stimulated Raman photoexcitation followed by transient absorption probing for a variety of ligand substitutions. We demonstrate that vibrational relaxation in layered perovskite formed from flexible alkyl-amines as organic barriers is fast and relatively independent of the lattice temperature. Relaxation in layered perovskites spaced by aromatic amines is slower, although still fast relative to bulk inorganic lead bromide lattices, with a rate that is temperature dependent. Using molecular dynamics simulations, we explain the fast rates of relaxation by quantifying the large anharmonic coupling of the optical modes with the ligand layers and rationalize the temperature independence due to their amorphous packing. This work provides a molecular and time-domain depiction of the relaxation of nascent optical excitations and opens opportunities to understand how they couple to the complex layered perovskite lattice, elucidating design principles for optoelectronic devices.

Near-Field Coupling with a Nanoimprinted Probe for Dark Exciton Nanoimaging in Monolayer WSe2.

Tip-enhanced photoluminescence (TRPL) is a powerful technique for spatially and spectrally probing local optical properties of 2-dimensional (2D) materials that are modulated by the local heterogeneities, revealing inaccessible dark states due to bright state overlap in conventional far-field microscopy at room temperature. While scattering-type near-field probes have shown the potential to selectively enhance and reveal dark exciton emission, their technical complexity and sensitivity can pose challenges under certain experimental conditions. Here, we present a highly reproducible and easy-to-fabricate near-field probe based on nanoimprint lithography and fiber-optic excitation and collection. The novel near-field measurement configuration provides an ∼3 orders of magnitude out-of-plane Purcell enhancement, diffraction-limited excitation spot, and subdiffraction hyperspectral imaging resolution (below 50 nm) of dark exciton emission. The effectiveness of this high spatial XD mapping technique was then demonstrated through reproducible hyperspectral mapping of oxidized sites and bubble areas.

Integrating collapsible plasmonic gaps on near-field probes for polarization-resolved mapping of plasmon-enhanced emission in 2D material.

Scanning near-field optical microscopy (SNOM) is an important technique used to study the optical properties of material systems at the nanoscale. In previous work, we reported on the use of nanoimprinting to improve the reproducibility and throughput of near-field probes including complicated optical antenna structures such as the 'campanile' probe. However, precise control over the plasmonic gap size, which determines the near-field enhancement and spatial resolution, remains a challenge. Here, we present a novel approach to fabricating a sub-20 nm plasmonic gap in a near-field plasmonic probe through the controlled collapse of imprinted nanostructures using atomic layer deposition (ALD) coatings to define the gap width. The resulting ultranarrow gap at the apex of the probe provides a strong polarization-sensitive near-field optical response, which results in an enhancement of the optical transmission in a broad wavelength range from 620 to 820 nm, enabling tip-enhanced photoluminescence (TEPL) mapping of 2-dimensional (2D) materials. We demonstrate the potential of this near-field probe by mapping a 2D exciton coupled to a linearly polarized plasmonic resonance with below 30 nm spatial resolution. This work proposes a novel approach for integrating a plasmonic antenna at the apex of the near-field probe, paving the way for the fundamental study of light-matter interactions at the nanoscale.

Transferable nano-patterned ALD membrane.

We demonstrate fabrication of nano-patterned thin ALD (Atomic layer deposition) membrane (suspended/transferable) by using a bi-layer resist process where the bottom layer resist acts as a sacrificial layer. This method enables an all dry deterministic transfer of nano-patterned ALD membrane on desired substrate, allowing assembly of multitude of hetero-structures and functionalities that are not yet accessible. Unlike conventional ways of achieving patterned alumina membrane reported in literature our technique requires significantly less fabrication steps and paves the way for novel ALD membrane-based technology.

Source noise suppression in attosecond transient absorption spectroscopy by edge-pixel referencing.

Attosecond transient absorption spectroscopy (ATAS) is used to observe photoexcited dynamics with outstanding time resolution. The main experimental challenge of this technique is that high-harmonic generation sources show significant instabilities, resulting in sub-par sensitivity when compared to other techniques. This paper proposes edge-pixel referencing as a means to suppress this noise. Two approaches are introduced: the first is deterministic and uses a correlation analysis, while the second relies on singular value decomposition. Each method is demonstrated and quantified on a noisy measurement taken on WS2 and results in a fivefold increase in sensitivity. The combination of the two methods ensures the fidelity of the procedure and can be implemented on live data collection but also on existing datasets. The results show that edge-referencing methods bring the sensitivity of ATAS near the detector noise floor. An implementation of the post-processing code is provided to the reader.

Ultrathin Free-Standing Oxide Membranes for Electron and Photon Spectroscopy Studies of Solid-Gas and Solid-Liquid Interfaces.

Free-standing ultrathin (∼2 nm) films of several oxides (Al2O3,TiO2, and others) have been developed, which are mechanically robust and transparent to electrons with Ekin ≥ 200 eV and to photons. We demonstrate their applicability in environmental X-ray photoelectron and infrared spectroscopy for molecular level studies of solid-gas (≥1 bar) and solid-liquid interfaces. These films act as membranes closing a reaction cell and as substrates and electrodes for electrochemical reactions. The remarkable properties of such ultrathin oxides membranes enable atomic/molecular level studies of interfacial phenomena, such as corrosion, catalysis, electrochemical reactions, energy storage, geochemistry, and biology, in a broad range of environmental conditions.

Shape-Selective Synthesis of Pentacene Macrocycles and the Effect of Geometry on Singlet Fission.

Pentacene's extraordinary photophysical and electronic properties are highly dependent on intermolecular through-space interactions. Macrocyclic arrangements of chromophores have been shown to provide a high level of control over these interactions, but few examples exist for pentacene due to inherent synthetic challenges. In this work, zirconocene-mediated alkyne coupling was used as a dynamic covalent C-C bond forming reaction to synthesize two geometrically distinct, pentacene-containing macrocycles on a gram scale and in four or fewer steps. Both macrocycles undergo singlet fission in solution with rates that differ by an order of magnitude, while the rate of triplet recombination is approximately the same. This independent modulation of singlet and triplet decay rates is highly desirable for the design of efficient singlet fission materials. The dimeric macrocycle adopts a columnar packing motif in the solid state with large void spaces between pentacene units of the crystal lattice.

Large Spin-Orbit Splitting of Deep In-Gap Defect States of Engineered Sulfur Vacancies in Monolayer WS_{2}.

Structural defects in 2D materials offer an effective way to engineer new material functionalities beyond conventional doping. We report on the direct experimental correlation of the atomic and electronic structure of a sulfur vacancy in monolayer WS_{2} by a combination of CO-tip noncontact atomic force microscopy and scanning tunneling microscopy. Sulfur vacancies, which are absent in as-grown samples, were deliberately created by annealing in vacuum. Two energetically narrow unoccupied defect states followed by vibronic sidebands provide a unique fingerprint of this defect. Direct imaging of the defect orbitals, together with ab initio GW calculations, reveal that the large splitting of 252±4 meV between these defect states is induced by spin-orbit coupling.

Spectroscopic elucidation of energy transfer in hybrid inorganic-biological organisms for solar-to-chemical production.

The rise of inorganic-biological hybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic-abiotic interface to drive the development of next-generation systems. The model system, Moorella thermoacetica-cadmium sulfide (CdS), combines an inorganic semiconductor nanoparticle light harvester with an acetogenic bacterium to drive the photosynthetic reduction of CO2 to acetic acid with high efficiency. In this work, we report insights into this unique electrotrophic behavior and propose a charge-transfer mechanism from CdS to M. thermoacetica Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates increase with increasing hydrogenase (H2ase) enzyme activity. On the same time scale as the TA spectroscopy, time-resolved infrared (TRIR) spectroscopy showed spectral changes in the 1,700-1,900-cm-1 spectral region. The quantum efficiency of this system for photosynthetic acetic acid generation also increased with increasing H2ase activity and shorter carrier lifetimes when averaged over the first 24 h of photosynthesis. However, within the initial 3 h of photosynthesis, the rate followed an opposite trend: The bacteria with the lowest H2ase activity photosynthesized acetic acid the fastest. These results suggest a two-pathway mechanism: a high quantum efficiency charge-transfer pathway to H2ase generating H2 as a molecular intermediate that dominates at long time scales (24 h), and a direct energy-transducing enzymatic pathway responsible for acetic acid production at short time scales (3 h). This work represents a promising platform to utilize conventional spectroscopic methodology to extract insights from more complex biotic-abiotic hybrid systems.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes.

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Atomic layer deposition for spacer defined double patterning of sub-10 nm titanium dioxide features.

The next generation of hard disk drive technology for data storage densities beyond 5 Tb/in2 will require single-bit patterning of features with sub-10 nm dimensions by nanoimprint lithography. To address this challenge master templates are fabricated using pattern multiplication with atomic layer deposition (ALD). Sub-10 nm lithography requires a solid understanding of materials and their interactions. In this work we study two important oxide materials, silicon dioxide and titanium dioxide, as the pattern spacer and look at their interactions with carbon, chromium and silicon dioxide. We found that thermal titanium dioxide ALD allows for the conformal deposition of a spacer layer without damaging the carbon mandrel and eliminates the surface modification due to the reactivity of the metal-organic precursor. Finally, using self-assembled block copolymer lithography and thermal titanium dioxide spacer fabrication, we demonstrate pattern doubling with 7.5 nm half-pitch spacer features.

Rate and mechanism of the photoreduction of birnessite (MnO2) nanosheets.

The photoreductive dissolution of Mn(IV) oxide minerals in sunlit aquatic environments couples the Mn cycle to the oxidation of organic matter and fate of trace elements associated with Mn oxides, but the intrinsic rate and mechanism of mineral dissolution in the absence of organic electron donors is unknown. We investigated the photoreduction of δ-MnO2 nanosheets at pH 6.5 with Na or Ca as the interlayer cation under 400-nm light irradiation and quantified the yield and timescales of Mn(III) production. Our study of transient intermediate states using time-resolved optical and X-ray absorption spectroscopy showed key roles for chemically distinct Mn(III) species. The reaction pathway involves (i) formation of Jahn-Teller distorted Mn(III) sites in the octahedral sheet within 0.6 ps of photoexcitation; (ii) Mn(III) migration into the interlayer within 600 ps; and (iii) increased nanosheet stacking. We propose that irreversible Mn reduction is coupled to hole-scavenging by surface water molecules or hydroxyl groups, with associated radical formation. This work demonstrates the importance of direct MnO2 photoreduction in environmental processes and provides a framework to test new hypotheses regarding the role of organic molecules and metal species in photochemical reactions with Mn oxide phases. The timescales for the production and evolution of Mn(III) species and a catalytic role for interlayer Ca(2+) identified here from spectroscopic measurements can also guide the design of efficient Mn-based catalysts for water oxidation.

Experimental and Ab Initio Ultrafast Carrier Dynamics in Plasmonic Nanoparticles.

Ultrafast pump-probe measurements of plasmonic nanostructures probe the nonequilibrium behavior of excited carriers, which involves several competing effects obscured in typical empirical analyses. Here we present pump-probe measurements of plasmonic nanoparticles along with a complete theoretical description based on first-principles calculations of carrier dynamics and optical response, free of any fitting parameters. We account for detailed electronic-structure effects in the density of states, excited carrier distributions, electron-phonon coupling, and dielectric functions that allow us to avoid effective electron temperature approximations. Using this calculation method, we obtain excellent quantitative agreement with spectral and temporal features in transient-absorption measurements. In both our experiments and calculations, we identify the two major contributions of the initial response with distinct signatures: short-lived highly nonthermal excited carriers and longer-lived thermalizing carriers.

Efficient and sustained photoelectrochemical water oxidation by cobalt oxide/silicon photoanodes with nanotextured interfaces.

Plasma-enhanced atomic layer deposition of cobalt oxide onto nanotextured p(+)n-Si devices enables efficient photoelectrochemical water oxidation and effective protection of Si from corrosion at high pH (pH 13.6). A photocurrent density of 17 mA/cm(2) at 1.23 V vs RHE, saturation current density of 30 mA/cm(2), and photovoltage greater than 600 mV were achieved under simulated solar illumination. Sustained photoelectrochemical water oxidation was observed with no detectable degradation after 24 h. Enhanced performance of the nanotextured structure, compared to planar Si, is attributed to a reduced silicon oxide thickness that provides more intimate interfacial contact between the light absorber and catalyst. This work highlights a general approach to improve the performance and stability of Si photoelectrodes by engineering the catalyst/semiconductor interface.

Chiral nanostructures studied using polarization-dependent NOLES imaging.

The Nonlinear Optical Localization using Electromagnetic Surface fields (NOLES) imaging technique was used to generate optical images in which the position of a chiral object could be determined with nanometer precision. Asymmetric gold bowtie nanostructures were used as a model system with 2D chirality. The bowties functioned as a chiral nonlinear medium that converted the fundamental of a Ti:sapphire laser to its second harmonic frequency. The bowties consisted of two lithographically prepared equilateral triangles (base = 75 nm, height = 85 nm, thickness = 25 nm) separated by a 20 nm gap. Asymmetric bowties were formed by lateral displacement of one triangle by 10 nm, yielding C2 point group symmetry. The chirality of the bowtie nanostructures was confirmed via nonzero second-harmonic generation circular dichroism (SHG-CDR) ratios, which came from single-particle SHG measurements. The SHG-CDR ratios were validated using numerical finite difference time domain simulations that quantified the relative magnitudes of gap-localized electromagnetic fields at the harmonic frequency resulting from excitation by left and right circularly (LCP and RCP) and linearly polarized fundamental waves. The relative electric dipolar and magnetic dipolar contributions to the SHG responses were determined using single-particle continuous polarization variation (CPV) SHG measurements. The spatial localization precision obtainable for individual chiral nanostructures was determined by statistical analysis of the SHG image point spread function. Our results demonstrated that both the chiral image contrast, which resulted from LCP and RCP excitation, and the corresponding localization precision was dependent upon the relative magnetic dipole/electric dipole ratio (G/F). A localization precision of 1.13 ± 0.13 nm and left-to-right image enhancements of 400% were obtained for bowties with the highest G/F ratios using 5 s frame exposure times. The polarization dependence and magnetic dipole amplification confirmed here demonstrate that the NOLES imaging technique is a powerful method for studying chiral specimens with high spatial precision.

The role of surface functionalization in quantum dot-based photocatalytic CO2 reduction: balancing efficiency and stability.

Photocatalytic CO2 reduction offers a promising strategy to produce hydrocarbons without reliance on fossil fuels. Visible light-absorbing colloidal nanomaterials composed of earth-abundant metals suspended in aqueous media are particularly attractive owing to their low-cost, ease of separation, and highly modifiable surfaces. The current study explores such a system by employing water-soluble ZnSe quantum dots and a Co-based molecular catalyst. Water solubilization of the quantum dots is achieved with either carboxylate (3-mercaptopropionic acid) or ammonium (2-aminoethanethiol) functionalized ligands to produce nanoparticles with either negatively or positively-charged surfaces. Photocatalysis experiments are performed to compare the effectiveness of these two surface functionalization strategies on CO2 reduction and ultrafast spectroscopy is used to reveal the underlying photoexcited charge dynamics. We find that the positively-charged quantum dots can support sub-picosecond electron transfer to the carboxylate-based molecular catalyst and also produce >30% selectivity for CO and >170 mmolCO gZnSe-1. However, aggregation reduces activity in approximately one day. In contrast, the negatively-charged quantum dots exhibit >10 ps electron transfer and substantially lower CO selectivity, but they are colloidally stable for days. These results highlight the importance of the quantum dot-catalyst interaction for CO2 reduction. Furthermore, multi-dentate catalyst molecules create a trade-off between photocatalytic efficiency from strong interactions and deleterious aggregation of quantum dot-catalyst assemblies.

A substitutional quantum defect in WS2 discovered by high-throughput computational screening and fabricated by site-selective STM manipulation.

Point defects in two-dimensional materials are of key interest for quantum information science. However, the parameter space of possible defects is immense, making the identification of high-performance quantum defects very challenging. Here, we perform high-throughput (HT) first-principles computational screening to search for promising quantum defects within WS2, which present localized levels in the band gap that can lead to bright optical transitions in the visible or telecom regime. Our computed database spans more than 700 charged defects formed through substitution on the tungsten or sulfur site. We found that sulfur substitutions enable the most promising quantum defects. We computationally identify the neutral cobalt substitution to sulfur (Co S 0 ) and fabricate it with scanning tunneling microscopy (STM). The Co S 0 electronic structure measured by STM agrees with first principles and showcases an attractive quantum defect. Our work shows how HT computational screening and nanoscale synthesis routes can be combined to design promising quantum defects.

Triggering and monitoring plasmon-enhanced reactions by optical nanoantennas coupled to photocatalytic beads.

Plasmonic metal/semiconductor nanocomposites promise to be a breakthrough for boosting and investigating photon-assisted processes at the nanoscale, with exciting perspectives for energy conversion and catalysis. However, the efficiency and selectivity of these surface processes are still far from being controlled. Here, shown for the first time, is a new class of photocatalyst which is based on the synergistic combination of bowtie-like gold nanoantennas and SiO2 /TiO2 core/shell oxide beads. These systems are exploited as efficient near-field optical light concentrators, stimulating photon-driven processes at the metal-semiconductor interface. Extraordinary enhancements of photodegradation rates (minutes instead of hours) result from matching the nanoantenna surface plasmon resonance with the optical absorption of organic dyes and the excitation source wavelength. Moreover, strong Raman enhancements are observed allowing for direct in-situ monitoring of reaction progress of different analytes on the same site.