Inverse design of a single-frequency diffractive biosensor based on the reporter cleavage detection mechanism.

Vertically interrogated porous silicon (PSi) interferometric biosensors have shown high potential for sensing bio-molecules as they combine high detection sensitivity with simplicity of fabrication, functionalization, optical coupling, and interfacing with microfluidic systems. However, most interferometric sensor designs require either broadband or wavelength-tunable light sources as well as wide-angle detection schemes, increasing their complexity and cost for point-of-care biosensing applications. The limit of detection of such sensors is also constrained by the small size and low refractive index of biological molecules, making it hard to detect very low concentrations of pathogens. In this work, we use a large-scale computational "inverse design" technique to demonstrate a single-frequency, fixed-angle PSi-based biosensor, which exploits a recently developed high-contrast reporter cleavage detection (HCCD) technique. The HCCD sensors detect high-index reporter cleavage events instead of low-index target analyte capture events as typical for traditional label-free optical biosensors. We use the inverse design approach to discover an optimal configuration of a PSi biosensor that makes use of the extended achievable range of cleavage-induced PSi effective index variations and can be interrogated at a single frequency and at a fixed angle. The optimized design in the form of a one-dimensional PSi grating exhibits the change in the reflectance up to 55 % at the interrogation angle of 12∘ and wavelength of 600 nm, which is caused by cleavage of Au nanoparticle reporters initially occupying 2% of the sensor surface area. The maximum possible change in reflectance is predicted to be 222 % (for a two-dimensional freeform design not amenable to fabrication). This demonstration may pave the way for developing new or redesigned conventional interferometric and colorimetric point-of-care biosensor systems in combination with the cleavage-based detection schemes.

High contrast cleavage detection for enhancing porous silicon sensor sensitivity.

Using porous silicon (PSi) interferometer sensors, we show the first experimental implementation of the high contrast cleavage detection (HCCD) mechanism. HCCD makes use of dramatic optical signal amplification caused by cleavage of high-contrast nanoparticle labeled reporters instead of the capture of low-index biological molecules. An approximately 2 nm reflectance peak shift was detected after cleavage of DNA-quantum dot reporters from the PSi surface via exposure to a 12.5 nM DNase enzyme solution. This signal change is 20 times greater than the resolution of the spectrometer used for the interferometric measurements, and the interferometric measurements agree with the response predicted by simulations and fluorescence measurements. These proof of principle experiments show a clear path to achieving a real-time, highly sensitive readout for a broad range of biological diagnostic assays that generate a signal via nucleic acid cleavage triggered by specific molecular binding events.

High contrast cleavage detection.

Photonic biosensors that use optical resonances to amplify signals from refractive index changes offer high sensitivity, real-time readout, and scalable, low-cost fabrication. However, when used with classic affinity assays, they struggle with noise from nonspecific binding and are limited by the low refractive index and small size of target biological molecules. In this Letter, we evaluate the performance of an integrated microring photonic biosensor using the high contrast cleavage detection (HCCD) mechanism, which we recently introduced. The HCCD sensors make use of dramatic optical signal amplification caused by the cleavage of large numbers of high-contrast nanoparticle reporters instead of the adsorption of labeled or unlabeled low-index biological molecules. We evaluate the advantages of the HCCD detection mechanism over conventional target-capture detection techniques with the same label and the same sensor platform, using an example of a silicon ring resonator as an optical transducer decorated with silicon nanoparticles as high-contrast reporters. In the practical realization of this detection scheme, detection specificity and signal amplification can be achieved via collateral nucleic acid cleavage caused by enzymes such as CRISPR Cas12a and Cas13 after binding to a target DNA/RNA sequence in solution.

Self-powered broadband photo-detection and persistent energy generation with junction-free strained Bi2Te3 thin films.

We experimentally demonstrate efficient broadband self-powered photo-detection and power generation in thin films of polycrystalline bismuth telluride (Bi2Te3) semiconductors under inhomogeneous strain. The developed simple, junction-free, lightweight, and flexible photo-detectors are composed of a thin active layer and Ohmic contacts on a flexible plastic substrate, and can operate at room temperature and without application of an external bias voltage. We attribute the observed phenomena to the generation of an electric field due to a spontaneous polarization produced by strain gradient, which can separate both photo-generated and thermally-generated charge carriers in bulk of the semiconductor material, without a semiconductor junction. We show that the developed photo-detectors can generate electric power during both the daytime and the nighttime, by either harnessing solar and thermal radiation or by emitting thermal radiation into the cold sky. To the best of our knowledge, this is the first demonstration of the power generation in a simple junction-free device under negative illumination, which exhibits higher voltage than the previously used expensive commercial HgCdTe photo-diode. Significant improvements in the photo-detector performance are expected if the low-charge-mobility polycrystalline active layer is replaced with high-quality single-crystal material. The technology is not limited to Bi2Te3 as the active material, and offers many potential applications in night vision, wearable sensors, long-range LIDAR, and daytime/nighttime energy generation technologies.

Spectral, spatial and polarization-selective perfect absorbers with large magnetic response for sensing and thermal emission control.

Spectral, spatial, and polarization selective perfect absorption of light in periodic metal-dielectric-metal nanoslits, each of which supporting a single electric-field anti-symmetric surface mode, is systematically studied. Our numerical analysis shows complete absorption of p-polarized light associated with large magnetic field enhancement at wavelengths from the visible to the mid-infrared range and roles played by the geometrical parameters of the structure. This understanding is then applied to the design of the structure with multiple nanoslits in a period that exhibits complete absorption at multiple wavelengths. Semi-analytical expression of the zeroth mode reflectance is derived, which shows a good agreement with numerical simulations and yields clear insight into the underlying physics of light-matter interactions in the structure.

Control of radiative processes for energy conversion and harvesting.

We review recent advances in the fundamental understanding and technological applications of radiative processes for energy harvesting, conversion, efficiency, and sustainability. State-of-the-art and remaining challenges are discussed, together with the latest developments outlined in the papers comprising this focus issue. The topics range from the fundamentals of the thermal emission manipulation in the far and near field, to applications in radiative cooling, thermophotovoltaics, thermal rectification, and novel approaches to photon detection and conversion.

Spectrally and spatially configurable superlenses for optoplasmonic nanocircuits.

Energy transfer between photons and molecules and between neighboring molecules is ubiquitous in living nature, most prominently in photosynthesis. While energy transfer is efficiently utilized by living systems, its adoption to connect individual components in man-made plasmonic nanocircuits has been challenged by low transfer efficiencies that motivate the development of entirely new concepts for energy transfer. We introduce herein optoplasmonic superlenses that combine the capability of optical microcavities to insulate molecule-photon systems from decohering environmental effects with the superior light nanoconcentration properties of nanoantennas. The proposed structures provide significant enhancement of the emitter radiative rate and efficient long-range transfer of emitted photons followed by subsequent refocusing into nanoscale volumes accessible to near- and far-field detection. Optoplasmonic superlenses are versatile building blocks for optoplasmonic nanocircuits and can be used to construct "dark" single-molecule sensors, resonant amplifiers, nanoconcentrators, frequency multiplexers, demultiplexers, energy converters, and dynamical switches.

Reversible two-way tuning of thermal conductivity in an end-linked star-shaped thermoset.

Polymeric thermal switches that can reversibly tune and significantly enhance their thermal conductivities are desirable for diverse applications in electronics, aerospace, automotives, and medicine; however, they are rarely achieved. Here, we report a polymer-based thermal switch consisting of an end-linked star-shaped thermoset with two independent thermal conductivity tuning mechanisms-strain and temperature modulation-that rapidly, reversibly, and cyclically modulate thermal conductivity. The end-linked star-shaped thermoset exhibits a strain-modulated thermal conductivity enhancement up to 11.5 at a fixed temperature of 60 °C (increasing from 0.15 to 2.1 W m-1 K-1). Additionally, it demonstrates a temperature-modulated thermal conductivity tuning ratio up to 2.3 at a fixed stretch of 2.5 (increasing from 0.17 to 0.39 W m-1 K-1). When combined, these two effects collectively enable the end-linked star-shaped thermoset to achieve a thermal conductivity tuning ratio up to 14.2. Moreover, the end-linked star-shaped thermoset demonstrates reversible tuning for over 1000 cycles. The reversible two-way tuning of thermal conductivity is attributed to the synergy of aligned amorphous chains, oriented crystalline domains, and increased crystallinity by elastically deforming the end-linked star-shaped thermoset.

Spatial and spectral detection of protein monolayers with deterministic aperiodic arrays of metal nanoparticles.

Light scattering phenomena in periodic systems have been investigated for decades in optics and photonics. Their classical description relies on Bragg scattering, which gives rise to constructive interference at specific wavelengths along well defined propagation directions, depending on illumination conditions, structural periodicity, and the refractive index of the surrounding medium. In this paper, by engineering multifrequency colorimetric responses in deterministic aperiodic arrays of nanoparticles, we demonstrate significantly enhanced sensitivity to the presence of a single protein monolayer. These structures, which can be readily fabricated by conventional Electron Beam Lithography, sustain highly complex structural resonances that enable a unique optical sensing approach beyond the traditional Bragg scattering with periodic structures. By combining conventional dark-field scattering micro-spectroscopy and simple image correlation analysis, we experimentally demonstrate that deterministic aperiodic surfaces with engineered structural color are capable of detecting, in the visible spectral range, protein layers with thickness of a few tens of Angstroms.

Electromagnetic field enhancement and spectrum shaping through plasmonically integrated optical vortices.

We introduce a new design approach for surface-enhanced Raman spectroscopy (SERS) substrates that is based on molding the optical powerflow through a sequence of coupled nanoscale optical vortices "pinned" to rationally designed plasmonic nanostructures, referred to as Vortex Nanogear Transmissions (VNTs). We fabricated VNTs composed of Au nanodiscs by electron beam lithography on quartz substrates and characterized their near- and far-field responses through combination of computational electromagnetism, and elastic and inelastic scattering spectroscopy. Pronounced dips in the far-field scattering spectra of VNTs provide experimental evidence for an efficient light trapping and circulation within the nanostructures. Furthermore, we demonstrate that VNT integration into periodic arrays of Au nanoparticles facilitates the generation of high E-field enhancements in the VNTs at multiple defined wavelengths. We show that spectrum shaping in nested VNT structures is achieved through an electromagnetic feed-mechanism driven by the coherent multiple scattering in the plasmonic arrays and that this process can be rationally controlled by tuning the array period. The ability to generate high E-field enhancements at predefined locations and frequencies makes nested VNTs interesting substrates for challenging SERS applications.

Quantification of differential ErbB1 and ErbB2 cell surface expression and spatial nanoclustering through plasmon coupling.

Cell surface receptors play ubiquitous roles in cell signaling and communication and their expression levels are important biomarkers for many diseases. Expression levels are, however, only one factor that determines the physiological activity of a receptor. For some surface receptors, their distribution on the cell surface, especially their clustering, provides additional mechanisms for regulation. To access this spatial information robust assays are required that provide detailed insight into the organization of cell surface receptors on nanometer length scales. In this manuscript, we demonstrate through combination of scattering spectroscopy, electron microscopy, and generalized multiple particle Mie theory (GMT) simulations that the density- and morphology-dependent spectral response of Au nanoparticle (NP) immunolabels bound to the epidermal growth factor receptors ErbB1 and ErbB2 encodes quantitative information of both the cell surface expression and spatial clustering of the two receptors in different unliganded in vitro cancer cell lines (SKBR3, MCF7, A431). A systematic characterization of the collective spectral responses of NPs targeted at ErbB1 and ErbB2 at various NP concentrations indicates differences in the large-scale organization of ErbB1 and ErbB2 in cell lines that overexpress these receptors. Validation experiments in the scanning electron microscope (SEM) confirm that NPs targeted at ErbB1 on A431 are more strongly clustered than NPs bound to ErbB2 on SKBR3 or MCF7 at overall comparable NP surface densities. This finding is consistent with the existence of larger receptor clusters for ErbB1 than for ErbB2 in the plasma membranes of the respective cells.

Tailoring the Desorption Behavior of Hygroscopic Gels for Atmospheric Water Harvesting in Arid Climates.

The ubiquitous nature of atmospheric moisture makes it a significant water resource available at any geographical location. Atmospheric water harvesting (AWH) technology, which extracts moisture from the ambient air to generate clean water, is a promising strategy to realize decentralized water production. The high water uptake by salt-based sorbents makes them attractive for AWH, especially in arid environments. However, they often have relatively high desorption heat, rendering water release an energy-intensive process. A  LiCl-incorporating polyacrylamide hydrogel (PAM-LiCl) capable of effective moisture harvesting from arid environments is proposed. The interactions between the hydrophilic hydrogel network and the captured water generate more free and weakly bonded water, significantly lowering the desorption heat compared with conventional neat salt sorbents. Benefiting from the affinity for swelling of the polymer backbones, the developed PAM-LiCl achieves a high water uptake of ≈1.1 g g-1 at 20% RH with fast sorption kinetics of ≈0.008 g g-1  min-1  and further demonstrates a daily water yield up to ≈7 g g-1 at this condition. These findings provide a new pathway for the synthesis of materials with efficient water absorption/desorption properties, to reach energy-efficient water release for AWH in arid climates.

Adaptive on-chip control of nano-optical fields with optoplasmonic vortex nanogates.

A major challenge for plasmonics as an enabling technology for quantum information processing is the realization of active spatio-temporal control of light on the nanoscale. The use of phase-shaped pulses or beams enforces specific requirements for on-chip integration and imposes strict design limitations. We introduce here an alternative approach, which is based on exploiting the strong sub-wavelength spatial phase modulation in the near-field of resonantly-excited high-Q optical microcavities integrated into plasmonic nanocircuits. Our theoretical analysis reveals the formation of areas of circulating powerflow (optical vortices) in the near-fields of optical microcavities, whose positions and mutual coupling can be controlled by tuning the microcavities parameters and the excitation wavelength. We show that optical powerflow though nanoscale plasmonic structures can be dynamically molded by engineering interactions of microcavity-induced optical vortices with noble-metal nanoparticles. The proposed strategy of re-configuring plasmonic nanocircuits via locally-addressable photonic elements opens the way to develop chip-integrated optoplasmonic switching architectures, which is crucial for implementation of quantum information nanocircuits.

Collective phenomena in photonic, plasmonic and hybrid structures.

Preface to a focus issue of invited articles that review recent progress in studying the fundamental physics of collective phenomena associated with coupling of confined photonic, plasmonic, electronic and phononic states and in exploiting these phenomena to engineer novel devices for light generation, optical sensing, and information processing.

Multi-wavelength mid-infrared plasmonic antennas with single nanoscale focal point.

We propose and demonstrate a novel photonic-plasmonic antenna capable of confining electromagnetic radiation at several mid-infrared wavelengths to a single sub-wavelength spot. The structure relies on the coupling between the localized surface plasmon resonance of a bow-tie nanoantenna with the photonic modes of surrounding multi-periodic particle arrays. Far-field measurements of the transmission through the central bow-tie demonstrate the presence of Fano-like interference effects resulting from the interaction of the bow-tie antenna with the surrounding nanoparticle arrays. The near-field of the multi-wavelength antenna is imaged using an aperture-less near-field scanning optical microscope. This antenna is relevant for the development of near-field probes for nanoimaging, spectroscopy and biosensing.

Formation of colorimetric fingerprints on nano-patterned deterministic aperiodic surfaces.

Periodic gratings and photonic bandgap structures have been studied for decades in optical technologies. The translational invariance of periodic gratings gives rise to well-known angular and frequency filtering of the incident radiation resulting in well-defined scattered colors in response to broadband illumination. Here, we demonstrate the formation of highly complex structural color patterns, or colorimetric fingerprints, in two-dimensional (2D) deterministic aperiodic gratings using dark field scattering microscopy. The origin of colorimetric fingerprints is explained by rigorous full-wave numerical simulations based on the generalized Mie theory. We show that unlike periodic gratings, aperiodic nanopatterned surfaces feature a broadband frequency response with wide angular intensity distributions governed by the distinctive Fourier properties of the aperiodic structures. Finally, we will discuss a range of potential applications of colorimetric fingerprints for optical sensing and spectroscopy.

Self-referenced photonic molecule bio(chemical)sensor.

We report a new type of optical biosensor capable of differentiating between bulk and surface perturbations of the ambient refractive index as well as between specific and nonspecific binding of molecules on the sensor surface. The proposed detection scheme is based on tracking the shifts of hybridized bonding and antibonding optical modes in coupled optical microcavities (photonic molecules). We demonstrate that by using two measurements of spectral shifts it is possible to discriminate between surface and volume index perturbation, to detect specific target molecules in a complex environment and to estimate the thickness of thin layers of adsorbed molecules.

Multiple-wavelength plasmonic nanoantennas.

We propose a type of photonic-plasmonic antennas capable of focusing light into subwavelength focal point(s) at several wavelengths, which are formed by embedding conventional dimer gap or bow-tie nanoantennas into multiple-periodic gratings. Fano-type coupling between localized surface plasmon resonances of dimer antennas and photonic modes in the gratings adds new functionalities, including multiple-wavelength operation and controllable enhancement of the field intensity in the focal point. Multiple-wavelength operation of nanoantennas provides tremendous opportunities for broadband single-molecule fluorescence and Raman sensing, emission enhancement, and near-field imaging.

Plasmonic nanogalaxies: multiscale aperiodic arrays for surface-enhanced Raman sensing.

The accurate and reproducible control of intense electromagnetic fields localized on the nanoscale is essential for the engineering of optical sensors based on the surface-enhanced Raman scattering (SERS) effect. In this paper, using rigorous generalized Mie theory (GMT) calculations and a combined top-down/bottom-up nanofabrication approach, we design and experimentally demonstrate approximately 10(8) spatially averaged, reproducible SERS enhancement in deterministic aperiodic arrays of Au nanoparticles with different length scales. Deterministic aperiodic arrays of 200 nm diameter nanocylinders are first fabricated using electron-beam lithography on quartz substrates, and smaller size (30 nm diameter) Au nanoparticles are subsequently positioned by in situ Au reduction at regions of maximum field enhancement. These multiscale structures, which we call "plasmonic nanogalaxies", feature a cascade enhancement effect due to the strong electromagnetic interactions of small satellite nanoparticles with localized fields in aperiodic arrays of nanocylinders. The development of SERS substrates based on aperiodic arrays with different length scales provides a novel strategy to engineer plasmon-enhanced biosensors with chemical fingerprinting capability.

The role of nanoparticle shapes and deterministic aperiodicity for the design of nanoplasmonic arrays.

In this paper, we study the role of nanoparticle shape and aperiodic arrangement in the scattering and spatial localization properties of plasmonic modes in deterministic-aperiodic (DA) arrays of metal nanoparticles. By using an efficient coupled-dipole model for the study of the electromagnetic response of large arrays excited by an external field, we demonstrate that DA structures provide enhanced spatial localization of plasmonic modes and a higher density of enhanced field states with respect to their periodic counterparts. Finally, we introduce and discuss specific design rules for the engineering and optimization of field enhancement and localization in DA arrays. Our results, which we fully validated by rigorous Generalized Mie Theory (GMT) and transition matrix (T-matrix) theory, demonstrate that DA arrays provide a robust platform for the design of a variety of novel optical devices with enhanced and controllable plasmonic fields.