Ultrasensitive Surface Refractive Index Imaging Based on Quasi-Bound States in the Continuum.

Herein, we demonstrate a cavity-enhanced hyperspectral refractometric imaging using an all-dielectric photonic crystal slab (PhCS). Our approach takes advantage of the synergy between two mechanisms, surface-enhanced fluorescence (SEF) and refractometric sensing, both based on high-Q resonances in proximity of bound states in the continuum (BICs). The enhanced local optical field of the first resonance amplifies of 2 orders of magnitude the SEF emission of a probe dye. Simultaneously, hyperspectral refractometric sensing, based on Fano interference between second mode and fluorescence emission, is used for mapping the spatially variant refractive index produced by the specimen on the PhCS. The spectral matching between first resonance and input laser is modulated by the specimen local refractive index, and thanks to the calibrated dependence with the spectral shift of the Fano resonance, the cavity tuning is used to achieve an enhanced correlative refractometric map with a resolution of 10-5 RIU within femtoliter-scale sampling volumes. This is experimentally applied also on live prostate cancer cells grown on the PhCS, reconstructing enhanced surface refractive index images at the single-cell level. This dual mechanism of quasi-BIC spatially variant gain tracked by quasi-BIC refractometric sensing provides a correlative imaging platform that can find application in many fields for monitoring physical and biochemical processes, such as molecular interactions, chemical reactions, or surface cell analysis.

Long-Range Exciton Diffusion in Two-Dimensional Assemblies of Cesium Lead Bromide Perovskite Nanocrystals.

Förster resonant energy transfer (FRET)-mediated exciton diffusion through artificial nanoscale building block assemblies could be used as an optoelectronic design element to transport energy. However, so far, nanocrystal (NC) systems supported only diffusion lengths of 30 nm, which are too small to be useful in devices. Here, we demonstrate a FRET-mediated exciton diffusion length of 200 nm with 0.5 cm2/s diffusivity through an ordered, two-dimensional assembly of cesium lead bromide perovskite nanocrystals (CsPbBr3 PNCs). Exciton diffusion was directly measured via steady-state and time-resolved photoluminescence (PL) microscopy, with physical modeling providing deeper insight into the transport process. This exceptionally efficient exciton transport is facilitated by PNCs' high PL quantum yield, large absorption cross section, and high polarizability, together with minimal energetic and geometric disorder of the assembly. This FRET-mediated exciton diffusion length matches perovskites' optical absorption depth, thus enabling the design of device architectures with improved performances and providing insight into the high conversion efficiencies of PNC-based optoelectronic devices.

Tuning the exponential sensitivity of a bound-state-in-continuum optical sensor.

In this work, we investigate the evanescent field sensing mechanism provided by an all-dielectric metasurface supporting bound states in the continuum (BICs). The metasurface is based on a transparent photonic crystal with subwavelength thickness. The BIC electromagnetic field is localized along the direction normal to the photonic crystal nanoscale-thin slab (PhCS) because of a topology-induced confinement, exponentially decaying in the material to detect. On the other hand, it is totally delocalized in the PhCS plane, which favors versatile and multiplexing sensing schemes. Liquids with different refractive indices, ranging from 1.33 to 1.45, are infiltrated in a microfluidic chamber bonded to the sensing dielectric metasurface. We observe an experimental exponential sensitivity leading to differential values as large as 226 nm/RIU with excellent FOM. This behavior is explained in terms of the physical superposition of the field with the material under investigation and supported by a thorough numerical analysis. The mechanism is then translated to the case of molecular adsorption where a suitable theoretical engineering of the optical structure points out potential sensitivities as large as 4000 nm/RIU.

Manipulating the Transition Dipole Moment of CsPbBr3 Perovskite Nanocrystals for Superior Optical Properties.

Colloidal cesium lead halide perovskite nanocrystals exhibit unique photophysical properties including high quantum yields, tunable emission colors, and narrow photoluminescence spectra that have marked them as promising light emitters for applications in diverse photonic devices. Randomly oriented transition dipole moments have limited the light outcoupling efficiency of all isotropic light sources, including perovskites. In this report we design and synthesize deep blue emitting, quantum confined, perovskite nanoplates and analyze their optical properties by combining angular emission measurements with back focal plane imaging and correlating the results with physical characterization. By reducing the dimensions of the nanocrystals and depositing them face down onto a substrate by spin coating, we orient the average transition dipole moment of films into the plane of the substrate and improve the emission properties for light emitting applications. We then exploit the sensitivity of the perovskite electronic transitions to the dielectric environment at the interface between the crystal and their surroundings to reduce the angle between the average transition dipole moment and the surface to only 14° and maximize potential light emission efficiency. This tunability of the electronic transition that governs light emission in perovskites is unique and, coupled with their excellent photophysical properties, introduces a valuable method to extend the efficiencies and applications of perovskite based photonic devices beyond those based on current materials.

Optical Biosensors Based on Photonic Crystals Supporting Bound States in the Continuum.

A novel optical label-free bio-sensing platform based on a new class of resonances supported in a photonic crystal metasurface is reported herein. Molecular binding is detected as a shift in the resonant wavelength of the bound states in the continuum of radiation modes. The new configuration is applied to the recognition of the interaction between protein p53 and its protein regulatory partner murine double minute 2 (MDM2). A detection limit of 66 nM for the protein p53 is found. The device provides an excellent interrogation stability and loss-free operation, requires minimal optical interrogation equipment and can be easily optimized to work in a wide wavelength range.

Tunable Anisotropic Photon Emission from Self-Organized CsPbBr3 Perovskite Nanocrystals.

We report controllable anisotropic light emission of photons originating from vertically aligned transition dipole moments in spun-cast films of CsPbBr3 nanocubes. By depositing films of nanocrystals on precoated substrates we can control the packing density and resultant radiation pattern of the emitted photons. We develop a technical framework to calculate the average orientation of light emitters, i.e., the angle between the transition dipole moment vector (TDM) and the substrate. This model is applicable to any emissive material with a known refractive index. Theoretical modeling indicates that oriented emission originates from an anisotropic alignment of the valence band and conduction band edge states on the ionic crystal lattice and demonstrates a general path to model the experimentally less accessible internal electric field of a nanosystem from the photoluminescent anisotropy. The uniquely accessible surface of the perovskite nanoparticles allows for perturbation of the normally isotropic emissive transition. The reported sensitive and tunable TDM orientation and control of emitted light will allow for applications of perovskite nanocrystals in a wide range of photonic technologies inaccessible to traditional light emitters.

Directed Assembly of Single Wall Carbon Nanotube Field Effect Transistors.

The outstanding electronic properties of single wall carbon nanotubes (SWCNTs) have made them prime candidates for future nanoelectronics technologies. One of the main obstacles to the implementation of advanced SWCNT electronics to date is the inability to arrange them in a manner suitable for complex circuits. Directed assembly of SWCNT segments onto lithographically patterned and chemically functionalized substrates is a promising way to organize SWCNTs in topologies that are amenable to integration for advanced applications, but the placement and orientational control required have not yet been demonstrated. We have developed a technique for assembling length sorted and chirality monodisperse DNA-wrapped SWCNT segments on hydrophilic lines patterned on a passivated oxidized silicon substrate. Placement of individual SWCNT segments at predetermined locations was achieved with nanometer accuracy. Three terminal electronic devices, consisting of a single SWCNT segment placed either beneath or on top of metallic source/drain electrodes were fabricated. Devices made with semiconducting nanotubes behaved as typical p-type field effect transistors (FETs), whereas devices made with metallic nanotubes had a finite resistance with little or no gate modulation. This scalable, high resolution approach represents an important step forward toward the potential implementation of complex SWCNT devices and circuits.

Directed Assembly of End-Functionalized Single Wall Carbon Nanotube Segments.

A key impediment to the implementation of a nanoelectronics technology based on single wall carbon nanotubes (SWCNTs) is the inability to arrange them in a manner suitable for integration into complex circuits. As a step toward addressing this problem, we explore the binding of fixed-length, end-functionalized SWCNT segments to lithographically defined nanoscale anchors, such that individual SWCNTs can be placed with control over position and orientation. Both monovalent and bivalent bindings are explored using covalent and noncovalent binding chemistries. Placement efficiency is assessed in terms of overall yield of SWCNT binding, as well as binding specificity and the degree of nonspecific binding. Placement yields as high as 93% and 79% are achieved, respectively, for covalent binding and for binding through DNA hybridization. Orientational control of the SWCNT segments is achieved with 95% and 51% efficiency for monovalent and bivalent bindings, respectively. This represents a new approach that could pave the way toward complex SWCNT devices and circuits.

Long-range charge transport in single G-quadruplex DNA molecules.

DNA and DNA-based polymers are of interest in molecular electronics because of their versatile and programmable structures. However, transport measurements have produced a range of seemingly contradictory results due to differences in the measured molecules and experimental set-ups, and transporting significant current through individual DNA-based molecules remains a considerable challenge. Here, we report reproducible charge transport in guanine-quadruplex (G4) DNA molecules adsorbed on a mica substrate. Currents ranging from tens of picoamperes to more than 100 pA were measured in the G4-DNA over distances ranging from tens of nanometres to more than 100 nm. Our experimental results, combined with theoretical modelling, suggest that transport occurs via a thermally activated long-range hopping between multi-tetrad segments of DNA. These results could re-ignite interest in DNA-based wires and devices, and in the use of such systems in the development of programmable circuits.

Controlled formation of carbon nanotube junctions via linker-induced assembly in aqueous solution.

Here we present a simple approach for the controlled formation of one-dimensional and multiterminal nanotube junctions. We describe a facile bottom-up strategy for joining the ends of single-walled carbon nanotubes. The geometry of the junctions can be varied and controlled by linker-induced assembly of DNA-wrapped nanotubes.

Selective biomolecular nanoarrays for parallel single-molecule investigations.

The ability to direct the self-assembly of biomolecules on surfaces with true nanoscale control is key for the creation of functional substrates. Herein we report the fabrication of nanoscale biomolecular arrays via selective self-assembly on nanopatterned surfaces and minimized nonspecific adsorption. We demonstrate that the platform developed allows for the simultaneous screening of specific protein-DNA binding events at the single-molecule level. The strategy presented here is generally applicable and enables high-throughput monitoring of biological activity in real time and with single-molecule resolution.