Organic-Inorganic Hybrid Glasses of Atomically Precise Nanoclusters.

Organic-inorganic atomically precise nanoclusters provide indispensable building blocks for establishing structure-property links in hybrid condensed matter. However, robust glasses of ligand-protected nanocluster solids have yet to be demonstrated. Herein, we show [Cu4I4(PR3)4] cubane nanoclusters coordinated by phosphine ligands (PR3) form robust melt-quenched glasses in air with reversible crystal-liquid-glass transitions. Protective phosphine ligands critically influence the glass formation mechanism, modulating the glasses' physical properties. A hybrid glass utilizing ethyldiphenylphosphine-based nanoclusters, [Cu4I4(PPh2Et)4], exhibits superb optical properties, including >90% transmission in both visible and near-infrared wavelengths, negligible self-absorption, near-unity quantum yield, and high light yield. Experimental and theoretical analyses demonstrate the structural integrity of the [Cu4I4(PPh2Et)4] nanocluster, i.e., iodine-bridged tetranuclear cubane, has been fully preserved in the glass state. The strong internanocluster CH-π interactions found in the [Cu4I4(PPh2Et)4] glass and subsequently reduced structural vibration account for its enhanced luminescence properties. Moreover, this highly transparent glass enables performant X-ray imaging and low-loss waveguiding in fibers drawn above the glass transition. The discovery of "nanocluster glass" opens avenues for unraveling glass formation mechanisms and designing novel luminescent glasses of well-defined building blocks for advanced photonics.

Tapered nanoscale chalcogenide fibers directly drawn from bulk glasses as optical couplers for high-index resonators.

We report production of air-clad tapered chalcogenide fibers by directly drawing bulk glasses between cleaved tips of tapered silica fibers. Exploiting these tapered fibers with nanoscale waists as evanescent optical couplers, we demonstrate phase-matched coupling of light into on-chip whispering gallery mode chalcogenide microresonators with coupling efficiencies as high as 95%. To the best of our knowledge, this is the first-time demonstration of critical coupling into high-index microresonators by using high-index tapered fibers. The tapered chalcogenide fibers can also be utilized as optical couplers for microresonators made of various high-index materials, as well as for nonlinear optical applications.

Binary coded identification of industrial chemical vapors with an optofluidic nose.

An artificial nose system for the recognition and classification of gas-phase analytes and its application in identifying common industrial gases is reported. The sensing mechanism of the device comprises the measurement of infrared absorption of volatile analytes inside the hollow cores of optofluidic Bragg fibers. An array of six fibers is used, where each fiber targets a different region of the mid-infrared in the range of 2-14 µm with transmission bandwidths of about 1-3 µm. The quenching in the transmission of each fiber due to the presence of analyte molecules in the hollow core is measured separately and the cross response of the array allows the identification of virtually any volatile organic compound (VOC). The device was used for the identification of seven industrial VOC vapors with high selectivity using a standard blackbody source and an infrared detector. The array response is registered as a unique six digit binary code for each analyte by assigning a threshold value to the fiber transmissions. The developed prototype is a comprehensive and versatile artificial nose that is applicable to a wide range of analytes.

Real-Time and Selective Detection of Single Nucleotide DNA Mutations Using Surface Engineered Microtoroids.

Mictoroids, as optical biosensors, can provide beneficial biosensing platforms to understand DNA alterations. These alterations could have significant clinical importance, such as the case of Pseudomonas aeruginosa, which is a commonly found pathogen in Cystic Fibrosis (CF) patients-causing poor prognosis by undergoing mutations during disease steps, gaining virulence and drug resistance. To provide a preliminary diagnosis platform for early-stage bacterial mutations, biosensing with a selective microtoroid surface was suggested. For this purpose, microtoroids with high quality factors were fabricated. The microtoroid surfaces were coated with (3-aminopropyl) triethoxysilane (APTES)/trimethylmethoxysilane (TMMS) mixed silane solution followed by EDC/NHS chemistry for covalent conjugation of DNA probes. Ethanolamine capping was applied to avoid unspecific interactions. The confocal studies confirmed homogeneous functionalization of the microtoroid surface. The DNA hybridization was demonstrated to be affected from the probe length. The optical biosensors showed a significant response (∼22 pm) to the complementary strand of the mutated type P. aeruginosa DNA, while showing substantially low and late response (∼5 pm) to the point mismatch strand. The limit of detection (LOD) for the complementary strand was calculated as 2.32 nM. No significant response was obtained for the noncomplementary strand. The results showed the microtoroids possessed selective surfaces in terms of distinguishing DNA alterations.

Nanosprings harvest light more efficiently.

Nanotechnology presents versatile architectural designs for the purpose of utilization as a building block of 1D optoelectronic nanodevices because current nanowire-based schemes require more effective solutions for low absorption capacity of nanoscale volumes. We report on the potential of nanospring absorbers as an alternative light-harvesting platform with significant advantages over conventional nanowires. Absorption capacity of nanospring geometry is found to be superior to cylindrical nanowire shape. Unlike nanowires, they are able to trap a larger amount of light thanks to characteristic periodic behavior that boosts light collection for the points matched with Mie resonances. Moreover, nanospring shape supplies compactness to a resulting device with area preservation as high as twofold. By considering that a nanospring array with optimal periods yields higher absorption than individual arrangements and core-shell designs, which further promote light collection due to unique antireflection features of shell layer, these nanostructures will pave the way for the development of highly efficient self-powered nanosystems.

Turn-on fluorescent dopamine sensing based on in situ formation of visible light emitting polydopamine nanoparticles.

Dopamine is the principle biomarker for diseases such as schizophrenia, Huntington's, and Parkinson's, and the need is urgent for rapid and sensitive detection methods for diagnosis and monitoring of such diseases. In this Article, we report a turn-on fluorescent method for rapid dopamine sensing which is based on monitoring the intrinsic fluorescence of in situ synthesized polydopamine nanoparticles. The assay uses only a common base and an acid, NaOH and HCl to initiate and stop the polymerization reaction, respectively, which makes the assay extremely simple and low cost. First, we studied the in situ optical properties of polydopamine nanoparticles, for the first time, which formed under different alkaline conditions in order to determine optimum experimental parameters. Then, under optimized conditions we demonstrated high sensitivity (40 nM) and excellent selectivity of the assay. With its good analytical figures of merit, the described method is very promising for detection of dopamine related diseases.

Controlled Synthesis of Terbium-Doped Colloidal Gd2O2S Nanoplatelets Enables High-Performance X-ray Scintillators.

Terbium-doped gadolinium oxysulfide (Gd2O2S:Tb3+), commonly referred to as Gadox, is a widely used scintillator material due to its exceptional X-ray attenuation efficiency and high light yield. However, Gadox-based scintillators suffer from low X-ray spatial resolution due to their large particle size, which causes significant light scattering. To address this limitation, we report the synthesis of terbium-doped colloidal Gadox nanoplatelets (NPLs) with near-unity photoluminescence quantum yield (PLQY) and high radioluminescence light yield (LY). In particular, our investigation reveals a strong correlation between PLQY, LY, particle size, and Tb3+concentration. Our synthetic approach allows precise control over the lateral size and thickness of the Gadox NPLs, resulting in a LY of 50,000 photons/MeV. Flexible scintillating screens fabricated with the solution-processable Gadox NPLs exhibited a 20 lp/mm X-ray spatial resolution, surpassing commercial Gadox scintillators. These high-performance and flexible Gadox NPL-based scintillators enable enhanced X-ray imaging capabilities in medicine and security. Our work provides a framework for designing nanomaterial scintillators with superior spatial resolution and efficiency through precise control of dimensions and dopant concentration.

Smelling in chemically complex environments: an optofluidic Bragg fiber array for differentiation of methanol adulterated beverages.

A novel optoelectronic nose for analysis of alcohols (ethanol and methanol) in chemically complex environments is reported. The cross-responsive sensing unit of the optoelectronic nose is an array of three distinct hollow-core infrared transmitting photonic band gap fibers, which transmit a specific band of IR light depending on their Bragg mirror structures. The presence of alcohol molecules in the optofluidic core quenches the fiber transmissions if there is an absorption band of the analyte overlapping with the transmission band of the fiber; otherwise they remain unchanged. The cumulative response data of the fiber array enables rapid, reversible, and accurate discrimination of alcohols in chemically complex backgrounds such as beer and fruit juice. In addition, we observed that humidity of the environment has no effect on the response matrix of the optoelectronic nose, which is rarely achieved in gas-sensing applications. Consequently, it can be reliably used in virtually any environment without precalibration for humidity or drying the analytes. Besides the discussed application in counterfeit alcoholic beverages, with its superior sensor parameters, this novel concept proves to be a promising contender for many other applications including food quality control, environmental monitoring, and breath analysis for disease diagnostics.

Plasmonically enhanced hot electron based photovoltaic device.

Hot electron photovoltaics is emerging as a candidate for low cost and ultra thin solar cells. Plasmonic means can be utilized to significantly boost device efficiency. We separately form the tunneling metal-insulator-metal (MIM) junction for electron collection and the plasmon exciting MIM structure on top of each other, which provides high flexibility in plasmonic design and tunneling MIM design separately. We demonstrate close to one order of magnitude enhancement in the short circuit current at the resonance wavelengths.

Macroscopic assembly of indefinitely long and parallel nanowires into large area photodetection circuitry.

Integration of nanowires into functional devices with high yields and good reliability turned out to be a lot more challenging and proved to be a critical issue obstructing the wide application of nanowire-based devices and exploitation of their technical promises. Here we demonstrate a relatively easy macrofabrication of a nanowire-based imaging circuitry using a recently developed nanofabrication technique. Extremely long and polymer encapsulated semiconducting nanowire arrays, mass-produced using the iterative thermal drawing, facilitate the integration process; we manually aligned the fibers containing selenium nanowires over a lithographically defined circuitry. Controlled etching of the encapsulating polymer revealed a monolayer of nanowires aligned over an area of 1 cm(2) containing a 10 × 10 pixel array. Each light-sensitive pixel is formed by the contacting hundreds of parallel photoconductive nanowires between two electrodes. Using the pixel array, alphabetic characters were identified by the circuitry to demonstrate its imaging capacity. This new approach makes it possible to devise extremely large nanowire devices on planar, flexible, or curved substrates with diverse functionalities such as thermal sensors, phase change memory, and artificial skin.

Copper Organometallic Iodide Arrays for Efficient X-ray Imaging Scintillators.

Lead-free organic metal halide scintillators with low-dimensional electronic structures have demonstrated great potential in X-ray detection and imaging due to their excellent optoelectronic properties. Herein, the zero-dimensional organic copper halide (18-crown-6)2Na2(H2O)3Cu4I6 (CNCI) which exhibits negligible self-absorption and near-unity green-light emission was successfully deployed into X-ray imaging scintillators with outstanding X-ray sensitivity and imaging resolution. In particular, we fabricated a CNCI/polymer composite scintillator with an ultrahigh light yield of ∼109,000 photons/MeV, representing one of the highest values reported so far for scintillation materials. In addition, an ultralow detection limit of 59.4 nGy/s was achieved, which is approximately 92 times lower than the dosage for a standard medical examination. Moreover, the spatial imaging resolution of the CNCI scintillator was further improved by using a silicon template due to the wave-guiding of light through CNCI-filled pores. The pixelated CNCI-silicon array scintillation screen displays an impressive spatial resolution of 24.8 line pairs per millimeter (lp/mm) compared to the resolution of 16.3 lp/mm for CNCI-polymer film screens, representing the highest resolutions reported so far for organometallic-based X-ray imaging screens. This design represents a new approach to fabricating high-performance X-ray imaging scintillators based on organic metal halides for applications in medical radiography and security screening.

High selectivity Boolean olfaction using hollow-core wavelength-scalable Bragg fibers.

A new odorant detection scheme, based on infrared absorption of volatile organics inside an optofluidic channel array, is discussed in terms of its selectivity. The sensor unit of the array is a hollow core Bragg fiber that selectively (spectrally) guides an incident continuum radiation. The presence of infrared absorbing molecules in the channel results in the quenching of the otherwise transmitted signal. Each fiber unit in the array is designed and fabricated so that it is sensitive to specific chemical bonds and the bond environment, but at the same time, each fiber is also broadly sensitive to a large number of chemicals due to their infrared absorbance spectra. The cumulative array response data, using an appropriate threshold, enable selective binary sampling of the infrared fingerprint of hundreds of molecules. The selectivity of the system is quantitatively investigated with computer simulations and found to be exponentially increasing with the number of fibers in the array. Relatively simple data analysis using binary logic combined with the high selectivity of the novel scheme paves the way for ubiquitous application of electronic noses in toxic gas detection, food quality control, environmental monitoring, and breath analysis for disease diagnostics.

Arrays of indefinitely long uniform nanowires and nanotubes.

Nanowires are arguably the most studied nanomaterial model to make functional devices and arrays. Although there is remarkable maturity in the chemical synthesis of complex nanowire structures, their integration and interfacing to macro systems with high yields and repeatability still require elaborate aligning, positioning and interfacing and post-synthesis techniques. Top-down fabrication methods for nanowire production, such as lithography and electrospinning, have not enjoyed comparable growth. Here we report a new thermal size-reduction process to produce well-ordered, globally oriented, indefinitely long nanowire and nanotube arrays with different materials. The new technique involves iterative co-drawing of hermetically sealed multimaterials in compatible polymer matrices similar to fibre drawing. Globally oriented, endlessly parallel, axially and radially uniform semiconducting and piezoelectric nanowire and nanotube arrays hundreds of metres long, with nanowire diameters less than 15 nm, are obtained. The resulting nanostructures are sealed inside a flexible substrate, facilitating the handling of and electrical contacting to the nanowires. Inexpensive, high-throughput, multimaterial nanowire arrays pave the way for applications including nanowire-based large-area flexible sensor platforms, phase-changememory, nanostructure-enhanced photovoltaics, semiconductor nanophotonics, dielectric metamaterials,linear and nonlinear photonics and nanowire-enabled high-performance composites.

Structural coloring in large scale core-shell nanowires.

We demonstrated two complementary size-dependent structural coloring mechanisms, interference and scattering, in indefinitely long core-shell nanowire arrays. The unusual nanostructures are comprised of an amorphous semiconducting core and a polymer shell layer with disparate refractive indices but with similar thermomechanical properties. Core-shell nanowires are mass produced from a macroscopic semiconductor rod by using a new top-to-bottom fabrication approach based on thermal size reduction. Nanostructures with diameters from 30 to 200 nm result in coloration that spans the whole visible spectrum via resonant Mie scattering. Nanoshell coloration based on thin film interference is proposed as a structural coloration mechanism which becomes dominant for nanowires having 700-1200 nm diameter. Controlled color generation in any part of visible and infrared spectral regions can be achieved by the simple scaling down procedure. Spectral color generation in mass-produced uniform core-shell nanowire arrays paves the way for applications such as spectral authentication at nanoscale, light-scattering ingredients in paints and cosmetics, large-area devices, and infrared shielding.

Large and dynamical tuning of a chalcogenide Fabry-Perot cavity mode by temperature modulation.

Te-enriched chalcogenide glass Ge(15)As(25)Se(15)Te(45) (GAST) is synthesized, thermo-optically characterized and used to fabricate a one dimensional photonic crystal cavity mode that is dynamically and reversibly tuned by temperature modulation. The optical cavity mode is designed using GAST and As(2)S(3) glasses after fully determining their temperature dependence of the complex refractive indices in the visible and near infrared spectrum using spectroscopic ellipsometry. By making use of the very large thermo-optic coefficient (dn/dT = 4 x 10(-4)/ degrees C) of GAST glass at 1.2 mum, the cavity mode of the multilayer was tuned reversibly more than 16 nm, which is, to the best of our knowledge, an order of magnitude larger for this kind of cavity modulation. Wide and dynamical spectral tuning of low bandgap chalcogenide glasses via temperature modulation can be utilized in photonic crystal based integrated optics, quantum dot resonance matching, solid state and gas laser components, and infrared photonic crystal fibers.

Metal-insulator-semiconductor optoelectronic fibres.

The combination of conductors, semiconductors and insulators with well-defined geometries and at prescribed length scales, while forming intimate interfaces, is essential in most functional electronic and optoelectronic devices. These are typically produced using a variety of elaborate wafer-based processes, which allow for small features, but are restricted to planar geometries and limited coverage area. In contrast, the technique of fibre drawing from a preformed reel or tube is simpler and yields extended lengths of highly uniform fibres with well-controlled geometries and good optical transport characteristics. So far, this technique has been restricted to particular materials and larger features. Here we report on the design, fabrication and characterization of fibres made of conducting, semiconducting and insulating materials in intimate contact and in a variety of geometries. We demonstrate that this approach can be used to construct a tunable fibre photodetector comprising an amorphous semiconductor core contacted by metallic microwires, and surrounded by a cylindrical-shell resonant optical cavity. Such a fibre is sensitive to illumination along its entire length (tens of meters), thus forming a photodetecting element of dimensionality one. We also construct a grid of such fibres that can identify the location of an illumination point. The advantage of this type of photodetector array is that it needs a number of elements of only order N, in contrast to the conventional order N2 for detector arrays made of photodetecting elements of dimensionality zero.

Photonic bandgap infrared spectrometer.

We propose and demonstrate an infrared (IR) absorption spectrometer, made with a spatially variable photonic bandgap (PBG) structure, a blackbody source, and a simple IR detector, to identify the IR molecular fingerprints of analyte molecules. The PBG-based structure consists of thermally evaporated, IR transparent, high-refractive-index chalcogenide quarter-wave stacks (QWS) with a cavity layer. Spatial variation of the very sharp transmission peak due to the QWS cavity mode allows the structure to be used as a variable IR filter. Our proposed IR-PBG spectrometer can be used for detection and identification of volatile organic compounds.

Label-Free Optical Biodetection of Pathogen Virulence Factors in Complex Media Using Microtoroids with Multifunctional Surface Functionality.

Early detection of pathogens or their virulence factors in complex media has a key role in early diagnosis and treatment of many diseases. Nanomolar and selective detection of Exotoxin A, which is a virulence factor secreted from Pseudomonas aeruginosa in the sputum of Cystic Fibrosis (CF) patients, can pave the way for early diagnosis of P. aeruginosa infections. In this study, we conducted a preliminary study to demonstrate the feasibility of optical biodetection of P. aeruginosa Exotoxin A in a diluted artificial sputum mimicking the CF respiratory environment. Our surface engineering approach provides an effective biointerface enabling highly selective detection of the Exotoxin A molecules in the complex media using monoclonal anti-Exotoxin A functionalized microtoroids. The highly resilient microtoroid surface toward other constituents of the sputum provides Exotoxin A detection ability in the complex media by reproducible measurements. In this study, the limit-of-detection of Exotoxin A in the complex media is calculated as 2.45 nM.

Evaporation-Induced Biomolecule Detection on Versatile Superhydrophilic Patterned Surfaces: Glucose and DNA Assay.

We introduce a droplet-based biomolecular detection platform using robust, versatile, and low-cost superhydrophilic patterned superhydrophobic surfaces. Benefitting from confinement and evaporation-induced shrinkage of droplets on wetted patterns, we show enrichment-based biomolecular detection using very low sample volumes. First, we developed a glucose assay using fluorescent polydopamine (PDA) based on enhancement of PDA emission by hydrogen peroxide (H2O2) produced in enzyme-mediated glucose oxidation reaction. Incubation in evaporating droplets resulted in brighter fluorescence compared to that in bulk solutions. Droplet assay was highly sensitive toward increasing glucose concentration while that in milliliter-volume solutions resulted in no fluorescence enhancement at similar time scales. This is due to droplet evaporation that increased the reaction rate by causing enrichment of PDA and glucose/glucose oxidase as well as increased concentration of H2O2 generated in shrinking droplet. Second, we chemically functionalized wetted patterns with single-stranded DNA and developed fluorescence-based DNA detection to demonstrate the adaptability of the patterned surfaces for a different class of assay. We achieved detection of glucose and DNA with concentration down to 130 µM and 200 fM, respectively. Patterned superhydrophobic surfaces with their simple production, sensitive response, and versatility present potential for bioanalysis from low sample volumes.

Oligonucleotide-based label-free detection with optical microresonators: strategies and challenges.

This review targets diversified oligonucleotide-based biodetection techniques, focusing on the use of microresonators of whispering gallery mode (WGM) type as optical biosensors mostly integrated with lab-on-a-chip systems. On-chip and microfluidics combined devices along with optical microresonators provide rapid, robust, reproducible and multiplexed biodetection abilities in considerably small volumes. We present a detailed overview of the studies conducted so far, including biodetection of various oligonucleotide biomarkers as well as deoxyribonucleic acids (DNAs), ribonucleic acids (RNAs) and proteins. We particularly advert to chemical surface modifications for specific and selective biosensing.