Flexible Chemiresistive Cyclohexanone Sensors Based on Single-Walled Carbon Nanotube-Polymer Composites.

We report a chemiresistive cyclohexanone sensor on a flexible substrate based on single-walled carbon nanotubes (SWCNTs) functionalized with thiourea (TU) derivatives. A wrapper polymer containing both 4-vinylpyridine (4VP) groups and azide groups (P(4VP-VBAz)) was employed to obtain a homogeneous SWCNT dispersion via noncovalent functionalization of SWCNTs. The P(4VP-VBAz)-SWCNT composite dispersion was then spray-coated onto an organosilanized flexible poly(ethylene terephthalate) (PET) film to achieve immobilizing quaternization between the pyridyl groups from the polymer and the functional PET substrate, thereby surface anchoring SWCNTs. Subsequent surface functionalization was performed to incorporate a TU selector into the composites, resulting in P(Q4VP-VBTU)-SWCNT, for the detection of cyclohexanone via hydrogen bonding interactions. An increase in conductance was observed as a result of the hydrogen-bonded complex with cyclohexanone resulting in a higher hole density and/or mobility in SWCNTs. As a result, a sensor device fabricated with P(Q4VP-VBTU)-SWCNT composites exhibited chemiresistive responses (ΔG/G0) of 7.9 ± 0.6% in N2 (RH 0.1%) and 4.7 ± 0.4% in air (RH 5%), respectively, upon exposure to 200 ppm cyclohexanone. Selective cyclohexanone detection was achieved with minor responses (ΔG/G0 < 1.4% at 500 ppm) toward interfering volatile organic compounds (VOC). analytes. We demonstrate a robust sensing platform using the polymer-SWCNT composites on a flexible PET substrate for potential application in wearable sensors.

Switchable Single-Walled Carbon Nanotube-Polymer Composites for CO2 Sensing.

We report a chemiresistive CO2 sensor based on single-walled carbon nanotubes (SWCNTs) noncovalently functionalized with a CO2 switchable copolymer containing amidine pendant groups that transform into amidinium bicarbonates in response to CO2. To fabricate a robust surface-anchored polymer-SWCNT dispersion via spray coating, we first designed and synthesized a precursor copolymer, P(4VP-VBAz), bearing both 4-vinylpyridine (4VP) groups and azide groups. The SWCNT dispersant group, 4VP, is capable of debundling and stabilizing nanotubes to improve their solubility in organic solvents for solution processing. Well-dispersed P(4VP-VBAz)-SWCNT composites are covalently immobilized onto a glass substrate functionalized with alkyl bromides, and then the amidine moieties are subsequently attached to form the resulting CO2-switchable P(Q4VP-VBAm)-SWCNT composites via a copper(I)-catalyzed azide-alkyne cycloaddition click reaction at the film surface. The amidine groups are strong donors that compensate or pin carriers in the SWCNTs. In the presence of CO2 under humid conditions, the generated amidinium bicarbonates from the polymer wrapping increase the concentration and/or liberate the hole carriers in the nanotubes, thereby increasing the net conductance of the composites. The amidinium moieties revert back to the amidines when purged with a CO2-free carrier gas with a reversible decrease in conductance. We also demonstrate high selectivity to CO2 over the other atmospheric gases such as O2 and Ar.

Parallel sorting of orbital and spin angular momenta of light in a record large number of channels.

Parallel sorting of orbital and spin angular momentum components of structured optical beams is demonstrated. Both spin channels are multiplexed within the novel orbital angular momentum (OAM) sorter, reducing the size, weight, and number of elements. The sorted states are linearly spaced over 70 topological charge values. We experimentally and theoretically evaluate the operational range and crosstalk between neighboring channels and find that 30 orbital angular momentum states are available per spin channel for quantum communication or cryptography. This is achieved using an angular momentum sorter that we developed based on geometric phase optical elements. We present two devices consisting of liquid crystal polymer films photoaligned with complex two-dimensional patterns.

Pancharatnam-Berry optical element sorter of full angular momentum eigenstate.

We propose and numerically demonstrate a Pancharatnam-Berry optical element (PBOE) device that simultaneously sorts spin (SAM) and orbital (OAM) angular momentum. This device exploits the circular polarization selective properties of PBOEs to modulate independently the orthogonal SAM eigenstates within a geometric optical transformation that sorts OAM, enabling single measurement characterization of the full angular momentum eigenstate. This expands the available state space for OAM communication and enables characterization of the eigenmode composition of structured polarization beams. We define the two-dimensional orientation patterns of the transversely varying half-waveplate PBOEs that implement the angular momentum sorter. We show that the device discriminates the OAM and SAM eigenstates of optical beams including laser cavity modes such as Laguerre-Gaussian OAM eigenmodes, Hermite-Gaussian modes, and hybrid modes with complex structured polarization. We also demonstrate that it can determine the m parameter of higher order LGml Laguerre-Gaussian modes. The ability of this device to decode information from spatially structured optical phase has potential for applications in communication, encryption, modal characterization, and scientific measurements.

Enhanced second harmonic generation from InAs nano-wing structures on silicon.

We demonstrate morphology-dependent second-harmonic generation (SHG) from InAs V-shaped nanomembranes. We show SHG correlation with the nano-wing shape and size, experimentally quantify the SHG efficiency, and demonstrate a maximum SHG enhancement of about 500 compared to the bulk. Experimental data are supported by rigorous calculations of local electromagnetic field spectra.

Enhanced second harmonic generation from Au nanoparticle arrays by femtosecond laser irradiation.

Ultrafast laser irradiation of planar Au nanoparticle arrays is shown to double the particle plasmon quality factor and to enhance second harmonic generation 40-fold. It is found that the irradiation induces a morphological change of nano-cylinders into asymmetric droplet-like shapes with reduced surface roughness without altering their lithographically defined locations. These findings can be used to improve the performance of linear and nonlinear plasmonic devices.

Enhanced second harmonic generation by photonic-plasmonic Fano-type coupling in nanoplasmonic arrays.

In this communication, we systematically investigate the effects of Fano-type coupling between long-range photonic resonances and localized surface plasmons on the second harmonic generation from periodic arrays of Au nanoparticles arranged in monomer and dimer geometries. Specifically, by scanning the wavelength of an ultrafast tunable pump laser over a large range, we measure the second harmonic excitation spectra of these arrays and demonstrate their tunability with particle size and separation. Moreover, through a comparison with linear optical transmission spectra, which feature asymmetric Fano-type lineshapes, we demonstrate that the second harmonic generation is enhanced when coupled photonic-plasmonic resonances of the arrays are excited at the fundamental pump wavelength, thus boosting the intensity of the electromagnetic near-fields. Our experimental results, which are supported by numerical simulations of linear optical transmission and near-field enhancement spectra based on the Finite Difference Time Domain method, demonstrate a direct correlation between the onset of Fano-type coupling and the enhancement of second harmonic generation in arrays of Au nanoparticles. Our findings enable the engineering of the nonlinear optical response of Fano-type coupled nanoparticle arrays that are relevant to a number of device applications in nonlinear nano-optics and plasmonics, such as on-chip frequency generators, modulators, switchers, and sensors.

Microfluidics integration of aperiodic plasmonic arrays for spatial-spectral optical detection.

We demonstrate successful integration of aperiodic arrays of metal nanoparticles with microfluidics technology for optical sensing using the spectral-colorimetric responses of nanostructured arrays to refractive index variations. Different aperiodic arrays of gold (Au) nanoparticles with varying interparticle separations and Fourier spectral properties are fabricated using Electron Beam Lithography (EBL) and integrated with polydimethylsiloxane (PDMS) microfluidics structures by soft-lithographic micro-imprint techniques. The spectral shifts of scattering spectra and the distinctive modifications of structural color patterns induced by refractive index variations were simultaneously measured inside microfluidic flow cells by dark-field spectroscopy and image correlation analysis in the visible spectral range. The integration of engineered aperiodic arrays of Au nanoparticles with microfluidics devices provides a novel sensing platform with multiplexed spatial-spectral responses for opto-fluidics applications and lab-on-a-chip optical biosensing.

Engineering plasmon-enhanced Au light emission with planar arrays of nanoparticles.

By systematically investigating the light emission and scattering properties of arrays of Au nanoparticles with varying size and separation, we demonstrate tunability and control of metal photoluminescence and unveil the critical role of near-field plasmonic coupling for the engineering of active metal nanostructures. We show that the decay of photoexcited electron-hole pairs into localized surface plasmons (LSPs) dramatically modifies the Au emission wavelength, line shape, and quantum efficiency depending both on particles size and separation. In particular, in arrays with near-field coupled nanoparticles we demonstrate broad light scattering and emission spectra that scale differently with respect to nanoparticle size due to the enhanced LSP nonradiative decay caused by near-field interparticle coupling. Our experimental results are fully supported by semianalytical extinction simulations based on rigorous coupled wave analysis, which demonstrate the importance of tuning plasmonic near-field coupling for the engineering of active devices based on light emitting arrays of metallic nanoparticles.

Multipolar second harmonic generation from planar arrays of Au nanoparticles.

We demonstrate optical Second Harmonic Generation (SHG) in planar arrays of cylindrical Au nanoparticles arranged in periodic and deterministic aperiodic geometries. In order to understand the respective roles of near-field plasmonic coupling and long-range photonic interactions on the SHG signal, we systematically vary the interparticle separation from 60 nm to distances comparable to the incident pump wavelength. Using polarization-resolved measurements under femtosecond pumping, we demonstrate multipolar SHG signal largely tunable by the array geometry. Moreover, we show that the SHG signal intensity is maximized by arranging Au nanoparticles in aperiodic spiral arrays. The possibility to engineer multipolar SHG in planar arrays of metallic nanoparticles paves the way to the development of novel optical elements for nanophotonics, such as nonlinear optical sensors, compact frequency converters, optical mixers, and broadband harmonic generators on a chip.

Plasmon-enhanced depolarization of reflected light from arrays of nanoparticle dimers.

Using spectroscopic ellipsometry and analytical multiple scattering theory, we demonstrate significant depolarization of far-field reflected light due to plasmonic near-field concentration in dimer arrays of metallic nanoparticles fabricated by electron beam lithography. By systematically investigating dimer arrays with varying sub-wavelength interparticle separations, we show that the measured depolarization presents a sharp peak at the Rayleigh cutoff condition for efficient in-plane diffraction. Moreover, by investigating the depolarization of reflected light as a function of the excitation angle, we demonstrate that maximum depolarization occurs in the spectral regions of plasmon-enhanced near-fields. Our results demonstrate that far-field reflection measurements encode information on the near-field spectra of complex nanoparticle arrays, and can be utilized to experimentally determine the optimal conditions for the excitation of sub-wavelength plasmonic resonances. The proposed approach opens novel opportunities for the engineering of nanoparticle arrays with optimized enhancement of optical cross sections for spectroscopic and sensing applications.

Particle-swarm optimization of broadband nanoplasmonic arrays.

We used the particle swarm optimization algorithm, an evolutionary computational technique, to design metal nanoparticle arrays that produce broadband plasmonic field enhancement over the entire visible spectral range. The resulting structures turn out to be aperiodic and feature dense Fourier spectra with many closely packed particle clusters. We conclude that broadband field-enhancement effects in nanoplasmonics can be achieved by engineering aperiodic arrays with a large number of spatial frequencies that provide the necessary interplay between long-range diffractive interactions at multiple length scales and near-field quasi-static coupling within small nanoparticle clusters.

Nanoplasmonics of prime number arrays.

In this paper, we investigate the plasmonic near-field localization and the far-field scattering properties of non-periodic arrays of Ag nanoparticles generated by prime number sequences in two spatial dimensions. In particular, we demonstrate that the engineering of plasmonic arrays with large spectral flatness and particle density is necessary to achieve a high density of electromagnetic hot spots over a broader frequency range and a larger area compared to strongly coupled periodic and quasi-periodic structures. Finally, we study the far-field scattering properties of prime number arrays illuminated by plane waves and we discuss their angular scattering properties. The study of prime number arrays of metal nanoparticles provides a novel strategy to achieve broadband enhancement and localization of plasmonic fields for the engineering of nanoscale nano-antenna arrays and active plasmonic structures.