Octupolar Cyclotriphosphazene-Cored Self-Standing Covalent Organic Framework Membranes as Nonlinear Optical Materials: Impact of Linkage Types and Material Forms.

Conjugated and processable self-standing vinylene-linked covalent organic framework membranes (COFMs) are highly demanding for photonics and optoelectronics. In this work, we have fabricated the first cyclotriphosphazene (CTP) cored vinylene-linked self-standing COFM (CTP-PDAN). For comparison purposes, we have successfully fabricated the imine-linked congener (CTP-PDA). Leveraging the inherent nonlinear optical (NLO) response of the CTP core, both membranes were directly mounted to evaluate NLO parameters using the open-aperture (OA) Z-scan technique. Direct measurement of NLO responses on membranes is advantageous and free from solvent and scattering effects, making it a more practical approach compared to the conventional dispersion mode. The OA Z-scan transmission yields a reverse saturable absorption signature exhibiting a higher NLO absorption coefficient (ß) of 58.37 cm/GW for CTP-PDAN, compared to that of the imine-linked CTP-PDA COFM (ß = 8.5 cm/GW). These results can be correlated to the efficient conjugation through the vinylene linkage in CTP-PDAN compared to the imine linked congener.

Influence of defects on the linear and nonlinear optical properties of Cu-doped rutile TiO2 microflowers.

Defects and disorder work as controlling parameters to alter the electronic structure of nanostructures and significantly influence their electronic, magnetic, and nonlinear optical (NLO) properties. In this study, we found that defect engineering is an effective strategy for tailoring the linear and nonlinear optical properties of Cu-doped titanium oxide (TiO2) flower-shaped nanostructures. The concentration of chemical doping of Cu in the TiO2 lattice creates intermediate defect states that impact electronic bandgap reduction and tunable defect luminescence. The estimation of the bandgap from density functional theory calculation follows the same trend of bandgap narrowing with Cu doping. The XPS study reveals that oxygen defects are responsible for bandgap narrowing and quenching of the PL intensity. A single-beam Z-scan technique with open and closed aperture configurations using ultrashort pulses centered at 532 nm excitation wavelength was used to study the NLO measurements. The open aperture reveals saturable absorption, whereas the closed aperture shows self-focusing behavior. The nonlinear absorption coefficient and refractive index extracted from NLO measurements demonstrate the linear dependence on the defect concentration and bandgap. The effects of heterogeneous dopants and lattice disorder on the nonlinear absorption behavior of these nanostructures are discussed in comparison with the figure of merit, non-linear refractive index, and absorption coefficient. The tunable NLO properties achieved by controlling such dopant-induced defects boost the scope of these nanostructures as optical limiting, optical switching, and optical photodiode applications.

Thiolumazines as Heavy-Atom-Free Photosensitizers for Applications in Daylight Photodynamic Therapy: Insights from Ultrafast Excited-State Dynamics.

Finding appropriate photosensitizers (PSs) for daylight photodynamic therapy (dPDT) applications is extremely challenging, even though heavy-atom-free photosensitizers (HAFPSs) such as thiocarbonyl-modified nucleobases have shown a ray of hope. Few attempts have been made to find alternative natural products for dPDT applications. Pteridine heterocycles consisting of a pyrazine ring and a pyrimidine ring, such as lumazine, which exhibit many structural similarities to the alloxazine ring of the flavin molecule, could be an option for HAFPSs. The photophysical and quantum mechanical studies of the thio-modified lumazines revealed that sequential thiomodifications in lumazine result in a bathochromic shift. Additionally, higher tissue penetration depths were observed for thiolumazines. The fluorescence quenching in the case of thiomodified lumazines was explained using triplet state formation, whereas the contribution from the photoinduced electron transfer process cannot be ignored. It was also noticed that a strong one-photon absorption influenced the two-photon absorption (TPA) process, leading to a self-focusing effect in the visible spectral region. The higher tissue penetration and larger TPA cross section are the hallmark characteristics of the thiolumazines to be considered as potential HAFPSs for dPDT applications.

Experimental evidence of a pump-wavefront-induced Stern-Gerlach-like splitting in optical parametric generators.

Quantum mechanical Stern-Gerlach (SG)-like effects are unusual to explore in the domain of optics due to the absence of any interaction of photons or optical waves with the conventional magnetic field. A few recent investigations point toward the possibility of observing an SG-like effect in nonlinear optics via wedge-shaped poling in a long lithium niobate (LN) crystal to generate a spatially varying analogous magnetic field (B→A). This leads to two different propagation directions for the mutually orthogonal states formed by superposition of signal and idler modes (states) with opposite phases. In this work, we present theoretical formalism to show an equivalent SG-like splitting in a frequency downconversion process and experimentally validate the assertion by producing a suitable transverse gradient in B→A through an in-homogeneous pump wavefront. The experimental results show SG-like splitting in an optical parametric generation (OPG) process using a widely used periodically poled LN (PPLN) crystal and a pump laser exhibiting a suitable spatial beam profile. The experimentally measured deviation angle for the mutual beam closely matches with the prediction from theoretical formalism using a Gaussian pump wavefront.

Synthesis, Photophysical, Electrochemical, and Non-linear Optical Properties of Triaryl Pyrazole-based B-N Coordinated Boron Compounds.

We report here a set of triaryl pyrazole based B-N coordinated boron compounds (11-17) synthesized by electrophilic aromatic borylation strategy. All the pyrazole boron compounds were thoroughly characterized using multinuclear NMR spectroscopy, LC-MS, and single crystal X-ray diffraction analysis (for 12-17). The photoluminescence measurements of 11-17 revealed that the emission peak maxima were tuned based on the substitution on N-phenyl. The photophysical and electrochemical properties were further supported by theoretical calculations. Z-scan based investigations at 515 nm pump wavelength showed that B-N coordination led to enhancement of nonlinear absorption (two-photon absorption (TPA)) in these compounds if an electron deficient moiety is attached. It has also been observed that an appropriate choice of moiety allows to optimally maneuver the molecular polarizability of the π-system and consequently, assists in controlling the third-order nonlinear optical response.

Temperature-dependent excitonic emission characteristics of lead-free inorganic double perovskites and their third-order optical nonlinearities.

We report temperature-dependent photoluminescence (PL) in the temperature range between 77 K and 300 K, and room temperature nonlinear optical (NLO) properties of solution processed lead-free Cs2NaBiI6 (CNBI) and Cs2KBiI6 (CKBI) perovskite films. The de-convolution analysis of temperature-dependent PL spectra showed thermal quenching behavior of free-exciton (FX) emission, an unusual blue-shift of PL emission, and line broadening with increasing temperature as a consequence of strong exciton-phonon interaction. The nonlinear refractive index (n2) and nonlinear absorption coefficient (ß) of both the CNBI and CKBI films are determined using a closed aperture (CA) and open aperture (OA) Z-scan technique, respectively. Both the CNBI and CKBI perovskites exhibited features of saturable absorption (SA) with ß âˆ¼ -6.23 × 10-12 cm W-1, and -1.14× 10-12 cm W-1, respectively. The CA measurements depicted a self-defocusing effect in both the samples with n2 values ∼-1.06 × 10-14 cm2 W-1 and -1.337× 10-14 cm2 W-1, respectively. With such emission and NLO characteristics, CNBI and CKBI perovskite films can be used for designing eco-friendly optoelectronic and NLO devices.

A nanolayered structure for sensitive detection of hemoglobin concentration using surface plasmon resonance.

The objective of the proposed work is to design a biosensor that monitors hemoglobin (Hb) concentration using the combination of nanolayer, i.e., barium titanate (BaTiO3) and antimonene based on surface plasmon resonance (SPR) technique. Antimonene is used here as bio-recognition element (BRE) layer to attach the Hb analyte through physical adsorption due to its hydrophilic nature, higher adsorption energy and larger active surface area. The use of BaTiO3 adlayer (7 nm) just before antimonene is to enhance the refractive index (RI) sensitivity up to 1.90 times for the proposed SPR biosensor. The reason behind sensitivity enhancement is its high dielectric constant which enhances the electromagnetic field with in analyte medium. The performance of the biosensor is demonstrated with performance parameters namely sensitivity, detection accuracy (DA), figure of merit (FOM) and resolution. The proposed biosensor has potential to achieve much higher performance in terms of RI sensitivity of 303.83°/RIU, FOM of 50.39 RIU-1 and resolution of 0.021 g/l in comparison with reported biosensors in the literature for detection of Hb concentration. Thus, based on the obtained results one can say that the proposed work unlocks a reliable sensing in the field of medical science to detect hemoglobin-related diseases in human being.

Infrared rainbow trapping via optical Tamm modes in an one-dimensional dielectric chirped photonic crystals.

The phenomenon of trapping a broad spectrum of light is known as "rainbow trapping" and is achieved by using all-dielectric, hybrid metallo-dielectric, or all-metallic configurations. The latter architectures allow strong confinement but exhibit very high ohmic losses. This results in practical lifetimes of trapped modes to less than 1 ps. Therefore, novel strategies are required to be devised for trapping and, subsequently, releasing broadband electromagnetic field with lifetime >1ps. We present a rainbow trapping configuration using the excitation of multiple optical Tamm (OT) modes in an one-dimensional chirped photonic crystal (CPC) designed for adiabatically coupling counterpropagating modes. In the geometry, the backscattered phase undergoes multiple discontinuities (=π), which enables excitation of many OT modes in the presence of a thin plasmon-active metal, which is placed adjacent to the terminating layer of CPC. All the OT modes are spatially separated in the CPC, and the strong modal confinement manifests into group velocities as low as 0.17c. The time-domain simulations depict mode-localization in the dielectric sections of CPC, which manifest into lifetimes ∼3ps.

Synthesis of pyrazole anchored three-coordinated organoboranes and their application in the detection of picric acid.

Three-coordinated organoboron fluorophores bearing 3,5-diphenyl pyrazoles have been synthesized. The pyrazole anchored boron fluorophores show selective fluorescence quenching response to trinitrophenol (or) picric acid (PA) and have the ability to discriminate picric acid over other analytes. We investigated nonlinear optical (NLO) properties of these three-coordinated organoboron compounds (in solutions) in the presence and absence of PA. In absence of PA, the two-photon-absorption coefficient (ß) of organoboron fluorophores exhibits a variation from 2 × 10-12 cm W-1 to 4 × 10-12 cm W-1. The results also reveal that the NLO characteristics of organoboron fluorophores exhibit a discernible variation with PA addition which has correlations with quenching observed in fluorescence measurements.

Synthesis of π-extended B ← N coordinated phenanthroimidazole dimers and their linear and nonlinear optical properties.

Intramolecular B ← N coordinated fluorophores have shown potential applications in optoelectronics and as sensors due to their unique photophysical properties. In this work, we report the synthesis and characterization of π-conjugated boron doped phenanthroimidazole dimers. All the π-conjugated B ← N coordinated phenanthroimidazole dimers exhibited high quantum yields in solution (up to 99%) and moderate quantum yields in the solid state (up to 51%). We investigated the nonlinear optical properties of phenanthroimidazole dimers and found that the measurement of two-photon-absorption cross-section is correlated with the conjugation length.

Tamm-plasmon polaritons in one-dimensional photonic quasi-crystals.

We present an investigation to ascertain the existence of Tamm-plasmon-polariton-like modes in one-dimensional (1D) quasi-periodic photonic systems. Photonic bandgap formation in quasi-crystals is essentially a consequence of long-range periodicity exhibited by multilayers and, thus, it can be explained using the dispersion relation in the Brillouin zone. Defining a "Zak"-like topological phase in 1D quasi-crystals, we propose a recipe to ascertain the existence of Tamm-like photonic surface modes in a metal-terminated quasi-crystal lattice. Additionally, we also explore the conditions of efficient excitation of such surface modes along with their dispersion characteristics.

Yb-fiber laser pumped high-power, broadly tunable, single-frequency red source based on a singly resonant optical parametric oscillator.

We present an efficient and tunable source generating multi-watt single-frequency red radiation by intra-cavity frequency doubling of the signal in a MgO-doped periodically poled LiNbO3 (MgO:PPLN)-based singly resonant optical parametric oscillator (SRO). By optimally designing the SRO cavity in a six-mirror configuration, we generate ≈276 nm tunable idler radiation in mid-infrared with a maximum power of Pi=2.05 W at a pump power of Pp=14.0 W. The resonant signal is frequency doubled using a 10 mm-long BiB3O6 (BiBO) crystal which resulted in tunability of a red beam from ≈753 to 780 nm band with maximum power Pr≈4.0 W recorded at λr≈756 nm. The deployment of a six-mirror SRO ensures single-frequency generation of red across the entire tuning range by inducing additional losses to Raman modes of LiNbO3 and, thus, inhibiting their oscillation. Using a scanning Fabry-Perot interferometer (FPI), nominal linewidth of the red beam is measured to ≈3 MHz which changes marginally over the entire tuning range. Long-term (over 1 h) peak-to-peak frequency fluctuation of the generated red beam is estimated to be about 3.3 GHz under free-running conditions at Pp=14.0 W. The generated red beam is delivered in a TEM00 mode profile with M2≤1.32 at maximum power in a red beam.

Tamm-plasmon and surface-plasmon hybrid-mode based refractometry in photonic bandgap structures.

The transverse magnetic (TM) polarized hybrid modes formed as a consequence of coupling between Tamm plasmon polariton (TM-TPP) mode and surface plasmon polariton (SPP) mode exhibit interesting dispersive features for realizing a highly sensitive and accurate surface plasmon resonance (SPR) sensor. We found that the TM-TPP modes, formed at the interface of distributed Bragg reflector and metal, are strongly dispersive as compared to SPP modes at optical frequencies. This causes an appreciably narrow interaction bandwidth between TM-TPP and SPP modes, which leads to highly accurate sensing. In addition, appropriate tailoring of dispersion characteristics of TM-TPP as well as SPP modes could ensure high sensitivity of a novel SPR platform. By suitably designing the Au/TiO2/SiO2-based geometry, we propose a TM-TPP/SPP hybrid-mode sensor and achieve a sensitivity ≥900 nm/RIU with high detection accuracy (≥30 µm⁻¹) for analyte refractive indices varying between 1.330 and 1.345 in 600-700 nm wavelength range. The possibility to achieve desired dispersive behavior in any spectral band makes the sensing configuration an extremely attractive candidate to design sensors depending on the availability of optical sources.

Broadband, high-power, continuous-wave, mid-infrared source using extended phase-matching bandwidth in MgO:PPLN.

We report a compact and viable source of broadband, high-power, cw, mid-IR radiation based on a singly resonant optical parametric oscillator (SRO) pumped by a wide-bandwidth cw Yb fiber laser centered at 1060 nm. By exploiting the extended phase-matching bandwidth in a 50 mm crystal of MgO:PPLN and a ring SRO cavity, we obtain 5.3 W of broadband idler output for 25.5 W of pump at >80% depletion, transferring a pump bandwidth of 73.9 cm(-1) to an idler spectrum spread across an equal bandwidth centered at 3454 nm. By deploying output coupling of the signal, we generate 11.2 W of total power at 44% extraction efficiency with a pump depletion of >73% at the maximum available pump power. Measurements of transverse modal power confirm Gaussian distribution of signal and idler beams.

Ultrabroadband midinfrared generation by using group-velocity-dispersion tailoring in a Bragg reflection waveguide for a difference-frequency-generation process.

We propose a novel scheme for ultrabroadband midinfrared (mid-IR) generation using quasi-phase-matched difference-frequency generation (DFG) in a GaN/Al(x)Ga(1-x)N based Bragg reflection waveguide (BRW). By optimally tailoring the phase- and group-velocity dispersion properties of symmetric BRWs, we show that the phase-matching condition for a DFG process could be maintained over a broad range of signal wavelengths. This could lead to generation of an approximately 700 nm broad idler close to 3.26 microm wavelength. Since the idea is based on dispersion compensation using photonic bandgap geometry, we can shift the broadband features to any desired spectral region and for any material system within the constraints imposed by the transparency of nonlinear materials. We also investigate the possibility of broadband mid-IR generation using pump sources with broad spectral width.

On the modal characteristics of surface plasmon polaritons at a metal-Bragg interface at optical frequencies.

A detailed mathematical analysis along with a theoretical model for the modes supported at the interface of a metal and periodically stratified medium (Bragg structure) is presented. The modes that are supported at the interface of a plasmon active metal (such as gold) and a Bragg structure are commonly known as surface plasmon-Bragg modes. We found that these modes have effective indices lower than any of the material indices of the layers comprising the Bragg structure, and they are highly dispersive when compared to the conventional surface plasmon modes that are supported at the metal and dielectric interface. The plausible physical explanation behind the strong dispersive behavior of the surface plasmon-Bragg mode is provided. Finally, the comparison of dissipation loss for the surface plasmon-Bragg modes is investigated and it has been shown that there is more than fivefold enhancement in the magnitude of propagation lengths as compared to the conventional surface plasmon mode.

Continuous-wave optical parametric oscillator pumped by a fiber laser green source at 532 nm.

We report a high-power, cw, singly resonant optical parametric oscillator (SRO) using a simple, compact fiber pump laser architecture in the green. The SRO, based on MgO:sPPLT, is pumped by 9.6 W of single-frequency cw radiation at 532 nm obtained by single-pass second-harmonic generation (SHG) of a 30 W Yb fiber laser, also in MgO:sPPLT. Using two identical crystals of 30 mm length for SHG and SRO, we generate cw idler powers of up to 2 W over 855-1408 nm, with a peak-to-peak power stability <11.7% over 40 min, in a TEM(00) spatial mode with M(2)<1.26. Using finite output coupling of the resonant wave, we extract 800 mW of signal power with peak-to-peak power stability <10.7% over 40 min, and a frequency stability <75 MHz over 15 min. The signal and idler output have TEM(00) beam profile with M(2)<1.52 across the tuning range.

Increased pump acceptance bandwidth in spontaneous parametric downconversion process using Bragg reflection waveguides.

In this paper we show that by suitably tailoring the dispersion characteristics of a Bragg reflection waveguide (BRW) mode, it is possible to achieve efficient photon pair generation over a large pump bandwidth while maintaining narrow signal bandwidth. The structure proposed consists of a high index core BRW with a periodically poled GaN core and periodically stratified cladding made up of alternate layers of Al(0.02)Ga(0.98)N and Al(0.45)Ga(0.55)N. Such photon-pair generators should find applications in realizing compact and stable sources for quantum information processing.

Broadening of the phase-matching bandwidth in quasi-phase-matched second-harmonic generation using GaN-based Bragg reflection waveguide.

We present an analysis of a high index core symmetric Bragg reflection waveguide (BRW) design based on a GaN/AlxGa1-xN system for efficient quasi-phase-matched second-harmonic generation for broadband applications. By choosing the fundamental frequency to be a BRW mode and suitably tailoring the overall dispersion characteristics, the strong dispersion of the second-harmonic mode is partially canceled, leading to phase matching between the fundamental and second-harmonic over a broad range of wavelengths. The crucial interplay between the dispersive behavior of the fundamental and second-harmonic wave manifests as a broad acceptance bandwidth of approximately 33 nm accompanied with appreciable conversion efficiency (22.8%/W) for a 10 mm long waveguide. The impact of tailoring the dispersion characteristics on the conversion efficiency is also discussed.