Third-order nonlinear optical properties and two-photon absorption in polymers doped with p-phenyl sydnone

We report the measurements of the third-order susceptibilities and two-photon absorption in three different polymers doped with p-phenyl sydnone moiety viz., 2-benzylhydrazono-5-(3-p-tolylsydnone-4-yl)1,3,4,-thiadiazine, which is recently synthesized and characterized, with the prospective of reaching a good compromise between processability and high nonlinear optical properties. The measurements were done using nano second Z-scan at 532nm. The Z-scan spectra reveal a large negative nonlinear refraction coefficient n₂ of the order 10⁻¹⁴ cm²/W and a two-photon absorption β, which is determined to be the order of cm/GW. The absorption cross section is 10⁻⁴⁶ cm⁴ s/photon. The molecular second-order hyperpolarizability in PMMA matrix was calculated to be 1.47 × 10⁻³¹ esu, comparable with stilbazolieum derivatives, a well-known class of optical materials for photonics and biophotonics applications. The chromophore shows its optical power limiting behavior in all the three polymer matrices. All these results suggest that this moiety has potential for the application of all-optical limiting and switching devices. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Role of surface defects in the third order nonlinear optical properties of pristine NiO and Cr doped NiO nanostructures

Pristine NiO and 2% Cr doped NiO nanostructures are successfully synthesized by the modified auto–combustion method for the determination and improvement of linear and nonlinear optical behaviours, and for identifying them as suitable materials for optical limiting applications. Vibrational and linear optical properties of both nanostructures are investigated, and structural and morphological studies are carried out using XRD, FE-SEM, and HR-TEM. From the Kubelka-Munk model, the energy band gaps for pristine and doped samples are found to be 3.52 eV and 3.44 eV, respectively. Both pristine as well as Cr-doped NiO nanostructures reveal substantial nonlinear optical behaviour at the excitation wavelength of 532 nm, arising from the presence of strong reverse saturable absorption. The third order nonlinear absorption coefficients have values of the order of 10^?10 m/W and 10^?6 m/W, under pulsed (5 ns) and continuous wave laser excitations, respectively. These values confirm the suitability of these nanostructures for fabricating efficient optical limiting devices for safeguarding human eyes and optical sensors from hazardous laser radiation.     

Studies on nonlinear optical parameters of bis-chalcone derivatives doped polymer

Two bis-chalcone derivatives, 1,5-[di(4-methoxyphenyl)]penta-1,4-dien-3-one and 1,5-[di(4-chlorophenyl)]penta-1,4-dien-3-one were synthesized. Their SHG conversion efficiencies are reported to be 6.0 and 5.0 times that of urea and hyper polarizabilities are 9.9×10⁻³⁰ and 10.2×10⁻³⁰ esu, respectively. The third-order nonlinear optical properties in PMMA matrix were studied by Z-scan technique using 7 ns laser pulses at 532 nm. The nonlinear refractive index γ, nonlinear absorption coefficient β, magnitude of effective third order susceptibility χ⁽³⁾ and the coupling factor ρ have been investigated. The values obtained are of the order of 10⁻¹⁴ cm²/W, 1.2 cm/GW, 10⁻¹⁴ esu and 0.2, respectively, which are comparable with the values obtained in stilbazoleum like dyes. The experimental investigation also shows that they are very interesting optical limiting materials and their optical limiting behaviour is mainly due to two photon absorption phenomenon.     

Modification of crystallization behavior,mechanical strength and optical property of Ge–S binary chalcogenide glass ceramics by trace CsCl incorporation

In present work, we discovered that nano-crystallization behavior of Ge–S binary chalcogenide glass can be remarkably improved by incorporating trace amount of CsCl as nucleating agent. After implementing an annealing process, the resultant Ge-S-CsCl chalcogenide glass ceramics (GSC ChGCs) possess fine distribution of crystallites belonging to GeS₂ and GeS mixture phase which could enhance mechanical strength and narrow bandgap energy of the original glass. By utilizing femtosecond Z-scan method, nonlinear optical properties of the GSC ChGCs were investigated in a spectral range from 750 to 900 nm. The results showed that the nonlinear absorption attribute of the GSC ChGCs can be enhanced by the crystallinity increase which led to the maximum two-photon absorption coefficient of 19.57 cm/GW at excitation wavelength of 750 nm, increased by 78% as compared to the original glass. This indicates the current GSC ChGCs a promising candidate for the optical limiting devices.     

Carbon nanodots with strong nonlinear optical response

The carbon nanodots (CNDs) were synthesized by a simple method of femtosecond laser ablation of bagasse in ethanol. Strong optical limiting effects of as-prepared CNDs to 800 nm femtosecond laser pulses were observed with the threshold of 74 mJ/cm². The strong two photon absorption of CNDs is responsible for the optical limiting response. The nonlinear coefficient was determined by the open-aperture Z-scan technique.     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

Design of SrZr0.1Mn0.4Mo0.4Y0.1O3-δ heterostructured with ZnO as electrolyte material: Structural,optical and electrochemical behavior at low temperatures

P-type semiconductor SrZr_0.1Mn_0.4Mo_0.4Y_0.1O_3-δ (SZMMY) is for the first time composited with n-type ZnO to prepare a solid oxide electrolyte used in fuel cell operable at low temperature. Prepared nanocomposite electrolyte material is considered as a novel material owing to the results obtained in terms of improved ionic conductivity, power density, and current density at lower operational temperature. The material has been analyzed as well crystalline material with a dual-phase as confirmed by X-Ray Diffraction (XRD). The structural morphology of designed electrolyte materials was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), including high-resolution TEM (HR-TEM). The electrochemical impedance spectra (EIS) showed a remarkably lower charge transfer resistance than conventional electrolyte materials. Obtained results illustrated that ionic conductivity increased, which lead to the acceleration of the electrode reactions. Heterostructure nanocomposite SZMMY-ZnO is beneficial to attain a high ionic conductivity due to the suppression of electronic conduction through the p-n junction. The maximum power density was noted as 841 mW cm^?2 at 550 °C with a maximum current density of 2287 mA cm^?2. Based on optical properties through the p-n junction, the internal electronic current was blocked, which further reduced the short circuit problem in the heterostructure. In addition, the performance and lifetime test indicated good stability of the cell at 550 °C with a very small degradation loss. The present study suggests that the SZMMY-ZnO is a promising electrolyte for low-temperature-SOFCs development.     

Nonlinear optical absorption studies of sol–gel derived Yttrium Iron Garnet (Y3Fe5O12) nanoparticles by Z-scan technique

Sol–gel synthesized Yttrium Iron Garnet (Y₃Fe₅O₁₂) nanoparticles were subjected to open aperture Z-scan studies in order to investigate the nonlinear optical (NLO) properties of these materials. The investigations were carried out using a Q-switched resonant Nd:YAG laser at a wavelength of 532 nm with different laser powers. Strong reverse saturable absorption (RSA) has been found when the sample is irradiated by the laser pulse of 10 Hz. The studies show that the material is highly nonlinear, which makes it useful for optical limiting applications.     

Lithium zirconate coated LiNi0.8Co0.15Al0.05O2 as a high-performance electrode material for advanced fuel cells

Surface modification of electrode materials could effectively enhance catalytic activity and stability for low temperature solid oxide fuel cells. In this paper, LiNi_0.8Co_0.15Al_0.05O₂ (NCAL), material with 1 wt % Li₂ZrO₃ (LZO) surface coating were successfully synthesized by a simple wet chemical method. The crystal structure, surface morphology and electrochemical properties of the modified NCAL materials were investigated by X-ray diffraction, scanning electron microscopy and photoelectron spectroscopy. The obtained results showed that the NCAL coated with LZO exhibited superior electrochemical performance. According to the EIS results, the polarization resistance of the 1 wt % LZO-modified NCAL based fuel cell at 550 °C was only 0.303 Ω cm², respectively, which were much lower than pure NCAL (1.33 Ω cm²). The results show that the LZO surfaced coated NCAL could be a promising anode material towards high-performance advanced fuel cells.Combined with XRD and XPS analysis, it can be inferred that: the surface modification of LZO did not affect the structure of the raw material, and during the test, LZO enabled the effective distribution of the oxygen vacancies on the surface of the material, which accelerated the catalytic activity of the electrode during the discharge process.     

Increased optical nonlinearities of graphene nanohybrids covalently functionalized by axially-coordinated porphyrins

Two graphene oxide (GO)-based nanohybrid materials possessing covalent linkages to axially-coordinated tetraphenylporphyrin (TPP), GO–TPP, were prepared and were characterized by Fourier transform infrared (FT-IR), Ultraviolet–visible (UV–Vis) absorption, steady state fluorescence, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), thermogravimetric analysis (TGA), elemental analysis and Raman spectroscopic techniques. The nonlinear optical properties and optical limiting performance of GO, GO–TPP nanohybrids and the free porphyrins dihydroxotin(IV) tetraphenylporphyrin (SnTPP) and the phosphorus-cored porphyrin (PTPP) were investigated using nanosecond and picosecond Z-scan measurements at 532 nm. At the identical mass concentration of 0.2 mg mL⁻¹, GO–TPP nanohybrids exhibited enhanced nonlinear optical properties and optical limiting performance, ascribed to a combination of nonlinear scattering and/or two-photon absorption with reverse saturable absorption, and the photo-induced electron or energy transfer from the electron-donor porphyrin moiety to the acceptor graphene.     

Improvement of electrochemical performance of titania nanowires for supercapacitor electrodes by in-situ growth of polyaniline nanoparticles

Supercapacitors with excellent electrochemical performance are considered the most promising candidates to meet the increasing energy demand. Herein, we developed a novel electrode material for supercapacitors, polyaniline (PANI)-3-aminopropyl triethoxysilane (APTEs)-titania nanowires (TNW), which was synthesized on potassium doped titanium foil via a simple two-step procedure. In the composite, the nano-mesh structure formed by APTEs-coated TNW serves as the framework for the growth of PANI nanoparticles, and PANI nanoparticles act as the electrochemically active part. The specific capacitance of PANI-APTEs-TNW of up to 315.16 mF cm^?2 at 0.2 mA cm^?2 in 1.0 M H₂SO₄ solution is achieved, while that of PANI-TNW is 271.67 mF cm^?2. Meanwhile, the capacitance retention rate of PANI-APTEs-TNW is 86.8% after 1000 cycles under 1.5 mA cm^?2. Compared to PANI-TNW, the better capacitive behavior of PANI-APTEs-TNW is attributed to the anchoring effect of APTEs, which is highly interactive and exhibits compact structures between the TNW and PANI nanoparticles, resulting in a stable structure during the rapid charge-discharge process. This strategy is characterized by its good electrochemical properties, simple equipment, low cost of raw materials, and large-area preparation. Thus, our findings provide an effective method for the design of high-performance supercapacitors and promote their practical applications.     

Synthesis and plasma treatment of nitrogen-doped graphene fibers for high-performance supercapacitors

Graphene fiber-based supercapacitor has aroused great interest as a flexible power source in future wearable electronics. However, the low electrochemical performance of graphene fibers (GFs) usually causes the serious limitation of use in practical applications due to the material stacking, hydrophobicity and fabrication process complexity. In this work, a facile and effective plasma-assisted strategy is put forward to increase specific surface area, tune hierarchically porous structure and promote wettability of nitrogen-doped graphene fibers (NGFs), resulting in the improvement of electrochemical performance. The supercapacitor assembled from plasma-treated NGFs shows superior capacitance (878 mF/cm² at 0.1 mA/cm² current density) and high energy density (19.5 μW h/cm² at 40 mW/cm² power density), which is 23.7% and 131.4% higher than that of NGFs and GFs, respectively. Additionally, the fiber-based supercapacitor based on plasma-treated NGFs exhibits high rate capability of 59.8% and excellent cyclic performance (95.8% retention over 10,000 cycles). These plasma-treated NGFs can be promising candidates for high-performance and flexible power sources in future wearable electronics.     

Processing of high-performance Co doped Y2O3 as a single-phase electrolyte for low temperature solid oxide fuel cell (LT-SOFC)

The high-performance single-phase semiconductor materials with higher ionic conductivity have drawn substantial attention in fuel cell applications. Semiconductor materials play a key role to enhance ionic conductivity subsequently promoting low temperature solid oxide fuel cell (LT-SOFC) research. Herein, we proposed a semiconductor Co doped Y₂O₃ (YCO) samples with different molar ratios, which may easily access the high ionic conductivity and electrochemical performances at low operating temperatures. The resulting fabricated fuel cell 10% Co doped Y₂O₃ (YCO-10) device exhibits high ionic conductivity of ∼0.16 S cm⁻¹ and a feasible peak power density of 856 mW cm⁻² along with 1.09 OCV at 530 °C under H₂/air conditions. The electrochemical impedance spectroscopy (EIS) reveals that YCO-10 electrolyte based SOFC device delivers the least ohmic resistance of 0.11–0.16 Ω cm² at 530-450 °C. Electrode polarization resistance of the constructed fuel cell device noticed from 0.59 Ω cm² to 0.28 Ω cm² in H₂/air environment at different elevated temperatures (450 °C to 530 °C). This work suggests that YCO-10 can be a promising alternative electrolyte, owing to its high fuel cell performance and enhanced ionic conductivity for LT-SOFC.     

Improving performance of proton ceramic electrolysis cell perovskite anode by Zn doping

As an important renewable energy, hydrogen energy becomes an important part of the future energy system. Proton ceramic electrolysis cell (PCEC) enables the efficient, clean, large-scale preparation of hydrogen, which is a new type of energy conversion device, attracting the attention of many researchers. Sr₂Fe_1.4Zn_0.1Mo_0.5O_6-δ (SFZM) anode materials were developed to investigate the effect of B-site doping of Zn on the electrochemical properties of the Sr₂Fe_1.5Mo_0.5O_6-δ (SFM) materials. The results reveal that the doping of Zn increases the concentration of oxygen vacancies and improves the electrocatalytic activity, which in turn improves the performance of the material. A current density of 408 mA cm⁻² has been achieved at 1.3 V when the SFZM-based single cell was operated in an electrolysis mode (50% H₂O in air) at 600 °C, higher than SFM-based single cells (286 mA cm⁻² at 1.3 V). In addition, the SFZM-based single cell exhibited good durability in a stability test at an electrolysis current density of 408 mA cm⁻². This work confirms that SFZM is a promising material for proton ceramic electrolysis cell anode.     

Tuning three-dimensional textures with graphene aerogels for ultra-light flexible graphene/texture composites of effective electromagnetic shielding

For extending graphene aerogels for broad applications, here we demonstrate a simple and universal approach for scalable fabricating novel dual carbon three-dimensional (3D) hybrid structures, where the interspace of a 3D carbon texture has been modified by in situ generating graphene aerogels. Owing to the unique exceptional 3D carbon bi-frameworks of enhanced electrical conductivity and flexibility, the as-prepared graphene aerogel–carbon texture hybrid presents an ultra-light feature (0.07 g cm⁻³ in density), with highly effective electromagnetic interference (EMI) shielding performance up to 27 dB and 37 dB (in the X band region) at thicknesses of 2 and 3 mm, respectively. According to the mechanisms in EMI shielding, the fundamental criteria for evaluating a shielding material has been discussed and the excellent shielding performance coupled with the ultra-low density allows such 3D all-carbon hybrids to show more advantageous than the other carbon-based shielding composites. Implication of the results suggests that the strategy of various advantages could be widely extended to a variety of applications, promising a great platform for large-scale fabricating porous graphene-based materials into high-performance products.     

Excellent energy storage performance of paraelectric Ba0.4Sr0.6TiO3 based ceramics through induction of polar nano-regions

Dielectric energy storage materials with congenitally high power densities and ultrafast discharge rates have been extensively studied for emergent applications. As a typical and traditional dielectric material, paraelectric Ba_0.4Sr_0.6TiO₃ (BST) ceramic exhibits a moderate dielectric constant (ε_r), low dielectric loss and slightly nonlinear P–E hysteresis. However, its energy storage density (W) is extremely low because of its low maximum polarisation (P_max) and weak breakdown strength (BDS). In this study, ferroelectric Na_0.5Bi_0.5TiO₃ (NBT) was introduced into paraelectric BST to enhance energy storage performance. The results show that the introduction of NBT induced polar nano-regions (PNRs) in the paraelectric matrix, resulting in a slim hysteresis loop with low remnant polarisation (P_r) and high P_max simultaneously. Furthermore, owing to a decrease in the oxygen vacancy concentration and an increase in the band gap energy, the BDS of the BST ceramic also significantly increased. As a consequence, a remarkable energy storage density (W_rec = 3.89 J/cm³) and a high energy storage efficiency (η = 83.8%) were realised in the 0.75Ba_0.4Sr_0.6TiO₃-0.25Bi_0.5Na_0.5TiO₃ (0.75BST–0.25NBT) ceramic under a practical electric field of 360 kV/cm. Moreover, the ceramic also exhibited an excellent current density (～1029.7 A/cm²) and ultrahigh power density (～128.7 MW/cm²). The attained energy storage performances indicate that the NBT-modified BST ceramics are promising materials for high energy storage capacitor applications field.     

Synthesis and Third-Order Nonlinear Optical Properties of Copper and Nickel Coordination Complexes of Azo Dyes

An azo dye, 2-(4,5-dicyano-1-H-imidazolyazo)-5-N, N-diethylaminophenol, and the corresponding divalent copper and nickel mononuclear coordination complexes were synthesized. The molecular third-order nonlinear optical characteristics of these azo transition metallic chelates were investigated in N,N′-dimethylformamide solution using a standard Z-scan technique with a 7-ns laser pulses at 1,064 nm. The results of n ₂ (the nonlinear refraction index) and γ (the hyperpolarizability) values of the two complexes indicated that metal chelating lead to considerable enhancement in third-order optical nonlinearities, which revealed that such coordination complexes exhibit strong nonlinear optical absorption effects and self-defocusing performance. These materials are promising candidates as large third-order nonlinear optical materials.     

Novel CO2-tolerant Co-based double perovskite cathode for intermediate temperature solid oxide fuel cells

For the commercial application of solid oxide fuel cells (SOFCs), CO₂-tolerant cathode materials with high electrochemical activity are required. Here, we discuss the performance of double perovskite Pr_0.2Sr_1.8CoTiO_6?δ (P02STC) as a potential cathode material for SOFCs. P02STC has a cubic structure and keeps lattice structure stable in the CO₂ atmosphere. The average thermal expansion coefficient is 17.8 × 10^–6 K^–1 at 30–900 °C in air. The P02STC cathode exhibits good electrochemical performance with a low polarization resistance of 0.080 Ωcm² at 700 °C. The P02STC cathode shows good structure stability, electrochemical performance stability, and excellent tolerance to CO₂ poisoning for the symmetrical cells based on the 350 h stability test in air and the 150 h stability test in O₂ containing 5%CO₂ at 700 °C. The electrolyte-supported single cell with a P02STC cathode shows a maximum power density of 677 mW cm^? 2 at 800 °C. The single cell operates stably for 250 h at a constant current of 0.3 A/cm² without obvious degrading performance. According to all of the experimental results, the P02STC sample might be a promising candidate cathode for SOFCs.     

Modifications in the structural,morphological, optical properties of Ag45Se40Te15 thin films by proton ion irradiation for optoelectronics and nonlinear applications

This current work reports the 30 keV proton ion irradiation induced structural, morphological, and optical properties change in Ag₄₅Se₄₀Te₁₅ films at different fluences. The thin films were irradiated with different ion fluences, such as 5 × 10¹⁵ ions/cm²,1 × 10¹⁶ ions/cm² and 5 × 10¹⁶ ions/cm². The electronic loss (S_e) dominates over the nuclear loss (S_n) in proton irradiation. The X-ray diffraction study shows the phase transformation from amorphous to crystalline upon ion irradiation. The Raman analysis confirms the change in chemical and vibrational bonds due to structural alterations in the films. The surface morphology has been studied by field emission scanning electron microscopy and the composition of the films has been checked by the energy dispersive X-ray analysis. The particle size increased upon the increase in ion irradiation fluence. The surface roughness of the films has been studied by atomic force microscopy. The transmission data is used to calculate the linear optical parameters. The absorption edge shifts towards the high wavelength region inferring the reduction in the optical bandgap. The linear refractive index of the films increased with ion fluence. The optical density increased at the high wavelength region while the skin depth decreased with fluence. The carrier concentration per effective mass decreased while the plasma frequency increased with proton irradiation. The nonlinearity (χ ⁽³⁾ and n₂) values increased significantly with the increase in fluences. Such kind of materials with optimization in their optical parameters are primarily essential for cutting-edge photonic, optoelectronic, and nonlinear optical applications.     

The third-order nonlinear optical properties of novel styryl dyes

The third-order nonlinear optical properties of two novel styryl dyes, namely, 1,3-diethyl-5-(4-methoxybenzylidene)-2-thioxodihydropyrimidine-4,6(1H,5H)-dione and 5-(3,4-dimethoxybenzylidene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione were studied using the Z-scan technique employing 7 ns laser pulses at 532 nm. The nonlinear refractive index, nonlinear absorption coefficient, magnitude of effective third-order susceptibility and coupling factor were determined. The optical power limiting behavior of the colorants was ascribed to two-photon absorption phenomenon. Nonlinear absorption cross-section increased with increase in π electron density and the effective two-photon absorption cross-section was two orders of magnitude larger than those of commercially available azo compounds. The results suggest that these colorants offer promise as nonlinear optical materials for device applications.