Nonlinear optical properties of Cu nanocluster composite fabricated by 180 keV ion implantation

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 5×10¹⁶ ions/cm² has been studied. The microstructural properties of the nanoclusters has been verified by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. Results of the investigation of nonlinear refraction by the off-axis Z-scan configuration were presented and the mechanisms responsible for the nonlinear response were discussed. Third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 8.7×10⁻⁸ esu at 532 nm and 6.0×10⁻⁸ esu at 1064 nm, respectively.     

Spectroscopic investigation and Judd–Ofelt analysis of silver nanoparticles embedded Er3+-doped tellurite glass

A series of silver nanoparticles (NPs) embedded zinc-tellurite glass is prepared by melt-quenching technique. The transmission electron microscopic images reveal spherical as well as anisotropic silver NPs having average diameter in the range of 14–48 nm. The Er³⁺-free glass sample containing AgCl exhibits surface plasmon resonance (SPR) band of Ag NPs centered at ∼ 501 nm. From Judd–Ofelt analysis, it is found that by increasing the concentration of NPs, the value of Ω₂ is enhanced suggesting increased covalency and decreased symmetry around the Er³⁺ ions. Integrated emission cross-section (IEC) is enhanced as the concentration of silver NPs is increased up to 0.5 mol% AgCl. Fourier infrared spectra show that the intensity of the vibrational band of the water molecule and fundamental stretching band of OH group are suppressed. Furthermore, under an excitation wavelength of 786 nm, three prominent upconversion emissions are observed at 520 nm, 550 nm and 650 nm which are attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 transitions, respectively. The upconversion emissions are enhanced significantly by introduction of silver NPs. The enhancement is mainly attributed to the local field effect of silver NPs. Studied nanocomposites are potential candidates for the development of solid state lasers.     

Green synthesis of silver-graphene nanocomposite-based transparent conducting film

In the present work, silver nanoparticles (Ag NPs)/graphene nanocomposite has been synthesized successfully by simple solvothermal method via green route. Citric acid is used as green reducing agent for the reduction of graphene oxide (GO) and Ag ions. Silver nitrate is used as a precursor material for Ag NPs. As synthesized Ag NPs/graphene nanocomposite has been characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infra-red spectroscopy, UV–vis spectroscopy, thermal gravimetric analysis, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy. Experimental results confirm the reduction of GO and the successful formation of Ag NPs decorated graphene nanosheets. In addition, spray coating technique is employed for the fabrication of transparent conducting films. Enhancement in the optoelectrical signatures has been achieved using thermal graphitization of fabricated films. Thermal graphitization at 800 °C for 1 h marks the best performance of fabricated film with sheet resistance of ~3.4 kΩ/□ and transmittance (550 nm) of ~66.40%, respectively.     

Large two-photon absorbance of chitosan–ZnS quantum dots nanocomposite film

ZnS semiconductor nanoparticles with average size of 3.4 nm were prepared in situ in chitosan film. TEM, UV–vis spectra and PL spectra show the ZnS nanoparticles in chitosan template were monodispersed and well passivated. The two-photon absorption coefficient (β) of the chitosan–ZnS quantum dots (QDs) nanocomposite film was obtained to be 2.29×10² cm/Gw from a standard Z-scan setup with femtosecond laser pusles at 790 nm wavelength. Results show the novel biomacromolecule/QDs nanocomposite film has large third-order optical nonlinear absorption, the mechanism responsible for which was discussed.     

Influence on SERS enhancement factor of the components of an artificial opal loaded with metal NPs: A systematic study

We have inquired about the influence of composite artificial opal components on its SERS enhancement factor (EF). Particularly, we considered metal (100 nm) and dielectric spheres (290 nm), and an excitation wavelength of 632 nm. We show that the electric field of a SiO₂ sphere is weaker and more uniform as its porosity increases. Additionally, a porous sphere promotes a lower EF compared to that of a non-porous sphere. The optical response of the composite opal is insensitive to the polarization state of the incident field. A SERS EF of 10⁴ is reachable with an opal loaded with Au or Ag NPs. In general, the dielectric spheres affect the SERS EF intensity of the metal NPs. From the optical spectra, we observed that with a 632 nm wavelength, the composite opal is out of resonance.     

Expandable photo-induced synthetic route to generate highly controlled noble metal nanoparticles

A photo-stimulation strategy was applied to synthesize colloidal noble-metal nanoparticles (NPs) with a highly controlling of size and morphology with high yield at room temperature. In this controlled synthesis, photoreduction of a mixture of the noble metal precursor and a chemical reducing agent under ultraviolet (UV) illumination was used to produce electrons that reduce metal ions (Au³⁺ and Ag⁺) in toluene. Prolonged UV irradiation at 365 nm at a power of 0.14 μmol S⁻¹ m⁻² induced ripening wherein the irradiation power, exposure time, and chemical interaction of the reducing and stabilizing agents were key factors in determining the nanoscale structure of the NPs. Under optimal irradiation and chemical conditions, size and shape deviations of <6% of the Au and Ag NPs were obtained.     

High surface area monodispersed Fe3O4 nanoparticles alone and on physical exfoliated graphite for improved supercapacitors

Highly conductive, unsophisticated and easy to be obtained physical exfoliated graphite (PHG) supporting well dispersed magnetite, Fe₃O₄/PHG nanocomposite, has been prepared by a one-step chemical strategy and physico-chemical characterized. The nanocomposite, favoured by the a-polar nanoparticles (NPs) capping, results in a self-assembled monolayer of monodispersed Fe₃O₄, covering perfectly the hydrophobic surfaces of PHG. The nanocomposite as an electrode material was fabricated into a supercapacitor and characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. It shows, after a suitable annealing, significant electrochemical properties (capacitance value of 787 F/g at 0.5 A g⁻¹ and a Fe₃O₄/PHG weight ratio of 0.31) and good cycling stability (retention 91% after 30,000 cycles). Highly monodispersed very fine Fe₃O₄ NPs, covered by organic chains, have been also synthesized. The high surface area Fe₃O₄ NPs, after washing to leave a low content of organic chains able to avoid aggregation without excessively affecting the electrical properties of the material, exhibit remarkable pseudocapacitive activities, including the highest specific capacitance over reported for Fe₃O₄ (300 F/g at 0.5 A g⁻¹).     

Enhanced UV-excited luminescence of europium ions in silver/tin-doped glass

Glasses containing silver, tin and europium were prepared by the melt-quenching technique with silver nanoparticles (NPs) being embedded upon heat treatment (HT). An intensification of Eu³⁺ ions emission was observed for non-resonant excitation around 270 nm, corresponding to UV absorption in the material. Optical measurements suggest that light absorption occurs at single Ag⁺ ions and/or twofold-coordinated Sn centers followed by energy transfer to europium which results in populating the ⁵D₀ emitting state in Eu³⁺. After HT at 843 K, a quenching effect is observed on Eu³⁺ luminescence with increasing holding time in the 350–550 nm excitation range. The quenching effect shows with the presence of Ag NPs which may provide multipole radiationless pathways for excitation energy loss in europium ions.     

Sonocatalytic degradation of EDTA in the presence of Ti and Ti@TiO2 nanoparticles

The sonocatalytic degradation of EDTA (C₀ = 5 10⁻³ M) in aqueous solutions was studied under 345 kHz (P_ac = 0.25 W mL⁻¹) ultrasound at 22–51 °C, Ar/20%O₂, Ar or air, and in the presence of metallic titanium (Ti⁰) or core-shell Ti@TiO₂ nanoparticles (NPs). Ti@TiO₂ NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti⁰ NPs in pure water. Ti⁰ is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti₃O. SHT treatment at 150–214 °C leads to the oxidation of Ti₃O and partial oxidation of Ti⁰ and formation of nanocrystalline shell (10–20 nm) composed of TiO₂ anatase. It was found that Ti⁰ NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti⁰ NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti⁰ NPs and Ar/20%O₂ gas mixture. Coating of Ti⁰ with TiO₂ nanocrystalline shell reduces sonocatalytic activity. Pristine TiO₂ anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO₂ radicals in solution and (ii) EDTA oxidation at the surface of Ti⁰ NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti⁰/O₂ species at cavitation bubble/solution interface.     

Importance of poly(ethylene glycol) conformation for the synthesis of silver nanoparticles in aqueous solution

Silver nanoparticles (NPs) were prepared using silver nitrate (AgNO₃) as a precursor in an aqueous solution of poly(ethylene glycol) (PEG), which acted as both a reducing and stabilizing agent. The UV/Vis spectra showed that PEG 100 (100 kg/mol) has a remarkable capability to produce silver NPs at 80 °C, but the production of silver NPs by both PEG 2 (2 kg/mol) and PEG 35 (35 kg/mol) was negligible. This difference was explained by the conformation of PEG in the reaction solution: the entangled conformation for PEG 100 and the single-coiled conformation for PEG 2 and PEG 35, which were confirmed by pulse-field-gradient ¹H NMR and viscosity measurements. In an aqueous solution, the entangled conformation of PEG 100 facilitated the reduction reaction by caging silver ions and effectively prevented the agglomeration of formed NPs. The reaction in an aqueous PEG 100 solution was observed to be stable under the conditions of a prolonged reaction time or an increased temperature, while no reduction reaction occurred in the PEG 2 solution. The synthesis of silver NPs by PEG 100 was well controlled to produce fine silver NPs with 3.68 ± 1.03 nm in diameter, the size of which remained relatively constant throughout the reaction.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

Ultrasonically assisted synthesis of barium stannate incorporated graphitic carbon nitride nanocomposite and its analytical performance in electrochemical sensing of 4-nitrophenol

We describe the ultrasonic assisted preparation of barium stannate-graphitic carbon nitride nanocomposite (BSO-gCN) by a simple method and its application in electrochemical detection of 4-nitrophenol via electro-oxidation. A bath type ultrasonic cleaner with ultrasonic power and ultrasonic frequency of 100 W and 50 Hz, respectively, was used for the synthesis of BSO-gCN nanocomposite material. The prepared BSO-gCN nanocomposite was characterized by employing several spectroscopic and microscopic techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, fourier transform infra-red, field emission scanning electron microscopy, and high resolution transmission electron microscopy, to unravel the structural and electronic features of the prepared nanocomposite. The BSO-gCN was drop-casted on a pre-treated glassy carbon electrode (GCE), and their sensor electrode was utilized for electrochemical sensing of 4-nitrophenol (4-NP). The BSO-gCN modified GCE exhibited better electrochemical sensing behavior than the bare GCE and other investigated electrodes. The electroanalytical parameters such as charge transfer coefficient (α = 0.5), the rate constant for electron transfer (k_s = 1.16 s⁻¹) and number of electron transferred were calculated. Linear sweep voltammetry (LSV) exhibited increase in peak current linearly with 4-NP concentration in the range between 1.6 and 50 μM. The lowest detection limit (LoD) was calculated to be 1 μM and sensitivity of 0.81 μA μM⁻¹ cm⁻²_. A 100-fold excess of various ions, such as Ca²⁺, Na⁺, K⁺, Cl⁻, I⁻, CO₃²⁻, NO₃, NH₄⁺ and SO₄²⁻ did not able to interfere with the determination of 4-NP and high sensitivity for detecting 4-NP in real samples was achieved. This newly developed BSO-gCN could be a potential candidate for electrochemical sensor applications.     

Structural characterization and X-ray analysis by Williamson–Hall method for Erbium doped Aluminum Nitride nanoparticles,synthesized using inert gas condensation technique

We have synthesized AlN nanoparticles (NPs) doped in-situ with Er (AlN:Er) using inert gas condensation technique. Using x-ray diffraction (XRD) peak broadening analysis with the Williamson–Hall (W–H) Uniform Deformation Model (UDM) the crystallite size of the NPs and the strain in NPs were found to be 80±38 nm and 3.07×10⁻³±0.9×10⁻³ respectively. In comparison, using the Debye–Scherrer's (DS) formula, we have inferred that the crystallite size of the NPs was 23±6 nm and the average strain was 4.3×10⁻³±0.4×10⁻³. The scanning electron microscopy images show that the NPs are spherical and have an average diameter of ∼300 nm. The crystallite size is smaller than the size of the NPs revealing their polycrystalline behavior. In addition, the NPs strain, stress and energy density were also calculated using W–H analysis combined with the Uniform Deformation Stress Model (UDSM) and the Uniform Deformation Energy Density Model (UDEDM). Suggested by the spherical geometry and polycrystalline nature of the AlN NPs, the strain computed from UDM, UDSM and UDEDM were in agreement confirming an isotropic mechanical nature of the particle. Luminescence measurements revealed the temperature dependence of the optical emission of the Er³⁺ ions, confirming the use of AlN:Er NPs for nano-scale temperature sensing.     

Nonlinear optical properties of nanometer-size silver composite azobenzene containing polydiacetylene film

Diacetylene monomer containing p-nitrophenyl azobenzene moiety (NADA) was synthesized. Silver nanoparticles with different concentrations were adulterated in the above polymerized NADA (PNADA) films and the third-order nonlinear optical properties were investigated in detail. UV–vis spectra and transmission electron microscopy were used to confirm the formation of PNADA/Ag nanocomposite films. The silver nanoparticles (average size of 10 nm) were well dispersed in the polymer films. The value of the nonlinear refractive index n ₂ for PNADA films (8.48×10⁻¹⁵ cm²/W) was much higher than that of pure polydiacetylene films. Further, the introduction of silver nanoparticles into the PNADA polymer films led to the further enhancement of nonlinear optical properties. The maximum value of n ₂ for PNADA/Ag nanocomposite films could be 11.6×10⁻¹⁵ cm²/W. This enhancement should be ascribed to the surface plasmon resonance of silver nanoparticles.     

A High-Efficiency MRI Contrast Agent as well as a Tumor Therapeutic Agent

Inorganic/polymercore/shell nanoparticles (NPs) for theranostics have always attracted research interest due to their flexible composition and facile synthesis. Here, core/shell NPs are prepared with gadolinium hydroxide nanorods cores and Mn ion-doped polydopamine shells. After PEG modification, the relaxation rate of Gd(OH)₃@MnPDA-PEG NRs achieved 35 s⁻¹mm ⁻¹. The characterization results indicate that the predoping Mn ions obviously promote the effect of MRI compared with the nanorods without or with postdoping Mn ions, and the predoping method can effectively control the actual doping account of metal ions. Considering the toxicity, dopamine and manganese in molar ratio of 8:1 is finally chosen. Gd(OH)₃@MnPDA-PEG nanorods are conducted in vivo and in vitro imaging and therapeutic experiments. The results show that the nanorods has low biological toxicity, excellent magnetic resonance imaging effects, clear photoacoustic imaging, and photothermal therapy effects.     

Electric field distribution around the chain of composite nanoparticles in ferrofluids

Composite nanoparticles (NPs) have the ability of combining materials with different properties together, thus receiving extensive attention in many fields. Here we theoretically investigate the electric field distribution around core/shell NPs (a type of composite NPs) in ferrofluids under the influence of an external magnetic field. The NPs are made of cobalt (ferromagnetic) coated with gold (metallic). Under the influence of the external magnetic field, these NPs will align along the direction of this field, thus forming a chain of NPs. According to Laplace's equations, we obtain electric fields inside and outside the NPs as a function of the incident wavelength by taking into account the mutual interaction between the polarized NPs. Our calculation results show that the electric field distribution is closely related to the resonant incident wavelength, the metallic shell thickness, and the inter-particle distance. These analytical calculations agree well with our numerical simulation results. This kind of field-induced anisotropic soft-matter systems offers the possibility of obtaining an enhanced Raman scattering substrate due to enhanced electric fields.     

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al³⁺-doped γ-Ga₂O₃ nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (D_av = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al₂O₃ or Al deposition. Thus, ultrafine Al³⁺-doped γ-Ga₂O₃ NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga₂O₃-based NPs were 59 nm and 181 m²/g, respectively. Compared with γ-Ga₂O₃, the optical bandgap of the Al³⁺-doped γ-Ga₂O₃ NPs was broadened, and the thermal stability improved, indicating Al³⁺-doping into the γ-Ga₂O₃ lattice. However, the lattice constant of γ-Ga₂O₃ was almost unchanged with or without Al³⁺-doping. Al³⁺ was introduced into the defect sites of Ga³⁺, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.     

Water-Soluble Ln<Superscript>3+</Superscript>-Doped LaF<Subscript>3</Subscript> Nanoparticles: Retention of Strong Luminescence and Potential as Biolabels

The use of optically robust, luminescent lanthanide-based particles is becoming an area of interest for biolabel-related chemistry, due to their long lifetimes and range of non-overlapping absorption and emission lines from the visible to the near-infrared. We report the synthesis and optical properties of water-soluble, luminescent Ln³⁺-doped nanoparticles (NPs) coordinated with a hydrophilic (RO)PO₃²⁻ ligand that facilitates the stabilization of the NPs in aqueous conditions, and that regulates particle growth to the nanometer range. The use of lanthanide ions as dopants, in particular Eu³⁺ and Er³⁺ ions, yields optically robust particles with narrow emission lines in the visible (591 nm) and in the near-infrared (1530 nm), respectively. Luminescent lifetimes range from the microsecond to the millisecond for Er³⁺ and Eu³⁺ ions, respectively, and the NPs are not expected to be susceptible to photo-bleaching due to the fact that the emissions arise from intra-4f transitions of the lanthanide ions.     

Structure dependence of ultrafast third-order optical nonlinearity for GeS2-In2S3-CsI chalcohalide glasses

Ultrafast third-order nonlinear optical responses of GeS₂-In₂S₃-CsI chalcohalide glasses have been measured by using the femtosecond time-resolved optical Kerr effect (OKE) technique at a wavelength of 820 nm. The third-order nonlinear susceptibility was estimated to be as large as 5.12×10⁻¹³ esu. The full width at half maximum of the Kerr signal was 120 fs and its response was dominantly assigned to the ultrafast distortion of the electron cloud. The relationship between the structural units and the third-order nonlinear optical responses was analysed by Raman spectra. It is suggested that the covalent bonds of S-Ge or S-In constituting the tetrahedral units [GeS_4/2] or [InS_4−xI_x], respectively, play an important role in the ultrafast third-order nonlinear optical responses of these chalcohalide glasses.     

Nonlinear optical study of palladium Schiff base complex using femtosecond differential optical Kerr gate and Z-scan techniques

A femtosecond differential optical Kerr gate (DOKG) and Z-scan techniques, have been applied to investigate the third-order optical nonlinearity of composite film of the coordination complex [PdLPPh₃] (L=N-(2-pyridyl)-N′-(salicylidene)hydrazine, PPh₃=triphenylphosphine). Film exhibits superior nonlinear optical properties in the near-infrared spectral region. The nonlinear response time and third-order nonlinear optical susceptibility of complex were found to be≤90 fs and 3.9×10^?10 esu, respectively. The Z-scan result shows that saturable absorption property of the film and its nonlinear absorption coefficient of the sample was found to be ?23 cm/GW.