Microstructures and the third-order optical nonlinearities of semimetal Bi nanocrystals in the sodium borosilicate glass

The sodium borosilicate glass doped with semimetal Bi nanocrystals is prepared by employing both sol-gel and atmosphere control methods. Microstructures and the third-order optical nonlinearities of the glass are investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), and Z-scan technique. The results show that semimetal Bi nanocrystals in hexagonal crystal system with spherical shape have formed uniformly in the glass, and the size of these nanocrystals is almost less than 40 nm. Furthermore, the third-order optical nonlinear refracitve index γ, absorption coefficient β, and susceptibility χ⁽³⁾ of the glass are determined to be 9.40 × 10⁻¹⁷ m²/W, 1.25 × 10⁻⁹ m/W, and 6.80 × 10⁻¹¹ esu, respectively.     

Exceptionally large third-order optical susceptibility in Ag:SrBi2Nb2O9 composite films

Thin films of SrBi₂Nb₂O₉ with and without the inclusion of Ag nanocrystals were prepared on MgO (001) substrates by alternative pulsed laser ablation of SrBi₂Nb₂O₉ ceramic and Ag metal in a nitrogen atmosphere. The size of the Ag nanocrystals can be brought down to ca. 5.0 nm, as revealed by transmission electron microscopy and X-ray diffraction. We measured the third-order susceptibility χ⁽³⁾ of the deposits by single beam z-scan technique at a wavelength of 532 nm. It is found that SrBi₂Nb₂O₉ is an effectively nonlinear optical medium, exhibiting a very large χ⁽³⁾. With the inclusion of Ag nanocrystals the χ⁽³⁾ was nearly doubled (Reχ⁽³⁾ = 8.052 × 10^− 7 esu, and Imχ⁽³⁾ = − 1.717 × 10^− 7 esu), which comes very close to the maximum value available in the current time. This indicates that the Ag:SrBi₂Nb₂O₉ composite structure can be an excellent candidate for nonlinear optical applications. A general approach for further enhanced third-order susceptibility by tailoring the dielectric constant of the metal inclusion is briefly discussed.     

The third-order optical nonlinearity of Bi3.25La0.75Ti3O12 ferroelectric thin film on quartz

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin film was prepared on quartz substrates using chemical solution deposition. The sign and magnitude of both real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ of the BLT thin film have been determined by the Z-scan technique performed at 800 nm with a femtosecond laser. The nonlinear refractive index coefficient γ and the nonlinear absorption coefficient β of the BLT thin film are − 1.915 × 10^− 12 cm² / W and − 6.764 × 10^− 8 m/W, respectively, the real part and imaginary part of the third-order nonlinear susceptibility χ⁽³⁾ of the BLT thin film are − 5.81 × 10^− 18 m² / V² and − 1.31 × 10^− 18 m² / V², respectively. Both the real and the imaginary parts of the third-order nonlinear susceptibility χ⁽³⁾ contribute to the nonlinearity of the film. These experimental results show that BLT thin film is a promising material for applications in nonlinear optical devices.     

Nonlinear optical properties of laser deposited CuO thin films

In this work we investigate the third-order optical nonlinearities in CuO films by Z-scan method using a femtosecond laser (800 nm, 50 fs, 200 Hz). Single-phase CuO thin films have been obtained using pulsed laser deposition technique. The structure properties, surface image, optical transmittance and reflectance of the films were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and UV-vis spectroscopy. The Z-scan results show that laser-deposited CuO films exhibit large nonlinear refractive coefficient, n₂ = − 3.96 × 10^− 17 m²/W, and nonlinear absorption coefficient, β = − 1.69 × 10^− 10 m/W, respectively.     

Optical properties of nanocrystalline SnS2 thin films

Thin films of nanocrystalline SnS₂ on glass substrates were prepared from solution by dip coating and then sulfurized in H₂S (H₂S:Ar = 1:10) atmosphere. The films had an average thickness of 60 nm and were characterized by X-ray diffraction studies, scanning electron microscopy, EDAX, transmission electron microscopy, UV-vis spectroscopy, and Raman spectroscopy. The influence of annealing temperature (150-300 °C) on the crystallinity and particle size was studied. The effect of CTAB as a capping agent has been tested. X-ray diffraction analysis revealed the polycrystalline nature of the films with a preferential orientation along the c-axis. Optical transmission spectra indicated a marked blue shift of the absorption edge due to quantum confinement and optical band gap was found to vary from 3.5 to 3.0 eV with annealing temperature. Raman studies indicated a prominent broad peak at ∼314 cm⁻¹, which confirmed the presence of nanocrystalline SnS₂ phase.     

Third order optical susceptibilities of the Cu2O thin film

By performing Z-scan method with a femtosecond laser (800 nm, 50 fs, 1 kHz), we investigated the third-order optical nonlinearities of a cuprous oxide (Cu₂O) film. Single-phase Cu₂O film deposited on a quartz substrate was obtained using the pulsed laser deposition technique. The structure properties, surface morphology and optical transmission spectrum were characterized by X-ray diffraction, scanning electron microscopy and double beam spectrophotometer, respectively. The Z-scan results show that the Cu₂O film exhibits large nonlinear refractive index, n₂ = 3 × 10^− 3 cm²/GW, while the two-photon absorption coefficient, α₂ = 40 cm/GW, is relatively small. It implies that the Cu₂O film is a promising candidate for nonlinear photonic devices.     

Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Optical nonlinearities of Au nanocluster composite fabricated by 250 keV ion implantation

Metal nanocluster composite glass prepared by 250 keV Au ions into silica with dose of 1 × 10¹⁷ ions/cm² has been studied. The microstructural properties of the nanoclusters are characterized by optical absorption spectra and transmission electron microscopy (TEM). Third-order optical properties of the nanoclusters are studied by the Z-scan technique under 1064 nm and 532 nm excitations. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility are deduced. The results of the investigation of nonlinear refraction using the off-axis Z-scan configuration are presented and the mechanisms responsible for the nonlinear response are discussed. The third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 1.6 × 10⁻⁷ esu at 532 nm and 1.3 × 10⁻⁷ esu at 1064 nm.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Synthesis, characterization and electrical conductivity studies on A3Bi2P3O12 (A = Na, K) materials

Crystalline Na₃Bi₂P₃O₁₂, K₃Bi₂P₃O₁₂ and glassy K₃Bi₂P₃O₁₂ compounds were prepared by solid-state reaction method. The prepared samples are characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry. The crystalline materials are found to be orthorhombic. The electrical conductivity measurements on the crystalline and glassy samples show that at ∼373 K, the σ_DC for crystalline K₃Bi₂P₃O₁₂ (0.81 × 10⁻⁸ S/cm) is about two orders of magnitude higher than the corresponding glassy phase (1.25 × 10⁻¹⁰ S/cm). The scaling results show that the conductivity relaxation mechanism is independent of temperature.     

Nonlinear optical properties of Ag nanocluster composite fabricated by 200 keV negative ion implantation

Metal nanocluster composite glass prepared by 200 keV Ag ions' implantation into silica with dose of 2 × 10¹⁷ ions/cm² has been studied. The formation of sandwiched nanocluster-nanovoid-nanocluster structures has been evidenced by in situ transmission electron microscopy experiment (TEM). Fast nonlinear optical refraction and nonlinear optical absorption coefficients were measured at 532 nm and 1064 nm of wavelength by the Z-scan technique. The third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 4.0 × 10⁻⁸ esu at 532 nm and 9.0 × 10⁻⁸ esu at 1064 nm, respectively.     

Z-scan measurement for the nonlinear absorption of Bi2.55La0.45TiNbO9 thin films

Bi_2.55La_0.45TiNbO₉ (BLTN-0.45) thin films with layered aurivillius structure were fabricated on fused silica substrates by pulsed laser deposition technique. Their structure, fundamental optical constants, and nonlinear absorption characteristics have been studied. The film exhibits a high transmittance (> 60%) in visible-infrared region. The optical band gap energy was found to be 3.44 eV. The optical constant and thickness of the films were characterized using spectroscopic ellipsometric (SE) method. The nonlinear optical absorption properties of the films were investigated by the single-beam Z-scan method at a wavelength of 800 nm laser with a duration of 80 fs. We obtained the nonlinear absorption coefficient β = 4.64 × 10^− 8 m/W. The results show that the BLTN-0.45 thin film is a promising material for applications in absorbing-type optical device.     

Nonlinear optical response of silica doped with copper nanoclusters under 1064 nm laser excitation

Metal nanocluster composite glass was formed by Cu ion implantation into silica using metal vapor vacuum arc (MEVVA) ion source. The microstructural properties of the nanoclusters were analyzed by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 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. The mechanisms responsible for the nonlinear response were discussed. Third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be (4.2 ± 1.0) × 10⁻⁸ esu.     

Bi4LnNb3O15 (Ln = La, Pr, Nd) and Bi4LaTa3O15: New intergrowth Aurivillius related phases

We describe the synthesis and characterization of new intergrowth Aurivillius related phases, Bi₄LnNb₃O₁₅ (Ln = La, Pr, Nd) and Bi₄LaTa₃O₁₅. Both powder X-ray diffraction and electron microscopy investigations show that the compounds adopt orthorhombic structures with the cell parameters a ∼ 5.5 Å, b ∼ 5.5 Å and c ∼ 20.9 Å, suggesting an ordered intergrowth structure that consists of n = 1 [Bi₂NbO₆]⁻ and n = 2 [Bi₂LnNb₂O₉]⁺ Aurivillius fragments which are stacked alternately along the c-axis. The oxides do not show a second harmonic generation (SHG) response toward 1064 nm laser radiation; they do not show a ferroelectric-paraelectric transition either between 30 and 900 °C in dielectric measurements, indicating a centrosymmetric structure. Optical absorption studies show that the intergrowth phases possess considerably smaller band gaps than the parent Nb₂O₅ and Ta₂O₅.     

Synthesis and crystal structure of a novel lithium bismuth phosphate, Li2Bi14.67(PO4)6O14

A lithium bismuth phosphate, Li₂Bi_14.67(PO₄)₆O₁₄, has been synthesized for the first time by the solid-state method. The crystal structure was determined by single crystal X-ray diffraction at 150 K. Li₂Bi_14.67(PO₄)₆O₁₄ crystallizes in the monoclinic system C2/c (No. 15), with a = 30.8189(4) Å, b = 5.2691(3) Å, c = 24.5302(3) Å, β = 122.84(2)°, V = 3346.81(1) Å³ and Z = 2. The structure along the b axis consists of layers of [Bi₂O₂] units as the basic building block. These are separated by isolated PO₄ and LiO₄ tetrahedra. The oxygen co-ordination around two of the phosphorus atoms is disordered. Solid-state ⁷Li NMR studies confirm the presence of lithium in the structure. The material shows ionic conductivity of the order of 10⁻⁵ S cm⁻¹ at 600 °C.     

Large third-order optical nonlinearity of SrBi2Nb2O9 thin films fabricated by pulsed laser deposition

SrBi₂Nb₂O₉ (SBN) thin films with a single phase of layered perovskite structure have been fabricated on fused quartz substrates at room temperature by pulsed laser deposition. The XRD and AFM analysis indicated that the films had better crystallinity, less rough surface morphology, and larger grain size with increasing oxygen pressure. The nonlinear optical properties of the samples were determined using a single beam Z-scan technique at a laser wavelength of 532 nm with laser duration of 25 ps. The real and imaginary parts of the third-order nonlinear optical susceptibility χ⁽³⁾ of the films were measured to be 3.18 × 10^− 8 esu and 5.94 × 10^− 9 esu, respectively.     

Upconversion luminescence of Ho sensitized by Yb in transparent glass ceramic embedding BaYF5 nanocrystals

Transparent SiO₂-Al₂O₃-BaCO₃-YF₃-BaF₂ glass ceramics co-doped with Yb³⁺/Ho³⁺ ions were prepared by melt quenching and subsequent heating. X-ray diffraction and transmission electron microscopy observation revealed that BaYF₅ nanocrystals incorporated with Yb³⁺ and Ho³⁺ were precipitated homogeneously among the oxide glass matrix. Three upconversion emission bands centered at 483 nm, 545 nm and 645 nm, corresponding to the ⁵F₃ → ⁵I₈, ⁵S₂, ⁵F₄ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺ respectively, were detected under 976 nm excitation, ascribing to the efficient energy transfer from Yb³⁺ to Ho³⁺. The red emission is prevailing in the precursor glass, while the green one turns to be dominant in the glass ceramic.     

Third-order optical nonlinear absorption in Bi1.95La1.05TiNbO9 thin films

Single phase Bi_1.95La_1.05TiNbO₉ (LBTN-1.05) thin films with a layered aurivillius structure have been fabricated on fused silica substrates by pulsed laser deposition at 700 °C. The X-ray diffraction pattern revealed that the films are single-phase aurivillius. The band gap, linear refractive index and linear absorption coefficient were obtained by optical transmittance measurements. The film exhibits a high transmittance (> 70%) in visible-infrared region and the dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The nonlinear optical absorption property of the film was determined by the single beam Z-scan method using 800 nm with a duration of 100 fs. A large positive nonlinear absorption coefficient β = 5.95 × 10^− 8 m/W was determined experimentally. The results showed that the LBTN-1.05 is a promising material for applications in absorbing-type optical devices.     

Preparation of Bi2S3 nanorods via a hydrothermal approach

Large-scale bismuth sulfide (Bi₂S₃) nanorods with uniform size have been prepared by hydrothermal method using bismuth chloride (BiCl₃) and sodium sulfide (Na₂S·9H₂O) as raw materials at 180 °C and pH = 1-2 for 12 h. The powder X-ray diffraction (XRD) pattern shows the Bi₂S₃ crystal belongs to the orthorhombic phase with calculated lattice constants a = 1.1187 nm, b = 1.1075 nm and c = 0.3976 nm. Furthermore, the quantification of X-ray photoelectron spectra (XPS) analysis peaks gives an atomic ratio of 1.9:3.0 for Bi:S. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopic (TEM) studies reveal that the appearance of the as-prepared Bi₂S₃ is rod-like with typical lengths in the range of 2-5 μm and diameters in the range of 10-30 nm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of Bi₂S₃ nanorods is proposed.     

Large nonlinear optical response of a Bi1.5Zn1.0Nb1.5O7 thin film fabricated by pulsed laser deposition

The Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin film has been fabricated on MgO (001) substrate by pulsed laser deposition. The nonlinear optical properties of the BZN film were investigated using Z-scan technique at a wavelength of 532 nm with 25 ps pulse duration. The two-photon absorption coefficient and the nonlinear refractive index of the BZN film were obtained to be 4.2 × 10^− 6 cm/W and 1.6 × 10^− 10 cm²/W respectively, which are comparable with those of some representative nonlinear optical materials. The large and fast response optical nonlinearities indicated that the BZN film is a promising candidate for future photonics devices.