Optical nonlinearities of BaTiO3 matrix-embedded Au nanoparticles

Composite thin films Au/BaTiO₃ comprising nanometer-sized gold particles embedded in BaTiO₃ matrices were synthesized on MgO(1 0 0) substrates by co-depositing Au and BaTiO₃ targets using pulsed laser deposition technique. The nanostructure of the films and the size distributions of the Au particles were analyzed by high-resolution transmission electron microscopy. Crystal lattice fringes from the Au nanocrystals and BaTiO₃ matrices were observed. The nonlinear optical properties of the Au/BaTiO₃ films were measured using z-scan method at the wavelength of 532 nm with a laser duration of 10 ns. The nonlinear refractive index n₂ and the nonlinear absorption coefficient β were determined to be 2.72 × 10⁻⁶ esu and −1.1 × l0⁻⁶ m/W, respectively.     

Laser stimulated piezoelectricity in Er3+ doped GeO2–Bi2O3 glasses containing silicon nanocrystals

We report the first observation of the laser stimulated piezoelectricity in Er³⁺ doped GeO₂–Bi₂O₃ glasses containing silicon nanocrystals, prepared using the simple well known melt quenching technique. Two split beams originated from the same nanosecond lasers were used for the performance of the bicolor laser treatment.The fundamental (λ = 1064 nm) and the doubled frequency (λ = 532 nm) signal of a pulsed nanosecond Nd:YAG laser, as the fundamental (λ = 1540 nm) and the doubled frequency (λ = 770 nm) signal of an Er:glass laser were used.The ratio of power densities between the fundamental and the doubled frequency beams has been varied from 4:1 to 8:1. This value was chosen to achieve the maximum output photoinduced piezoelectric response. The present photoinduced piezoelectricity effect opens a new road for obtaining optically operated piezoelectric devices in germanate composites doped with rare-earth ions.     

Thickness dependence of optical parameters for Ge–Se–Te thin films

The present work deals with thickness dependent study of the thin films of Ge₁₀Se_90 − xTe_x (x = 0, 10) chalcogenide glasses. Bulk samples of Ge₁₀Se₉₀ and Ge₁₀Se₈₀Te₁₀ have been prepared by melt quenching technique. Thin films (thickness d = 800 nm and 1100 nm) of the prepared samples have been deposited on glass substrate using vacuum evaporation technique. The optical parameters i.e. optical band gap (E_g^opt), absorption coefficient (α), refractive index (n) and extinction coefficient (k) are calculated from the transmission spectrum in the range 400–1500 nm. The optical band gap decreases with the increase of thickness from 1.87 ± 0.01 eV (d = 800 nm) to 1.80 ± 0.01 eV (d = 1100 nm) for Ge₁₀Se₉₀ and from 1.62 ± 0.01 eV (d = 800 nm) to 1.48 ± 0.01 eV (d = 1100 nm) for Ge₁₀Se₈₀Te₁₀ thin films.     

Comparative study on Pulsed Laser Deposition and Matrix Assisted Pulsed Laser Evaporation of urease thin films

Urease thin films were produced by Matrix Assisted Pulsed Laser Evaporation (MAPLE) and Pulsed Laser Deposition from two types of targets: frozen water solutions of urease with different concentrations (1-10% m/v) and pure urease pellets. The fluence of the ablating KrF excimer laser was varied between 300 and 2200 mJ/cm². Fourier transform infrared spectra of the deposited films showed no difference as compared to the original urease. Morphologic studies proved that the films consist of a smooth “base” layer with embedded micrometer-sized droplets. Absorption-coefficient measurements contradicted the traditional “absorptive matrix” model for MAPLE deposition. The laser energy was absorbed by urease clusters leading to a local heating-up and evaporation of the frozen matrix from the uppermost layer accompanied by the release of dissolved urease molecules. Significant enzymatic activity of urease was preserved only during matrix assisted transfer.     

High-speed deposition of dense,dendritic and porous SiO2 films by Nd: YAG laser chemical vapor deposition

Dense, dendritic and porous SiO₂ films were prepared by laser chemical vapor deposition (LCVD) using a high-power continuous-wave mode Nd: YAG laser (206 W) and a TEOS (tetraethyl orthosilicate) precursor. The effects of laser power (P_L) and total chamber pressure (P_tot) on the microstructure and deposition rate (R_dep) were investigated. Amorphous SiO₂ films were obtained independent of P_L and P_tot. Flame formation was observed between the nozzle and the substrate at P_L > 160 W and P_tot > 15 kPa. At P_L = 206 W, dense, dendritic and porous SiO₂ films were obtained at P_tot < 20 kPa, P_tot = 23 kPa and P_tot > 25 kPa, respectively. The R_dep increased thousands of times under flame formation conditions, the highest R_dep being reached at 1200 μm h^?1, 22,000 μm h^?1 and 28,000 μm h^?1 for the dense, dendritic and porous SiO₂ films, respectively.     

Fluorescence spectroscopy of Er3+:LaOBr prepared by NH4Br solid state reaction

The steady luminescent materials La_1−xEr_xOBr (x = 0, 0.0003, 0.01) were synthesized by a new NH₄Br solid state reaction, and the structures were studied using XRD and Raman methods. Under 514.5 nm Ar⁺ laser excitation, the upconversion fluorescence spectra in LaOBr:Er³⁺ were recorded and investigated. It was found that four upconverted emission bands with peaks at 388 nm, 399 nm, 405 nm (violet) and 477 nm (blue) were observed. All these upconverted emissions were assigned, and the upconversion mechanism was deduced to be excited state absorption (ESA), by analyzing the energy level structures of Er³⁺ ions and measuring the power dependence of upconverted emission intensities.     

Polymer–inorganic nano-composite thin film upconversion light emitters prepared by double-beam matrix assisted pulsed laser evaporation (DB-MAPLE) method

The work was to investigate the possibility of making polymer–inorganic nano-composite films with upconversion fluorescence properties using the double beam matrix-assisted pulsed laser evaporation (DB-MAPLE) method. The existing pulsed laser deposition vacuum chamber was modified to accommodate two laser beams of different wavelengths for simultaneous ablation of two separate targets: a polymer host and a rare earth containing rare earth ion enriched upconversion fluoride dopant. The polymer target was prepared in chlorobenzene and kept frozen during the ablation with circulating liquid nitrogen in accordance with the MAPLE procedure. It was ablated with 1064 nm beam from a pulsed Nd:YAG laser. The pellets made of the synthesized powders of inorganic phosphors of NaYF₄:Yb³⁺, Er³⁺ and NaYF₄:Yb³⁺, Ho³⁺were ablated with 532-nm beam from the same laser. The plumes from both targets were kept overlapping on the substrate during the deposition. X-ray diffraction analysis revealed that the most favorable for upconversion emission of the inorganic target materials was the hexagonal, beta phase of the NaYF₄ matrix existing at a baking temperature between 400 and 600 °C. The fabricated nano-composite films were characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM) and optical fluorescence spectroscopy. The polymer nano-composite films generally retained the crystalline structure and the upconversion fluorescence properties of the initial rare earth compounds due to better control of the deposition process of the materials with substantially different properties. The proposed method can be potentially used for making a wide variety of nano-composite films.     

Spectroscopic ellipsometry and magneto-transport investigations of Mn-doped ZnO nanocrystalline films deposited by a non-vacuum sol–gel spin-coating method

Nanocrystalline Zn_1?xMn_xO films (x = 0, 0.05, 0.1, 0.15, and 0.2) were deposited onto corning glass substrates by a non-vacuum sol–gel spin coating method. All of the films were annealed at 450 °C for 2 h. The structural, optical and magneto-transport properties were investigated by X-ray diffraction, spectroscopic ellipsometry and a system for the measurement of the physical properties. X-ray diffraction analysis of the films reveals that the Mn-doped ZnO films crystallize in the form of a hexagonal wurtzite-type structure with a crystallite size decreases with an increase of the Mn concentration. It was also found that the microstrain increases with the increase of the Mn content. Evidence of nanocrystalline nature of the films was observed from the investigation of surface morphology using transmission, scanning electron microscopy and atomic force microscopy. The optical constants and film thicknesses of nanocrystalline Zn_1?xMn_xO films were obtained by fitting the spectroscopic ellipsometric data (ψ and Δ) using a three-layer model system in the wavelength range from 300 to 1200 nm. The refractive index was observed to increase with increasing Mn concentration. This increase in the refractive index with increasing Mn content may be attributed to the increase in the polarizability due to the large ionic radius of Mn²⁺ compared to the ionic radius of Zn²⁺. The optical band gap of the nanocrystalline Mn–ZnO films was determined by an analysis of the absorption coefficient. The direct transition of the series of films was observed to have energies increasing linearly from 3.17 eV (x = 0) to 3.55 eV (x = 0.2). Magnetoresistance (MR) was measured from 5 K to 300 K in a magnetic field of up to 6 T. Low-field positive MR and high-field negative MR were detected in Mn-doped ZnO at 5 K. Only negative MR was observed for temperatures above 200 K. The positive MR in Mn-doped ZnO films was observed to decrease drastically when the temperature increased from 5 K to 100 K. The isothermal MR of Zn_1?xMn_xO films with different Mn concentrations at 5 K reveals that the increase of the Mn content induces a giant positive MR above x = 0.05 and reaches up to 55% at an applied field of 30 kOe for x = 0.2.     

Preparation of calcium-doped boron nitride by pulsed laser deposition

Calcium-doped BN thin films Ca_xBN_y (x = 0.05–0.1, y = 0.7–0.9) were grown on α-Al₂O₃(0 0 1) substrates by pulsed laser deposition (PLD) using h-BN and Ca₃N₂ disks as the targets under nitrogen radical irradiation. Infrared ATR spectra demonstrated the formation of short range ordered structure of BN hexagonal sheets, while X-ray diffraction gave no peak indicating the absence of long-range order structure in the films. It was notable that Ca-doped film had 5.45–5.55 eV of optical band gap, while the band gap of Ca-free films was 5.80–5.85 eV. This change in the band gap is ascribed to interaction of Ca with the BN sheets; first principle calculations on h-BN structure indicated that variation of inter-plane distance between the BN layers did not affect the band gap. This study highlights that PLD could prepare BN having short-range structure of h-BN sheets and being doped with electropositive cation which varies the optical band gap of the films.     

Effect of solvent ratio on the properties of highly oriented sprayed fluorine-doped tin oxide thin films

Transparent conducting thin films of F:SnO₂ have been deposited onto preheated glass substrates by a spray pyrolysis technique using pentahydrate stannic chloride (SnCl₄·5H₂O) and ammonium fluoride (NH₄F) as precursors and mixture of water and propane-2-ol as solvent. The concentration of SnCl₄·5H₂O and NH₄F is kept fixed and the ratio of water and propane-2-ol solvent in the spraying solution is varied. A fine spray of the source solution using air as a carrier gas has grown films of thickness up to 995 nm. Optical absorption, X-ray diffraction, Van der Pauw technique for measurement of a sheet resistance and Hall effect measurements at room temperature for determination of carrier density and conductivity have been used. The as-deposited films are of polycrystalline SnO₂ with a tetragonal crystal structure and are preferentially having orientation along the (200) direction with texture coefficient as high as 6.16. The average grain size for the as-deposited sample is found to be of the order of 44 nm. The films have moderate optical transmission (up to 70–85% at 550 nm). The figure of merit (ϕ) values vary from 1.95 · 10^− 3 to 35.68 · 10^− 3 Ω^− 1. The films are heavily doped, degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (R_s) for the optimized sample is 5.1 Ω. The films have a resistivity of 5.43 · 10^− 4 Ω cm and mobility around 7.38 cm² V^− 1 s^− 1.     

Deposition and DC electrical characterisation of rf magnetron sputtered silicon nitride thin films

Silicon nitride (Si₃N₄) is an important insulator, frequently used in VLSI technology and for encapsulation. Conventionally it is prepared by low pressure and plasma-enhanced chemical vapour deposition, but may also be successfully deposited by RF sputtering. In the present work the sputtering process was characterised, together with some measurements on the high-field DC electrical properties in sandwich samples with Au electrodes. Films were Ar-sputtered using a Si₃N₄ sputtering target at gas pressures up to 2.12 Pa and RF discharge powers of 60–200 W. The deposition rate R was in the range 0.03–0.19 nm s^− 1 and was directly proportional to the discharge power and varied linearly with the pressure. Au electrodes formed sandwich structures with thicknesses of 50 nm–1 μm. Conductivity was essentially ohmic below 300 nm, while for the thicker films space-charge limited conductivity, dominated by an exponential distribution of traps, was observed. A mobility value of μ = 2.89 × 10^− 6 m² V^− 1 s^− 1 was derived from temperature measurements, and further analysis of the J–V data indicated a thermally generated electron concentration of 3.23 × 10¹⁹ m^− 3 and a trap concentration of 1.57 × 10²⁴ m^− 3. It was concluded that this method is suitable for the deposition of thin films, which have similar electrical properties to those prepared by chemical vapour deposition methods.     

Sugar response of boronic acid-substituted azobenzene dye-modified polymer

We synthesized a boronic acid-appended azobenzene dye (BA) and attached it to poly(ethyleneimine) (polyBA) for studying its sugar response. The addition of d-glucose induced a significant change in the UV–visible absorption spectra of the polyBA solution. The binding constants for d-glucose (K_glu) and d-fructose (K_fru) were calculated to be 54 M^? 1 and 110 M^? 1, respectively. The selectivity for d-glucose was higher in polyBA as compared with that of monomeric BA (K_glu = 1.2 M^? 1, K_fru = 17 M^? 1). We also fabricated multilayered films composed of polyBA and polyanions {poly(vinyl sulfate) (PVS), carboxymethylcellulose (CMC)} using a layer-by-layer deposition technique. In (PVS/polyBA)₁₀ films, the affinity for d-glucose was relatively low (K_glu = 1.7 M^? 1, K_fru = 28 M^? 1). In contrast, (CMC/polyBA)₅ films showed a high affinity for d-glucose (K_glu = 18 M^? 1, K_fru = 42 M^? 1). The loosely packed structure of the (CMC/polyBA)₅ film and the suitable chemical structures of CMC probably led to a high affinity for d-glucose.     

Random laser performance of NdxY1−xAl3(BO3)4 laser crystal powders

We report random laser action in ground powders of Nd_xY_1?xAl₃(BO₃)₄ (x = 0.5–1) laser crystals under nanosecond pulse excitation at 802 nm. The dependence of the random laser threshold energy on the neodymium concentration and focusing conditions is investigated. The slope efficiency of the output random laser emission is determined as a function of Nd³⁺ concentration.     

Growth,thermal and optical properties of Yb:GdYAl3(BO3)4 crystal

Single crystal of Yb:GdYAl₃(BO₃)₄(Yb:GdYAB) has been grown by the flux method. The structure of Yb:GdYAB crystal has been determined by X-ray diffraction analysis. The experiment show that the crystal has the same structure as that of YAl₃(BO₃)₄ crystal and its unit cell constants have been measured to be a = 9.30146 Å, c = 7.24164 Å, Vol = 542.59 Å³. The absorption and fluorescence spectrum of Yb:GdYAl₃(BO₃)₄ crystal have also been measured at room temperature. In the absorption spectra, there are two absorption bands at 938 nm and 974 nm, respectively, which is suitable for InGaAs diode laser pumping. In the fluorescence spectra, there are two fluorescence peaks at 992 and 1040 nm. The thermal properties of Yb:GdYAl₃(BO₃)₄ crystal have been studied for the first time. The thermal expansion coefficient along c-axis is almost 5.4 times larger than that along a-axis. The specific heat of the crystal has been measured to be 0.77 J/g °C at room temperature. The calculated thermal conductivity is 5.26 Wm⁻¹ K⁻¹ along a-direction.     

Structural and optical properties of BaTi2O5 thin films prepared by pulsed laser deposition at different substrate temperatures

BaTi₂O₅ thin films were prepared on MgO (1 0 0) substrates by pulsed laser deposition. The effect of substrate temperature (T_sub) on the structural and optical properties of the films, such as crystal phase, preferred orientation, crystallinity, surface morphology, optical transmittance and bandgap energy, was investigated. The preferred orientation of the films changed form (7 1 0) to (0 2 0) depending on T_sub, and the b-axis oriented BaTi₂O₅ thin film could be obtained at T_sub = 973–1023 K. The surface morphology of the films was different with changing T_sub, which showed a dense surface with an elongated granular texture at T_sub = 973–1023 K. The crystallinity and surface roughness increased at the elevated substrate temperatures. The as-deposited BaTi₂O₅ thin films were highly transparent with an optical transmittance of ～70%. The bandgap energy was found to decrease with increasing substrate temperature, from 3.76 eV for T_sub = 923 K to 3.56 eV for T_sub = 1023 K.     

Green EuAlO3:Eu2+ nanophosphor for applications in WLEDs

Green-emitting aluminate nanophosphors fabricated by a pressure-assisted combustion synthesis (P₀ = 1.4, 2.8 and 3.4 MPa) and annealed in pure H₂ is reported. The XRD analysis indicates the formation of the EuAlO₃ orthorhombic phase. Transmission electron microscopy (TEM) shows coalesced irregular grains with lengths in the range of 35–140 nm. In addition, the nanophosphor synthesized at an initial pressure of 3.4 MPa produced the highest green luminescence centered at 530 nm, which was associated to 4f⁷–4f⁶5d¹ allowed transitions of the Eu²⁺ located into the EuAlO₃:Eu²⁺ compound. A weak red emission peak corresponding to Eu³⁺ was also observed by cathodoluminescence. The CIE coordinates for green emission are x = 0.2613 and y = 0.3892, and the luminance produced from nanophosphors when they are excited with a commercial UV-396 nm LED (8.0 μW) was 285 ± 4.3 Cd/m².     

Laser-assisted vibrational control of precursor molecules in diamond synthesis

Control of chemical reactions is the essence of chemistry, producing designed outcomes while suppressing unwanted side products. Laser-assisted molecular vibrational control has been demonstrated to be a potential approach to influencing the outcome of a chemical reaction. In this article, we reviewed recent progress in the laser control of diamond synthesis through vibrational excitation of precursor molecules in a laser-assisted combustion chemical vapor deposition process. Significantly promoted diamond deposition rate (139 μm/h) and crystalline quality were achieved by resonantly exciting the Q-branch (ΔJ = 0) of the CH₂-wagging mode (v₇ mode 949.3 cm⁻¹) of C₂H₄ molecules. Resonant excitation of the fundamental vibrational modes is more effective in promoting diamond growth than random vibrational excitation. Control of diamond crystallographic orientation was also realized by resonantly exciting the R branch (ΔJ = 1) of the CH₂-wagging mode of C₂H₄ molecules and resulted in the preferential growth of {1 0 0}-oriented diamond crystals. Nitrogen-doped diamond films with a nitrogen concentration of 1.5 × 10²⁰ atoms/cm³ were synthesized by resonantly exciting the rotational–vibrational transition (J = 5 → J′ = 6, K = 0) of the N–H wagging mode (v₂ mode) in ammonia molecules. The findings demonstrate the feasibility of laser-assisted vibrational control in steering chemical reactions and controlling reaction outcomes.     

AgTaO3 and AgNbO3 thin films by pulsed laser deposition

Silver tantalate AgTaO₃ (ATO) and silver niobate AgNbO₃ (ANO) films have been grown on to the LaAlO₃ (001) and sapphire Al₂O₃ (0112, r-cut) single crystals by pulsed laser deposition technique from stoichiometric ATO and ANO targets. X-ray diffraction study revealed epitaxial quality of ATO and ANO films on the LaAlO₃ (001) whereas on the sapphire r-cut substrate they are preferential (110) and (001) oriented. To characterize microwave films properties in the range from 1 to 40 GHz, coplanar line interdigital capacitors were fabricated by photolithography and lift-off technique. ANO film capacitors show superior properties: frequency dispersion was as low as 13%, voltage tunability (40 V, 200 kV/cm) was about 4.6% at 20 GHz, loss tangent ∼0.106 at 20 GHz, K-factor = tunability / tanδ from 49% @ 10 GHz to 33% at 40 GHz.     

Preparation and optical characterization of e-beam deposited cerium oxide films

Cerium oxide films, of 0.3–1 μm thickness, were reactively deposited in the oxygen atmosphere onto quartz plates by the PVD method. An electron gun was used as an evaporation source. Films were characterized with the AFM method, Raman spectroscopy and spectrophotometrically. Optical properties of these films were examined for the wavelength range 0.2–2.5 μm. Films were characterized by high transparency, between 0.38 and 2.5 μm. The complex refractive index, n^*=n − jk, was evaluated. The dispersion characteristics for n(λ) and k(λ) were presented. We found that the refractive index strongly depends on the temperature of substrates (300 K ⩽ T_s ⩽ 673 K) during film deposition. Estimated values of the refractive index (at λ = 0.55 μm) were in the range 1.91–2.34.     

Oxygen partial pressure dependence of the structural properties of CdO thin films deposited by a modified reactive vacuum evaporation process

Thin films of cadmium oxide were thermally deposited on glass substrates at partial pressures of oxygen, pO₂ in the range 1.33×10⁻² to 0.133 Pa at a substrate temperature of 160 °C. Energy dispersive analysis of X-ray fluorescence (EDAX) revealed that the CdO films deposited at pO₂ value of 4.00×10⁻² Pa were nearly stoichiometric. X-ray diffractometry (XRD) confirmed the polycrystalline nature of the film structure. All the films showed an fcc structure of the NaCl-type, as the dominant phase. The films exhibited preferred orientation along the (1 1 1) diffraction plane. The texture coefficients calculated for the various planes at different oxygen partial pressures (pO₂) indicated that the maximum preferred orientation of the films occurred along the (1 1 1) plane at an oxygen partial pressure of 4.00×10⁻² Pa. This was interpreted in terms of oxygen chemisorption and desorption processes. The lattice parameters determined from the diffraction peaks were in the range 4.655–4.686 Å. The average lattice parameter a₀ found by extrapolation using the Nelson–Riley function was 4.696 Å. Both the lattice parameter and the crystallite size were found to increase with increased partial pressure of oxygen. On the other hand, the strain and dislocation density were found to decrease as the partial pressure of oxygen was raised. A maximum (80%) in the optical transmittance at λ=600 nm and minimum in the electrical resistivity (9.1×10⁻⁴ Ω cm) of the films occurred at an optimum partial pressure of oxygen of 4.00×10⁻² Pa. The results are discussed.