Growth and characterization of a new organic NLO material: Glycine nitrate

Single crystals of glycine nitrate [(C₂H₆NO₂)⁺ · (NO₃)⁻] were grown using submerged seed solution method. The crystals were characterized by using single crystal X-ray diffraction and density measurements. Spectroscopic, thermal and optical studies were carried out for analyzing the presence of the functional groups, thermal stability, decomposition and transparency of the sample. These studies showed that the crystals are thermally stable upto 145 °C and transparent for the fundamental and second harmonic generation of Nd:YAG (λ = 1064 nm) laser. Second harmonic generation (SHG) conversion efficiency was investigated to explore the NLO characteristics of this material. Microhardness and dielectric studies were also carried out.     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Second-harmonic generation in the thermal/electrical poling (100−x)GeS2·x(0.5Ga2S3·0.5CdS) chalcogenide glasses

Utilizing Maker fringe (MF) method, second-harmonic generation (SHG) has been observed within the GeS₂-Ga₂S₃-CdS pseudo-ternary glasses through thermal/electrical poling technique. The SHG phenomenon was considered to be the result of breakage of the glassy macroscopic isotropy originated from the reorientations of dipoles during the thermal/electrical poling process. Under the same poling condition conducted with 5 kV and 280 °C for 30 min, the maximum value of second-order nonlinear susceptibility χ⁽²⁾ of the poled (100−x)GeS₂·x(0.5Ga₂S₃·0.5CdS) glasses was obtained to be ≈4.36 pm/V when the value of x is equal to 30. Nonlinear dependence of χ⁽²⁾ on compositions of these glasses can be well explained according to the theory related to the reorientation of dipoles.     

Thermal, mechanical, and electronic properties of glycine-sodium nitrate crystal

Glycine-sodium nitrate, C₂H₅N₂NaO₅ (GSN), crystals were grown from aqueous solutions by slow cooling with a temperature lowering rate of 1 °C/day in the range of 40-22 °C. These crystals were analyzed by differential thermal and thermogravimetric analysis (DTA-TGA) and mechanical hardness tester in order to obtain their thermal and mechanical properties. Mechanical characterization was done by studying the variation of microhardness with applied load. The dielectric properties of GSN were calculated by using the CASTEP code within the framework of the generalized gradient approximation (GGA). For better understanding of the optical properties of GSN, the second derivative of ε₂(E) was evaluated. DTA-TGA analysis showed that the material has a thermal stability up to 198 °C. The microhardness test was carried out for several faces of GSN crystals, and the tests revealed a load dependence to hardness. Analysis of the second derivative of ε₂(E) allowed to obtain better resolution of the electronic transitions involving the energy bands. Besides, a theoretical representation of the orbitals’ energy diagram was obtained. A discussion about the relation of structure-properties and molecular character of GSN is presented here.     

Planar quarter wave stacks prepared from chalcogenide Ge-Se and polymer polystyrene thin films

Planar quarter wave stacks based on amorphous chalcogenide Ge-Se alternating with polymer polystyrene (PS) thin films are reported as Bragg reflectors for near-infrared region. Chalcogenide films were prepared using a thermal evaporation (TE) while polymer films were deposited using a spin-coating technique. The film thicknesses, d∼165 nm for Ge₂₅Se₇₅ (n=2.35) and d∼250 nm for polymer film (n=1.53), were calculated to center the reflection band round 1550 nm, whose wavelengths are used in telecommunication. Optical properties of prepared multilayer stacks were determined in the range 400-2200 nm using spectral ellipsometry, optical transmission and reflection measurements. Total reflection for normal incidence of unpolarized light was observed from 1530 to 1740 nm for 8 Ge-Se+7 PS thin film stacks prepared on silicon wafer. In addition to total reflection of light with normal incidence, the omnidirectional total reflection of TE-polarized light from 8 Ge-Se+7 PS thin film stacks was observed. Reflection band maxima shifted with varying incident angles, i.e., 1420-1680 nm for 45° deflection from the normal and 1300-1630 nm for 70° deflection from the normal.     

Preparation of Cu2ZnSnS4 thin films by hybrid sputtering

In order to fabricate Cu₂ZnSnS₄ thin films, hybrid sputtering system with two sputter sources and two effusion cells is used. The Cu₂ZnSnS₄ films are fabricated by the sequential deposition of metal elements and annealing in S flux, varying the substrate temperature. The Cu₂ZnSnS₄ films with stoichiometric composition are obtained at the substrate temperature up to 400 °C, whereas the film composition becomes quite Zn-pool at the substrate temperature above 450 °C. The Cu₂ZnSnS₄ film shows p-type conductivity, and the optical absorption coefficient and the band gap of the Cu₂ZnSnS₄ film prepared in this experiment are suitable for fabricating a thin film solar cell.     

Highly thermal stable transparent conducting SnO2:Sb epitaxial films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Antimony-doped tin oxide (SnO₂:Sb) single crystalline films have been prepared on α-Al₂O₃ (0 0 0 1) substrates by metal organic chemical vapor deposition (MOCVD). The antimony doping was varied from 2% to 7% (atomic ratio). Post-deposition annealing of the SnO₂:Sb films was carried out at 700-1100 °C for 30 min in atmosphere ambient. The effect of annealing on the structural, electrical and optical properties of the films was investigated in detail. All the SnO₂:Sb films had good thermal stability under 900 °C, and the 5% Sb-doped SnO₂ film exhibited the best opto-electrical properties. Annealed above 900 °C, the 7% Sb-doped SnO₂ film still kept high thermal stability and showed good electrical and optical properties even at 1100 °C.     

Enhanced thermal stability of optical nonlinearity for anilino–silane derived inorganic–organic hybrid thin films

A series of chromophore-bonded inorganic–organic hybrid films were successfully prepared via a sol–gel process using the alkoxysilane dye (ICTES-DR1), anilinomethyltriethoxysilane (AMTES) and tetraethoxysilane (TEOS) as precursors. Second-order NLO properties and their thermal stability of the hybrid films were investigated by in situ second harmonic generation (SHG) measurement. The poled films exhibit large second harmonic coefficient (d₃₃) in the range of 32–41 pm/V at 1064 nm. The aniline group of the AMTES was found to be effective for improving the thermal stability of optical nonlinearity due to the formation of hydrogen bonds between the carbonyl and aniline group, which was confirmed by virtue of FTIR and UV–visible spectra.     

Compositional dependence of the optical properties of novel Ge-Ga-Te-CsI far infrared transmitting chalcohalide glasses system

A systematic series of (Ge₁₅Ga₁₀Te₇₅)_1−x(CsI)_x (x=0, 5, 10, 15 at%) far infrared transmitting chalcohalide glasses were prepared by the traditional melt-quenching method. The physical, thermal and optical properties were determined. The allowed direct transition and indirect transition of samples were calculated according to the Tauc equation. The results show that glass transition temperatures (T_g) were in the range 133-175 °C, with ΔT values between 81 and 130 °C. The highest values of metallization criterion (0.244) and energy gap (1.191 eV) were obtained for (Ge₁₅Ga₁₀Te₇₅)₈₅(CsI)₁₅. When the dissolved amount of CsI increased from 0 to 15 at%, the direct optical band gap and indirect optical band gap were in the ranges 0.629-1.075 eV and 0.438-0.524 eV, respectively. The Ge-Ga-Te-CsI glasses have an effective transmission window between 1.7 and 25 μm, encompassing the region of interest for bio-sensing applications.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Third-order nonlinear optical properties of Bi2S3 and Sb2S3 nanorods studied by the Z-scan technique

Bismuth sulfide (Bi₂S₃) and antimony sulfide (Sb₂S₃) nanorods were synthesized by hydrothermal method. The products were characterized by UV-vis spectrophotometer, X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Bi₂S₃ and Sb₂S₃ nanorods were measured by Z-scan technique to investigate the third-order nonlinear optical (NLO) properties. The result of NLO measurements shows that the Bi₂S₃ and Sb₂S₃ nanorods have the behaviors of the third-order NLO properties of both NLO absorption and NLO refraction with self-focusing effects. The third-order NLO coefficient χ⁽³⁾ of the Bi₂S₃ and Sb₂S₃ nanorods are 6.25×10⁻¹¹ esu and 4.55×10⁻¹¹ esu, respectively. The Sb₂S₃ and Bi₂S₃ nanorods with large third-order NLO coefficient are promising materials for applications in optical devices.     

Effect of post-annealing on the properties of copper oxide thin films obtained from the oxidation of evaporated metallic copper

Thin films of copper oxide were obtained through thermal oxidation (100-450 °C) of evaporated metallic copper (Cu) films on glass substrates. The X-ray diffraction (XRD) studies confirmed the cubic Cu phase of the as-deposited films. The films annealed at 100 °C showed mixed Cu-Cu₂O phase, whereas those annealed between 200 and 300 °C showed a single cubic Cu₂O phase. A single monoclinic CuO phase was obtained from the films annealed between 350 and 450 °C. The positive sign of the Hall coefficient confirmed the p-type conductivity in the films with Cu₂O phase. However, a relatively poor crystallinity of these films limited the p-type characteristics. The films with Cu and CuO phases show n-type conductivity. The surface of the as-deposited is smooth (RMS roughness of 1.47 nm) and comprised of uniformly distributed grains (AFM and SEM analysis). The post-annealing is found to be effective on the distribution of grains and their sizes. The poor transmittance of the as-deposited films (<1%) is increased to a maximum of ∼80% (800 nm) on annealing at 200 °C. The direct allowed band gap is varied between 2.03 and 3.02 eV.     

Preparation, structure and oxide ion conductivity in Ce6−xYxMoO15−δ (x=0.1-1.4) solid solutions

The Ce_6−xY_xMoO_15−δ solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce_5.5Y_0.5MoO_15−δ ranging from 5.9×10⁻⁵ (S cm⁻¹) at 300 °C to 1.3×10⁻² (S cm⁻¹) at 650 °C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 °C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.     

Nanocrystalline formation and optical properties of germanium thin films prepared by physical vapor deposition

Amorphous and nanocrystalline germanium thin films were prepared on glass substrates by physical vapor deposition (PVD). The influence of thermal annealing on the characteristics of the Ge thin films has been investigated. X-ray diffraction (XRD) and SEM show amorphous structure of films deposited at room temperature. After thermal annealing, the crystallinity was improved when the annealing temperature increases. The Ge thin films annealed at different temperatures in air were nanocrystalline, having the face-centered cubic structure with preferred orientation along the 〈1 1 1〉 direction. The nanostructural parameters have been evaluated by using a single-order Voigt profile analysis. Moreover, the analysis of the optical transmission and reflection behavior was carried out. The values of direct and indirect band gap energies for amorphous and nanocrystalline phases are 0.86±0.02, 0.65±0.02 and 0.79±0.02, 0.61±0.02 eV, respectively. In addition, the complex optical functions for the wavelength range 600-2200 nm are reported. The refractive index of the nanocrystalline phase drops from 4.80±0.03 to 2.04±0.02, and amorphous phase changes from 5.18±0.03 to 2.42±0.02 for the whole wavelength range. The dielectric functions ε₁ and ε₂ of the deposited films were recorded as a function of wavelength within the range from 600 to 2200 nm.     

Spatially controlled dissolution of Ag nanoparticles in irradiated SiO2 sol-gel film

In this paper, we report the spatially controlled dissolution of silver nanoparticles in irradiated SiO₂ sol-gel films. The Ag nanoparticles have been formed in the sol-gel solution before the film deposition by adding Triton and ascorbic acid and also after the film deposition using a heat treatment at 700 °C for few minutes or at 550 °C for 6 h in reducing atmosphere. Using a spectrometer, a new view white light interferometer and a micro-thermal analyzer, we demonstrate that the silver nanoparticles can be dissolved using a continuous black ray UV lamp or with a near-infrared (NIR) femtosecond laser, due to a significantly increase in the local temperature. We confirm that the micro-thermal analyzer can be used as a new tool to study the dissolution of metallic nanoparticles in thin film if located at the surface of the films.     

Structural, compositional, thermal resistant and hydro-oleophobic properties of fluorine based block-co-polymer films on quartz substrates by wet chemical process

Crack free and smooth surfaces of poly [4,5-difluoro 2,2-bis (trifluoromethyl)-(1,3 dioxole)-co-tetrafluoroethylene] (TFE-co-TFD) thin films have been deposited by wet chemical dip coating technique on polished quartz and glass slide substrates. The deposited films have been subjected to annealing at different temperatures ranging from 100 to 500 °C for 1 h in argon atmosphere. The elemental composition of the as-deposited (xerogel) thin film as well as film annealed at 400 °C was measured by X-ray photoelectron spectroscopy and observed that there was no change in the composition of the film. X-ray diffraction pattern revealed the amorphous behaviour of both as-deposited and film annealed at 400 °C. Surface morphology and elemental composition of the films have been examined by employing scanning electron microscopy attached with energy dispersive X-ray analyser, respectively. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures have been grown, which in turn has shown increase in the water contact angle from 122^o to 148^o and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.     

Growth and characterization of two new NLO materials from the amino acid family: l-Histidine nitrate and l-Cysteine tartrate monohydrate

Single crystals of organic nonlinear optical (NLO) materials l-Histidine nitrate (C₆H₁₀N₃O₂)⁺ · (NO₃)⁻ and l-Cysteine tartrate monohydrate (C₃H₈NO₂S)⁺ · (C₄H₅O₆)⁻ · H₂O were grown by submerged seed solution method. Characterization of the crystals was made using single crystal X-ray diffraction. Fourier transform infrared (FTIR) spectroscopic studies, optical behaviour such as UV-visible-NIR absorption spectra and second harmonic generation (SHG) conversion efficiency were investigated to explore the NLO characteristics of the above materials. Microhardness measurements and dielectric studies of the compounds were also carried out.     

The important role of Mn in the room-temperature ferromagnetism of Mn-doped GaN films

Mn-doped GaN films (Ga_1−xMn_xN) were grown on sapphire (0 0 0 1) using Laser assisted Molecular Beam Epitaxy (LMBE). High-quality nanocrystalline Ga_1−xMn_xN films with different Mn concentration were then obtained by thermal annealing treatment for 30 min in the ammonia atmosphere. Mn ions were incorporated into the wurtzite structure of the host lattice by substituting the Ga sites with Mn³⁺ due to the thermal treatment. Mn³⁺, which is confirmed by XPS analysis, is believed to be the decisive factor in the origin of room-temperature ferromagnetism. The better room-temperature ferromagnetism is given with the higher Mn³⁺ concentration. The bound magnetic polarons (BMP) theory can be used to prove our room-temperature ferromagnetic properties. The film with the maximum concentration of Mn³⁺ presents strongest ferromagnetic signal at annealing temperature 950 °C. Higher annealing temperature (such as 1150 °C) is not proper because of the second phase Mn_xGa_y formation.     

Effect of nanostructured AlN coatings on the oxidation-resistant properties of optical diamond films

Diamond film is an ultra-durable optical material with high thermal conductivity and good transmission in near-infrared and far-IR (8-14 μm) wavebands. CVD diamond is subjected to oxidation at temperature higher than 780 °C bared in air for 3 min, while it can be protected from oxidation for extended exposure in air at temperature up to 900 °C by a coating of aluminum nitride. Highly oriented AlN coatings were prepared for infrared windows on diamond films by reactive sputtering method and the average surface roughness (R_a) of the coatings was about 10 nm. The deposited films were characterized by X-ray diffraction (XRD) and atom force microscope (AFM). XRD confirmed the preferential orientation nature and AFM showed nanostructures. Optical properties of diamond films coated AlN thin film was investigated using infrared spectrum (IR) compared with that for as-grown diamond films.     

Investigation of IrO2-SnO2 thin film evolution from aqueous media

The thermal evolution process of IrO₂-SnO₂/Ti mixed oxide thin films of varying noble metal content has been investigated under in situ conditions by thermogravimetry-mass spectrometry, Fourier transform infrared emission spectroscopy and cyclic voltammetry. The gel-like films prepared from aqueous solutions of the precursor salts Sn(OH)₂(CH₃COO)_2−xCl_x and H₂IrCl₆ on titanium metal support were heated in an atmosphere containing 20% O₂ and 80% Ar up to 600 °C.The thermal decomposition reactions practically take place in two separate temperature ranges from ambient to about 250 °C and between 300 and 600 °C. In the low temperature range the liberation of solution components and - to a limited extent - an oxidative cracking reaction of the acetate ligand takes place catalyzed by the noble metal. In the high temperature range the evolution of chlorine as well as the decomposition of surface species formed (carbonyls, carboxylates, carbonates) can be observed. The acetate ligand shows extreme high stability and is decomposed in the 400-550 °C range, only.Since the formation and decomposition of the organic surface species can significantly influence the morphology (and thus the electrochemical properties) of the films, the complete understanding of the film evolution process is indispensable to optimize the experimental conditions of electrode preparation.