Growth of high performance piezoelectric crystal Pb(Zn1/3Nb2/3)O3-PbTiO3 using PbO flux

Novel piezoelectric crystal (1 − x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃ (PZNT) has attracted much attention due to its high piezoelectric properties and potential applications in medical ultrasonic devices, sonar transducers, solid state actuators. However, the applications of PZNT crystals are limited by the lack of a simple and reproducible growth technique. In this work, large size PZNT crystals were grown by the vertical Bridgman method using 50 mol% PbO as a flux. The growth conditions were optimized as mole ratio of raw materials and flux = 1:1, soaking temperature 1150-1200 °C, soaking time 10 h, the lowering rate of the crucible 0.5 mm/h and the temperature gradient near solid-liquid interface about 50 °C/mm. The maximum size of as-grown PZNT crystal was about 60 mm in length. The crystal was oriented and its piezoelectric constant d₃₃ and coupling coefficient k₃₃ were measured over 2000 pC/N and 0.92, respectively.     

Growth of thin Fe(0 0 1) films for terahertz emission experiments

The electrical and magnetic properties of thin iron (Fe) films have sparked significant scientific interest. Our interest, however, is in the fundamental interactions between light and matter. We have discovered a novel application for thin Fe films. These films are sources of terahertz (THz) radiation when stimulated by an incident laser pulse. After intense femtosecond pulse excitation by a Ti:sapphire laser, these films emit picosecond, broadband THz frequencies. The terahertz emission provides a direct measure of the induced ultrafast change in magnetization within the Fe film. The THz generation experiments and the growth of appropriate thin Fe films for these experiments are discussed. Several criteria are used to select the substrate and film growth conditions, including that the substrate must permit the epitaxial growth of a continuous, monocrystalline or single crystal film, yet must also be transparent to the emitted THz radiation. An Fe(0 0 1) film grown on the (0 0 1) surface of a magnesium oxide (MgO) substrate makes an ideal sample. The Fe films are grown by physical vapor deposition (PVD) in an ultrahigh vacuum (UHV) system. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are used to characterize the Fe(0 0 1) films. Two substrate surface preparation methods are investigated. Fe(0 0 1) films grown on MgO(0 0 1) substrates that are used as-received and films grown on MgO(0 0 1) substrates that have been UV/ozone-cleaned ex vacuo and annealed in vacuo produce the same results in the THz generation experiments. Either substrate preparation method permits the growth of samples suitable for the THz emission experiments.     

Comparative study on BIS thiourea cadmium acetate crystals using HRXRD, etching, microhardness, UV-visible and dielectric characterizations

〈1 1 1〉 oriented bis thiourea cadmium acetate (BTCA) crystal of diameter 15 mm and length 45 mm was grown for the first time by the unidirectional Sankaranarayanan-Ramasamy (SR) method. The conventional and SR method grown BTCA crystals were characterized by using high-resolution X-ray diffraction (HRXRD), chemical etching, Vickers microhardness, UV-vis, dielectric studies and differential scanning calorimetry. The HRXRD analysis indicates that the crystalline perfection of SR method grown crystal is good without having any low angle internal structural grain boundaries. The transmittance of SR method grown BTCA is 14% higher than that of conventional grown crystal. The dielectric constant was higher and the dielectric loss was less in SR method grown crystal. The crystals grown by SR method possess less dislocation density and higher microhardness.     

Catalyst-free synthesis of novel brush-shaped ZnO particles by a simple oxidation in air

Brush-shaped ZnO particles were synthesized by controlling the growth time in the direct melt oxidation process of Al-Zn mixture in air at atmospheric pressure. Particles with two kinds of structures were formed. One was consisted of nanowires grown along [0 0 0 1] direction at the six corners and the center of (0 0 0 1) basal plane on hexagonal ZnO microrod. The other was constructed by nanobelts between the corner-nanowires as well as nanowires at the corners on ZnO microrod. The structural configuration that the nanowires and the nanobelts have a well coherent orientation alignment with the base microrod implies that the brush-shaped ZnO is single crystal. Room temperature PL spectrum of the brush-shaped ZnO particles displayed predominant green emission with a wavelength of 510 nm.     

Unidirectional growth,optical, mechanical and dielectric studies on a novel NLO crystal: l-Arginine 4-nitrophenolate 4-nitrophenol dihydrate

The bulk single crystal of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP), an efficient organic NLO material of size 74 mm in length, 18 mm in diameter, was grown successfully by Sankaranarayanan–Ramasamy (SR) method. Single crystal X-ray diffraction study reveals that LAPP crystallizes into monoclinic system with the space group P2₁. The unidirectional growth along the plane (1 1 0) was confirmed from the powder XRD pattern with the sharp peak having maximum intensity. Optical absorption spectrum shows that LAPP has highly transparent in the entire visible and IR region with a wide band gap of 3.9 eV for large photon absorption. Vickers micro hardness measurement was performed to know the mechanical strength of the crystal. Dielectric profile of LAPP at room temperature brings forth low value of dielectric loss and dielectric constant at higher frequencies. Photoluminescence study reveals that LAPP exhibit green emission in the wavelength region 538 nm. The SHG efficiency of the crystal is measured by Kurtz's powder test using Nd:YAG Laser.     

Growth process of β-FeSi2 epitaxial film on Si(1 1 1) by molecular beam epitaxy

We have reported a one step growth of a high quality β-FeSi₂ epitaxial film on hydrogen terminated Si(1 1 1) by using molecular beam epitaxy (MBE) without template layer or post-growth annealing. In the present work, the growth process was studied by analyzing X-ray diffraction (XRD) spectra, reflective high energy electron diffraction (RHEED) and atomic force microscopy (AFM) observations on the samples grown with different growth times from 10 s to 1 h. A phase transformation from γ-FeSi₂ to β-FeSi₂ was confirmed existing in the crystal film growth, as well as the growth mode changing from three-dimensional (3D) to two-dimensional (2D) mode.     

Thermal, mechanical, electrical, linear and nonlinear optical properties of a nonlinear optical l-ornithine monohydrochloride single crystal

Optically transparent semiorganic nonlinear optical bulk single crystal of l-ornithine monohydrochloride (LOMHCL) of dimension 11×3×2 mm³ has been grown from its aqueous solution by slow solvent evaporation technique. The grown crystal was characterized by powder X-ray diffraction to confirm the crystal structure. Investigation has been carried out to assign the vibrational frequencies of the grown crystals by Fourier transform infrared spectroscopy technique. Thermal behavior of the grown crystals was studied by thermogravimetric analysis. The second harmonic generation (SHG) efficiency of LOMHCL was determined by Kurtz and Perry powder technique. The optical absorption study confirms the suitability of the crystal for device applications. The mechanical properties of the grown crystals have been studied using Vickers microhardness tester. Dielectric and photoconductivity studies are also carried out for the grown samples.     

Nonvolatile hologram storage properties of tri-doped Zn:Ce:Cu:LiNbO3 crystals

Congruent Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was grown by the Czochralski method in air. The occupation mechanism of the Zn²⁺ was discussed by an infrared transmittance spectrum. The nonvolatile holographic recording in Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was measured by two-photon fixed method. Zn(7 mol%):Ce:Cu:LiNbO₃ single crystals present the faster recording time and higher light-induced scattering resistance ability comparing with Ce:Cu:LiNbO₃ single crystals.     

Growth and field emission of tungsten oxide nanotip arrays on ITO glass substrate

High-density and uniformly aligned tungsten oxide nanotip arrays have been deposited by a conventional thermal evaporation on ITO glass substrates without any catalysts or additives. The temperature of substrate was 450-500 °C. It was shown that the tungsten oxide nanotips are single-crystal grown along [0 1 0] direction. For commercial applications, field emission of the tungsten oxide nanotip arrays was characterized in a poor vacuum at room temperature. The field emission behaviors are in agreement with Fowler-Nordheim theory. The turn-on field is 2.8 V μm⁻¹ as d is 0.3 mm. The excellent field emission performances indicated that the tungsten oxide nanotip arrays grown by the present approach are a good candidate for application in vacuum microelectronic devices.     

Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

Synthesis,crystal growth and characterisation of 2-aminomethylpyridinium picrate (2-ampp)-a charge transfer molecular complex and organic nonlinear optical material

Single crystals of 2-aminomethylpyridinium picrate (2-AMPP) were grown by slow evaporation-solution growth technique at room temperature. The cell and structural parameters of the grown crystal were determined by single crystal X-ray diffraction analysis. The characteristic functional groups in the compound were identified from Fourier transform infrared spectroscopy. The transmission and absorption spectra of this crystal show that the lower cut-off wavelength lies at 360 nm. Thermal analysis was performed to study the thermal stability of the grown crystal. The powder second harmonic generation efficiency of the grown crystal measured by Kurtz technique is 2 times efficient than potassium dihydrogen orthophosphate (KDP). Vicker's microhardness test showed that the hardness value increases with increasing the applied load up to 50 g. The dielectric measurements of the compound in the frequency region from 50 Hz to 5 MHz showed that the material has lesser defects and can be used for optical application.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

Microstructure and dielectric properties of (Ba0.6Sr0.4)TiO3 thin films grown on super smooth glazed-Al2O3 ceramics substrate

Modified substrates with nanometer scale smooth surface were obtained via coating a layer of CaO-Al₂O₃-SiO₂ (CaAlSi) high temperature glaze with proper additives on the rough-95% Al₂O₃ ceramics substrates. (Ba_0.6Sr_0.4)TiO₃ (BST) thin films were deposited on modified Al₂O₃ substrates by radio-frequency magnetron sputtering. The microstructure, dielectric, and insulating properties of BST thin films grown on glazed-Al₂O₃ substrates were investigated by X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric properties measurement. These results showed that microstructure and dielectric properties of BST thin films grown on glazed-Al₂O₃ substrates were almost consistent with that of BST thin films grown on LaAlO₃ (1 0 0) single-crystal substrates. Thus, the expensive single-crystal substrates may be substituted by extremely cheap glazed-Al₂O₃ substrates.     

New design of nozzle structures and its effect on the surface and crystal qualities of thick GaN using a horizontal HVPE reactor

High-quality thick GaN films without cracks were achieved by using a new nozzle structure in the reactor grown by the hydride vapor phase epitaxy on sapphire substrates. Optical contrast microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray double diffraction (XRD) and cathodoluminescence (CL) were carried out to reveal the surface, crystal and optical properties of the GaN epilayer. It was found that the nozzle structure in the reactor has a large effect on the growth rate, surface flat, crystal quality, and the uniformity of the growth. Compared with the old one, the new nozzle structure (denoted as multi-layers nozzle) can improve dramatically the properties of thick GaN. Mirror, colorless and flat GaN thick film was obtained and its (0 0 0 2) FWHM results were reduced from 1000 to 300 arcsec when the new nozzle was used. AFM result revealed a step flow growth mode for GaN layer with the new nozzle. Room-temperature CL spectra on the GaN films showed a strong near-band-edge peak for the new nozzle, but there is only weak emitting peak for the old nozzle. New nozzle structure can improve the uniform of flow field near the surface of substrates compared with the old one, which leads to the improvement of properties of GaN thick film by hydride vapor phase epitaxy (HVPE).     

A new Yb-doped oxyorthosilicate laser crystal: Yb:Gd2SiO5

A new Yb-doped oxyorthosilicate laser crystal, Yb:Gd₂SiO₅ (Yb:GSO), has been grown by the Czochralski (Cz) method. The crystal structure was determined by means of X-ray diffraction analysis. Room temperature absorption and fluorescence spectra of Yb³⁺ ions in GSO crystal were measured. Then, spectroscopic parameters of Yb:GSO were calculated and compared with those of another Yb-doped oxyorthosilicate crystal Yb:YSO. Results indicated that Yb:GSO crystal seemed to be a very promising laser gain media in generating ultra-pulses and tunable solid state laser applications. As expected, the output power of 2.72 W at 1089 nm was achieved in Yb:GSO crystal with absorbed power of only 4.22 W at 976 nm, corresponding to the slope efficiency of 71.2% through the preliminary laser experiment.     

Dielectric relaxation in single crystal NH4H2PO4 in the high-temperature regime

The dispersion curves of the dielectric response in single crystal NH₄H₂PO₄ were obtained in the radio frequency range and below the high-temperature transition at T_p−160 °C. The results reveal dielectric relaxation at low frequency, which is about 10⁵ Hz at 70 °C, and it shifts to higher frequencies (∼3×10⁶ Hz) as the temperature increases. The relaxation frequency was determined from the peak obtained in the imaginary part of the permittivity as well as from the derivative of the real part of the permittivity. The activation energy E_a=0.55 eV, obtained from the relaxation frequency is very close to that derived from the dc conductivity. We suggest that this dielectric relaxation could be due to the proton jump and phosphate reorientation that cause distortion and change the local lattice polarizability inducing dipoles like      

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Sol-gel synthesis of sub-50 nm ZnO nanowires on pulse laser deposited ZnO thin films

A simple synthesis route to high-quality sub-50 nm ZnO nanowires is reported, utilizing ZnO thin films grown by pulse laser deposition (PLD) as seed layers. Depending upon the PLD growth conditions, the surface morphology of the ZnO nanowires on ZnO film was distinctively different whereas the diameters were almost the same. With the increase of the concentration of zinc nitrate/methenamine solution from 0.002 to 0.02 M, the average diameter of the ZnO nanowire increased but remained sub-50 nm. The grown ZnO nanowires showed a high crystallinity with a low defect density confirmed by a sharp photoluminescence spectrum.     

Substrate orientation-induced distinct ferromagnetic moment in Co:ZnO films

Dilute (3.8 at.%) cobalt-doped ZnO thin films are deposited on LiTaO₃ (LT) substrates with three different orientations [LT(1 1 0), LT(0 1 2) and LT(0 1 8)] by direct current reactive magnetron co-sputtering. The experimental results indicate that Co atoms with 2+ chemical valence are successfully incorporated into the ZnO host matrix on various oriented substrates, and the substrate orientations have a profound influence on the crystal growth and magnetization of Co:ZnO films. A large magnetic moment of 2.42μ_B/Co at room temperature is obtained in the film deposited on LT(0 1 2), while the corresponding values of the other films deposited on LT(1 1 0) and LT(0 1 8) are 1.21μ_B/Co and 0.65μ_B/Co, respectively. Furthermore, the crystal growth mode of Co:ZnO films on various oriented LT, the relationship between the microstructures and corresponding ferromagnetic properties are also discussed.     

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.