Synthesis of luminescent SrMoO4 thin films by a non-reversible galvanic cell method

Well-crystallized SrMoO₄ thin films were synthesized directly on a molybdenum substrate by a non-reversible galvanic cell method through 150 h electrochemical reaction at room temperature. The as-synthesized thin films are a single phase SrMoO₄ with a scheelite-type structure and show uniform and homogeneous surfaces. When excited by 290 nm ultraviolet ray at room temperature, the thin films emit the maximum peaks at 485 nm. The densification, chemical-physical and photoluminescence properties of the SrMoO₄ thin films synthesized by the non-reversible galvanic cell method are significantly improved.     

Oxidant-assisted preparation of CaMoO4 thin film using an irreversible galvanic cell method

CaMoO₄ thin films were prepared by an irreversible galvanic cell method at room temperature; the crystalline phase structure, surface morphology, chemical composition and room temperature photoluminescence property were characterized by X-ray diffraction, Raman spectroscopy, scanning electronic microscopy, X-ray photoelectron spectroscopy as well as photoluminescence spectroscopy. Our results reveal that it is very difficult to directly deposit dense and uniform CaMoO₄ thin films in saturated Ca(OH)₂ solution at room temperature by the irreversible galvanic cell method. After adding some oxidant (NaClO solution or H₂O₂ solution), the growth of CaMoO₄ grains has been promoted, and well-crystallized, dense, and uniform CaMoO₄ films were obtained. The as-prepared CaMoO₄ films exhibit a good green photoluminescence, with the excitation of various wavelengths (220 nm, 230 nm, 240 nm, 250 nm and 270 nm) of ultraviolet irradiation.     

Synthesis of the nanocrystalline CoFe2O4 ferrite thin films by a novel sol-gel method using glucose as an additional agent

Polycrystalline and nanometer-sized CoFe₂O₄ ferrite thin films are successfully synthesized using glucose as an addition agent. The thermal gravimetric/differential thermal analyzer, X-ray diffractometer, electron diffraction, scanning electron microscope, atomic force microscope and vibrating sample magnetometer are used to characterize the effects of the calcination temperature on the crystalline structure, morphology and magnetic properties of the Co-ferrite thin films. CoFe₂O₄ ferrite thin films have a single phase inverse spinel structure and are crystallized at and above 300 °C which is much lower than the required temperature in the traditional ceramic method (about 500-600 °C). Co-ferrite thin films annealed at relative low temperature of 400 °C show very small particle size with average of 32 nm and excellent magnetic properties for information storage applications.     

Cathodoluminescence of CaWO4 and SrWO4 thin films prepared by spray pyrolysis

Thin films of CaWO₄ and SrWO₄ were prepared on glass substrates by spray pyrolysis. The effects of preparation conditions and monovalent, bivalent and trivalent cation doping on cathodoluminescence (CL) properties of the films were studied. Polycrystalline CaWO₄ and SrWO₄ films formed a scheelite structure after being annealed above 300°C. They exhibited analogous cathodoluminescence consisting of a blue emission band at 447 nm and a blue-green emission band at 487 nm. The blue and blue-green emission intensities increased with substrate and annealing temperature. Annealing atmosphere and doping with Ag⁺, Pb²⁺ and La³⁺ did not influence the characteristics of the blue and blue-green emissions, whereas Eu³⁺ did. The results indicated both the blue and blue-green emissions originated from the WO₄²⁻ molecular complex. The luminance and efficiency for CaWO₄ film were 150 cd/m² and 0.7 lm/W at 5 kV and 57 μA/cm².     

Growth of crystalline HgCr2S4 thin films at mild reaction conditions

Thin films of crystalline HgCr₂S₄ have been deposited on glass substrates at low temperature as low as 65 °C using a chemical bath deposition method. Typical thickness of the deposited HgCr₂S₄ thin films was 264 nm.The films were composed of closely packed irregular grains of 165-175 nm in diameter. The X-ray diffraction analysis and the selected area electron diffraction analysis revealed the deposited thin films were polycrystalline with highly (2 2 0) preferential orientation. The films exhibit a pure faint black. Their direct band gap energy was 2.39 eV with room temperature electrical resistivity of the order of 10⁻³ Ω cm.     

Structural, thermal and optical characterization of TiO2:ZrO2 thin films prepared by sol-gel method

We have studied the structural and optical properties of thin films of TiO₂, doped with 5% ZrO₂ and deposited on glass substrate (by the sol-gel method). The dip-coated thin films have been examined at different annealing temperatures (350 to 450 °C) and for various layer thicknesses (63-286 nm). Refractive index and porosity were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.62-2.29 and the porosity is in the range of 0.21-0.70. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZrO₂, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 14.8 nm grains). However, the undoped TiO₂ exhibits an amorphous phase. After heat treatments of thin films, titanium oxide starts to crystallize at the annealing temperature 350 °C. The obtained structures are anatase and brookite. The calculated grain size, depending on the annealing temperature and the layer thickness, is in the range (8.58-20.56 nm).     

Hydrothermal synthesis and photoluminescence of SrWO4:Tb novel green phosphor

Tb³⁺-doped SrWO₄ phosphors with a scheelite structure have been prepared by hydrothermal reaction. X-ray powder diffraction, field-emission scanning electron microscopy, photoluminescence excitation and emission spectra and decay curve were used to characterize the resulting samples. Scanning electron microscopy image showed that the obtained SrWO₄:Tb³⁺ phosphors appeared to be nearly spherical and their sizes ranged from 1 to 3 μm. Photoluminescence spectra indicated the phosphors emitted strong green light centered at 545 nm under ultraviolet light excitation. Because 12 at.% SWO₄:Tb³⁺ phosphor exhibits intensive green emission under 254 nm excitation in comparison with the commercial green fluorescent lamp phosphor (LaPO₄:Ce,Tb), the excellent luminescence properties make it a new promising green phosphor for fluorescent lamps application.     

Stress-induced shifting of the morphotropic phase boundary in sol-gel derived Pb(Zr0.5Ti0.5)O3 thin films

The structure evolution of Pb(Zr_0.5Ti_0.5)O₃ thin films with different thicknesses on the Pt(1 1 1)/Ti/SiO₂/Si substrates has been investigated using X-ray diffraction and Raman scattering. Differing from Pb(Zr_0.5Ti_0.5)O₃ bulk ceramic with a tetragonal phase, our results indicate that for PZT thin films with the same composition monoclinic phase with Cm space group coexisting with tetragonal phase can appear. It is suggested that tensile stress plays a role in shifting the morphotropic phase boundary to titanium-rich region in PZT thin films. The deteriorated ferroelectric properties of PZT thin films can be attributed mainly to the presence of thin non-ferroelectric layer and large tensile stress.     

Influence of 150 MeV Ni swift heavy ion irradiation on CuFe2O4 thin films prepared by radio frequency magnetron sputtering: Modification on structure and surface morphology

The bulk copper ferrite nanomaterials are synthesized by co-precipitation technique. The vibrating sample magnetometer measurement for bulk CuFe₂O₄ reveals its unsaturated superparamagnetic behavior. The crystallites of the synthesized nanomaterial are in cubic form having an average size of ~ 100 Å and are used as target to prepare thin films of various thicknesses (600, 900 and 1100 nm) by radio frequency magnetron sputtering technique. X-ray peaks arise only when films are annealed at 1200 °C and also they are found to be in tetragonal structure. The magnetic characteristics of 900 nm unirradiated CuFe₂O₄ thin film exhibit superparamagnetic behavior and have an unsaturated magnetic moment at high field. Magnetic force microscopy images of unirradiated CuFe₂O₄ thin films confirm the soft nature of the magnetic materials. The 150 MeV Ni¹¹⁺ swift heavy ion irradiation on these thin films at the fluence of 1 × 10¹⁴ ions/cm² modifies the polycrystalline nature due to electron-phonon coupling. Atomic force microscopy image shows that the swift heavy ion irradiation induces agglomeration of particles in 600 and 900 nm thin films and increases rms surface roughness from 33.43 to 39.65 and 69.7 to 102.46 nm respectively. However, in 1100 nm film, holes are created and channel-like structures are observed along with a decrease in the rms surface roughness from 75.12 to 24.46 nm. Magnetic force microscopy images of 900 nm irradiated thin film explain the formation of domains on irradiation and are also supported by the ferromagnetic hysteresis observed using vibrating sample magnetometer.     

Organic/inorganic nanocomposite films based on poly(3-methoxythiophene) and WO3

Organic/inorganic nanocomposite films based on poly(3-methoxythiophene) (PMOT) and WO₃ were prepared by a consecutive two-step electrochemical method. The products were characterized in detail by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS) and Fourier-transform infrared spectroscopies (FTIR). The results show that the PMOT/WO₃ nanocomposite films consist of two layers, the substrate WO₃ with 30 nm grains and superstratum PMOT, which average grain size is 60 nm. The obtained PMOT/WO₃ nanocomposite films were also characterized by cyclic voltammetry to investigate their electrochemistry properties which display significant enhancement of electrochemical activity than that of pure PMOT and WO₃ films.     

Phase stabilization and microstructural studies of lead lanthanum titanate thin films

Thin ferroelectric films of PLTx (Pb_1−xLa_xTi_1−x/4O₃) have been prepared by a sol-gel spin coating process. As deposited films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various concentrations of La (x = 0.04, 0.08 and 0.12) on ITO coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out on films annealed at temperatures (350, 450, 550 and 650 °C). Characterization of these films by X-ray diffraction shows that the films annealed at 650 °C exhibit tetragonal phase with perovskite structure. Atomic force microscope (AFM) images are characterized by slight surface roughness with a uniform crack free, densely packed structure. Fourier transform infrared spectra (FTIR) studies of PLTx thin films (x = 0.08) deposited on Si substrates have been carried out to get more information about the phase stabilization.     

Morphology and growth of e-beam deposited YSZ thin films

Yttria-stabilized zirconium (YSZ) thin films were grown from the tetragonal phase of ZrO₂ stabilized by 8 wt% of Y₂O₃ (8% of YSZ) ceramic powders using e-beam deposition technique (EB-PVD). The influence of the type of substrate on the microstructure of deposited YSZ thin films was analysed. YSZ thin films (2-3 μm of thickness) were deposited on three different types of substrates: optical quartz (SiO₂), porous Ni-YSZ substrates and Alloy 600 (Fe-Ni-Cr). The dependence of the substrate temperature (from 20 to 600 °C) on the thin film structure and the surface morphology were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that (i) the substrate temperature has an influence on the crystallite size, which varied between 12 and 50 nm, (ii) the substrate type has an influence on the growth mechanism of YSZ thin films, and (iii) a bias voltage applied to the substrate during the deposition of thin films has an influence on the densification of YSZ layers.     

Luminescent properties of BaWO4 films prepared by cell electrochemical technique

Highly crystallized BaWO₄ films (45 × 30 mm²) have been prepared by cell electrochemical technique at room temperature. X-ray diffraction measurement reveals that the as-prepared BaWO₄ thin films have a scheelite structure. Under cell conditions, due to the decrease of crystal size and disappearance of large clusters, films' homogeneity has been improved markedly. With the UV excitation the peculiar and tunable luminescence of BaWO₄ films has been observed. Investigations uncover that exciting energies can be transferred among different emission centers, and that the yellow emission is probably relevant to the vacancies of Ba in the outermost layers of films.     

Temperature dependence of the microstructure and resistivity of indium zinc oxide films deposited by direct current magnetron reactive sputtering

Indium zinc oxide (IZO) films were deposited as a function of the deposition temperature using a sintered indium zinc oxide target (In₂O₃:ZnO = 90:10 wt.%) by direct current (DC) magnetron reactive sputtering method. The influence of the substrate temperature on the microstructure, surface roughness and electrical properties was studied. With increasing the temperature up to 200 °C, the characteristic properties of amorphous IZO films were improved and the specific resistivity was about 3.4 × 10^− 4 Ω cm. Change of structural properties according to the deposition temperature was also observed with X-ray diffraction patterns, transmission electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. IZO films deposited above 300 °C showed polycrystalline phases evolved on the amorphous IZO layer. Very flat surface roughness could be obtained at lower than 200 °C of the substrate temperature, while surface roughness of the films was increased due to the formation of grains over 300 °C. Consequently, high quality IZO films could be prepared by DC magnetron sputtering with O₂/Ar of 0.03 and deposition temperature in range of 150-200 °C; a specific resistivity of 3.4 × 10^− 4 Ω cm, and the values of peak to valley roughness and root-mean-square roughness are less than 4 nm and 0.5 nm, respectively.     

Characterization of Al2O3/ZrO2 nano multilayer thin films prepared by pulsed laser deposition

Microstructural characterization of pulsed laser deposited Al₂O₃/ZrO₂ multilayers on Si (1 0 0) substrates at an optimized oxygen partial pressure of 3 × 10⁻² mbar and at room temperature (298 K) has been carried out. A nanolaminate structure consisting of alternate layers of ZrO₂ and Al₂O₃ with 40 bi-layers was fabricated at different zirconia layer thicknesses (20, 15 and 10 nm). The objective of the work is to study the effect of ZrO₂ layer thickness on the stabilization of tetragonal ZrO₂ phase for a constant Al₂O₃ layer thickness of 5 nm. The Al₂O₃/ZrO₂ multilayer films were characterized using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1473 K. The studies showed that the thickness of the zirconia layer has a profound influence on the crystallization temperature for the formation of tetragonal zirconia phase. The tetragonal phase content increased with the decrease of ZrO₂ layer thickness. The cross-sectional transmission electron microscope (XTEM) investigations were carried out on a multilayer thin films deposited at room temperature. The XTEM studies showed the formation of uniform thickness layers with higher fraction of monoclinic and small fraction of tetragonal phases of zirconia and amorphous alumina.     

Nanocrystalline TiO2 thin films for NH3 monitoring: microstructural and physical characterization

Nanocrystalline titanium oxide thin films have been deposited by spin coating technique and then have been analyzed to test their application in NH₃ gas-sensing technology. In particular, spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of titanium oxide thin films. The structure and the morphology of such material have been investigated by X ray diffraction, Scanning microscopy, high resolution electron microscopy and selected area electron diffraction. The X-ray diffraction measurements confirmed that the films grown by this technique have good crystalline tetragonal mixed anatase and rutile phase structure. The HRTEM image of TiO₂ thin film showed grains of about 50–60 nm in size with aggregation of 10–15 nm crystallites. Selected area electron diffraction pattern shows that the TiO₂ films exhibited tetragonal structure. The surface morphology (SEM) of the TiO₂ film showed that the nanoparticles are fine with an average grain size of about 50–60 nm. The optical band gap of TiO₂ film is 3.26 eV. Gas sensing properties showed that TiO₂ films were sensitive as well as fast in responding to NH₃. A high sensitivity for ammonia indicates that the TiO₂ films are selective for this gas.     

Effect of film thickness, type of buffer layer, and substrate temperature on the morphology of dicyanovinyl-substituted sexithiophene films

The influence of film thickness, type of buffer underlayer, and deposition substrate temperature on the crystal structure, microstructure, and morphology of the films of dicyanovinyl-substituted sexithiophene with four butyl-chains (DCV6T-Bu₄) is investigated by means of X-ray diffraction (XRD) and X-ray reflectivity methods. A neat Si wafer or a Si wafer covered by a 15 nm buffer underlayer of fullerene C₆₀ or 9,9-Bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-fluorene (BPAPF) is used as a substrate. The crystalline nature and ordered molecular arrangement of the films are recorded down to 6 nm film thickness. By using substrates heated up to 90 °C during the film deposition, the size of the DCV6T-Bu₄ crystallites in direction perpendicular to the film surface increases up to value of the film thickness. With increasing deposition substrate temperature or film thickness, the DCV6T-Bu₄ film relaxes, resulting in reducing the interplane distances closer to the bulk values. For the films of the same thickness deposited at the same substrate temperature, the DCV6T-Bu₄ film relaxes for growth on Si to BPAPF to C₆₀. Thicker films grown at heated substrates are characterized by smaller density, higher roughness and crystallinity and better molecular ordering. A thin (up to about 6 nm-thick) intermediate layer with linear density-gradient is formed at the C₆₀/DCV6T-Bu₄ interface for the films with buffer C₆₀ layer. The XRD pattern of the DCV6T-Bu₄ powder is indexed using triclinic unit cell parameters.     

Structural and luminescence correlation of annealed Er-ZnO/Si thin films deposited by AACVD process

Er doped ZnO thin films have been synthesized from zinc acetates dihydrate (C₄H₆O₄Zn·2H₂O) and Erbium tris (2,2,6,6-tetramethyl-3,5-heptadionate) (Er(TMHD)₃) by aerosol assisted chemical vapor deposition AACVD atmospheric pressure technique. Films were deposited in the temperature range of [370–500 °C] on Si (1 1 1) substrate. Nano-disk shaped grains were grown on the top of the film surface. The morphology of the as-deposited films was found to be dependent on the substrate temperature. After annealing in air atmosphere, XRD patterns revealed a highly oriented c-axis Er:ZnO films with hexagonal wurtzite structure without any second phase. Under 488 nm excitation, the intra 4f–4f green emission (²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) gradually increased with increasing annealing temperature. Also, the local structure of Er changes to a pseudo-octahedral structure with C_4v symmetry. The ZnO film with 2.504 at.% Er³⁺ doping has the best crystalline structure and the best resolved PL spectra. Using 325 nm excitation, all the samples showed an ultraviolet emission centered at 380 nm originating from a near band EDGE emission and a broad band green emission centered at 520 nm from deep levels. The optical response was correlated with crystallinity of the synthesized thin films.     

Structural,electrical and photoluminescence properties of ZnO:Al network films grown on nanochannel Al2O3 substrates by direct current magnetron sputtering with an oblique target

ZnO:Al network films were grown on nanochannel Al₂O₃ substrates at 300 K by direct current magnetron sputtering with an oblique target. The film thicknesses are 60 nm, 160 nm and 190 nm. The holes of the network films diminish with increasing film thickness. For the 60-nm thick film, the network is formed by connecting grains. For the 160-nm and 190-nm thick films, however, the network is formed by connecting granules. The granules consist of many small grains. All the network films have a wurtzite structure. The 60-nm and 160-nm thick network films mainly have a [1 0 1] orientation in the film growth direction while the 190-nm thick network film grows with a random crystallographic orientation. A temperature dependence of the resistance within 160–300 K reveals that the network films exhibit a semiconducting behavior and their carrier transport mechanism is thermally activated band conduction. Room temperature photoluminescence spectra for wavelengths between 300 nm and 700 nm reveal a violet emission centered at 405 nm for the 60-nm thick network film and a blue emission centered at 470 nm for both the 160-nm and the 190-nm thick network films. Annealing decreases the resistivity of the network film.     

Nanocrystalline scheelite SrWO4: a low temperature co-fired ceramic optical material-synthesis and properties

Nanocrystalline strontium tungstate (SrWO₄) is synthesized through a single step modified combustion process. The X-ray diffraction, Fourier transform Raman and Infrared spectroscopy studies reveal that the as-prepared powder is single phase and possess tetragonal structure. The transmission electron microscopic investigations have shown that the particle size of the as prepared powder is in the range 18–22 nm. The optical constants are estimated from the UV–Visible studies and calculated optical band gap is 4.28 eV. The sample showed maximum transmission in the visible regions but poor transmittance in the ultraviolet region. The photoluminescence spectra recorded at different temperatures showed intense blue emission. The nanocrystalline SrWO₄ obtained by the present combustion method was sintered to 95 % density at a relatively lower temperature of 810 °C for 3 h. The dielectric constant (ε_r) and loss factor (tan δ) of the sintered SrWO₄ pellets at 5 MHz measured at room temperature were 9.9 and 6.29 × 10^?3 respectively. The experimental results obtained in this work demonstrate the application of SrWO₄ as UV filters, transparent films for window layers on solar cells, anti-reflection coatings, scintillators, detectors and for low-temperature co-fired ceramic applications.