Kinetics of luminescence of interface defects and resonant Er ions in nanostructured SnO2:SiO2

Silica glass with SnO₂ nanocrystals and Er³⁺ ions are prepared by the sol-gel route and treatment above 1000 °C. Transmission electron microscopy evidences a homogeneous dispersion of nanoclusters 4-6 nm in size in the amorphous silica matrix. Photoluminescence spectra excited at 3.5 eV, outside erbium transitions, show an inhomogeneous spectral distribution of light emission from interface defects, in the range 1.9-2.4 eV, resonant with transitions of erbium ions. The analysis of kinetics and temperature dependence of luminescence allows to quantify the efficiency of the energy transfer channel between nanoclusters and erbium ions.     

Waveguiding and photoluminescence in Er-doped Ta2O5 planar waveguides

The optimization of erbium-doped Ta₂O₅ thin film waveguides deposited by magnetron sputtering onto thermally oxidized silicon wafer is described. Optical constants of the film were determined by ellipsometry. For the slab waveguides, background losses below 0.4 dB/cm at 633 nm have been obtained before post-annealing. The samples, when pumped at 980 nm yielded a broad photoluminescence spectrum (FWHM∼50 nm) centred at 1534 nm, corresponding to ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ion. The samples were annealed up to 600 °C and both photoluminescence power and fluorescence lifetime increase with post-annealing temperature and a fluorescence lifetime of 2.4 ms was achieved, yielding promising results for compact waveguide amplifiers.     

Effect of sintering aid (CdCl2) on the optical and structural properties of CdZnS screen-printed film

Sulphides of zinc and cadmium have been utilized effectively in various opto-electronic devices. In the present work cadmium zinc sulphide (Cd_0.4Zn_0.6S) thin film has been deposited on ultra clean glass substrate by a simple inexpensive screen-printing method using cadmium sulphide, zinc sulphide, anhydrous cadmium chloride and ethylene glycol. Cadmium chloride has been used as sintering aid and ethylene glycol as a binder. Effect of sintering aid on the optical and structural properties of prepared cadmium zinc sulphide film has been investigated. The optical band gap (E_g) of the film has been studied by using reflection spectra in wavelength range 325–600 nm. It is found that reflection spectra suffer a drastic fall at two places, which is indicative of two band gaps of film viz. 2.38 eV and 2.9 eV corresponding to CdS and Cd_0.6Zn_0.4S, respectively. This is suggestive of the fact that cadmium zinc sulphide is a wide band gap semiconducting material. X-ray diffraction also confirms the formation of Cd_0.6Zn_0.4S composition.     

Photoluminescence and Raman spectra of the ordered vacancy compound CuGa5Se8

We studied the photoluminescence (PL) and Raman properties of the ordered defect compound CuGa₅Se₈. Twelve peaks were detected from the room-temperature Raman spectra with the A₁ mode around 160 cm⁻¹. Due to the stress in the polycrystalline thin film the corresponding frequencies of the Raman modes of a CuGa₅Se₈ single crystal were slightly shifted. One broad asymmetric PL band at 1.788 and 1.765 eV was observed at 10 K in the PL spectra of CuGa₅Se₈ single crystal and polycrystalline layer, respectively. The temperature and laser power dependencies of the PL spectra were also studied. The shape and properties of the PL band assure the presence of potential fluctuations and the analyses of the PL data suggest that the emission is due to band-to-tail (BT) or band-to-impurity (BI) recombination.     

Optical properties of sol-gel fabricated Mn/SiO2 nanocomposites: Observation of surface plasmon resonance in Mn nanoparticles

Manganese nanoparticles were grown in silica glass and silica film on silicon substrate by annealing of the sol-gel prepared porous silicate matrices doped with manganese nitrate. Annealing of doped porous silicate matrices was performed at various conditions that allowed to obtain the nanocomposite glasses with various content of metallic Mn. TEM of Mn/SiO₂ glass indicates the bimodal size distribution of Mn nanoparticles with mean sizes of 10.5 nm and 21 nm. The absorption and photoluminescence spectra of Mn/SiO₂ glasses were measured. In the absorption spectra at 300 nm (4.13 eV) we observed the band attributed to the surface plasmon resonance in Mn nanoparticles. The spectra proved the creation of Mn²⁺ and Mn³⁺ ions in silica glass as well. The absorption spectra of Mn/SiO₂ glasses annealed in air prove the creation of manganese oxide Mn₂O₃. The measured reflection spectra of Mn/SiO₂ film manifest at 240-310 nm the peculiarity attributed to surface plasmons in Mn nanoparticles.     

Optical properties and thermal stability of LaYbO3 ternary oxide for high-k dielectric application

A new ternary rare oxide dielectric LaYbO₃ film had been prepared on silicon wafers and quartz substrates by reactive sputtering method using a La-Yb metal target. A range of analysis techniques was performed to determine the optical band gap, thermal stability, and electrical property of the deposited samples. It was found the band gap of LaYbO₃ film was about 5.8 eV. And the crystallization temperature for rapid thermal annealing (20 s) was between 900 and 950 °C. X-ray photoelectron spectroscopy results indicate the formation of the SiO₂ and silicate in the interface between silicon wafer and LaYbO₃ film. The dielectric constant is about 23 from the calculation of capacitance-voltage curve, which is comparable higher than previously reported La₂O₃ or Yb₂O₃ film.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Room temperature photoluminescence from amorphous silicon nanoparticles in SiOx thin films

Amorphous SiO_x thin films with four different oxygen contents (x=1.15, 1.4, 1.5, and 1.7) have been prepared by thermal evaporation of SiO in vacuum and then annealed at 770 or 970 K in argon for various times ?40 min. The influence of annealing conditions and the initial film composition on photoluminescence (PL) from the annealed films has been explored. Intense room temperature PL has been observed from films with x?1.5, visible with a naked eye. It has been shown that PL spectra of most samples consists of two main bands: (i) a ‘green’ band centered at about 2.3 eV, whose position does not change with annealing conditions and (ii) an ‘orange-red’ band whose maximum moves from 2.1 to 1.7 eV with increasing annealing time and temperature and decreasing initial oxygen content. These observations have been explained assuming recombination via defect states in the SiO_x matrix for the first band and emission from amorphous Si nanoparticles for the second one.     

Characteristics of sandwich-structured Al2O3/HfO2/Al2O3 gate dielectric films on ultra-thin silicon-on-insulator substrates

Sandwich-structure Al₂O₃/HfO₂/Al₂O₃ gate dielectric films were grown on ultra-thin silicon-on-insulator (SOI) substrates by vacuum electron beam evaporation (EB-PVD) method. AFM and TEM observations showed that the films remained amorphous even after post-annealing treatment at 950 °C with smooth surface and clean silicon interface. EDX- and XPS-analysis results revealed no silicate or silicide at the silicon interface. The equivalent oxide thickness was 3 nm and the dielectric constant was around 7.2, as determined by electrical measurements. A fixed charge density of 3 × 10¹⁰ cm⁻² and a leakage current of 5 × 10⁻⁷A/cm² at 2 V gate bias were achieved for Au/gate stack /Si/SiO₂/Si/Au MIS capacitors. Post-annealing treatment was found to effectively reduce trap density, but increase in annealing temperature did not made any significant difference in the electrical performance.     

Nanoindentation on carbon thin films obtained from a C60 ion beam

Raman spectra, atomic force microscope (AFM) images, hardness (H) and Young's modulus (E) measurements were carried out in order to characterize carbon thin films obtained from a C₆₀ ion beam on silicon substrates at different deposition energies (from 100 up to 500 eV). The mechanical properties were studied via the nanoindentation technique. It has been observed by Raman spectroscopy and AFM that the microstructure presents significant changes for films deposited at energies close to 300 eV. However, these remarkable changes have not been noticeable on the mechanical properties: apparently H and E increase with higher deposition energy up to ∼11 and ∼116 GPa, respectively. These values are underestimated if the influence of the film roughness is not taken into account.     

Microstructure and dielectric properties of La2O3 doped amorphous SiO2 films as gate dielectric material

As a potential gate dielectric material, the La₂O₃ doped SiO₂ (LSO, the mole ratio is about 1:5) films were fabricated on n-Si (0 0 1) substrates by using pulsed laser deposition technique. By virtue of several measurements, the microstructure and electrical properties of the LSO films were characterized. The LSO films keep the amorphous state up to a high annealing temperature of 800 °C. From HRTEM and XPS results, these La atoms of the LSO films do not react with silicon substrate to form any La-compound at interfacial layer. However, these O atoms of the LSO films diffuse from the film toward the silicon substrate so as to form a SiO₂ interfacial layer. The thickness of SiO₂ layer is only about two atomic layers. A possible explanation for interfacial reaction has been proposed. The scanning electron microscope image shows the surface of the amorphous LSO film very flat. The LSO film shows a dielectric constant of 12.8 at 1 MHz. For the LSO film with thickness of 3 nm, a small equivalent oxide thickness of 1.2 nm is obtained. The leakage current density of the LSO film is 1.54 × 10⁻⁴ A/cm² at a gate bias voltage of 1 V.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

1.54 μm emission mechanism of Er-doped zinc oxide thin films

Zinc oxide (ZnO) and Er-doped zinc oxide (ZnO:Er) thin films were formed by pulsed laser deposition, and characterized by photoluminescence (PL) and X-ray diffraction (XRD) in order to clarify the 1.54 μm emission mechanism in the ZnO:Er films. Er ions were excited indirectly by the 325 nm line of a He-Cd laser, and the comparison of the ultraviolet to infrared PL data of ZnO and ZnO:Er films showed that the 1.54 μm emission of Er³⁺ in ZnO:Er film appears at the expense of the band edge emission and the defect emission of ZnO. The crystallinity of the films was varied with the substrate temperature and post-annealing, and it was found that the intensity of the 1.54 μm emission is strongly related with the crystallinity of the films. There are three processes leading to the 1.54 μm emission; absorption of excitation energy by the ZnO host, energy transfer from ZnO to Er ions, and radiative relaxation inside Er ions, and it is suggested that the crystallinity plays an important role in the first two processes.     

Characterizations of n-type ferromagnetic GaMnN thin film grown on GaN/Al2O3 (0 0 0 1) by metal-organic chemical vapor deposition

A high-quality ferromagnetic GaMnN (Mn=2.8 at%) film was deposited onto a GaN buffer/Al₂O₃(0 0 0 1) at 885 °C using the metal-organic chemical vapor deposition (MOCVD) process. The GaMnN film shows a highly c-axis-oriented hexagonal wurtzite structure, implying that Mn doping into GaN does not influence the crystallinity of the film. No Mn-related secondary phases were found in the GaMnN film by means of a high-flux X-ray diffraction analysis. The composition profiles of Ga, Mn, and N maintain nearly constant levels in depth profiles of the GaMnN film. The binding energy peak of the Mn 2p_3/2 orbital was observed at 642.3 eV corresponding to the Mn (III) oxidation state of MnN. The presence of metallic Mn clusters (binding energy: 640.9 eV) in the GaMnN film was excluded. A broad yellow emission around 2.2 eV as well as a relatively weak near-band-edge emission at 3.39 eV was observed in a Mn-doped GaN film, while the undoped GaN film only shows a near-band-edge emission at 3.37 eV. The Mn-doped GaN film showed n-type semiconducting characteristics; the electron carrier concentration was 1.2×10²¹/cm³ and the resistivity was 3.9×10⁻³ Ω cm. Ferromagnetic hysteresis loops were observed at 300 K with a magnetic field parallel and perpendicular to the ab plane. The zero-field-cooled and field-cooled curves at temperatures ranging from 10 to 350 K strongly indicate that the GaMnN film is ferromagnetic at least up to 350 K. A coercive field of 250 Oe and effective magnetic moment of 0.0003 μ_B/Mn were obtained. The n-type semiconducting behavior plays a role in inducing ferromagnetism in the GaMnN film, and the observed ferromagnetism is appropriately explained by a double exchange mechanism.     

1.54 μm room temperature emission from Er-doped Si nanocrystals deposited by ECR-PECVD

In this work, silicon nanocrystals (Si-nc) embedded in a silicon-rich silicon oxide (SRSO) matrix doped with Er³⁺ ions for different erbium and silicon concentrations have been deposited by electron-cyclotron resonance plasma-enhanced chemical-vapor-deposition (ECR-PECVD) technique. Their optical properties have been investigated by photoluminescence (PL) and reflectance spectroscopy.Room temperature emission bands centered at ∼1.54 and at 0.75 μm have been obtained for all samples. The most intense emission band at ∼1.54 μm was obtained for samples with concentrations of 0.45% and 39% for erbium and silicon, respectively. Moreover, it has been found that the broad emission band centered at ∼0.75 μm for all samples shows a very strong interference pattern related to the a specific sample structure and a high sample quality.     

Band offsets at the epitaxial anatase TiO2/n-SrTiO3(0 0 1) interface

We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO₂(0 0 1)/n-SrTiO₃(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO₃ exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.     

Ellipsometric characterization of PbI2 thin film on glass

The optical properties of polycrystalline lead iodide thin film grown on Corning glass substrate have been investigated by spectroscopic ellipsometry. A structural model is proposed to account for the optical constants of the film and its thickness. The optical properties of the PbI₂ layer were modeled using a modified Cauchy dispersion formula. The optical band gap E_g has been calculated based on the absorption coefficient (α) data above the band edge and from the incident photon energy at the maximum index of refraction. The band gap was also measured directly from the plot of the first derivative of the experimental transmission data with respect to the light wavelength around the transition band edge. The band gap was found to be in the range of 2.385±0.010 eV which agrees with the reported experimental values. Urbach's energy tail was observed in the absorption trend below the band edge and was found to be related to Urbach's energy of 0.08 eV.     

Photoemission investigations on nanostructured TiO2 grown by cluster assembling

Nanostructured titanium dioxide (ns-TiO₂) films were grown by supersonic cluster beam deposition method. Transmission electron microscopy demonstrated that films are mainly composed by TiO₂ nanocrystals embedded in an amorphous TiO₂ phase while their electronic structure was studied by photoemission spectroscopy. The cluster assembled ns-TiO₂ films are expected to exhibit several structural and chemical defects owing to the large surface to volume ratio of the deposited clusters. Ultraviolet photoemission spectra (hv = 50 eV) from the valence band unveil the presence of a restrained amount of surface Ti 3d defect states in the band gap, whereas Ti 2p core level X-ray photoelectron (hv = 630 eV) spectra do not manifestly disclose these defects.     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.