The role of defect states in the creation of photoluminescence in SrTiO<Subscript>3</Subscript>

We discuss the nature of visible photoluminescence at room temperature in amorphous strontium titanate in the light of the results of a recent experimental and quantum mechanical theoretical study. Our calculation of the electronic structure involves the use of first-principles molecular calculations to simulate the variation of the electronic structure in the strontium titanate crystalline phase, which is known to have a direct band gap, and we also make an in-depth examination of amorphous strontium titanate. The results of our simulations of amorphous strontium titanate indicate that the formation of five-fold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied molecular orbital and the lowest unoccupied molecular orbital. These delocalized electronic levels are ascribed to the formation of a tail in the absorbance-spectrum curve. Optical absorption measurements experimentally showed the presence of a tail. The results are interpreted by the nature of these exponential optical edges and tails associated with defects promoted by the disordered structure of the amorphous material. We associate them with localized states in the band gap. Received: 15 January 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +55-16/2615-215, E-mail: derl@power.ufscar.br     

Room-temperature photoluminescence in amorphous SrTiO3– the influence of acceptor-type dopants

Room-temperature photoluminescence (PL) was observed in undoped and 2 mol % Cr-, Al- and Y-doped amorphous SrTiO₃ thin films. Doping increased the PL, and in the case of Cr significantly reduced the associated PL wavelength. The optical bandgaps, calculated by means of UV–vis absorption spectra, increased with crystallinity and decreased with the doping level. It was considered that yttrium and aluminum substituted Sr²⁺, whereas chromium replaced Ti⁴⁺. It is believed that luminescence centers are oxygen-deficient BO₆ complexes, or the same centers with some other defects, such as oxygen or strontium vacancies, or BO₆ complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO₆ defect complexes in doped SrTiO₃ results in various broadband luminescence peak positions. The results herein reported are an indicative that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence. Received: 20 November 2001 / Accepted: 22 November 2001 / Published online: 27 March 2002     

A novel electrochemical approach for fabrication of photoluminescent erbium-doped porous silicon

21 /cm³. After this new ECD treatment, PS:Er was found to emit much more intense room-temperature visible photoluminescence than both the porous silicon control and the PS:Er prepared by constant-current ECD. Room-temperature IR photoluminescence around 1.54 μm was observed for the first time without any post-doping annealing. Received: 3 September 1998/Accepted: 9 September 1998     

Photoluminescence in amorphous TiO2-PbO systems

Photoluminescence (PL) at room temperature has been achieved in amorphous thin films and powders of the TiO₂–PbO system. They were prepared by the polymeric precursor method with [PbO]/[TiO₂] molar ratios ranging from 0.0 to 1.0. The energy position of maximum PL emission and the PL intensity showed dependence on Pb concentration. The Pb addition suggests an increase in the number of non-bridging oxygens (NBO) in the amorphous TiO₂ network. These results support the relationship between photoluminescence and structure in TiO₂-based amorphous materials. Received: 7 February 2001 / Accepted: 8 February 2001 / Published online: 27 June 2001     

Photoluminescence characteristics of neodymium oxide nanocrystal/titania/ormosil composite sol-gel thin films

Neodymium (III) oxide nanocrystal/titania/organically-modified silane (ormosil) composite thin films have been prepared using a chemical approach consisting of a combination of inverse microemulsion and sol-gel techniques at low temperature. Transmission electron microscopy shows that the neodymium (III) oxide nanoparticles have a needle-like nanocrystal structure. A strong room temperature emission at 1064 nm, corresponding to the ⁴ F _3/2?⁴ I _11/2 transition, has been observed as a function of the heat treatment temperature used for the production of the composite thin films. In addition to this emission, two other main emissions at 890 nm and at 1336 nm have also been observed. In particular, there was a clear shoulder peak at 1145 nm, probably be due to the host matrix, which was observed in all the measured samples and this shoulder peak gave a maximum intensity after heat treatment at 300 °C. Received: 6 September 2000 / Accepted: 15 November 2000 / Published online: 20 June 2001     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Luminescence properties from erbium oxide nanocrystals dispersed in titania/organically modified silane composite sol–gel thin films

Luminescence properties from erbium (III) oxide nanocrystals dispersed in titania/organically modified silane composite thin films were studied. Erbium oxide nanocrystals were prepared by an inverse microemulsion technique. A strong room-temperature photoluminescence was observed at 1.531 μm, with the full width at half maximum (FWHM) of 22 nm due to intra-atomic transitions between ⁴ I _13/2 and ⁴ I _15/2 levels in the erbium (III) ion. The shape, peak position, and FWHM of the photoluminescence signals from the composite thin films were quite comparable to those prepared by other methods. The photoluminescence peak of the composite thin films showed a maximum intensity at the heat-treatment temperature of 300 °C. A room-temperature green up-conversion emission at 543 nm (⁴ S _3/2?⁴ I _15/2) was observed for the composite thin films with different heat-treatment temperatures upon excitation at 993 nm. The up-conversion emission mechanism was explained by means of an energy-level diagram and the lifetime of the visible up-conversion emission was measured. Received: 10 July 2000 / Accepted: 11 July 2000 / Published online: 5 October 2000     

Strong enhancement of spontaneous emission in amorphous-silicon-nitride photonic crystal based coupled-microcavity structures

We investigated photoluminescence (PL) from one-dimensional photonic band gap structures. The photonic crystals, a Fabry–Perot (FP) resonator and a coupled-microcavity (CMC) structure, were fabricated by using alternating hydrogenated amorphous-silicon-nitride and hydrogenated amorphous-silicon-oxide layers. It was observed that these structures strongly modify the PL spectra from optically active amorphous-silicon-nitride thin films. Narrow-band and wide-band PL spectra were achieved in the FP microcavity and the CMC structure, respectively. The angle dependence of PL peak of the FP resonator was also investigated. We also observed that the spontaneous emission increased drastically at the coupled-cavity band edge of the CMC structure due to extremely low group velocity and long photon lifetime. The measurements agree well with the transfer-matrix method results and the prediction of the tight-binding approximation. Received: 8 March 2001 / Accepted: 17 March 2001 / Published online: 23 May 2001     

Strong blue photoluminescence from aligned silica nanofibers

Photoluminescence (PL) and infrared spectra of aligned silica nanofibers are investigated. Two striking strong blue luminescence emissions have been found at room temperature. This suggests that the silica nanofibers could be a candidate material for a blue-light emitter. The intensity of the PL emission decreases after annealing, which can be interpreted as the decrease of the oxygen deficiency resulting in the reduction of radiative recombination centers. Infrared spectra provide further evidence of this conclusion, where the enhancement of Si–O absorption is observed in annealed samples. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-10/8264-9531, E-mail: ldai@vip.sina.com     

Study on size-dependent optical property of 4,4′-dibromobiphenyl nanocrystals

4,4^′-dibromobiphenyl nanocrystals with different sizes in the range from 20 nm to 300 nm were prepared by the reprecipitation method. It was found that their absorption peaks experienced a red shift while the size of the nanocrystals increased. Through analyzing these spectra of the nanocrystals with different sizes, it is suggested that this size-dependent optical property is contributed by two factors, the size effect and the J-aggregate formation. Received: 28 August 2000 / Accepted: 2 March 2001 / Published online: 23 May 2001     

Germania/ormosil hybrid materials derived at low temperature for photonic applications

We report on germania/organically modified silane (ormosil) hybrid materials produced by the sol–gel technique for photonic applications. Acid-catalyzed solutions of γ-glycidoxypropyltrimethoxysilane mixed with germanium isopropoxide have been used as precursors for the hybrid materials. Planar waveguide films with a thickness of about 2 μm have been prepared by a single spin-coating process and low-temperature heat treatment from these high germanium content hybrid materials. Atomic force microscopy, thermal gravimetric analysis, UV–visible spectroscopy, and Fourier-transform infrared spectroscopy have been used to investigate the optical and structural properties of the films. The results have indicated that a dense, low absorption, and high transparency (in the visible range) waveguide film could be achieved at a low temperature. A strong UV-absorption region at short wavelengths ∼200 nm, accompanied by a shoulder peaked at ∼240 nm, has been noticed due to the neutral oxygen monovacancy defects. The propagation mode and loss properties of the planar waveguide films have also been investigated by using a prism-coupling technique. Received: 5 November 2002 / Revised version: 27 December 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +65-67909081, E-mail: ewxque@ntu.edu.sg     

Charge compensation on the luminescence properties of ZnWO4:Tb phosphors via hydrothermal synthesis

A phosphor Tb³⁺-doped ZnWO₄ (ZWO:Tb) phosphors were prepared by a hydrothermal method. X-ray powder diffraction (XRD) analysis revealed that the as-obtained sample is pure ZnWO₄ phase. The excitation and emission spectra indicated that the phosphor could be well excited by ultraviolet light (272 nm) and emit blue light at about 491 nm and green light at about 545 nm. Significant energy transfer from WO₄²⁻ groups to Tb³⁺ ions has been observed. Two approaches to charge compensation are investigated: (a) 2Zn²⁺ = Tb³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Zn²⁺ = 2Tb³⁺ + vacancy. Compared with two charge compensation patterns in the ZnWO₄:Tb³⁺, it has been found that ZnWO₄:Tb³⁺ phosphors used Li⁺ as charge compensation show greatly enhanced bluish-green emission under 272 nm excitation.     

Photoluminescence excitation properties of porous silicon with and without Er-Yb-containing complex

Two bands in the photoluminescence excitation spectra have been studied for the red, blue, and IR emission of oxidized porous silicon (PS) and PS with Er³⁺- and Yb³⁺-containing gadolinium oxychloride complex (PS:Er,Yb), introduced by thermal diffusion. These two spectral bands were shown to reflect contributions of two different mechanisms of excitation-emission processes. The UV band for the IR emission of PS:Er,Yb rose sharply at about 290 nm and was explained by the direct photoemission of carriers from the valence band of Si crystallites into the conduction band of the oxide shell. The second band was found to be common for the red and blue emission and assosiated with the carriers photoexcitation inside the Si crystallites. Lifetimes for both bands were measured and the structure of the blue emission from PS:Er,Yb with peaks at 416, 440, 466, and 500 nm from PS:Er,Yb was observed.     

High refractive index and transparent heavy metal oxide glassy thin films

Heavy metal oxide thin films of the ternary system Nb₂O₅–GeO₂–PbO have been prepared by pulsed laser deposition in an O₂ environment from either glassy or crystalline bulk samples. The range of ([Pb]+[Nb]) content in which the films are optically homogeneous and transparent is much broader (0.5–1.0) than that of the bulk samples considered in the present work (0.55–0.62). The imaginary part of the refractive index is very low in all cases (k<10^-3), whereas the real part increases linearly with the ([Pb]+[Nb]) content up to values as high as 2.35. The optical energy gap has been found to be strongly dependent on [Pb], whereas it is almost independent of [Nb]. This dependence is discussed in terms of the role of Pb and Nb as network modifiers or formers. Received: 5 August 2002 / Accepted: 8 August 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/564-5557, E-mail: j.gonzalo@io.cfmac.csic.es     

Y2O3:Eu phosphor particles prepared by spray pyrolysis from a solution containing citric acid and polyethylene glycol

Y₂O₃:Eu phosphor particles were prepared by large-scale spray pyrolysis. The morphological control of Y₂O₃:Eu particles in spray pyrolysis was attempted by adding polymeric precursors to the spray solution. The effect of composition and amount of polymeric precursors on the morphology, crystallinity and photoluminescence characteristics of Y₂O₃:Eu particles was investigated. Particles prepared from a solution containing polyethylene glycol (PEG) with an average molecular weight of 200 had a hollow structure, while those prepared from solutions containing adequate amounts of citric acid (CA) and PEG had a spherical shape, filled morphology and clean surfaces after post-treatment at high temperature. Y₂O₃:Eu particles prepared from an aqueous solution with no polymeric precursors had a hollow structure and rough surfaces after post-treatment. The phosphor particles prepared from solutions with inadequate amounts of CA and/or PEG also had hollow and/or fragmented structures. The particles prepared from the solution containing 0.3 M  CA and 0.3 M  PEG had the highest photoluminescence emission intensity, which was 56% higher than that of the particles prepared from aqueous solution without polymeric precursors. Received: 22 March 2002 / Accepted: 26 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +82-42/861-4245, E-mail: yckang@pado.krict.re.kr     

Preparation and characterizations of SiO2/TiO2/γ-glycidoxypropyltrimethoxysilane composite materials for optical waveguides

SiO₂/TiO₂/γ-glycidoxypropyltrimethoxysilane composite materials processed by the sol-gel technique were studied for optical waveguide applications. Waveguide films with thickness more than 1.7 μm were prepared on a silicon substrate by a single-coating process and low-temperature heat treatment from these high-titanium-content composite materials. Scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal gravimetric analysis (TGA), UV-visible spectroscopy (UV-VIS), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) have been used to characterize the waveguide films. TGA curves showed that organic compounds in the composite materials would decompose in the temperature range from 200 °C to 480 °C. SEM, AFM and UV-VIS results showed that a dense, porous-free, and high transparency in the visible range waveguide film could be obtained at a low heat-treatment temperature. It was also noted that the carbon content in the film with higher titanium content heated at high temperature was evidenced by XPS. The waveguide propagation loss properties of the composite material films were also investigated and showed a dependence on the titanium molar fraction. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 20 September 2000     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Microstructures and photoluminescence of hydrogenated amorphous carbon films produced by using organic hydrocarbon source

Thin layers of hydrogenated amorphous carbon were prepared by using organic hydrocarbon source, xylene (C₈H₁₀), in plasma-enhanced chemical vapor deposition (PECVD) system. The microstructures were characterized by using Fourier-transform infrared and Raman scattering spectra. The appearance of a sharp vibration signal in 1600 cm^-1 strongly suggests the existence of sp² carbon clusters with aromatic rings. With increasing the deposition rf power, the content of these aromatic structures is increased in the films. In contrast to a broad single PL peak in methane (CH₄)-baseda-C:H films, the PL band of xylene-based a-C:H films contains multiple peaks in blue-green light region, which is influenced by rf power. We tentatively attributed it to the radiative recombination of electron-hole pairs through some luminescent centers associated with aromatic structures. Received: 26 April 2000 / Accepted: 9 May 2000 / Published online: 13 September 2000     

First applicability of ZnGa2O4 : Ge, Li, Mn phosphor for a plasma display panel

The green emission intensity of ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ excited by the vacuum ultraviolet line of 147 nm reaches 70% of commercial green Zn₂SiO₄:Mn²⁺. The vacuum ultraviolet excitation spectra consist of four peaks. In a plasma display test bed filled with Ar and Ne plasma discharged by a radio-frequency generator of 13.6 MHz, ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ and commercial Zn₂SiO₄:Mn²⁺ phosphor screens show a linear increase in luminance with increasing self bias voltages. Increasing gas pressures cause the luminance to increase. Also, on increasing the self bias voltages and the gas pressures, the current densities of ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ phosphor screens are increased; this is the same behavior as that of the commercial phosphor.     

The relationship between the macroscopic properties of PECVD silicon nitride and oxynitride layers and the characteristics of their networks

Silicon nitride and oxynitride films have been deposited on silicon wafers using plasma-enhanced chemical vapour deposition. Various amounts of ammonia, silane and nitrous oxide gases were applied at fixed total gas flow and at the same deposition temperature. The dependence of the macroscopic properties of the layers such as refractive index, internal stress and etch rate on the reaction atmosphere during deposition has been demonstrated. The chemical structure of amorphous layers was studied using infrared spectroscopy. The network was found to be characterised by SiN_xO_yH_z tetrahedra, joined to each other by common corners. The characteristic vibrational bands due to species that join tetrahedral units (N(-Si≡)₃, ≡Si-N-Si≡, ≡Si-O-Si≡) and species that stop this interconnection (Si-H, N-H) were determined and discussed with reference to the corresponding species available during deposition. The analysis resulted in the determination of the relationship between the chemical structure of the network and the layer’s refractive index, internal stress and etch rate. Received: 24 July 2000 / Accepted: 30 May 2001 / Published online: 30 August 2001