Characterization and antibacterial functions of Ag–TiO<Subscript>2</Subscript> and W–TiO<Subscript>2</Subscript> nanostructured thin films prepared by sol-gel/laser-induced technique

A novel sol-gel/laser-induced technique (SGLIT) has been developed to form nanocrystalline titanium dioxide (TiO₂) based thin films with an improved antibacterial performance. TiO₂ precursor films loaded with W⁺⁶ and Ag⁺² ions (W–TiO₂, Ag–TiO₂) were prepared separately by sol-gel method and spin-coated on microscopic glass slides. As-dried films were subjected to KrF excimer laser pulses at optimized parameters to generate mesoporous anatase and rutile phases at room temperature. The anatase phase was obtained after irradiation with 10 laser pulses only at 75–85 mJ/cm² fluence in W–TiO₂ films. However, higher number of laser pulses and higher W⁺⁶ content favored the formation of rutile. Whereas Ag–TiO₂ films exhibited anatase up to 200 laser pulses at the same fluence. The films were characterized by using XRD, FEG-SEM, TEM and UV-Vis spectrophotometer to investigate the crystallographic structure, phase transformation, surface morphology, film thickness and the optical properties. A crystallite size of approximately 20 nm was achieved from the anatase prepared by SGLIT. The films exhibited an enhanced antibacterial function against E-Coli cells under the UV excitation.     

The development of the physical and electrical characteristics of multi-layer TiO<Subscript>2</Subscript>–W–TiO<Subscript>2</Subscript> thin films

In this study, two different thin films, TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films (W, tungsten), are prepared by RF magnetron sputtering onto glass substrates. The crystal structure, morphology, and transmittance of TiO₂ and TiO₂–W–TiO₂ multi-layer thin films are investigated by X-ray diffraction, SEM, and UV-Vis spectrometer, respectively. The amorphous, rutile, and anatase TiO₂ phases are observed in the TiO₂ thin film and in the TiO₂–W–TiO₂ multi-layer thin films. The deposition of tungsten as the inter-layer will have large effect on the transmittance and phase ratios of rutile and anatase phases in the TiO₂–W–TiO₂ multi-layer thin films. The crystal intensities of amorous TiO₂ will decrease as the tungsten is used as the middle layer in the multi-layer structure. The band gap energy values of TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films are evaluated from (αhν)^1/2 versus energy plots, and the calculated results show that the energy gap decreases from 3.21 eV (TiO₂ thin film) to 3.08∼3.03 EV (TiO₂–W–TiO₂ multi-layer thin films).     

Photoluminescence from TiO2/PMMA Nanocomposite Prepared by γ Radiation

The surface of anatase TiO₂ nanocrystals with an average size of ~20 nm was modified by PMMA through γ radiation. The modified nanocrystals were investigated with photoluminescence (PL) and Fourier transform infrared (FTIR) spectra. A stable blue luminescence peak (~420 nm) can be observed for the modified anatase TiO₂ nanocrystal.     

Blue photo- and electroluminescence of silicon dioxide layers ion-implanted with group IV elements

The microstructural, optical and electrical properties of Si-, Ge- and Sn-implanted silicon dioxide layers were investigated. It was found, that these layers exhibit strong photoluminescence (PL) around 2.7 eV (Si) and between 3 and 3.2 eV (Ge, Sn) at room temperature (RT), which is accompanied by an UV emission around 4.3 eV. This PL is compared with that of Ar-implanted silicon dioxide and that of Si- and Ge-rich oxide made by rf magnetron sputtering. Based on PL and PL excitation (PLE) spectra we tentatively interpret the blue–violet PL as due to a T₁→S₀ transition of the neutral oxygen vacancy typical for Si-rich SiO₂ and similar Ge- or Sn-related defects in Ge- and Sn-implanted silicon dioxide. The differences between Si, Ge and Sn will be explained by means of the heavy atom effect. For Ge-implanted silicon dioxide layers a strong electroluminescence (EL) well visible with the naked eye and with a power efficiency up to 5×10^-4 was achieved. The EL spectrum correlates very well with the PL one. Whereas the EL intensity shows a linear dependence on the injection current over three orders of magnitude, the shape of the EL spectrum remains unchanged. The I-V dependence exhibiting the typical behavior of Fowler–Nordheim tunneling shows an increase of the breakdown voltage and the tunnel current in comparison to the unimplanted material. Finally, the suitability of Ge-implanted silicon dioxide layers for optoelectronic applications is briefly discussed. Received: 9 March 2000 / Published online: 30 June 2000     

The excitation mechanism of rare-earth ions in silicon nanocrystals

A detailed investigation on the excitation mechanisms of rare-earth (RE) ions introduced in Si nanocrystals (nc) is reported. Silicon nanocrystals were produced by high-dose 80-keV Si implantation in thermally grown SiO₂ followed by 1100 °C annealing for 1 h. Subsequently some of the samples were implanted by 300-keV Er, Yb, Nd, or Tm at doses in the range 2×10¹²–3×10¹⁵ /cm². The energy was chosen in such a way to locate the RE ions at the same depth where nanocrystals are. Finally an annealing at 900 °C for 5 min was performed in order to eliminate the implantation damage. These samples show intense room-temperature luminescence due to internal 4f shell transitions within the RE ions. For instance, luminescence at 1.54 μm and 0.98 μm is observed in Er-doped nc, at 0.98 μm in Yb-doped nc, at 0.92 μm in nc and two lines at 0.78 μm and 1.65 μm in Tm-doped nc. Furthermore, these signals are much more intense than those observed when RE ions are introduced in pure SiO₂ in the absence of nanocrystals, demonstrating the important role of nanocrystals in efficiently exciting the REs. It is shown that the intense nc-related luminescence at around 0.85 μm decreases with increasing RE concentration and the energy is preferentially transferred from excitons in the nc to the RE ions which, subsequently, emit radiatively. The exact mechanism of energy transfer has been studied in detail by excitation spectroscopy measurements and time-resolved photoluminescence. On the basis of the obtained results a plausible phenomenological model for the energy transfer mechanism emerges. The pumping laser generates excitons within the Si nanocrystals. Excitons confined in the nc can either give their energy to an intrinsic luminescent center emitting at around 0.85 μm nor pass this energy to the RE 4f shell, thus exciting the ion. The shape of the luminescence spectra suggests that excited rare-earth ions are not incorporated within the nanocrystals and the energy is transferred at a distance while they are embedded within SiO₂. Rare-earth excitation can quantitatively be described by an effective cross section σ_eff taking into account all the intermediate steps leading to excitation. We have directly measured σ_eff for Er in Si nc obtaining a value of ≈2×10⁻¹⁷ cm². This value is much higher than the cross section for excitation through direct photon absorption (8×10⁻²¹ cm²) demonstrating that this process is extremely efficient. Furthermore, the non-radiative decay processes typically limiting rare-earth luminescence in Si (namely back-transfer and Auger) are demonstrated to be absent in Si nc further improving the overall efficiency of the process. These data are reported and their implications. Received: 9 April 1999 / Accepted: 10 April 1999 / Published online: 2 June 1999     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Visible photoluminescence from Ge+-implanted SiO2 films thermally grown on crystalline Si

+ -implanted SiO₂ films is studied as a function of different fabricating conditions (implantation dose, annealing temperature and time). The SiO₂ films containing Ge nanocrystals exhibit two photoluminescence (PL) bands peaked at 600 nm and 780 nm. There are two excitation bands in the PL excitation (PLE) spectra. With variation in Ge nanocrystal size, the PL and PLE peak energies show no appreciable shift. The PL and PLE spectral analyses suggest that during the PL process, electron–hole pairs are generated by the E(l) and E(2) direct transitions inside Ge nanocrystals, which then radiatively recombine via luminescent centers in the matrix or at the interface between the nanocrystal/matrix. Received: 27 January 1998/Accepted: 18 March 1998     

Thermally stimulated currents in semi-insulating GaAs Schottky diodes and their simulation

We report the investigation of the non-irradiated and irradiated-with-pions Schottky diodes made on semi-insulating GaAs. Thermally stimulated currents have been measured experimentally and modeled numerically. To reveal the influence of the single levels, we used the thermal emptying of the traps by fractional heating. Attention is paid to the comparative analysis of the distribution of the parameters of different samples produced and processed by the same technique, contrary to the usual approach of the analysis of a few different samples. The following main conclusions are drawn. First of all, many different levels (from 8 to 12) have been found in the temperature range from 90 K to 300 K in all samples. Their activation energies range from 0.07 up to 0.55 eV, their capture cross-sections are 10^-22–10^-14 cm², and initial occupation is 2×10¹¹–5×10¹⁴ cm^-3. The irradiation with pions does not influence the density of most levels significantly. On the other hand, levels with activation energies of about 0.07–0.11 eV, 0.33–0.36 eV, 0.4–0.42 eV, and 0.48–0.55 eV have been found only in the irradiated samples. Irradiation also increases the inhomogeneity of the crystals, which causes the scattering of the activation energies obtained by fractional heating technique. Received: 13 November 1998 / Accepted: 16 April 1999 / Published online: 4 August 1999     

Self-cleaning characteristics on a thin-film surface with nanotube arrays of anodic titanium oxide

Self-cleaning of a surface of nanotube arrays of anodic titanium oxide (ATO) is demonstrated. The ATO was prepared in fluoride ion containing sulfate electrolytes with a structure of 0.4 μm length, 100 nm pores diameter, 120 nm interpore distance, 25 nm pore wall thickness, a 8×10⁹ pores cm⁻² pore density, and 68.2% porosity. Prepared as thin films either directly from a Ti foil or on a glass substrate, these arrays have the property that water drops spread quickly over the surface of the films without irradiation. In contrast, a flat anatase TiO₂ film requires irradiation with UV light for several minutes before the contact angle decreases to zero. The observed self-cleaning behavior of the ATO thin films is due to the capillary effect of the nanochannel structure and the superhydrophilic property of the anatase TiO₂ surface inside the tube.     

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     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Temperature behaviour of optical properties of Si+-implanted SiO2

Silicon nanocrystals were prepared by Si⁺-ion implantation and subsequent annealing of SiO₂ films thermally grown on a c-Si wafer. Different implantation energies (20-150 keV) and doses - cm ^-2 ) were used in order to achieve flat implantation profiles (through the thickness of about 100 nm) with a peak concentration of Si atoms of 5, 7, 10 and 15 atomic%. The presence of Si nanocrystals was verified by transmission electron microscopy. The samples exhibit strong visible/IR photoluminescence (PL) with decay time of the order of tens of μs at room temperature. The changes of PL in the range 70-300 K can be well explained by the exciton singlet-triplet splitting model. We show that all PL characteristics (efficiency, dynamics, temperature dependence, excitation spectra) of our Si⁺-implanted SiO₂ films bear close resemblance to those of a light-emitting porous Si and therefore we suppose similar PL origin in both materials. Received 1st September 1998 and Received in final form 7 September 1999     

Raman spectroscopy of carbon nitride films deposited using the filtered cathodic vacuum-arc technique combined with a radio-frequency nitrogen-ion beam

TiO₂–Fe₂O₃ semiconducting films were prepared by the resistive evaporation method on a glass substrate. Impedance and optical absorption measurements were made on these samples. From the impedance analysis (assuming an equivalent RC circuit), it was observed that the admittance and impedance functions are frequency dependent. From the optical absorption spectrum, the energy band-gap value was found to be 1.15 eV. The charge-carrier concentration (N) is calculated by using Mott–Schottky relations. I-V measurements were also made on these samples. Received: 2 November 1999 / Accepted: 24 August 2000 / Published online: 9 November 2000     

TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> nanoparticles synthesized using He/Ar thermal plasma and their effectiveness on low-concentration mercury vapor removal

Oxygen-vacant titanium dioxide (TiO_2−x ) nanoparticles were synthesized using thermal plasma as a heating source at various applied plasma currents and He/Ar ratios. Samples with diverse characteristics were developed and the mercury removal effectiveness was subsequently evaluated. TiO₂ nanoparticles possessing high purity and uniform particle sizes were successfully synthesized using metal titanium and O₂ as precursors and Ar as plasma gas. TiO_2−x in anatase phase with a particle size at 5–10 nm was formed at the He/Ar volume ratio of 25/75. Further increasing the He/Ar ratio elevated the plasma temperature, causing the tungsten to melt, vaporize from the cathode, and then dope into the formed TiO₂ nanoparticles. The doped W appeared to inhibit the growth of nanoparticles and decrease the crystallinity of formed anatase. The effectiveness of oxygen-vacant sites on Hg⁰ removal under the visible light circumstance was confirmed. Hg⁰ removal by the TiO_2−x nanoparticles was enhanced by increasing the O₂ concentration. However, moisture reduced Hg⁰ capture, especially when light irradiation was applied. The reduction in Hg⁰ capture may be resulted from the competitive adsorption of H₂O on the active sites of TiO_2−x with Hg⁰ and transformed Hg²⁺.     

Effect of the excimer laser irradiation on sol–gel derived tungsten–titanium dioxide thin films

A novel technique based on the excimer laser induced crystallization and modification of TiO₂ thin films is being reported. W⁺⁶ ions loaded TiO₂ (WTO) precursor films were prepared by a modified sol–gel method and spin-coated onto microscopic glass slides. Pulsed KrF (248 nm, 13 ns) excimer laser was used to irradiate the WTO amorphous films at various laser parameters. Mesoporous and nanostructured films consisting of anatase and rutile were obtained after laser irradiation at room temperature. The effect of varying W⁺⁶ ions concentrations on structural and optical properties the WTO films was analyzed by X-ray diffraction, field-emission scanning electron microscope, UV-Vis spectrophotometer and transmission electron microscope before and after laser treatment. Films irradiated for 10 pulses at 65–75 mJ/cm² laser fluence, exhibited anatase whereas higher parameters promoted the formation of rutile. XPS results revealed WO₃ along with minor proportion of WO₂ compounds after laser irradiation. Photo-absorbance of the WTO films was increased with increase in W⁺⁶ ions concentration in the film. TEM results exhibited a crystallite size of 15 nm which was confirmed from SEM results as well.     

Photoluminescence studies of nitrogen-doped TiO2 powders prepared by annealing with urea

Photoluminescence and excitation spectra have been investigated for undoped and nitrogen-doped TiO₂ powders at low temperatures. A broad luminescence band peaking at 2.25?eV is observed in the undoped TiO₂ powders. The 2.25?eV luminescence band exhibits a sharp rise from 3.34?eV in the excitation spectrum reflecting the fundamental absorption edge of anatase TiO₂. On the other hand, the N-doped TiO₂ powders obtained by annealing with urea at 350 and 500°C exhibit broad luminescence bands around 2.89 and 2.63?eV, respectively. The excitation spectra for these luminescence bands rise from the lower energy side of the fundamental absorption edge of anatase TiO₂. The origin of the luminescence bands and N-related energy levels formed in the band-gap of TiO₂ are discussed.     

A comparison of NMR spectral parameters of 47Ti and 49Ti nuclei in rutile and anatase

The paper reports on a measurement of the chemical-shift tensor for ⁴⁷Ti and ⁴⁹Ti in TiO₂ single crystals (rutile and anatase). The nature of the chemical shift anisotropy is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1204–1206 (July 1999)     

Variable-temperature Raman scattering study on anatase titanium dioxide nanocrystals

The temperature dependence of the Raman modes in anatase TiO₂ nanocrystals has been investigated over the temperature range 77-873 K. With increasing temperature, the frequency of the E_g mode at 639 cm⁻¹ shifts sublinearly to the lower frequencies, however, the frequency of the lowest-frequency E_g mode shifts sublinearly to the higher frequencies from 138 cm⁻¹ at 77 K to 152 cm⁻¹ at 873 K and the frequency of the B_1g mode at 397 cm⁻¹ increases firstly and attains a maximum near 350 K. The linewidth of all of the three modes increases linearly with increasing temperature. The anharmonic effects contribute a lot to the temperature dependence behavior of the frequency and linewidth of Raman modes in anatase TiO₂ nanocrystals.     

Study of surface-bulk mass transport and phase transformation in nano-TiO2 using hyperfine interaction technique

Phase transition from anatase to rutile for the 70 nm TiO₂ crystallite has been investigated by the time differential perturbed angular correlation (TDPAC) technique. The study involved the annealing of the TiO₂ nanocrystals, adsorbed with the nuclear probe (¹⁸¹Hf/¹⁸¹Ta) at trace level, at different temperatures for different durations. The TDPAC measurement was also supported by XRD measurement where the width of the peaks increases with the increase in annealing temperature indicating a crystal growth. The samples annealed up to 823 K for 4 h showed no phase transition, except for the growth of the crystallites. However, it showed phase transition at the same temperature (823 K), when annealed for longer duration, indicating the slower kinetics of the phase transition process. Further the sample, when annealed at 1123 K for 4 h, showed phase transition. It has also been observed that the ¹⁸¹Hf tracer, adsorbed on 70 nm anatase TiO₂, diffuses from surface to bulk during the phase transition process and the extent of diffusion in anatase differs from that in rutile phase. However, surface to bulk mass-transfer is found to play a significant role in the phase transition process.     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000