Fabrication and Magnetic Properties of Co-Doped TiO2 Powders Studied by Nuclear Magnetic Resonance

Co0.04 Ti0.96O2 powders are fabricated by sol-gel method. The structure and magnetic properties are investigated under different annealing conditions systematically with emphasis on the influence of oxygen pressure. Pure anatase structure was acquired for all the samples annealed at 450℃ for one hour. The samples annealed in air exhibit evident room-temperature ferromagnetism (RTFM) with a small magnetic moment of 0.029μB per Co atom and coercivity Hc of 26 Oe, while the samples annealed in vacuum have strong RTFM with a larger magnetic moment of 1.18μB per Co atom and Hc of 430 Oe. The zero-field spin echo nuclear magnetic resonance spectrum of ^59Co is obtained to prove the existence of Co dusters in the latter samples, implying that the Co dusters are responsible for the strong RTFM in the samples annealed in vacuum. No Co cluster could be observed using both XPS and NMR techniques in the samples annealed in air, implying that the RTFM found in these sample sis intrinsic.     

Effects of Rapid Thermal Processing on Microstructure and Optical Properties of As-Deposited Ag2O Films by Direct-Current Reactive Magnetron Sputtering

（111） preferentially oriented Ag2O film deposited by direct current reactive magnetron sputtering is annealed by rapid thermal processing at different annealing temperatures for 5 min. The film microstructure and optical properties are then characterized by x-ray diffractometry, scanning electron microscopy, and spectrophotometry, respectively. The results indicate that no clear Ag diffraction peak is discernable in the Ag2O film annealed below 200°C. In comparison, the Ag2O film annealed at 200°C begins to exhibit characteristic Ag diffraction peaks, and in particular the Ag2O film annealed at 250°C can demonstrate enhanced Ag diffraction peaks. This implies that the threshold of the thermal decomposition reaction to produce Ag particles is approximately 200°C for the Ag2O film. In addition, an evolution of the film surface morphology from compact and pyramid-like to a rough and porous structure clearly occurred with increasing annealing temperature. The porous structure might be attributable to the escape of the oxygen produced during annealing, while the rough surface might originate from the reconstruction of the surface. The dispersion of interference peak intensity in the reflectance and transmission spectra could be attributed to the Ag particles produced. The lowered crystallinity and Ag particles produced induce a lattice defect, which results in an enhanced transmissivity in the violet region and a weakened transmissivity in the infrared region.     

Defect types and room temperature ferromagnetism in N-doped rutile TiO2single crystals

The magnetic properties and defect types of virgin and N-doped TiO2 single crystals are probed by superconducting quantum interference device （SQUID）, X-ray photoelectron spectroscopy （XPS）, and positron annihilation analysis （PAS）. Upon N doping, a twofold enhancement of the saturation magnetization is observed. Apparently, this enhancement is not related to an increase in oxygen vacancy, rather to unpaired 3d electrons in Ti3＋, arising from titanium vacancies and the replacement of O with N atoms in the futile structure. The production of titanium vacancies can enhance the room temperature ferromagnetism （RTFM）, and substitution of O with N is the onset of ferromagnetism by inducing relatively strong ferromagnetic ordering.     

Ferroelectric Properties of Bi3.25La0.75Ti3O12 Thin Films Crystallized inDifferent N2/O2 Ambients

Bi3.25La0.75 Ti3O12 （BLT） ferroelectric thin films are deposited by sol-gel method and annealed for crystallizaion in total l eccm N2/02 mixed gas with various ratio at 750℃ for 30rain. The effect of crystallization ambient on the structural and ferroelectric properties of the BLT films is studied. The growth direction and grain size of BLT film are revealed to affect ferroeleetric properties. Alter the BLT film is annealed in 20%O2, the largest P~ value is obtained, which is ascribed to an increase of random orientation and large grain size. The fatigue property is improved with the concentration of oxygen in the ambient increasing, which is ascribed to annealing in the ambient with high concentrated oxygen adequately decreasing the defects related to lack of oxygen.     

Origin of Room-Temperature Ferromagnetism for Cobalt-Doped ZnO Diluted Magnetic Semiconductor

The pure single phase of Zn0.95 Co0.05 O bulks is successfully prepared by solid-state reaction method. The effects of annealing atmosphere on room-temperature ferromagnetic behaviour for the Zn0.95 Co0.05 O bulks are investigated. The results show that the air-annealed samples has similar weak ferromagnetic behaviour with the as-sintered samples, but the obvious ferromagnetic behaviour is observed for the samples annealed in vacuum or Ar/H2 gas, indicating that the strong ferromagnetism is associated with high oxygen vacancies density. High saturation magnetization Ms = 0.73μg/Co and coercivity Hc = 233.8 Oe are obtained for the Ar/H2 annealed samples with pure single phase structure. The enhanced room-temperature ferromagnetic behaviour is also found in the samples with high carrier concentration controlled by doping interstitials Zn （Zni）.     

Influence of annealing temperature on passivation performance of thermal atomic layer deposition Al_2O_3 films

Chemical and field-effect passivation of atomic layer deposition （ALD） Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy （TEM） and X-ray photoelectron spectroscopy （XPS）, respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.     

Rotation of ferromagnetic clusters induced magnetoresistance in the junction composed of La0.9Ca0.1MnO3 +δ and 1 wt.% Nb-doped SrTiO3

A junction composed of ultrathin La0.9Ca0.1MnO3＋δ （LCMO） film and 1 wt.% Nb-doped SrTiO3 was fabricated and its magnetoresistance （MR） was studied and compared with LCMO film. It was found that the resistance of the junction has a similar dependence on magnetic field as that of the LCMO film： the curvature of R-H curves is upward above Curie temperature （Tc） and downward below TC. These behaviours strongly suggest that the rotation of ferromagnetic clusters in manganite also causes MR in the corresponding junction. This MR can be qualitatively understood by the change of the width of the barrier induced by the rotation of ferromagnetic clusters. These results suggest a possibility to obtain junctions with large low-field MR.     

Influence of Annealing Temperature on Structure, Optical Loss and Laser-Induced Damage Threshold of TiO2 Thin Films

TiO2 thin films are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for 4h, the spectra and XRD patterns of the TiO2 thin film are obtained. Weak absorption of coatings is measured by the surface thermal lensing technique, and laser-induced damage threshold （LIDT） is determined. It is found that with the increasing annealing temperature, the transmittance of TiO2 films decreases. Especially when coatings are annealed at high temperature over 1173K, the optical loss is very serious. Weak absorption detection indicates that the absorption of coatings decreases firstly and then increases, and the absorption and defects play major roles in the LIDT of TiO2 thin films.     

Temperature dependences of optical properties,chemical composition,structure,and laser damage in Ta2O5 films

Ta2O5 films are prepared by e-beam evaporation with varied deposition temperatures,annealing temperatures,and annealing times.The effects of temperature on the optical properties,chemical composition,structure,and laserinduced damage threshold(LIDT) are systematically investigated.The results show that the increase of deposition temperature decreases the film transmittance slightly,yet annealing below 923 K is beneficial for the transmittance.The XRD analysis reveals that the film is in the amorphous phase when annealed below 873 K and in thehexagonal phase when annealed at 1073 K.While an interesting near-crystalline phase is found when annealed at 923 K.The LIDT increases with the deposition temperature increasing,whereas it increases firstly and then decreases as the annealing temperature increases.In addition,the increase of the annealing time from 4 h to 12 h is favourable to improving the LIDT,which is mainly due to the improvement of the O/Ta ratio.The highest LIDT film is obtained when annealed at 923 K,owing to the lowest density of defect.     

Evolution of Structural Defects in SiOx Films Fabricated by Electron Cyclotron Resonance Plasma Chemical Vapour Deposition upon Annealing Treatment

We study the structural defects in the SiO, film prepared by electron cyclotron resonance plasma chemical vapour deposition and annealing recovery evolution. The photoluminescence property is observed in the as-deposited and annealed samples. [-SiO3]^2- defects are the luminescence centres of the ultraviolet photoluminescence （PL） from the Fourier transform infrared spectroscopy and PL measurements. [-SiO3]^2- is observed by positron annihilation spectroscopy, and this defect can make the S parameters increase. After 1000℃ annealing, [-SiO3]^2- defects still exist in the films.     

Room-Temperature Ferromagnetism in Semiconducting TiO2-δ Nanoparticles

TiO2-δ nanoparticles are synthesized by the sol-gel method and annealed under different reducing atmosphere. The x-ray diffraction patterns show that anatase is the dominant phase with small amounts of the futile phase of TiO2-δ for all the samples. Magnetic measurements indicate that the samples annealed in reducing atmosphere exhibit unprecedented room-temperature ferromagnetism, in particular, the saturation magnetization Ms is up to about 8.6 × 10^-3 emu/g for the sample annealed in H2/Ar mixture. Analysis of the x-ray photoelectron spectroscopy spectra for the samples processed under different conditions indicates that the amounts of Ti^3＋ or Ti^2＋ cations, namely, the concentration of oxygen vacancies, increase with intensifying reducing atmosphere during processing, which shows that ferromagnetism in this material strongly depends on the concentration of oxygen vacancies. The relationships between the ferromagnetism and the crystal structure as well as the grain size in this material are also discussed.     

Room-Temperature Ferromagnetism of Co-Doped CeO2 Thin Films on Si（111） substrates

Using Co2O3 as the Co source, doped cerium oxide thin films with the composition of Ce0.97C00.03O2-δ （CCO） are deposited on Si（111） and glass substrates by pulse laser deposition technique. X-ray diffraction reveals that CCO films with （111） preferential orientation are grown on Si, while the fihn on glass is polycrystalline with nanocrystal. X-ray photoelectron spectroscopy shows that the （Jo displaces the （;e atom and exists in high spin state rather than low spin state, which contributes to the room-temperature ferromagnetism confirmed by vibration sample magnetometer. I~ilms on Si and glass are different in ferromagnetism, which is believed to be induced by different film microstructures. Based on these results, the possible ferromagnetism in this insulating film is discussed. Anyway, successful fabrication of CCO films with room-temperature ferromagnetism on Si substrates is of great importance in both technological and theoretical aspects.     

Additional Y3+ Doping Effect on Ferromagnetism of Ce0.97Co0.03O2-δ Compounds

Y^3＋ doping effect on magnetic properties of Ce0.97Co0.03O2-δ are examined. Vibrating sample magnetometer （VSM） measurements indicate that Ce0.97Co0.03O2-δ is ferromagnetic at room temperature. The saturated magnetization Ms is altered by additional Y^3＋ doping, i.e., with the increase of the amount of Y^3＋ doping concentration in Ce0.97-yYyCo0.03O2-δ（y = 0.01, 0.05 and 0.10）, Ms increases persistently, Raman spectra measurements indicate that additional oxygen vacancies are introduced with the amount of Y^3＋ doping content. The results can be well elucidated by the F-centre exchange coupling （FCE） mechanism proposed recently, thus they are important for understanding the ferromagnetism origination in transitional metal-doped insulating oxides.     

Influences of annealing temperature on properties of Fe~(2+):ZnSe thin films deposited by electron beam evaporation and their applications to Q-switched fiber laser

Fe~(2+):ZnSe thin films are prepared on sapphire substrate at room temperature by electron beam evaporation and then annealed in vacuum(about 1 × 10~(-4) Pa) at different temperatures. The influences of thermal annealing on the structural and optical properties of these films such as grain size and optical transmittance are investigated. The x-ray diffraction patterns show that the Fe~(2+):ZnSe thin film is preferred to be oriented along the(111) plane at different annealing temperatures.After the film is annealed, the full-width-at-half-maximum( FWHM) of the x-ray diffraction peak profile(111) of the film decreases and its crystal quality is improved. Scanning electron microscope images show that the films are more dense after being annealed. Finally, the sample is used as a saturable absorber in ZBLAN fiber laser. The annealed Fe~(2+):ZnSe thin films can be used to realize stable Q-switching modulation on ZBLAN fiber laser. The results demonstrate that the Fe~(2+):ZnSe thin film is a promising material for generating the high-power pulses of mid-infrared Q-switched fiber lasers.     

Laser-Induced Damage Threshold of TiO2 Films with Different Preparation Methods and Annealing Temperatures

Sol-gel TiO2 films are prepared by the dip-coating method and the spin-coating method, and then annealing is performed at different temperatures. The structures, optical properties, surface morphologies, absorption and laser-induced damage threshold （LIDT） at 1064 nm and 12 ns of the films are investigated. The results show that the dip-coating method can be used to obtain a higher LIDT than the spin-coating method. When the annealing temperature increases from 80℃ to 120℃, the dip-coated film obtains a higher LIDT, whereas the spin-coated film obtains a lower LIDT. In addition, the damage morphology is a spalling pit for the dip-coated film annealed at 80℃. When the annealing temperature increases to 120℃, it shows a melting area. For both the spin-coated films annealed at different temperatures, the damage morphologies are the combination of spelling and melting. The differences in LIDT and damage morphologies of the films are discussed.     

Optimization of TiO_2/Cu/TiO_2 multilayers as a transparent composite electrode deposited by electron-beam evaporation at room temperature

Highly transparent indium-free composite electrodes of Ti O2/Cu/Ti O2 are deposited by electron-beam evaporation at room temperature. The effects of Cu thickness and annealing temperature on the electrical and optical properties of the multilayer film are investigated. The critical thickness of Cu mid-layer to form a continuous conducting layer is found to be 11 nm. The multilayer with a mid-Cu thickness of 11 nm is optimized to obtain a resistivity of 7.4×10-5Ω·cm and an average optical transmittance of 86% in the visible spectral range. The figure of merit of the Ti O2/Cu(11 nm)/Ti O2 multilayer annealed at 150ΩC reaches a minimum resistivity of 5.9×10-5Ω·cm and an average optical transmittance of 88% in the visible spectral range. The experimental results indicate that Ti O2/Cu/Ti O2 multilayers can be used as a transparent electrode for solar cell and other display applications.     

Effect of Pyrolysis Atmosphere on Ferroelectric Properties of Bi3.25La0.75Ti3O12 Films Prepared by Sol-Gel Method

The effect of pyrolysis atmosphere is investigated for Bi3.25 La0.75 Ti3O12 （BLT） films prepared on Pt/TiO2/SiO2/p-Si（100substrates by sol-gel processes. The pyrolysis is carried out at 400℃ for 20 min under air or O2 atmosphere and the successive anneal is performed at 700℃ for 30min under O2 atmosphere. The pyrolysis under O2 is enough for complete removal of organic species, however after pyrolysis under air, carbon and hydrogen atomic species as organic fragment are partly remained in the film. This incomplete removal of organic fragments affects the grain growth and cause more defects in the film or between interfaces during the annealing for the crystallization of BLT film. The growth direction and grain size of the BLT film is revealed to affect ferroelectric properties. The remanent polarization PTfor the BLT films of pyrolysis in O2 and air are measured to be 18.85μC/cm^2 and 12.56μC/cm^2,respectively. The defects degrade the fatigue property dramatically for the film of pyrolysis in air. It can be concluded that the pyrolysis is an important procedure to control ferroeleetrie properties.     

Fabrication and Characterization of Multi-layer Heat Mirror with Photocatalytic Properties

A novel TiO2（5）/TiO2（buffer）/Ti（4）/Ag（3）/Ti（2）/TiO2（1） multi-layer film coating with corning glass is designed and fabricated by a dc magnetron sputtering method as a renovation of the well-known TiO2/Ti/Ag/Ti/TiO2 system in order to obtain a heat mirror system with photocatalytic properties due to sufficient thickness of the Ti02 layer. The outer TiO2 layer is fabricated in two steps, possibly claimed as two layers TiO2（5） and TiO2（buuer）, among which TiO2（buffer） the 70-nm-thick layer deposited in poor oxygen effectively minimizes the oxidation toward its neighbor Ti（4） layer. The optimal total thickness of the TiO2（5） and TiO（buffer） di-layer is found to be 300nm to yield a highly photo-catalytic property of the film without affecting the optical properties considerably. This multi-layer film can transmit light of above 75-85% in the visible spectrum （380 ≤ λ≤ 760 nm） and reflect radiation of above 90% in the infrared spectrum （ λ≥760 nm）. Such multi-layer coatings are strongly recommended not only as promising transparent heat mirrors but also as photo-catalytic films for architectural window coatings.     

Photoinduced Resistance Change in an Oxygen-Deficient La 0.9 Sr 0.1 MnO 3-δ Thin Film

Photoinduced resistance change （ △ R/R） in an oxygen-deficient La0.9Sr0.1MnO3-δ thin film is studied. At room temperature, the resistance change of about 30% and response time of about 75 ns are observed under the illumination with a 532nm laser pulse of 7ns and light power of 750mW. It is also found that △ R/R changes with the light power. The phenomena are explained in terms of the photoinduced hole carriers and localized insulator-to-metal transition, which may have potential applications in optoelectronic devices.     

Optical characterization of antimony-based bismuth-doped thin films with different annealing temperatures

Antimony-based bismuth-doped thin film,a new kind of super-resolution mask layer,is prepared by magnetron sputtering.The structures and optical constants of the thin films before and after annealing are examined in detail.The as-deposited film is mainly in an amorphous state.After annealing at 170-370℃,it is converted to the rhombohedral-type of structure.The extent of crystallization increased with the annealing temperature.When the thin film is annealed,its refractive index decreased in the most visible region,whereas the extinction coefficient and reflectivity are markedly increased.The results indicate that the optical parameters of the film strongly depend on its microstructure and the bonding of the atoms.