SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF TITANIUM DIOXIDE NANOPARTICLES AND NANOPARTICLES-DYE COMPOSITES

Hyper-Rayleigh Scattering (HRS) technique was used to study the second-order nonlinear optical (NLO) responses of aqueous titanium dioxide (TiO₂) nanoparticles of 10nm in size, and two nanoparticles-dye composites prepared by adding rhodamine B (Rh610) or the organic tosylate salt of dimethylaminostilbazolium (DAST). Results showed that the "per particle" first hyperpolarizability β for TiO₂ nanoparticles is very large, in the range of 10²⁶ esu. With adding Rh610 and DAST, the HRS signals of the composites were further enhanced. And in TiO₂/Rh610 composite the enhancement was obviously greater than that of TiO₂/DAST composite. It has proved that non-centrosymmetry of the nanocrystal/solution interface contributes mainly to its large "per particle" β, overwhelming the nanocrystal core. So the interactions between nanoparticles surfaces and adsorbed dyes were very important for their second-order NLO responses. HRS technique provides a useful new NLO method to characterize the surface structures and microenvironment of nanoscale materials.     

Optical properties of poly(methyl methacrylate)–titania nanostructure thin films containing ellipsoid-shaped titania nanoparticles from ex-situ sol-gel method at low growth temperature

This paper reports on the linear and nonlinear optical responses of the PMMA-TiO₂ nanohybrid thin films which are synthesized by a flexible ex-situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. Triethanolamine (TEOA) as surfactant and shape controller is used to modify the interface between PMMA and TiO₂, allowing a highly homogeneous dispersion of the ellipsoid-shaped TiO₂ nanoparticles. The resulting nanohybrid thin films have highly optical transparency as proved by the linear absorption photon-energy spectra and indicate an enhanced nonlinear optical (NLO) response as confirmed by the Z-scan technique using 800-nm, 120-femtosecond (fs) laser pulses, highlighting the potential of the nanocomposites for efficient optical devices.     

Microstructural, optical and photocatalytic properties of CdS doped TiO2 thin films

CdS doped TiO₂ thin films (with CdS content=0, 3, 6, 9 and 12 at%) were grown on glass substrates. The X-ray diffraction analysis revealed that the films are polycrystalline of monoclinic TiO₂ structure. The microstructure parameters of the films such as crystallite size (D_ν) and microstrain (e) are calculated. Both the crystallites size and the microstrain are decreased with increasing CdS content. The optical constants have been determined in terms of Murmann's exact equations. The refractive index and extinction coefficient are increased with increasing CdS content. The optical band gap is calculated in the strong absorption region. The possible optical transition in these films is found to be an allowed direct transition. The values of E_g^opt are found to decrease as the CdS content increased. The films with 3 at% CdS content have better decomposition efficiency than undoped TiO₂. The films with 6 at% and 9 at% CdS content have decomposition efficiency comparable to that of undoped TiO₂, although they have lower band gap. The CdS doped TiO₂ could have a better impact on the decomposing of organic wastes.     

Diatom-templated TiO2 with enhanced photocatalytic activity: biomimetics of photonic crystals

The siliceous frustules with sophisticated optical structure endow diatoms with superior solar light-harvesting abilities for effective photosynthesis. The preserved frustules of diatom (Cocconeis placentula) cells, as biophotonic crystals, were thus employed as both hard templates and silicon resources to synthesize TiO₂ photocatalyst. Characterizations by a combination of physicochemical techniques proved that the bio-inspired sample is TiO₂-coated SiO₂ with biogenic C self-doped in. It was found that the synthesized composites exhibited similar morphologies to the original diatom templates. In comparison with commercial Degussa P25 TiO₂, the C-doped TiO₂/SiO₂ catalyst exhibited more light absorption in the visible region and higher photocatalytic efficiency for photodegradation of rhodamine B under visible light due to the biomorphic hierarchical structures, TiO₂ coating and C-doping.     

Preparation and the optical nonlinearity of surface chemistry improved titania nanoparticles in poly(methyl methacrylate)-titania hybrid thin films

With 800-nm, 120-fs laser pulses, optical nonlinearity has been studied in a series of thin films containing poly(methyl methacrylate) (PMMA), filled with surfactant acetylacetone (Acac) capped TiO₂ nanoparticles, which were synthesized by a simple in situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. The resulting nanohybrid thin films have highly optical transparency and demonstrate a unique nonlinear optical (NLO) response. The highest nonlinear refractive index (n₂) is observed up to 6.55 × 10⁻² cm² GW⁻¹ in the nanohybrid thin film of 60 wt% Ti(OBu)₄ in PMMA, with a negligible two-photon absorption (TPA), as confirmed by the Z-scan technique. The titanium precursor loading combined with the nature of the capping molecules are used to influence the ability of nanoparticles to nonlinear optical response. Indeed, the ligands at the nanoparticles’ surface can not only control the extent of the interaction between the organic molecules and the embedded nanoparticles but also influence the optical nonlinearities of nanoparticles.     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.     

The C-V characteristics of TiO2/p-Si/Ag,GNR doped TiO2/p-Si/Ag and MWCNT doped TiO2/p-Si/Ag heterojunction devices

The TiO₂/p-Si/Ag, graphene (GNR) doped TiO₂/p-Si/Ag and multi-walled carbon nanotube (MWCNT) doped TiO₂/p-Si/Ag heterojunction devices were fabricated by electrospinning technique at same conditions. Their structural, morphological properties, thermal analyses (TGA), and capacitance voltage characteristics were studied and compared. The undoped, GNR and MWCNT doped TiO₂ structures obtained successfully according to XRD measurements. Morphological properties of the undoped, GNR and MWCNT doped TiO₂ composite structures have rod or ribbon like structures. The TGA result confirmed the GNR and MWCNT doped TiO₂ structures. The C-V and G-V measurements were employed for electrical characterization of the TiO₂/p-Si/Ag, GNR doped TiO₂/p-Si/Ag and MWCNT doped TiO₂/p-Si/Ag devices for various frequencies at room temperatures. The results imparted that the capacitance and conductance behaviors of all devices are strong functions of the frequency and voltage. The electrical parameters were calculated from C⁻²-V plots of the heterojunction devices and compared for three devices. The transient photocapacitance plots revealed that the devices can be employed for optical communication applications.     

V+注入锐钛矿TiO2第一性原理研究

用金属离子注入方法在锐钛矿TiO₂薄膜中掺杂了V⁺，采用全势线性缀加平面波方法计算了锐钛矿TiO₂及V⁺掺杂TiO₂超原胞的电子结构，通过紫外-可见吸收光谱测试方法检测了注入不同剂量的V⁺对TiO₂薄膜吸收光谱的影响.理论计算和实验结果表明，锐钛矿TiO₂薄注入V⁺后，带隙宽度变小，吸收光谱发生红移，并且TiO 关键词： +注入')" href="#">V⁺注入 2')" href="#">TiO₂ 全势线性缀加平面波方法 能带结构     

Influences of the iron ion (Fe)-doping on structural and optical properties of nanocrystalline TiO2 thin films prepared by sol-gel spin coating

Titanium dioxide (TiO₂) thin films doping of various iron ion (Fe³⁺) concentrations were deposited on silicon (Si) (100) and quartz substrates by sol-gel Spin Coating technique followed by a thermal treatment at 600 °C. The structure, surface morphology and optical properties, as a function of the doping, have been studied by X-ray diffractometer (XRD), Raman, ultraviolet-visible (UV-vis) and Spectroscopic Ellipsometry (SE). XRD and Raman analyzes of our thin films show that the crystalline phase of TiO₂ thin films comprised only the anatase TiO₂, but the crystallinity decreased when the Fe³⁺ content increased from 0% to 20%. During the Fe³⁺ addition to 20%, the phase of TiO₂ thin film still maintained the amorphous state. The grain size calculated from XRD patterns varies from 29.3 to 22.6 nm. The complex index and the optical band gap (E_g) of the films were determined by the spectroscopic ellipsometry analysis. We have found that the optical band gap decreased with an increasing Fe³⁺ content.     

Third-order nonlinear optical properties of Bi2S3 and Sb2S3 nanorods studied by the Z-scan technique

Bismuth sulfide (Bi₂S₃) and antimony sulfide (Sb₂S₃) nanorods were synthesized by hydrothermal method. The products were characterized by UV-vis spectrophotometer, X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Bi₂S₃ and Sb₂S₃ nanorods were measured by Z-scan technique to investigate the third-order nonlinear optical (NLO) properties. The result of NLO measurements shows that the Bi₂S₃ and Sb₂S₃ nanorods have the behaviors of the third-order NLO properties of both NLO absorption and NLO refraction with self-focusing effects. The third-order NLO coefficient χ⁽³⁾ of the Bi₂S₃ and Sb₂S₃ nanorods are 6.25×10⁻¹¹ esu and 4.55×10⁻¹¹ esu, respectively. The Sb₂S₃ and Bi₂S₃ nanorods with large third-order NLO coefficient are promising materials for applications in optical devices.     

Zum Lumineszenzmodell manganaktivierter Titanate

The emission spectra and the temperature dependence of the relative intensity of luminescence of three manganese activated titanate phosphors [Zn₂TiO₄, (Mg, Zn)₂TiO₄, Mg₂TiO₄] after optical excitation with radiation from 300–500 nm were measured for various temperatures above 4,2 °K. The luminescence of the Mn⁴⁺-centre is influenced by the cations (Mg²⁺ or Zn²⁺) of the lattice. The temperature dependence of the relative intensity of the luminescence depends on the excitation wavelength. The results are discussed and found to be in good agreement with those of aC-C-model which assumes two energy parabolas for the excited state.     

Probe the accumulation modes of the Au–C22H14 dimer on the structure and NLO properties

In 2006, the Au–C₂₂H₁₄ with a covalent bond between an individual pentacene (C₂₂H₁₄) and a gold (Au) atom was synthesised and characterised, and its nonlinear optical (NLO) properties were explored. To further investigate the NLO properties from molecules to materials, three kinds of different dimers (Au–C₂₂H₁₄)₂ (2, 3 and 4) were designed to probe the monomer accumulation modes on the structures and NLO properties. The results indicate that Au atoms doping breaks the conjugate structures of the two pentacenes to different extent. On the other hand, their NLO properties investigated by three density functional theory methods Becke-Half-and-Half-LYP (BHandHLYP), Coulomb-attenuating method Becke-3-Lee–Yang–Parr (CAM-B3LYP) and Minnesota 2005 double the amount of nonlocal exchange (M05-2X) show the same order, and 2 has the largest first hyperpolarisability (β_tot) than the other molecules. At the same time, natural bond orbital analysis shows the Au atoms play a crucial role in pushing electron density. Meanwhile, the frontier molecular orbital analysis shows that charge transfer has occurred between the two pentacene molecules and Au atoms. As a result, the order of transition energy is opposite to the order of β_tot values. Because the pentacene is taken as a simplified fragment of the graphene, our present work may be beneficial to the development of high-performance NLO materials.     

Concentration-dependent electronic structure and optical absorption properties of B-doped anatase TiO2

The concentration-dependent electronic structures and optical properties of B-doped anatase TiO₂ have been calculated using the density functional theory. The calculated results indicate that the electronic structures of B-doped TiO₂ have changed compared with those of pure TiO₂, which is mainly due to the new midgap states induced by B doping. As to the optical properties, we calculate the imaginary part of dielectric function ε₂(ω) and optical absorption spectra of pure and B-doped TiO₂. Two transitions E₁ and E₂ emerged after B doping. The intensity of absorption is enhanced by B doping both in the UV and visible regions. According to the results of imaginary part of dielectric function ε₂(ω) and DOS, it can be concluded that the two optical transitions correspond to the transitions from the O 2p states in the top of valence band to the midgap states and from the midgap states to the Ti 3d states in the bottom of conduction band, respectively. These results have important implications for the further development of photocatalytic materials.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Study on the influence of TiO2 on the insulating strength of ZnO-ZnF2-B2O3 glasses by means of dielectric properties

ZnO-ZnF₂-B₂O₃ glasses containing small concentrations of TiO₂ ranging from 0 to 0.6 mol% were prepared. Dielectric properties (constant ε′, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature at room temperature in air medium) of these glasses have been studied. The results of these studies were analyzed with the aid of data on optical absorption, ESR and IR spectra of these glasses. The analysis suggests that when the concentration of TiO₂>0.2 mol%, the titanium ions, in addition to Ti⁴⁺ state, co-exist in Ti³⁺ state, act as modifiers and reduce the breakdown strength.     

Stabilization of the anatase phase in TiO2(Fe, PEG) nanostructured coatings

Multilayered TiO₂(Fe³⁺, PEG) films were deposited on glass and SiO₂/glass substrates by sol-gel dipping method. The influence of Fe³⁺ and PEG(polyethylene glycol) concentrations, the number of layers, the thermal treatment time and the temperature on the optical and microstructural properties of the TiO₂ films were studied.As-deposited TiO₂(Fe³⁺, PEG) films were very porous, but after the thermal treatment at 500 °C, the PEG decomposed and burned out to porosity decreasing. Homogeneous nanostructured films were obtained, where the amorphous and the anatase phases coexist. XRD analysis showed that no rutile phase is observed in the films deposited on SiO₂/glass as compared with those deposited directly on glass and that the presence of the anatase phase in the films without PEG is more evident in the three-layers film. The XRD intensity of the main peak of anatase from 25° decreases with the increase of PEG concentration.The optical gap of the TiO₂(Fe³⁺, PEG) films is found in 2.52-2.56 eV range and does not essentially depend on the PEG content.     

Niveaux d'énergie et spectres de rayons X du rutile

The electronic levels of the complex TiO^?8₆ in the D_2h symmetry are determined according to an extended L. C. A. O. method. The results can explain the X-ray spectra of TiO₂. The absoption L_III and K rays are related to transitions from the 2p_3/2 and 1 s levels to the conduction band levels since the emission L_III and K components are explained by the transitions from the valence band levels to the 2p_3/2 and 1 s states. Interband transitions are related to the components of the optical reflexion spectrum of TiO₂ for the energies 0–20 eV. A comparaison is made with the electronic band structures of SnO₂, TiO₂ and BaTiO₃. At the center of the Brillouin zone, we obtain a forbidden gap of 3,01 eV, the corresponding widths of the valence and conduction band are 4,8 and 2,9 eV.     

Large negative refractive index modification induced by irradiation of femtosecond laser inside optical glasses

We report on the refractive index modification (Δn) and its cross sectional profile of the created lines inside the different types of optical glasses, containing BaO, TiO₂, or La₂O₃ as a metal oxide. The lines were fabricated by scanning a stage and focusing the femtosecond laser pulses, 800 nm wavelength, a 250 kHz repetition rate and 200 fs pulse duration, from the Ti:sapphire regenerative amplifier system. The Δn measurements were performed with the qualitative phase microscopy technique. As a result, it was found that the Δn and its sign are different depending on glass types. For example, in the glasses containing TiO₂, the Δn became smaller in the modified region and some of them showed relatively large decrease of the Δn, Δn < −0.01, with about 10 μm width. Such a glass material could be useful for the compact optics and optical devices.     

Influence of anions stabilizing the sols in synthesis of powders of highly dispersed titanium dioxide and three-dimensional nanocomposites based on SiO2/TiO2

This paper reports on the results of investigations into the influence of anions (Cl^?, SO ₄ ^2? ,NO ₃ ^? ), which stabilize the sol-gel synthesis of highly dispersed titanium dioxide, on the crystallization and phase transition of TiO₂ upon dehydration. The effect of the size factor on the phase composition of TiO₂ in SiO₂/TiO₂ nanocomposites has been investigated using a three-dimensional opal matrix as a set of nanoreactors for the sol-gel synthesis of TiO₂ · nH₂O. It has been shown that there is a possibility of extending the region of the existence of a thermodynamically metastable modification of TiO₂ (anatase) to the temperature of 1100°C due to the changes in the conditions of the sol-gel synthesis of TiO₂ · nH₂O.     

Titanium oxide thin layers deposed by dip-coating method: Their optical and structural properties

TiO₂ thin films were prepared by sol-gel method. The structural investigations performed by means of X-ray diffraction (XRD) technique and scanning electron microscopy (SEM) showed the shape structure at T = 600 °C. The optical constants of the deposited film were obtained from the analysis of the experimentally recorded transmittance spectral data in the wavelength of 200–3000 nm range. The values of some important parameters of the studied films are determined, such as refractive index n and thickness d. In this work, using the transmission spectra, we have calculated the dielectric constant (ε_∞) for four layered TiO₂ films; a simple relation is suggested to estimate the third-order optical nonlinear susceptibility χ⁽³⁾. It has been found that the dispersion data obeyed the single oscillator of the Wemple–DiDomenico model, from which the dispersion parameters and high-frequency dielectric constant were determined. The estimations of the corresponding band gap E_g, χ⁽³⁾ and ε_∞ are 2.57 eV, 0.021 · 10⁻¹⁰ esu and 5.20, respectively.