Laser induced memory bits in photorefractive LiNbO3 and LiTaO3

We study experimentally the formation of refractive index voxels (volume elements) in photorefractive LiNbO₃ and LiTaO₃ crystals illuminated with high irradiance femtosecond laser pulses. We used 150 fs pulses at 800 nm wavelength (energy 6–50 nJ) tightly focused inside the crystals in a single shot regime. This resulted in a formation of a micrometer size region of elevated refractive index, which may be used as memory bits in information storage/retrieval application. The maximum refractive index change of 5×10⁻⁴ was recorded in undoped LiNbO₃ at an average light intensity of ∼TW/cm² that is close to the breakdown threshold. A simple setup for photorefractive recording and in situ monitoring of the refractive index changes has been proposed. M. Sūdžius leaves from: the Institute of Materials Science and Applied Research of Vilnius University, Lithuania.     

Nanocrystalline CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> powder by PVA sol–gel route: synthesis,characterization and its giant dielectric constant

Nanocrystalline CaCu₃Ti₄O₁₂ powders were synthesized by a simple PVA sol–gel route and calcined at 700 and 800°C in air for 8 h. The diameter of the powders ranges from 40–100 nm. The calcined CaCu₃Ti₄O₁₂ powders were characterized by TG-DTA, XRD, FTIR, SEM, and TEM. Sintering of the powders was conducted in air at 1100°C for 16 h. The XRD results indicated that all sintered samples had a typical perovskite CaCu₃Ti₄O₁₂ structure although the sintered samples contained some amount of CaTiO₃. SEM of the sintered CaCu₃Ti₄O₁₂ ceramics showed the average grain sizes of 13–15 μm. The samples exhibit a giant dielectric constant, ε′∼10⁵ at 150 to 200°C with weak temperature dependence below 1 kHz in the sample sintered using the powders calcined at 700°C. The Maxwell–Wagner polarization mechanism is used to explain the high permittivity in these ceramics. It is also found that all sintered samples have the same activation energy of grains, which is ∼0.122 eV.     

Real-time measurement of oxidation dynamics of sub-stoichiometric tungsten oxide films by pulsed laser deposition

In this study WO _x films were deposited by laser ablation of ultra-pure (5N) tungsten trioxide targets onto SiO₂ or silicon substrates at 250°C temperature, 100 mTorr oxygen partial pressure and 1×10⁻⁵ Torr vacuum. Surface chemical states and compositions of the deposits were determined by X-ray photoelectron spectroscopy. The results showed that deposits in oxygen partial pressure contain W⁶⁺ with x∼3.1, while vacuum-deposited films have different W states with various percentage distributions as W⁴⁺>W⁵⁺>W⁶⁺>W⁰, and x∼1. We used fast electrical resistance measurement as a probe to study the deposition process. Film resistance as a function of deposition time in vacuum revealed some microsecond fluctuations modulated on the time variation curve of electrical resistance. We attribute these data to surface absorption and desorption of oxygen during layer deposition. Finally, the effect of the laser beam on the target’s structure, surface morphology and chemical state was studied. Our results revealed that in spite of structural variation by laser irradiation, the O/W ratio remained about 3.     

Generalized multiple-prism dispersion theory for laser pulse compression: higher order phase derivatives

An exact, and explicit, expression for the second derivative of the generalized multiple-prism angular dispersion is provided. This corresponds to the third derivative of the generalized exit angle with respect to the refractive index (∇ _n ³ φ _2,m ). Higher derivatives, in abstract notation, are also given. The generalized equations are presented in a format applicable to practical prismatic configurations utilized in laser pulse compression schemes in the femtosecond domain. Exact values, as a function of the refractive index, are given for the first, second, and third angular derivatives for compensating double-prism and four-prism configurations of practical interest.     

Nonlinear refraction of silver nanowires from nanosecond to femtosecond laser excitation

In order to investigate the effect of pulse width and solvent on the nonlinear properties of metal nanostructures, silver nanowires were fabricated in a direct current electric field (DCEF) using a solid-state ionic method and characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The nonlinear refractive index (γ) of silver nanowires suspended in ethanol was measured using the Z-scan technique and laser radiation of various (femto-, pico-, and nanosecond) pulse durations. Experimental results indicated that silver nanowires have obvious positive refractive nonlinearities and γ (the Kerr-induced self-focusing) increases as the pulse duration increases from 7.4×10⁻⁸ cm²/GW at 110 fs to 1.6×10⁻⁴ cm²/GW at 8 ns, due to the additional influence of the atomic reorientational Kerr effect in the case of longer pulses. Due to the solvent dependence of the nonlinear behavior of the silver nanowires, the nonlinear absorption and refraction of silver nanowires suspended in de-ionized water are smaller than those of silver samples suspended in ethanol. The thermal nonlinearities are insignificant in our experimental conditions.     

Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Thin film iron-tetracyanoethylene Fe(TCNE) _x , x∼2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organic-based molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe²⁺ valency. The highest occupied molecular orbital of Fe(TCNE) _x is located at ∼1.7 eV vs. Fermi level and is derived mainly from the TCNE⁻ singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)-derived states appear at higher binding energy, ∼4.5 eV, which is in contrast to V(TCNE)₂ where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe²⁺ (3d⁶) configuration with a crystal field parameter 10Dq∼0.6 eV for the Fe(TCNE) _x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)₂ (10Dq∼2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (T _C ) seen for Fe(TCNE) _x -type magnets.     

Investigations on the local structure and g factors for the interstitial Ti3+ in TiO2

The EPR g factors gi (i = x, y, z) for the interstitial Ti³⁺ in rutile are theoretically studied from the perturbation formulas of these parameters for a 3d¹ ion in rhombically compressed octahedra. The ligand octahedron in the impurity center is found to be less compressed than that on the host interstitial site due to the Jahn-Teller effect. The local compression parameter (≈0.026) and the rhombic distortion angle δϕ′ (≈0.7°) around the impurity Ti³⁺ are smaller than the host values (≈0.091 and 3.5°). The theoretical g factors based on the above local structural parameters are in good agreement with the experimental data. In addition, the g factors for a tetragonal interstitial Ti³⁺ center are also reasonably interpreted.      

The nonlinear optical property and photoinduced anisotropy of?a?novel azobenzene-containing fluorinated polyimide

A novel azobenzene-containing fluorinated polyimide was synthesized. The nonlinear optical property and photoinduced birefringence of a polyimide thin film were investigated. Large third-order nonlinear refraction (n ₂=−4.49×10⁻¹¹ cm²/W) was observed in the polyimide thin film by carrying out Z-scan measurement. The polyimide thin film exhibited larger nonlinear refraction than that of a mono-azo dye doped PMMA thin film (n ₂=−1.63×10⁻¹² cm²/W). The photoinduced birefringence of the polyimide thin film (▵ n∼10⁻²) under different pump intensities was investigated; it was much larger than that of the mono-azo dye doped PMMA thin film (▵ n∼10⁻³). Moreover, the time constants for birefringence growth and relaxation processes were determined.     

Formation of highly organised,periodic microstructures on steel surfaces upon pulsed laser irradiation

We present results on the growth of highly organised, reproducible, periodic microstructure arrays on a stainless steel substrate using multi-pulsed Nd:YAG (wavelength of 1064 nm, pulse duration of 7 ns, repetition rate of 25 kHz, beam quality factor of M ²∼1.5) laser irradiation in standard atmospheric environment (room temperature and normal pressure) with laser spot diameter of the target being ∼50 μm. The target surface was irradiated at laser fluence of ∼2.2 J/cm² and intensity of ∼0.31×10⁹ W/cm², resulting in the controllable generation of arrays of microstructures with average periods ranging from ∼30 to ∼70 μm, depending on the hatching overlap between the consecutive scans. The received tips of the structures were either below or at the level of the original substrate surface, depending on the experimental conditions. The peculiarity of our work is on the utilised approach for scanning the laser beam over the surface. A possible mechanism for the formation of the structures is proposed.     

Nonlinear optical absorption in Bi3TiNbO9 thin films using Z-scan?technique

Bi₃TiNbO₉ (BTN) thin films with layered perovskite structure were fabricated on fused silica by pulsed laser deposition. The XRD pattern revealed that the films are single-phase perovskite and highly (00l) textured. Their fundamental optical constants, such as band gap, linear refractive index, and linear absorption coefficient, were obtained by optical transmittance measurements. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The nonlinear optical absorption of the films was investigated by single beam Z-scan method at a wavelength of 800 nm with laser duration of 80 fs. We obtained the nonlinear absorption coefficient β=1.44×10⁻⁷ m/W. The results show that the BTN thin films are promising for applications in absorbing-type optical devices.     

Optical switching of 2-(2<Superscript>′</Superscript>-hydroxyphenyl) benzoxazole in different solvents

All-optical switching and beam deflection of 2-(2^′-hydroxyphenyl) benzoxazole (HBO) in three species of solvent (cyclohexane, ethanol and dimethyl sulfoxide) have been investigated by using third-harmonic generation (355 nm) of a mode-locked Nd:YAG laser as a pump beam and a continuous-wave He-Ne laser (632.8 nm) as a probe beam. The nonlinear refractive indices of HBO in different solvents are determined by using the Z-scan technique. The optical switching and beam-deflection effects are due to the change of the refractive index of HBO under the pump beam. Through the study of the absorption spectra and the fluorescence spectra of HBO in different solvents, we conclude that the principal reason for the change of the refractive index of HBO is not the thermal effect because of absorption of the pump beam, but the excited-state intramolecular proton-transfer (ESIPT) effect of HBO under the pump beam. As the ESIPT process is very fast, HBO might be an excellent material for high-speed optical switching. Received: 28 October 2002 / Revised version: 18 March 2003 / Published online: 2 June 2003 RID="*" ID="*"Corresponding author. Fax: +86-22/2350-1242, E-mail: zhanggl@nankai.edu.cn     

Property study of Si + -ion-implanted Nd:YVO 4 waveguides

Planar waveguides were formed in Nd:YVO₄ crystals by 3.0-MeV Si⁺-ion implantation at doses of 1×10¹³–1.5×10¹⁵ ions/cm² at room temperature. The effective refractive indices of the waveguide propagation modes were measured by using a prism-coupling method. It was found that the number of the propagation modes is dependent on the doses for the waveguides in Nd:YVO₄. The atom displacement in the near-surface region (about 2 μm beneath the surface) of the Nd:YVO₄ crystal induced by the implantation was simulated by using the TRIM 98 (transport and range of ions in matter) code. The possible reasons for the waveguide formation are discussed in a primary way. Received: 17 July 2002 / Revised version: 20 September 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-531-8565167, E-mail: drfchen@sdu.edu.cn     

Comparison of gold and silver dispersion laws suitable for FDTD simulations

We report optical planar waveguide formation and modal characterization in β-BaB₂O₄ crystals by Cu²⁺-ion implantation at an energy of 3.0 MeV and doses of ∼ 10¹⁴ ions/cm². The prism-coupling method was used to investigate the dark-mode property at wavelengths of 633 nm and 1539 nm. The refractive-index profile of the waveguide was reconstructed by an effective refractive index method. The modal analysis indicates that the fields of TM modes can be well restricted in the guiding region, which means the formation of a non-leaky waveguide in the crystal. The results show that the β-BaB₂O₄ waveguides may be used in the application of high efficiency frequency conversion. PACS 61.80.Jh; 42.70.Mp; 42.65.Wi     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Reconstruction of extraordinary refractive index profile of O ion-implanted LiNbO3 single-mode channel waveguide based on beam propagation method and image processing

A method bases on beam propagation method and image processing is brought forward to reconstruct the extraordinary refractive index profile of the ion-implanted single-mode channel waveguide in lithium niobate. Channel waveguide is formed by O²⁺ ion implantation at three energies of (3.0, 3.6 and 4.5 MeV) and respective doses of (1.8, 2.2 and 4.8) × 10¹⁴ ions/cm² in vacuum at room temperature. Only one enhanced-index mode is observed for extraordinary light at 1539 nm by prism-coupling method. TRIM’98 code is used to simulate the damage profile in channel waveguide. The modes pattern of TE and TM are measured by use of end-face coupling method.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Nonlinear optical and optical limiting studies of alkoxy phthalocyanines in solutions studied at 532 nm with nanosecond pulse excitation

We report our results on the nonlinear optical and optical limiting properties of two alkoxy phthalocyanines namely 2,3,9,10,16,17,23,24-octakis-(heptyloxy) phthalocyanine and 2,3,9,10,16,17,23,24-octakis-(heptyloxy) phthalocyanine zinc(II) studied at a wavelength of 532 nm using 6 ns pulses. Using the standard Z-scan technique we observed that both the phthalocyanines exhibited negative nonlinearity as revealed by the signature of closed aperture data. The magnitude of the nonlinear refractive index n₂ evaluated from the closed aperture data was ∼ 1.61×10^-11 cm²/W for the free-base phthalocyanine and ∼ 1.56×10^-11 cm²/W for the metallic phthalocyanine. Open aperture Z-scan data indicates strong nonlinear absorption in both the phthalocyanines with measured nonlinear coefficients of ∼ 1650 cm/GW and ∼ 1850 cm/GW respectively. We also report optical limiting properties of these phthalocyanines with limiting thresholds (I_1/2) of ∼ 0.5 J/cm². Our studies suggest that these phthalocyanines are one of the best molecules for nonlinear optical applications studied recently. PACS 42.65.-k; 42.70.Jk, 42.65.Jx     

Reconstruction of extraordinary refractive index profiles of optical planar waveguides with single or double modes fabricated by O ion implantation into lithium niobate

A method named intensity calculation method (ICM), which is based on beam propagation method (BPM) and image processing, was carried out to reconstruct the extraordinary refractive index profile (RIP) of single-mode planar waveguide in lithium niobate (LiNbO₃), which was fabricated by multi-energy megaelectron-volt (MeV) O²⁺ ion implantation. In addition, it has been proved reasonable that the alternation of extraordinary refractive index induced by ion implantation into LiNbO₃ is mainly due to the degradation of polarization and reduction of material physical density. As a result, the possible extraordinary RIP of the double-mode planar waveguide could be reconstructed using BPM according to such a hypothesis and the calculated guiding mode values. The end-fire coupling and m-line arrangements were carried out to obtain the near-field modal patterns and dark-mode spectra of waveguides, respectively.     

ZrO2 films deposited by photo-CVD at low temperatures

Zirconium oxide layers have been successfully deposited by photo-CVD at low temperatures. ZrO₂ growth was observed at temperatures as low as 100 °C. When deposited at 250 °C and above, these films exhibited a polycrystalline structure with a mixture of different crystal phases. Deposition at 300 °C was found to form moisture-free ZrO₂ films with a high refractive index of 2.1, a very low effective density of trapped electrons of ∼8.8×10⁸ cm^-2 and an interface trap density of 6.6×10⁹ cm^-2 eV^-1 being readily obtained. Received: 17 December 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002