Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Effect of oxygen partial pressure and VO<Subscript>2</Subscript> content on hexagonal WO<Subscript>3</Subscript> thin films synthesized by pulsed laser deposition technique

We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO₃ thin films. XRD results show the hexagonal phase of deposited WO₃ thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO₃ thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO₂ content on structural, electrochemical, and optical properties of (WO₃)_1−x (VO₂) _x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO₂–WO₃ thin film electrode with higher VO₂ content (x ≥ 0.2). Increase of VO₂ content in (WO₃)_1−x (VO₂) _x films leads to red shift in optical band gap.     

Excimer laser deposited CuO and Cu<Subscript>2</Subscript>O films with third-order optical nonlinearities by femtosecond <Emphasis Type="Italic">z</Emphasis>-scan measurement

By controlling the oxygen pressure, single-phase CuO and Cu₂O thin films have been obtained on quartz substrates using a pulsed laser deposition technique. The structure properties and linear optical absorption of the films were characterized by X-ray diffraction and UV–VIS spectroscopy. By performing z-scan measurements using a femtosecond laser (800 nm, 50 fs), the real and imaginary parts of the third-order nonlinear susceptibility, Re χ ⁽³⁾ and Im χ ⁽³⁾, of the films were determined. Both CuO and Cu₂O films exhibited large optical nonlinearities, which is comparable to those in some representative semiconductor films such as ZnO and GaN films using femtosecond laser excitation. Compared with Cu₂O films, the CuO films showed larger third-order nonlinear optical effects under off-resonance excitation. Furthermore, the mechanisms of the optical nonlinearities in CuO and Cu₂O films are explained in the main text. It was suggested that the reasons of the difference in their nonlinear refractive effects may be related to the different electronic structure in CuO and Cu₂O materials.     

Nonlinear optical characterization of LaEr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> thin films using the <Emphasis Type="BoldItalic">Z</Emphasis> -scan technique

The nonlinear optical properties of thin films of LaEr(MoO₄)₃ were studied using a ∼30 ps Nd:YAG laser at 532 nm with a repetition rate of 250 Hz. Closed aperture Z-scan measurement revealed a negative nonlinearity in the LaEr(MoO₄)₃. The nonlinear refractive index γ=1.38×10^-10 cm²/W and nonlinear absorption coefficient β=16.8×10^-6 cm/W were calculated from the Z-scan data. The fluorescent upconversion spectra were recorded with 980 nm excitation. An optical switching mechanism based on nonlinear absorption is also presented experimentally. PACS 81.15.Fg; 77.84.Bw; 33.50.Dq; 42.70.Mp     

Optical properties of SrTiO<Subscript>3</Subscript> thin films by pulsed laser deposition

SrTiO₃ thin films were prepared on a fused-quartz substrate by pulsed laser deposition (PLD). Dense and homogeneous films with a thickness of 260 nm were prepared. Optical constants (refractive index n and extinction coefficient k) were determined from the transmittance spectra using the envelope method. The optical band gap energy of the films was found to be 3.58 eV, higher than the 3.22 eV for bulk SrTiO₃, attributable to the film stress exerted by the substrate. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The refractive index and the packing density for the PLD-prepared SrTiO₃ thin films are higher than those for the SrTiO₃ films prepared by physical vapor deposition, sol–gel and RF sputtering. Received: 18 March 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: mszhang@nju.edu.cn     

Exciton absorption spectra of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic solid solutions

The exciton absorption spectra of thin films of (Cs_{1 − x} Rb _x )₂CdI₄ solid solutions have been investigated and the refractive index n(λ) in their transparency window in the concentration range of 0 ≤ x ≤ 1 has been measured. The exciton-band parameters and optical permittivity ɛ_∞(x) have been found to linearly depend on the concentration. It is established that excitons are incorporated into the CdI₂ sublattice of the solid solutions and belong to intermediate-coupling ones. The characteristics of excitons in ferroelastics are compared with the corresponding parameters for CdI₂, RbI, and CsI, which are used as components to synthesize ternary compounds.     

Negative thermo-optical coefficients and athermal directions in monoclinic KGd(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> and KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> laser host crystals in the visible region

The temperature dependence of three principal refractive indices of the biaxial KGd(WO₄)₂ and KY(WO₄)₂ crystals in the temperature range of 288–673 K was measured at wavelengths of 438.5 and 632.8 nm. Their thermo-optical coefficients (TOC) of the first and second orders were determined on the basis of the experimental data obtained. TOC were found to be negative for the n_g and n_p refractive indices of the KY(WO₄)₂ crystal and for the n_g refractive index of the KGd(WO₄)₂ crystal. It was established that in a fairly wide temperature range contributions of the positive and negative TOC to the refractive index of a light wave propagating in these crystals in certain directions compensate each other. Such athermal directions were determined for the index ellipsoid principal planes of these crystals on the basis of experimental data. PACS 78.20.Ci; 78.20.Nv     

Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Quasi-direct optical transitions in Ge nanocrystals embedded in GeO<Subscript>2</Subscript> matrix

GeO₂ films with germanium nanocrystals (NCs) were deposited from supersaturated GeO vapor with subsequent dissociation on Ge:GeO₂. The films were studied using photoluminescence (PL), Raman scattering, IRspectroscopy techniques. Ge NCs in initial film have sizes about 6–8 nm and have no visible PL signal. The broad green-red PL peak was detected in Ge:GeO₂ films after thermal annealings. According to effective mass approach, maximum of PL signal from such relatively big Ge NCs should be in IR region. The experimentally observed PL signal is presumably originated due to quasi-direct L ₁-L ₃’ optical transitions “folded” in germanium NCs. The article is published in the original.     

Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)<Subscript>3</Subscript> using supercritical CO<Subscript>2</Subscript>

Optical properties (photoluminescence and absorption) of Eu(bta)₃(B) _n (B = H₂O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO₂ (SC CO₂) were investigated. It was established that impregnation of Eu(bta)₃phen into the FAPs using an SC CO₂ solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu³⁺ ions in the range 25–100°C. A comparative analysis of quantum yields (λ_ex = 300 and 380 nm) and photoluminescence decay times (λ_ex = 337.1 nm) for Eu(bta)₃B _n and for Eu(bta)₃B _n -doped FAPs was performed.     

Optical characteristics of nickel and boron carbonitride films in Si(100)/Ni/BC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> structures

The optical characteristics of nickel films deposited on Si(100) substrates by vacuum thermal evaporation have been studied. The thickness and optical constants of the films are determined using monochromatic zero ellipsometry, while the inverse problems are solved within the three-layer optical model of the samples. It is shown that thermal annealing leads to a change in the optical constants of nickel films in the heating-temperature range of 500–900°C. Boron carbonitride layers deposited on silicon substrates with a nickel sublayer are analyzed within multilayer optical models, which make it possible to determine the refractive index and absorption coefficient distributions along the thickness of the synthesized Si(100)/Ni/BC _x N _y structure.     

Electrical and optical properties of pulse plated CdS<Subscript><Emphasis Type="BoldItalic">x</Emphasis></Subscript>Te<Subscript>1-<Emphasis Type="BoldItalic">x</Emphasis></Subscript> films

Thin films of CdS_xTe_1-x were deposited by the pulse electrodeposition technique using cadmium sulfate, sodium thiosulfate, and tellurium dioxide on titanium and conducting glass substrates. Structural studies indicated the formation of polycrystalline films possessing hexagonal structure. The resistivity varies from 53 Ω cm to 8 Ω cm as the stochiometric coefficient “x” value decreases from 1 to 0. The carrier concentration increases with CdTe concentration. It is observed that as the post-heat treatment temperature increases, the photosensitivity also increases. It is observed that a post-heat treatment temperature of 550 °C results in high photosensitivity as well as low light resistance. The optical constants, refractive index (n) and extinction coefficient (k) were evaluated from the transmission spectra of the films of different composition.     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.     

Gamma irradiation effects on structural and optical properties of amorphous and crystalline Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films

The structural and optical properties of RF sputtered Nb₂O₅ thin films are studied before and after gamma irradiation. The films are subjected to structural and surface morphological analyses by using X-ray (XRD) and field emission scanning electron microscope techniques. In the wavelength range of 300–2000 nm, the optical parameters for amorphous and crystalline Nb₂O₅ thin films are estimated at differently exposed γ-irradiation doses (0, 50, 100 and 200 kGy). The optical constants, such as optical energy band gap, absorption coefficient, refractive index and oscillators parameters of amorphous and crystalline Nb₂O₅ thin films are calculated. The optical band gaps of γ-irradiated amorphous and crystalline Nb₂O₅ thin films are determined. In the non-absorbing region, the real part of the refractive index of amorphous and crystalline Nb₂O₅ thin films slightly increases with the increase in the exposed γ-irradiation dose.     

Effect of thermal annealing on r.f. sputtering-deposited nanocrystalline GaN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> thin films

GaNAs thin films were deposited on Corning glass substrates by radio frequency (r.f.) sputtering in molecular nitrogen ambient. The stoichiometry in the GaNAs alloy was controlled by changing the nitrogen incorporation in the film during the growth process, through the variation of the r.f. power in the range 30–80 watts which produced films with N concentrations in the range: x = 0.85–0.90. The structural and optical properties of the GaNAs thin films were studied by X-ray diffraction (XRD), photoacoustic (PA) and photoluminescence (PL) spectroscopies. XRD measurements show a broad diffraction band with a peak close to the (002) diffraction line of the GaN hexagonal phase, and a slight shoulder at the position corresponding to the (111) GaAs cubic phase. The PA absorption spectra showed a remarkable shift to higher energies of the absorption edge as the r.f. power decreases corresponding to the films with higher N concentrations. Thermal annealing of the GaNAs films at temperatures of 450 °C produced a GaAs nanocrystalline phase with grain sizes in the range 10–13 nm, as confirmed by the XRD measurements that showed a well-defined peak in the (111) GaAs direction, and also by the PA spectra which showed an absorption band at energies around 1.45 eV due to the quantum confinement effects. PL spectra of thermal-annealed GaNAs films showed a very intense emission at 1.5 eV which we have associated to transitions between the first electron excited level and acceptor states in the GaAs nanocrystallites.     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Photodesorption from ultra-thin metal films – a comparison of SO<Subscript>2</Subscript> and NO<Subscript>2</Subscript> on Ag/Si(100)

The photochemistry of SO₂ on thin epitaxial Ag films (5–60 nm) deposited on Si(100) has been studied using laser light with the wavelengths of 266, 355, and 532 nm. SO₂ desorbs with cross sections of 1.7×10^-19,1.7×10^-20 and 2.9×10^-21 cm², respectively. The average translation energy, 〈E_trans/2k〉, is 440 K for 266 and 355 nm light, and 270 K for 532 nm light. Cross sections for a 60 nm thick Ag film are practically identical to the ones for Ag(111) as the substrate. An increase by a factor of ∼3.5 is observed when the film thickness is reduced to 5 nm for 266 and 355 nm light. No significant change is observed for 532 nm excitation. The film thickness has no significant influence on the translational energy of the photodesorbed molecules. The data are discussed in connection with the change of absorptivity of the metal film–semiconductor system. A model is put forward which takes into account the light absorption in the Si substrate and the reduced relaxation of excited electrons in Si. Modelling indicates that electrons excited in the Si substrate with energies and parallel momenta not allowed in Ag contribute to the surface chemistry after crossing the gap in the projected band structure of Ag(111). PACS 82.45.MP; 73.63.-b; 82.50.Bc     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci