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 H irradiation on the optical properties of vacuum evaporated AgInSe2 thin films

We prepared polycrystalline AgInSe₂ thin films by vacuum evaporation on glass substrate at a high temperature using the stoichiometric powder. The thin films were characterized by X-ray diffraction and UV-vis-NIR spectroscopy. The samples were subjected to the irradiation of 1.26 MeV protons (H⁺). The effect of irradiation on the optical properties has been investigated for different doses of H⁺. It is observed that the band gap of silver indium selenide thin films decreases gradually with ion irradiation dose.     

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     

Investigation of the dielectric,optical and photorefractive properties of Sb-doped Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals

In this work we report results on electro-physical, optical and photorefractive investigations for Sb-doped Sn₂P₂S₆ crystals. The crystals are obtained by two methods: the vapour-transport technique and the Bridgman technique using stoichiometric Sn₂P₂S₆ composition with different amounts of antimony in the initial compound. The good optical quality of the crystals obtained with the Bridgman technique is underlined. The dependences of the photorefractive two-beam coupling coefficient and the grating build-up time are investigated at the wavelength of 633 nm. It is found that the sample doped with 1.5% of Sb is characterized by an optimal combination of the main photorefractive parameters exhibiting a fairly high two-beam coupling coefficient (up to 20 cm⁻¹) and a short response time (1.3 ms) that is the shortest among all the previously studied Sn₂P₂S₆ crystals in the red spectral region.     

Optical properties of ZnCr<Subscript>2</Subscript>Se<Subscript>4</Subscript>

We studied the optical properties of antiferromagnetic ZnCr₂Se₄ by infrared spectroscopy up to 28,000 cm^-1 and for temperatures from 5 to 295 K. At the magnetic phase transition at 21 K, one of the four phonon modes reveals a clear splitting of 3 cm^-1 as a result of spin-phonon coupling, the other three optical eigenmodes only show shifts of the eigenfrequencies. The antiferromagnetic ordering and the concomitant splitting of the phonon mode can be suppressed in a magnetic field of 7 T. At higher energies we observed a broad excitation band which is dominated by a two-peak-structure at about 18,000 cm^-1 and 22,000 cm^-1, respectively. These energies are in good agreement with the expected spin-allowed crystal-field transitions of the Cr³⁺ ions. The unexpected strength of these transitions with d-d character is attributed to a considerable hybridization of the selenium p with the chromium d orbitals.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> plasma production during pulsed laser deposition

A Nd:YAG laser operating in second harmonic (532 nm), 3 ns pulse duration, 150 mJ pulse energy, and 10 Hz repetition rate, is employed to irradiate Al₂O₃ target placed in high vacuum. The produced plasma is investigated by an ion collector used in time-of-flight configuration and by a mass quadrupole spectrometer, in order to determine the equivalent plasma temperature and the atomic and molecular composition. Pulsed laser deposition technique has been used to produce thin films on different substrates placed close to the target. Different surface analyses, such as energy dispersive X-ray fluorescence (EDXRF), X-ray photoelectron spectroscopy (XPS) and surface profilometry are employed to characterize the produced films. Measurements of ablation yield, plasma equivalent temperature, acceleration voltage and characterization of grown thin films are presented and discussed.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

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.     

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.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Charge dynamics of the spin-density-wave state in BaFe<Subscript>2</Subscript>As<Subscript>2</Subscript>

We report on a thorough optical investigation of BaFe₂As₂ over a broad spectral range and as a function of temperature, focusing our attention on its spin-density-wave (SDW) phase transition at T_SDW = 135 K. While BaFe₂As₂ remains metallic at all temperatures, we observe a depletion in the far infrared energy interval of the optical conductivity below T_SDW, ascribed to the formation of a pseudogap-like feature in the excitation spectrum. This is accompanied by the narrowing of the Drude term consistent with the dc transport results and suggestive of suppression of scattering channels in the SDW state. About 20% of the spectral weight in the far infrared energy interval is affected by the SDW phase transition.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Characterization of Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Thin Films Prepared by RF Magnetron Sputtering

Zn₂SnO₄ (ZTO) is a stable semiconductor in ZnO–SnO₂ system and important transparent conducting oxide (TCO) predominantly used in optoelectronic devices. ZTO thin films were prepared by RF magnetron sputtering using Zn₂SnO₄ ceramic target in this paper. The effects of annealing temperatures and oxygen contents on characterization of ZTO thin films were studied. The results show that ZTO thin films prepared by RF magnetron sputtering are amorphous with an optical band gap of 3.22 eV. After annealing at 650°C in Ar atmosphere for 40 min, ZTO films possess a spinel structure with an optical band gap of 3.62 eV. The atomic force microscope (AFM) data of morphology reveals that the surface roughness of films is about 2 nm. The results of energy dispersive spectrometer (EDS) show that the concentration ratio of Zn to Sn is in the range from 1.44 to 1.57. The results of Hall-effect-measurement system reveal that the resistivity of films varies from 102 to 10–1 Ωcm, carrier concentration is about 10¹⁷ cm^–3, and mobility ranges from 10⁰ to 10¹ cm² v^–1 s^–1.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Optical and IR studies on r.f. magnetron sputtered ultra-thin MoO3 films

Ultra-thin MoO₃ films were deposited onto glass and Si substrates by r.f. magnetron sputtering. The optical and IR properties of the films were studied in the range of 250 to 1000 nm and 400 to 1500 cm⁻¹, respectively. The optical transmission spectra show a significant shift in absorption edge. The energy gap of the films deposited at 373 K and 0.1 mbar was found to be 3.93 eV, and it decreases with increasing substrate temperature and decreasing sputtering pressure. The IR transmittance spectra shows strong modes of vibrations of Mo=O and Mo–O–Mo units of MoO₃ molecule. A significant change in energy gap and a shift in frequency of IR modes were observed in ultra-thin MoO₃ films.     

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