Lead zirconate titanate–barium titanate by mechanical activation of mixed oxides

For the first time, the perovskite phase in 0.9Pb (Zr_0.52Ti_0.48)O₃-0.1BaTiO₃(0.9PZT-0.1BT) is triggered to form in an oxide matrix consisting of PbO, ZrO₂, BaO, and TiO₂. Unlike in the solid-state reaction activated by calcination at an intermediate temperature, intermediate phases, such as PbTiO₃, were not observed with increasing degree of mechanical activation prior to the formation of perovskite 0.9Pb(Zr_0.52Ti_0.48)O₃-0.1BaTiO₃ phase. This suggests that the nucleation and subsequent growth of perovskite crystallites in the activated oxide composition are not a result of the interfacial reactions that normally occur in the temperature-driven solid-state reaction. The mechanical activation-derived powders can be sintered to a relative density of >97% theoretical at 1100 °C. Sintered 0.9Pb(Zr_0.52Ti_0.48)O₃-0.1BaTiO₃ derived from mechanical activation of constituent oxides exhibits a maximum dielectric constant of 775 and a minimum dielectric loss of <2% at room temperature when measured at 1.0 kHz. Received: 3 December 1998 / Accepted: 18 March 1999 / Published online: 24 June 1999     

Fabrication of surface relief gratings on transparent dielectric materials by two-beam holographic method using infrared femtosecond laser pulses

Fabrication of surface relief-type gratings in transparent dielectrics, which are hard to machine, has been achieved by a holographic technique using two infrared femtosecond (fs) pulses from a mode-locked Ti:sapphire laser. The present method can be applied for a variety of transparent dielectrics, Al₂O₃ (sapphire), TiO₂, ZrO₂, LiNbO₃, SiC, ZnO, CdF₂, MgO, CaF₂ crystals, and SiO₂ glass. It is found that the grating formation is due primarily to laser ablation processes. Planar surface relief gratings can be fabricated by colliding two fs laser pulses on the surface of substrates which move at a constant speed, synchronized with the laser repetition rate. Received: 1 March 2000 / Published online: 7 June 2000     

Laser deposition of amorphous diamond films from liquid aromatic hydrocarbons

6 H₅CH₃, C₆H₆, and C₆H₅CH(CH₃)₂) to pulsed visible laser radiation of a copper vapor laser (λ=510.6 nm). The X-ray Auger electron spectroscopy (XAES), reflection high energy electron diffraction (RHEED), and Raman analysis are employed to characterize the deposited films. The sp³ fraction in deposited films amounts to 60–70% and depends on the precursor. The average film thickness on a glass substrate is about 100 nm. The films show excellent adherence, are transparent in the visible and have microhardness of 50–70 GPa, as measured by nanoindentor. Received: 28 September 1998 / Accepted: 13 January 1999     

Diamond coating deposition by synergy of thermal and laser methods—A problem revisited

Diamond coatings were deposited by synergy of the hot filament CVD method and the pulse TEA CO₂ laser, in spectroactive and spectroinactive diamond precursor atmospheres. Resulting diamond coatings are interpreted relying on evidence of scanning electron microscopy as well as microRaman spectroscopy. Thermal synergy component (hot filament) possesses an activating agent for diamond deposition, and contributes significantly to quality and extent of diamond deposition. Laser synergy component comprises a solid surface modification as well as the spectroactive gaseous atmosphere modification. Surface modification consists in changes of the diamond coating being deposited and, at the same time, in changes of the substrate surface structure. Laser modification of the spectroactive diamond precursor atmosphere means specific consumption of the precursor, which enables to skip the deposition on a defined substrate location. The resulting process of diamond coating elimination from certain, desired locations using the CO₂ laser might contribute to tailoring diamond coatings for particular applications. Additionally, the substrate laser modification could be optimized by choice of a proper spectroactive precursor concentration, or by a laser radiation multiple pass through an absorbing medium.     

Synthesis of nanocrystalline material by sputtering and laser ablation at low temperatures

Physical vapor deposition techniques such as sputtering and laser ablation – which are very commonly used in thin film technology – appear to hold much promise for the synthesis of nanocrystalline thin films as well as loosely aggregated nanoparticles. We present a systematic study of the process parameters that facilitate the growth of nanocrystalline metals and oxides. The systems studied include TiO₂, ZnO, γ-Al₂O₃, Cu₂O, Ag and Cu. The mean particle size and crystallographic orientation are influenced mainly by the sputtering power, the substrate temperature and the nature, pressure and flow rate of the sputtering gas. In general, nanocrystalline thin films were formed at or close to 300 K, while loosely adhering nanoparticles were deposited at lower temperatures. Received: 31 October 2000 / Accepted: 9 January 2001 / Published online: 26 April 2001     

Elasticity, electronic structure, chemical bonding and optical properties of monoclinic ZrO2 from first-principles

Structural parameters as well as elastic, electronic, bonding and optical properties of monoclinic ZrO₂ were investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT). The calculated structural properties and independent elastic constants of monoclinic ZrO₂ are in favorable agreement with previous work. We have derived the bulk and shear moduli, Young’s modulus and Poisson coefficients for monoclinic ZrO₂ and estimated the Debye temperature of monoclinic ZrO₂ from acoustic velocity. Electronic and bonding properties are studied from the calculation of band structure, densities of states and charge densities. Furthermore, in order to clarify the mechanism of optical transitions in monoclinic ZrO₂, the dielectric functions are calculated and analyzed by means of the electronic structure, which shows significant optical anisotropy in the components of polarization directions (1 0 0), (0 1 0) and (0 0 1).     

Electronic,dielectric and mechanical properties of MoS2/SiC hybrid bilayer: A first principle study

The electronic, mechanical and dielectric properties of lateral MoS₂/SiC heterobilayer are investigated using first principles calculations. Among various stacking conformations, the energetically favorable stackings namely AA₂ and AB′₁ have been considered in the present study. The band gap of the heterobilayer shows reduction as compared to constituent monolayers which also remains stacking dependent. The electronic band-gap is further tunable by applying mechanical strain and perpendicular electric field that rendered heterostructures from semiconductor to metal at critical value of applied strain/field. The stacking of heterobilayer strongly influence its mechanical properties e.g. ultimate tensile strength of considered two favorable stacking differ by more than 50%; the ultimate tensile strain of 17% and 21% respectively has been calculated for two different stackings. The static dielectric constant also shows tunability on heterostructuring the constituent monolayers as well as applying strain and field. These tunable properties of MoS₂/SiC may be useful for the device applications at nanoscale.     

A new view of the electronic structure of the spin-Peierls compound -NaVO

The present understanding of the electronic and magnetic properties of -NaV₂O₅ is based on the hypothesis of strong charge disproportionation into V⁴⁺ and V⁵⁺, which is assumed to lead to a spin-1/2 Heisenberg chain system. A recent structure analysis shows, however, that the V-ions are in a mixed valence state and indistiguishable. We propose an explanation for the insulating state, which is not based on charge modulation, and show that strong correlations together with the Heitler-London character of the relevant intermediate states naturally lead to antiferromagnetic Heisenberg chains. The interchain coupling is weak and frustrated, and its effect on the uniform susceptibility is found to be small. Received: 28 January 1998 / Accepted: 17 March 1998     

Reduced dielectric loss and leakage current in CaCu3Ti4O12/SiO2/CaCu3Ti4O12 multilayered films

The CaCu₃Ti₄O₁₂/SiO₂/CaCu₃Ti₄O₁₂ (CCTO/SiO₂/CCTO) multilayered films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition method. It has been demonstrated that the dielectric loss and the leakage current density were significantly reduced with the increase of the SiO₂ layer thickness, accompanied with a decrease of the dielectric constant. The CCTO film with a 20 nm SiO₂ layer showed a dielectric loss of 0.065 at 100 kHz and the leakage current density of 6×10⁻⁷ A/cm² at 100 kV/cm, which were much lower than those of the single layer CCTO films. The improvement of the electric properties is ascribed to two reasons: one is the improved crystallinity; the other is the reduced free carriers in the multilayered films.     

Synthesis of Ni-doped InTaO4 nanocrystallites by reactive pulsed laser ablation for application to visible-light-operating photocatalysts

Ni-doped InTaO₄ nanocrystallites were synthesized by a reactive pulsed laser ablation process, aiming at visible-light-operating photocatalysts. The third harmonics beam of a Nd:YAG laser was focused onto a sintered In_0.9Ni_0.1TaO_4−δ target in mixture background gases (O₂ + He). The deposited species were columnar-structured porous films consisting of primary nanocrystallites. The mean diameter of the primary nanocrystallites was 4 nm. Optical absorption characteristics, especially in low absorbance (sub-band) regions, were evaluated by photoacoustic spectroscopy. Absorption in the sub-band region decreased drastically with increasing O₂ partial pressures. It is inferred that oxygen deficiencies are suppressed, because of enough oxygen vapors in the reactive background gases. An absorption band around 420 nm appeared obviously in O₂ partial pressures above 5%, in the Ni-doped InTaO₄ nanocrystallites. The visible region absorption band is presumably attributed to the Ni 3d-eg orbitals. In contrast, pure InTaO₄ nanocrystallites showed a sharp band edge, without the visible absorption band.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

Photoemission study of electronic structure evolution across the metal-insulator transition of heavily B-doped diamond

We studied the electronic structure evolution of heavily B-doped diamond films across the metal-insulator transition (MIT) using ultraviolet photoemission spectroscopy (UPS). From high-temperature UPS, through which electronic states near the Fermi level (E_F) up to ∼5k_BT can be observed (k_B is the Boltzmann constant and T the temperature), we observed the carrier concentration dependence of spectral shapes near E_F. Using another carrier concentration dependent UPS, we found that the change in energy position of sp-band of the diamond valence band, which corresponds to the shift of E_F, can be explained by the degenerate semiconductor model, indicating that the diamond valence band is responsible for the metallic states for samples with concentrations above MIT. We discuss a possible electronic structure evolution across MIT.     

Structural and dielectric properties of Bi4Ti3O12 thin films prepared by metalorganic solution deposition

Ferroelectric Bi₄Ti₃O₁₂ thin films with single phase and nanosized microstructure were prepared on Pt/Ti/SiO₂/Si(111) substrate by metalorganic solution deposition using titanium butoxide and bismuth nitrate at relatively low annealing temperatures. The internal strain in Bi₄Ti₃O₁₂ thin films was calculated from the peak shifts and broadening of XRD patterns. With increase in annealing temperature, the uniform strain decreased from positive to zero and then to negative, and the non-uniform strain decreased and was negative. The total strain was negative and in the range of -0.2%–-1.0%, from which the stress of the films was calculated to be about -1.4×10⁹ N/m². The mode values of strain decreased with increase in annealing temperature and increased with increase in film thickness. The dielectric constant increased with increase in annealing temperature and film thickness. The dielectric properties were interpreted by considering the influence of strain, grain size, and grain boundaries. The strain lowered the polarization and increased the dielectric constant. The larger the grain size and the thinner the grain boundary, the greater the dielectric constant. The influence of grain size and grain boundary was stronger than that of the strain. Received: 23 September 1998 / Accepted: 6 January 1999 / Published online: 24 March 1999     

First-principles study on electronic structure of Sr2Bi2O5 crystal

The electronic structure of Sr₂Bi₂O₅ is calculated by the GGA approach. Both of the valence band maximum and the conduction band minimum are located at Γ-point. This means that Sr₂Bi₂O₅ is a direct band-gap material. The wide energy-band dispersions near the valence band maximum and the conduction band minimum predict that holes and electrons generated by band gap excitation have a high mobility. The conduction band is composed of Bi 6p, Sr 4d and O 2p energy states. On the other hand, the valence band can be divided into two energy regions ranging from −9.5 to −7.9 eV (lower valence band) and from −4.13 to 0 eV (upper valence band). The former mainly consists of Bi 6s states hybridizing with O 2s and O 2p states, and the latter is mainly constructed from O 2p states strongly interacting with Bi 6s and Bi 6p states.     

Enhanced diamond nucleation on copper substrates by graphite seeding and CO2 laser irradiation

Diamond nucleation on copper (Cu) substrates was investigated by graphite seeding and CO₂ laser irradiation at initial stages of the combustion-flame deposition. A graphite aerosol spray was used to generate a thin layer of graphite powders (less than 1 μm) on Cu substrates. The graphite-seeded Cu substrates were then heated by a continuous CO₂ laser to about 750 °C within 1 min. It was found that diamond nucleation density after this treatment was more than three times as much as that on the virgin Cu substrates. As a consequence, diamond films up to 4 μm were obtained in 5 min. The enhancement of diamond nucleation on the graphite-seeded Cu substrates was attributed to the formation of defects and edges during the etching of the seeding graphite layers by the OH radicals in the flame. The defects and edges served as nucleation sites for diamond formation. The function of the CO₂ laser was to rapidly heat the deposition areas to create a favorable temperature for diamond nucleation and growth.     

First principles study of electronic structure and optical properties of LiMTe2 (M=Al, Ga, In) crystals

The results of first principles calculations of the electronic band structure, density of states and frequency dependent dielectric functions of LiAlTe₂, LiGaTe₂ and LiInTe₂ chalcopyrite crystals are reported. The calculations have been carried out within the density functional theory using norm-conserving pseudopotentials and a plane-wave basis. The peculiarities of the imaginary part ε₂(ω) of the complex permittivity are discussed and interpreted on the basis of the obtained band spectra. Our calculations show that the Ga-containing compound is characterized by the largest optical anisotropy compared to Al- and In-containing compounds and, therefore, is the most promising candidate for nonlinear optical applications among considered crystals.     

Mg,Al掺杂对LiCoO2体系电子结构影响的第一原理研究

为了研究Mg, Al掺杂对锂二次电池正极材料LiCoO₂体系的电子结构的影响，进而揭示Mg掺杂的LiCoO₂具有高电导率的机理，对Li(Co, Al)O₂和Li(Co, Mg)O₂进行了基于密度泛函理论的第一原理研究. 通过对能带及态密度的分析，发现在Mg掺杂后价带出现电子态空穴，提高了电导，并且通过歧化效应（disproportionation）改变了Co-3d电子在各能级的分布，而Al掺杂则没有这些作用. O关键词： 2')" href="#">LiCoO₂ 电子结构 第一原理 电导     

Non-destructive reading of laser-induced single-shot incubation in dielectric coatings

Two-dimensional photothermal displacement measurements were carried out on TiO₂, ZrO₂, and HfO₂ coatings to uncover single shot incubation produced by 248 nm laser light at fluences below the damage threshold. The incubation behavior of the three coatings differs and correlates with the ratio of band gap to photon energy. The non-destructive nature of the photothermal displacement technique, its high lateral resolution, and its sensitivity for reading single shot imprints by an excimer laser lends this scheme a capacity for use in optical storage.Alexander von Humboldt fellow 1991/92     

DFT study on the electronic structure and chemical state of Americium in an (Am,U) mixed oxide

We investigated the electronic state of an (Am,U) mixed oxide with the fluorite structure using the all-electron full potential linear augmented plane wave method and compared it with those of Am₂O₃, AmO₂, UO₂, and La_0.5U_0.5O₂. The valence of Am in the mixed oxide was close to that of Am₂O₃ and the valence of U in the mixed oxide was pentavalent. The electronic structure of AmO₂ was different from that of Am₂O₃, particularly just above the Fermi level. In addition, the electronic states of Am and U in the mixed oxide were similar to those of trivalent Am and pentavalent U oxides. These electronic states reflected the high oxygen potential of AmO₂ and the heightened oxygen potential resulting from the addition of Am to UO₂ and also suggested the occurrence of charge transfer from Am to U in the solid solution process.