Self-assembled 3D La(OH)3 and La2O3 nanostructures: Fast microwave synthesis and characterization

Self-assembled three-dimensional (3D) urchin-like and flower-like La(OH)₃ nanostructures were successfully prepared for the first time via a facile and fast microwave-assisted solution-phase chemical method in 15 min. The obtained products were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The SEM results reveal that the urchin-like and flower-like La(OH)₃ nanostructures are ca. 3 μm and 6 μm in diameter, respectively. The urchin-like La(OH)₃ nanostructures are constructed by nanorods with diameters of about 300 nm and lengths of about 500 nm. The flower-like La(OH)₃ nanostructures are built from nanopetals about 100 nm thick. The effects of reaction time, microwave power, amount of tetraethyl ammonium bromide (TEAB), and surfactants on the preparation were systematically investigated. The possible formation mechanism of the 3D La(OH)₃ nanostructures was preliminarily discussed. Urchin-like and flower-like La₂O₃ nanostructures were obtained after calcining the La(OH)₃ nanostructures at 800 °C for 4 h. Urchin-like and flower-like La₂O₃:Eu³⁺ nanostructures were also prepared and their photoluminescence (PL) properties were investigated.     

Study of the thermally processed lanthanum hexaboride surface

We study the possibility to grow lanthanum oxide (La₂O₃) on the surface of lanthanum hexaboride (LaB₆) with (100)- and (100/110)-orientation in conditions of thermal annealing, in order to produce a metal-oxide-metal structure. Electron microscopic images, X-ray and optical spectra revealed a La₂O₃ layer of cubic symmetry. The features of the current-voltage and capacitance-voltage characteristics of the Al/La₂O₃/(100)LaB₆ and Al/La₂O₃/(100/110)LaB₆ structures are analyzed. The electrical conductance mechanism is explained on the basis of space-charge limited current.     

La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> electrolyte thin films for IT-SOFC application deposited by a HIPIMS/DC hybrid magnetron sputtering process

Apatite-type La_9.33Si₆O₂₆ thin films were elaborated by co-sputtering of two metallic La and Si targets powered, respectively, by high power impulse magnetron sputtering and direct current sources, in pure Ar atmosphere, followed by a subsequent high temperature oxidation treatment in air. The structural and chemical features of these films have been assessed by X-ray diffraction and scanning electron microscopy (SEM). The film with near lanthanum silicate La/Si atomic ratio deposited on a porous Ni-YSZ cermet substrates was initially amorphous. After thermal oxidation at 1,173 K in air, the coating crystallised under the expected apatite structure. SEM observation revealed that both film compactness and thickness increased after thermal oxidation. The conductivity evolution with temperature of the pure apatite-like lanthanum silicate coatings, as measured by complex impedance spectroscopy, showed that the activation energy of is quite low compared to the literature data.     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

Structural characterization and properties of lanthanum film as chromate replacement for tinplate

Sulfide-stain resistance of La-passivated, unpassivated and Cr-passivated tinplate was measured using a cysteine tarnish test. Corrosion behavior of these tinplates was investigated using electrochemical impedance spectroscopy (EIS) measurement. The morphology, composition and thickness of lanthanum film were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence spectrometry (XRF), respectively. La-passivation treatment remarkably enhances sulfide-stain resistance of tinplate, and sulfide-stain resistance of La-passivated tinplate is slightly higher than that of Cr-passivated tinplate. La-passivation treatment also significantly improves corrosion protection property of tinplate. In contact with 3.5% NaCl solution, corrosion resistance of La-passivated tinplate is close to that of Cr-passivated tinplate, and in contact with 0.1 M citric-citrate buffer solution, corrosion resistance of La-passivated tinplate is higher than that of Cr-passivated tinplate. Lanthanum film is composed of spherical particles about 50-1000 nm in diameter, while most part of tinplate's surface is covered with the small particles about 50-200 nm. The film mainly consists of lanthanum and oxygen, which mainly exist as La₂O₃ and its hydrates such as La(OH)₃ and LaOOH. The amount of lanthanum in the film is about 0.0409 g/m².     

Lanthanum Oxide Effects on the Structure of Calcium Phosphate Glasses

Calcium phosphate glasses, in which part of calcium oxide was replaced by lanthanum oxide, were prepared by using the conventional melt quench method. The structures of xLa₂O₃ · (50-x)CaO · 50P₂O₅ (x = 0, 1, 3, 6, 12 mol%) samples were investigated by X-ray diffraction (XRD), Raman spectrum, Fourier transform infrared spectrum (FTIR), and differential scanning calorimetry (DSC). The results show that lanthanum oxide acts as network modifier in the network space of glass structure. The glass formation occurs at an O/P ratio of about 3.0–3.12. At larger values, the crystalline phases calcium pyrophosphate (Ca₂P₂O₇) and calcium lanthanum phosphate [Ca₉La(PO₄)₇] are detected in the samples. Raman and FTIR spectra indicate that the structure of lanthanum-free sample is chain P–O–P bond metaphosphate–based Q² units. Glass structure will change to Q² and Q¹ units when the lanthanum oxide content is less then 6 mol%. When lanthanum oxide content increases to 9 and 12 mol% more nonbridging oxygen in the glass, resulting in the depolymerization of the phosphate network, the network of glass transforms to Q², Q¹, and Q⁰ units mixture. Based upon DSC results, T_g slightly decreases because of the depolymerization of microstructure. Endothermal peak of DSC curves indicate that crystal phases separate out from vitreous body with the addition of lanthanum oxide content.     

纯锆上离子注入钇和镧后的表面分析

用金属蒸汽真空弧源，以40kV加速电压对纯锆样品分别进行了10¹⁶—10¹⁷/cm²的钇、镧离子注入，注入温度约为130℃.然后对注入样品进行表面分析.x射线光电子能谱分析表明，注入的钇以Y₂O₃形式存在，镧以La₂O₃形式存在.俄歇电子能谱表明，纯锆基体表面的氧化膜厚度随着离子注入剂量的增加而增加，当离子注入剂量达到10¹⁷/cm²时，氧化膜的厚度达到了最大值.卢瑟福背散射显示镧层的厚度约为30nm，同时直接观察到当离子注入剂量为(La+Y)10¹⁷/cm²时，纯锆样品表面发生了严重的溅射. 关键词： 纯锆 钇和镧离子共注入 卢瑟福背散射 x射线光电子能谱     

Efficient UV–visible up-conversion emission in Er3+/Yb3+ co-doped La2O3 nano-crystalline phosphor

A nano-crystalline La₂O₃: Er³⁺/Yb³⁺ phosphor sample has been synthesized through the solution combustion route using urea as a reducing agent. Thermal, structural and optical characterizations have been carried out to explore several of its properties. By thermal analysis one concludes to the presence of moisture and hydroxide phases [La(OH)₃ and LaOOH] of lanthanum in the as-synthesized sample, which further changes to La₂O₃ phase above 600°C temperature. Up-conversion (UC) study shows the intense emission bands in the UV, blue, green and red regions. This paper also reports the first observation of UC emission bands extending up to the UV (240 nm) region on excitation with 976 nm wavelength. Heat treatment of the samples shows a change in the crystallite phase along with crystallite growth and relative UC luminescence intensities. The input pump power dependence shows the involvement of up to four photons.     

Silica-scavenging effect in zirconia electrolytes: assessment of lanthanum silicate formation

Yttria-stabilized zirconia (YSZ)-based composite electrolytes were produced by mixture and firing of the base electrolyte, namely with silica, and silica and lanthanum oxide, to study the impact of presence and formation of new phases on the electrical performance of the composite materials. Combined information obtained from structural, microstructural, and electrical characterization confirmed the formation of an apatite-type solid solution based on La_9.33Si₆O₂₆. The effectiveness of lanthanum oxide addition to remove silica by reaction was demonstrated. However, the conductivity of the composite electrolytes is lower than that of YSZ, probably due to lanthanum zirconate formation in-between the ceramic grains and/or relatively poor transport properties of the formed lanthanum silicate phase. The adopted procedure can be extended to other systems and combinations of properties based on predictable phase interactions.     

Luminescence study of cerium-doped La2Hf2O7: Effects due to trivalent and tetravalent cerium and oxygen vacancies

X-ray excited emission spectra, photoluminescence excitation and emission spectra, optical reflectivity spectra, and pulsed X-ray and optical excited luminescence decay measurements are reported for cerium-doped La₂Hf₂O₇ powders prepared by solid state synthesis. A broad luminescence associated with oxygen vacancies is observed in the region 350–750 nm with a peak around 460 nm. The photoluminescence spectra and the number of oxygen vacancies vary for samples annealed in oxidizing or reducing atmospheres and with the temperature of the synthesis process. Increasing the cerium concentration reduces the oxygen-vacancy-related emission due to the presence of Ce⁴⁺. First principles calculations predict that Ce⁴⁺ can substitute in Hf sites; this is confirmed from the optical reflectivity spectrum of cerium-doped La₂Hf₂O₇. Photoluminescence excitation and emission spectra characteristic of Ce⁴⁺ charge transfer transitions and possibly Ce³⁺ are also observed. Although trivalent cerium may be present, no emission observed from cerium-doped La₂Hf₂O₇ can be attributed to Ce³⁺ in La sites.     

Compositional effects on the structure and magnetotransport properties of lacunar La<Subscript>1-x</Subscript>MnO<Subscript>3-δ</Subscript> films (x>0) grown by MOCVD

Liquid-injection MOCVD was successfully applied to the growth of La_1-xMnO_3-films. A structural study by means of X-ray diffraction and transmission electron microscopy was performed on lanthanum manganite films grown under different (P[O₂]–T) conditions. The phase relations of lanthanum manganite with different manganese oxide phases (MnO, Mn₃O₄) are discussed, together with structural relations. Tuning of T_C via the concentration of La vacancies allows significant magnetoresistance at room temperature to be obtained (about 10% in a 1T field). PACS 68.55; 75.30; 81.15     

Spectral properties of Ce3+ doped yttrium lanthanum oxide transparent ceramics

Ce3+-doped yttrium lanthanum oxide (Y0.9La0.1)2O3 transparent ceramics is fabricated with nanopowders and sintered in H2 atmosphere. The spectral properties of Ce:(Y0.9La0.1)2O3 transparent ceramics are investigated. There appear two characteristic absorption peaks of Ce3+ ions at 230 nm and 400 nm, separately. It is found that Ce3+ ions can efficiently produce emission at 384 nm from (Y0.9La0.1)2O3 transparent ceramic host, while the emission is completely quenched in Re2O3 (Re=Y, Lu, La) host materials.     

Influence of valence band states on the core hole screening in lanthanide perovskite compounds

Investigation on core level and valence band photoelectron spectra of lanthanide perovskite samples (Ag _x La_1–x CoO₃;x<0,3) and reinvestigations of metallic lanthanum and La-oxide layers are reported. Differences in preparation method during perovskite formation are leading to different quality of sample purity and different electronic properties. This could be followed by changes in the density of states near the Fermi energy. On the other hand the screening mechanism after ionization of a La 3d core hole is affected by the relative energy position of occupied valence band states with respect to the empty La 4f ^* level in the core ionized state. Changes in La 3d line profile are discussed as changes in multi electron processes (e.g. shake up or energy gain) during photoionization. We attribute the two electron process during photoemission of La 3d electrons to the well screened energy gain transition in LaCoO₃, whereas the two electron process results in a shake up transition in La₂O₃ and La(OH)₃.     

Physico-chemical investigations on selected gallium doped lanthanum chromites

Investigations on lanthanum gallium chromium mixed oxides of the compositions La_1.0Ga_0.2Cr_0.8O_3−d and La_0.9Ga_0.2Cr_0.8O_3-d are presented regarding their structure, redox stability, conductivity and catalytic activity for the oxidation of propene. The mixed oxide has perovskite-type structure, high redox stability, an electronic p-type conductivity and low catalytic activity. If the perovskite-type compound has a deficiency of lanthanum, the electronic conductivity, surface area and catalytic activity are significantly higher. The catalytic activity is likely comparable to that of gold. Similar to gold electrodes of solid electrolytes, oxygen electrodes formed with gallium doped lanthanum chromite show a relatively high sensitivity to hydrocarbons such as propene at temperatures of about 700 °C. The mixed oxide is possibly suitable as electrode material for exhaust gas sensors using oxide-ion conducting solid electrolytes. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, September 13–20, 1998.     

Electron energy loss spectroscopy study of the initial stage of lanthanum oxidation

The electron energy loss spectra (EELS) of a pure metallic lanthanum surface and variations in these spectra at the initial stages of surface oxidation were studied. The measurements were performed at primary-electron beam energies E _p from 200 to 1000 eV. A very pronounced peak at a loss energy of about 7.5 eV arises due to transitions from the La4d electronic states of the valence band into the empty La4f electronic states of the conduction band at 5.0–5.5 eV above the Fermi level. Marked changes are observed in the EELS during the oxidation of lanthanum: the peak at an energy of 7.5 eV disappears, and the peak at 13.5 eV corresponding to bulk collective energy loss in lanthanum oxide becomes more pronounced. The results obtained are discussed in terms of the electronic structure of lanthanum and lanthanum oxide.     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Features of LaBO3 phase formation during solid-phase synthesis from the amorphous precursor state

The features of the phase formation of pure lanthanum borate during solid-phase synthesis from an amorphous precursor state and from a homogenized mixture of initial oxide micropowders have been investigated using X-ray diffraction methods. It has been shown that LaBO₃ phase sequences obtained in both cases significantly differ from each other. The role of cross doping with Y, Sc, and La on the La_0.95Sc_0.05BO₃, La_0.95Y_0.05BO₃, Y_0.95La_0.05BO₃, and Sc_0.95La_0.05BO₃ phase sequence during synthesis from the amorphous precursor state has been clarified.     

Band bending measurement of HfO2/SiO2/Si capacitor with ultra-thin La2O3 insertion by XPS

The flat band voltage shifts of HfO₂/SiO₂/nSi capacitors with ultra-thin La₂O₃ insertion at HfO₂/SiO₂ interface have been confirmed using hard X-ray photoelectron spectroscopy (HX-PES). By increasing the amount of La₂O₃ insertion, the binding energy of Si 1s core spectra increases, which means that the surface potential of Si substrate also increases. A voltage drop difference of HfO₂ and La₂O₃ at SiO₂ interface can be estimated to be 0.40 V.     

Mechanochemically assisted synthesis of La0.7Sr0.3MnO3 nanoparticles and induction heating properties of the composites with hydroxyapatite

Perovskite lanthanum strontium manganese oxide (LSMO, strontium-substituted lanthanum manganite) La_0.7Sr_0.3MnO₃ nanoparticles were synthesized via the low-temperature calcination of the precursor, which was prepared using a mechanochemical route. A powder mixture of lanthanum chloride, strontium chloride, manganese chloride and sodium carbonate was high-energy milled by a planetary ball mill under semiwet (moist) conditions to obtain the precursor. To study the mechanochemical effects on the formation of LSMO, a thermogravimetric (TG) analysis was conducted for the precursors prepared under various conditions; the precursors and the intermediates formed during calcination were identified by X-ray diffraction (XRD). The calcination of the milled precursor at 600 °C resulted in the formation of LSMO nanoparticles with good induction heating properties. The LSMO/hydroxyapatite composites exhibited rapid temperature increases in an AC magnetic field. The obtained results demonstrate that the LSMO nanoparticles and LSMO/hydroxyapatite composites are promising candidates for magnetic hyperthermia treatments.     

Application of mechanochemical treatment to the synthesis of A- and G-forms of La2Si2O7

The impact of mechanochemical treatment on a mixture of La₂O₃ and silica gel (in molar ratio La₂O₃/SiO₂=1:2) was examined by X-ray powder diffractometry, infrared spectroscopy and thermal analysis. Unlike pure La₂O₃, complete amorphization of the mixture takes place after 3-h milling. A lanthanum orthosilicate is formed in an amorphous state as a precursor of La₂Si₂O₇. Subsequent thermal treatment of the milled samples leads to the crystallization of pure A- or G-La₂Si₂O₇, depending on the temperature.