Influence of acceptor doping on ionic conductivity in alkali earth titanate perovskites

The electrical conductivity of the SrTi_1−xFe_xO_3−δ, BaTi_1−xFe_xO_3−δ and SrTi_1−xMn_xO_3−δ systems has been studied in a range of oxygen partial pressures between 10⁻¹⁶ and 0.21 atm at 900 and 1000 °C. The materials exhibit predominantly ionic conductivity in a wide range of intermediate oxygen partial pressures. It has been found that in Fe doped strontium and barium titanates, the dependencies of the ionic conductivity on the acceptor concentration show a local maximum near x=0.2. Taking into account that in the CaTi_1−xFe_xO_3−δ system (x=0−0.5), the concentration dependence of the ionic conductivity also has a maximum near x=0.2, it can be concluded that this is a common phenomenon for Fe doped alkali earth titanates. An assumption has been made that a scheme of defect formation devised earlier for Fe doped calcium titanate is applicable for other alkali earth titanates.     

High-temperature electrical transport in Al-doped calcium and strontium titanates

The electrical conductivity of perovskite-related oxides CaTi_1−xAl_xO_3−δ and SrTi_1−xAl_xO_3−δ (x=0−0.4) were investigated within the temperature range 900 to 1000 °C and the oxygen partial pressure range between 10⁻²⁰ and 0.21 atm using a dc four-point technique. The materials investigated show predominantly p-type electronic conductivity at high, n-type electronic conductivity at low, and ionic conductivity at intermediate oxygen partial pressures. The values of ionic conductivity in CaTi_1−xAl_xO_3−δ were found to be lower than those in CaTi_1−xFe_xO_3−δ. The effect of aluminium concentration on the high-temperature transport properties was examined. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Synthesis and electrical characterisation of different doped magnesium titanates

The synthesis and characterization are reported for the cubic spinel titanate Mg_(2−x)Ni_xTiO₄ (x≤0.25) and Mg_(2−x)Mn_xTiO₄ (x≤1). Single phase samples were observed for Mg_(2−x)Ni_xTiO₄ and with x≤0.4 for Mg_(2−x)Mn_xTiO₄. AC measurements were carried out on four different compositions (x=0.01, 0.03, 0.04 and 0.15) in the Mg_(2−x)Ni_xTiO₄ series and for Mg_1.9Mn_0.1TiO₄. For all these compounds, increasing conductivity with temperature and Arrhenius conductivity dependence are observed, the activation energy is around 0.28 eV for the Ni compounds and is 0.184 eV for Mg_1.9Mn_0.1TiO₄. The DC conductivity was recorded over a range of oxygen partial pressures (10⁻¹⁹ to 1 atm) at 930 °C. The Mg_(2−x)Ni_xTiO₄ compounds show a n-type behaviour whereas the Mg_(2−x)Mn_xTiO₄ show a p-type behaviour at high p(O₂) and n-type at low p(O₂). The stability under reduced conditions was checked and discussed for the different synthesized compounds. Paper presented at the 5th Euroconference onSolid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Study of the oxygen incorporation and diffusion in Sr(Ti0.65Fe0.35)O3 ceramics

For applications in high temperature fast conductometric gas sensors and oxygen membranes, several mixed conductors show promising features. In particular, acceptor-doped strontium titanate (STO) has been widely investigated for an application as a fast conductometric oxygen sensor. By a B-site substitution with 35% iron, the resulting ceramic solid solution SrTi_0.65Fe_0.35O₃ (STF35) exhibits a temperature-independent conductivity, an ideal prerequisite for a gas sensor.In the presented study, the oxygen tracer exchange behavior and the tracer diffusion of dense ceramic STF35 bulks have been investigated in the temperature range between 600 and 900 °C by means of ¹⁸O₂ tracer exchange experiments and subsequent secondary ion mass spectrometry (SIMS), resulting in the determination of k* and D* values, respectively.Furthermore, by coating the samples with a thin alkaline earth metal oxide layer (CaO), a significantly enhanced oxygen surface exchange reaction was observed. These findings are in good agreement with previous results on STO single crystals.     

Structural position and charge state of nickel in SrTiO3

The properties of nickel-doped strontium titanate are studied using X-ray diffraction and XAFS spectroscopy. It is shown that, independently of preparation conditions, the most stable phases in the samples are single-phase SrTi_{1 ? x} Ni _x O₃ solid solution and NiTiO₃ which can coexist. According to the EXAFS data, in the single-phase SrTi_0.97Ni_0.03O₃ sample the nickel atoms substitute the titanium atoms and are on-center ones. In this case, no distortions of the oxygen octahedron which would appear in the presence of oxygen vacancies in the nickel environment were detected. An analysis of the XANES spectra shows that the nickel charge state in NiTiO₃ is 2+, whereas in the SrTi_{1 ? x} Ni _x O₃ solid solution it is close to 4+. It is shown that the strongest light absorption in doped samples is associated with the presence of tetravalent Ni in the SrTi_{1 ? x} Ni _x O₃ solid solution. This doping seems to be the most promising for solar energy converters based on the bulk photovoltaic effect.     

Electrical characterization of highly Titania doped YSZ

The defect fluorite region of the ternary system ZrO₂-Y₂O₃-TiO₂ encompasses compositions which offer both, good electronic and oxygen ion conductivity which enable good catalytic activity for the direct oxidation of methane in a solid oxide fuel cell (SOFC). The electrical properties of compositions Y_xTi_yZr_1−(x+y)O_2−x/2 (with x=0.15, 0.2, 0.25 and y=0.15, 0.18) were characterised in order to find the composition with highest ionic and electronic conductivity. High titanium dopant concentrations (Y) of 15 and 18 atom%, near the solubility limit of Ti⁴⁺ in the fluorite structure, have been introduced to achieve a high electronic conductivity at low oxygen partial pressure. The yttrium content x has been varied between 15 and 25 atom% to find the fluorite composition with the highest ionic conductivity for each titanium level. In the pO₂-range from 0.21 to 10⁻¹³ atm the conductivity is predominantly ionic and constant over that range. The maximum ionic conductivity is 0.01 Scm⁻¹ for the compositions, which contain 15 atom% yttrium. Substantial electronic conductivity is introduced into the system at low oxygen pressures below 10⁻¹³ atm via reduction of Ti⁴⁺ ions to Ti³⁺. The maximum electronic conductivity of 0.2 Scm⁻¹ at 930 °C has been measured for a sample with 18 atom% titanium. The slope of all log(σ) vs. log(pO₂) plots follows a pO ₂ ^−1/4 -dependence. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Quasi-ordered nanostructures on the surface of strontium titanate

The results of the investigation of the surface of strontium titanate single crystals after treatment with high-energy plasma are presented. The surface morphology of the strontium titanate single crystals and the change in its characteristics after plasma treatment have been studied using electron scanning and atomicforce microscopy. A change in the electronic state of a part of the titanium ions and a change in the stoichiometry in the modified near-surface layer have been found by the method of valence shift of X-ray lines. A preliminary analysis has been made of the conditions providing the formation of single- and two-level systems of ordered crystallites with sizes of 10⁻⁷–10⁻¹⁰ m on the surface of single-crystal strontium titanate with impurities of ions of the iron and lanthanum groups.     

Hydrothermally prepared oxide-ion and Mixed Conductors based on CeO2

The structure, thermal expansion coefficients, electrical and electrochemical properties of Ce_1−xM_xO_2−δ (M=Bi, La, Pr, Eu, Tb; x=0–0.30) solid solutions, prepared hydrothermally for the first time, are surveyed. For all cation substitution a solubility limit depending on the cation size was found. The uniformly small particle size (10–50 nm) of the hydrothermally prepared materials allows sintering of the samples into highly dense ceramic pellets at 1300–1400 °C, a significantly lower temperature, compared to that at 1600–1650 °C required for samples prepared by solid state techniques. X-ray absorption near edge spectroscopy (XANES) was used for the identification of Tb³⁺/Tb⁴⁺ or Pr³⁺/Pr⁴⁺ ions. The maximum of total conductivity in all solid solutions was found for x ∼ 0.15–0.25 with electronic contribution to the total conductivity ∼ 50 % for Tb/Pr substitution and close to zero in all other cases. The conductivity becomes more ionic with decreasing Tb/Pr substitution. The thermal expansion coefficients, determined from high-temperature X-ray diffraction data, are 11.7×10⁻⁶ K⁻¹ for CeO₂ and slowly decrease for Tb and increase for all other cases with increasing substitution. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Electrical conductivity of Sr1−xTiO3−δ materialsmaterials

The high temperature conductivity of polycrystalline Sr_1−xTiO_3−δ samples in air was found to be lower than the conductivity of SrTiO₃ samples. However, the dependence of the electrical conductivity on the oxygen partial pressure showed that this trend can be reverted under reducing conditions. Both trends contradict the expected effects of A-site deficiency on the defect chemistry. Differences in average grain sizes give a plausible explanation for these findings. The dependence of the conductivity on the oxygen partial pressure suggests that p-type conductivity is dominant in air, for every sample, and one can thus assume that the number of grain boundaries plays a negative role on this contribution. Electrochemical permeability measurements confirmed that the ionic transport number of strontium titanate in air remains small. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Investigations of electronic minority charge carrier conductivity in La0.9Sr0.1Ga0.8Mg0.2O2.85

The perovskite structured material LaGaO₃ doped with 10 mol-% strontium and 20 mol-% magnesium was prepared by two different wet-chemical synthesis routes. The total conductivity was measured in air and under an oxygen partial pressure of 10⁻²⁰ bar. There was a decrease by 10 % in 4 days when the atmosphere was changed from air to 10⁻²⁰ bar. This process is reversible. Hebb-Wagner measurements resulted in values for the electronic minority charge carrier conductivities in pure oxygen of log σ_h [S/cm]=−4.02 and log σ_e [S/cm]=−15.5 for the holes and electrons, respectively, at 600 °C. In the partial pressure range 10⁻³ bar≤p(O₂)≤1 bar, a slope of +1/4 was observed for d(log (σ_h)) / d(log (p(O₂)) at T=600, 650 and 700 °C. That is in agreement with the assumption of a large number of oxygen vacancies. The diffusion coefficient of the holes was evaluated from the relaxation curves to be 1.1*10⁻⁷ cm²/s at 600 °C. Degradation effects were observed under highly reducing conditions which are attributed to the formation of gallium-platinum alloys and the loss of gallium oxide if O₂ is available in the gas phase. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Effect of Mg doping on the structural and dielectric properties of strontium titanate ceramics

The influence of Mg incorporation into A- and B-sites of the perovskite lattice of SrTiO₃ ceramics on the structural, microstructural and low-frequency dielectric properties is studied in this work. Compounds in the systems Sr_1-xMg_xTiO₃ and SrTi_1-yMg_yO_3- were synthesised by a conventional solid-state method. The solid solubility of Mg is restricted to x<1% for A-site occupancy (Sr_1-xMg_xTiO₃) and to y<15% for B-site occupancy (SrTi_1-yMg_yO_3-). The lattice parameter is found to increase with Mg content for the SrTi_1-yMg_yO_3- system, while it is almost invariant in the Sr_1-xMg_xTiO₃ one. The dependence on the lattice-site occupancy is also verified for the grain growth of ceramics. For SrTi_1-yMg_yO_3- the average grain size markedly decreases with increasing Mg content. For Sr_1-xMg_xTiO₃ the inverse dependence is observed. Contrary to expectations, Mg does not induce ferroelectricity or relaxor-like behaviour in strontium titanate, located in either A- or B-sites of the SrTiO₃ lattice. Moreover, fitting the dielectric behaviour to Barretts law demonstrates that B-site doping drives the system away from the ferroelectric instability. In Mg-doped strontium titanate ceramics the dielectric permittivity and dielectric losses decrease. The results are discussed based on the correlation between cation-site occupancy, charge and chemical stoichiometry in both systems. PACS 61.10.Nz; 68.37.Hk; 68.37.Lp; 77.22.Ch; 77.22.Gm; 77.84.Dy     

Study on structural, thermal, sintering and conductivity of Cu-Co doubly substituted Bi4V2O11

Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi₄V₂O₁₁, has led to the formation of the Bi₄V_1.8Cu_0.2−xCo_xO_10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form, is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10⁻² S·cm⁻¹ at 600 °C.     

Specifics of the Electrical Properties of Composite Solid Oxide Membranes Based on SrTi<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3–δ</Subscript>

The electrical properties of dual-phase fluorite-pervoskite oxide systems based on strontium titanate- ferrite (SrTi_0.5Fe_0.5O_3–δ) are studied. We find that the oxygen ionic and ambipolar conductivities of strontium titanate-ferrite can be considerably improved by introducing the fluorite phase Ce_0.8(Sm_0.8Sr_0.2)_0.2O_2–δ. This is advantageous considering the prospects of applying these types of composite materials in different electrochemical devices, e.g., as membrane materials in electrochemical converters for the production of hydrogen and syngas and anode materials in solid oxide fuel cells.     

Ionic and electronic transport in perovskite-type La(Ga,M)O3−δ (M=Mg, Cr, Fe, Co, Ni, Nb)

Oxygen ion conduction in La_0.9Sr_0.1Ga_1−xM_xO_3−δ (M=Cr, Fe; x=0 – 0.20), LaGa_1−xM_xO_3−δ (M=Co, Ni; x=0.20 – 0.60), LaGa_1−x−yCo_xMg_yO_3−δ (x=0.35 – 0.60; y=0.10 – 0.25) and LaGa_0.85−xMg_0.15(Nb_0.33Mg_0.66)_xO_3−δ (x=0 – 0.20) is reported. At temperatures below 1200 K the ionic conductivity of La(Ga,M)O_3−δ (M=Co, Ni) increases with increasing oxygen nonstoichiometry, but is lower than for La(Ga,Mg)O_3−δ and (La,Sr)GaO_3−δ. Co-doping with Nb and Mg was found to result in decreasing ionic transport in La(Ga,Nb,Mg)O_3−δ due to blocking of oxygen sites by Nb⁵⁺. Small additions of Fe to the B-site of La_0.9Sr_0.1GaO_3−δ increase the ionic conductivity, whereas substitution of Cr for Ga has the opposite effect. Incorporation of transition metal cations into the Ga site leads to a higher p-type electronic conductivity in all studied perovskites. Paper presented at the 6th Euroconference on Solid Sate Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Synthesis and ionic conduction of apatite-type materials

Apatite is a mineral with general formula M₁₀(XO₄)₆Z₂, where M are metallic elements such as Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ln³⁺ etc.; X=P, V, S, Si, Ge, Re, Cr etc; Z=F⁻, Cl⁻, I⁻, OH⁻, O²⁻, S²⁻ etc. Some materials with apatite structure (S.G. P6₃/m) exhibit quite high cationic (Li⁺, H⁺ etc.) and/or anionic (F⁻, Cl⁻ etc.) conduction. Recently, it was reported that some rare earth silicates, e.g., La₁₀(SiO₄)₆O₃, exhibit quite high oxide-ion conductivity. In this paper, we discuss chemical composition, structure, synthetic procedure and ionic conduction of apatite-type materials. Recent improvements are briefly reviewed. High ionic conductivity has been observed for both cation deficient, oxygen stoichiometric La_9.33(SiO₄)₆O₂ and cation stoichiometric, oxygen excess La₁₀(SiO₄)₆O₃ compositions. Grain boundary conductivity is usually low, which tends to dominate the impedance response. The resistance, particularly the grain boundary resistance is also found to depend on pO₂. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Mixed conductive electrode materials for sensors and SOFC

Modified active electrode materials based upon rare earth manganites were developed for different solid electrolyte electrochemical cells. The preparation, structure, thermal expansion, the state of oxygen on the surface, the electronic and ionic conductivity of the perovskites Ln_1−xCa(Sr)_xMn_1−y(Co, Ni)_yO_3−δ with various compositions and electrode kinetics on the manganite electrode/solid electrolyte interfaces were investigated. The value of the bulk conductivity was larger than 150 S/cm (at 1100 K) and increased significantly with increasing contents of Ni or Co. The thermal expansion coefficients of rare earth manganites were close to those of ZrO₂ based solid electrolytes. The expansion coefficients of Co or Ni subsituted lanthanum manganites increase with Co or Ni substitution and are over 12•10⁻⁶K⁻¹. The ionic conductivities were determined using encapsulated zirconia microelectrodes based on a Hebb-Wagner analysis of the currentvoltage curves. The relatively high oxide ion conductivity of 10⁻⁵ S/cm at 900...1000 K was found by Ni or Co doped manganites. Studies of the electrode kinetics using complex impedance spectroscopy show that Co and Ni doped manganites have advantages if used as electrodes as compared with these for noble metals. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994     

Spectra and color centers of strontium titanate crystals

The results of studying the spectral properties of strontium titanate single crystals (grown under different conditions), both pure and activated by iron-group or lanthanide ions, are presented. The data on the main color centers and the formation of systems of ordered crystallites from 10⁻⁷ to 10⁻⁹ m in size on the sample surface after treatment in plasma are obtained by optical and X-ray spectroscopy, cathodoluminescence, electron microscopy, and atomic-force microscopy.     

Electron-stimulated desorption of negative O? ions from the oxidized O/Ru surface

This paper reports on a study of the electron-stimulated desorption of negative oxygen ions from the O/Ru surface, which represents an additional factor responsible for the destruction of the protective oxide layer of the mirrors used in ultraviolet lithography. The cross section of degradation of the O/Ru layer due to the electron-stimulated desorption of the O⁺ and O⁻ ions and the O atoms has been found to be 1.6 × 10⁻¹⁹ cm². A comparison of the dependences of the electron-stimulated desorption yield of O⁺ and O⁻ ions on the incident electron energy E with the ionization cross section of the adsorbate core level σ _O2s (E) has revealed that the ionization of the O 2s level is the main channel of the electron-stimulated desorption of O⁻ ions.     

Investigations on selected gallium and strontium doped lanthanum chromites as electrode materials for HC detection

Perovskite-type mixed oxides with the formula LaCr_1−yGa_yO_3−δ and La_0.95Sr_0.02Cr_1−yGa_yO_3−δ with y=0.1; 0.2; 0.3 were investigated in view of their usability as electrode materials in exhaust gas sensors for hydrocarbon (HC) detection. The electrode materials were characterized regarding their catalytic activity for propylene and propane oxidation and their potentiometric behavior in oxygen containing gaseous mixtures of these combustibles. The potentiometric measurements with propane indicate higher sensitivities of the strontium doped materials than of the materials without strontium. The comparison of these results with those of the catalytic investigations using propane show, that a lower catalytic activity comes along with a higher sensitivity. The electrodes show non-Nernstian behavior. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Structure, morphology and electrochemistry of doped lithium cobalt oxides

The structure, morphology and electrochemical performance of LiCoO₂ powders doped with various trivalent cations such as M³⁺=Ni³⁺, Al³⁺, and B³⁺ have been investigated. X-ray diffraction patterns and FTIR data show that LiCo_1−yNi_yO₂ oxides display a solid solution in the whole range 0≤y≤1, while the solubility limit of LiCo_1−yAl_yO₂ and LiCo_1−yB_yO₂ materials is about y=0.35. Electrochemical features of LiCo_1−yNi_yO₂ cathode materials show remarkable stability in their charge-discharge profiles. Aluminum substitution also stabilizes the two-dimensional framework and induces an increasing average cell potential than for LiCoO₂. The overall capacity of the LiCo_1−yB_yO₂ oxides has been reduced due to the sp metal substitution, however, a more stable charge-discharge cycling characteristic has been observed when electrodes are charged up to 4.4 V as compared to the performances of the native oxides. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.