Epitaxial stabilization of (110)-layered perovskites of the RE2Ti2O7 (RE=La, Nd, Sm, Gd) family

Thin films of RE₂Ti₂O₇ (RE=La, Nd, Sm, Gd) were deposited on single crystal SrTiO₃ (110) substrates at 900 °C using pulsed laser deposition. X-ray diffraction (XRD) results showed sharp (00k) peaks (in θ-2θ scans) with narrow rocking curves (ω-scan peak widths of 0.4-0.9°), indicating that all compositions adopted the (110)-layered perovskite structure. While this is the stable structure for RE=La and Nd, it is metastable for RE=Sm and Gd. The metastable compounds are formed directly through epitaxial stabilization at these high temperatures and are shown to be isostructural to monoclinic La₂Ti₂O₇. The a, b, and c lattice parameters decreased monotonically with decreasing size of the RE cation, while the monoclinic angle remained fairly constant. The epitaxial relationship between the (110)-layered RE₂Ti₂O₇ films and the SrTiO₃(110) substrate was found by XRD and transmission electron microscopy to be . The single-phase, metastable, epitaxial, 100 nm thick films maintained the layered perovskite structure even after annealing at 900 °C for two hours in 200 Torr of oxygen.     

Growth of HfO2 films using an alternate reaction of HfCl4 and O2 under atmospheric pressure

HfO₂ films were deposited onto a Si(1 0 0) substrate using an alternate reaction of HfCl₄ and O₂ under atmospheric pressure. Self-limiting growth of the HfO₂ was achieved in the range of the growth temperature above 873 K. The X-ray diffraction of the HfO₂ films showed a typical diffraction pattern assigned to the monoclinic polycrystalline phase. Residual chloride concentration in HfO₂ films were not higher than 0.1 at%. When the growth temperature was 973 K, the HfSiO_x is formed in HfO₂ film. This gives effective permittivity value of 9.6 for the HfO₂ film grown at 573 K.     

Control of retention and fatigue-free characteristics in CaBi4Ti4O15 thin films prepared by chemical method

Ferroelectric CaBi₄Ti₄O₁₅ (CBTi144) thin films were deposited on Pt/Ti/SiO₂/Si substrates by the polymeric precursor method. The films present a single phase of layered-structured perovskite with polar axis orientation after annealing at 700 °C for 2 h in static air and oxygen atmosphere. The a/b-axis orientation of the ferroelectric film is considered to be associated with the preferred orientation of the Pt bottom electrode. It is noted that the films annealed in static air showed good polarization fatigue characteristics at least up to 10¹⁰ bipolar pulse cycles and excellent retention properties up to 10⁴ s. On the other hand, oxygen atmosphere seems to be crucial in the decrease of both, fatigue and retention characteristics of the capacitors. Independently of the applied electric field, the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s.     

Microstructure and ferroelectric properties of r.f. magnetron sputtering derived PZT thin films deposited on interlayer (PbO/TiO2)

Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO₂/Si and interlayer/Pt/Ti/SiO₂/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb_1.1Zr_0.53Ti_0.47O₃ target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO₂) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (_r=475.97, tanδ=0.0591, P_r=23 μC/cm²). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.     

A many-body theory of the Ti M2,3-VV Auger-photoelectron coincidence spectroscopy (APECS) spectrum of TiO2(1 1 0)

We calculated the Ti M_2,3-VV Auger-photoelectron coincidence spectroscopy spectrum of TiO₂(1 1 0) by a many-body theory. The spectral main line is governed by the DOS of the two O 2p holes living longer than the Ti ∣cd²L²〉 → ∣L²〉 super Coster-Kronig (sCK) decay. The two O 2p holes are created by the charge transfer core-hole screening at the Ti atomic site. Here c and L are the Ti 3p hole and the ligand O 2p hole, respectively. Analysis of the spectrum shows that the two (or three) CT O 2p holes in the π bonding states are localized, whereas those in the σ bonding states are delocalized. The three localized CT O 2p (π) holes in ∣cd³L³〉 in Ti M_2,3 main line (or satellite) of TiO₂(1 1 0) live longer than the Ti ∣cd³L³〉 → ∣d¹L³〉 sCK decay so that the Coulomb repulsion from the surrounding Ti ions gives the O⁺ ion desorption from the surface.     

Synthesis and characterization of monodisperse spherical SiO2@RE2O3 (RE=rare earth elements) and SiO2@Gd2O3:Ln (Ln=Eu, Tb, Dy, Sm, Er, Ho) particles with core-shell structure

Spherical SiO₂ particles have been coated with rare earth oxide layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO₂@RE₂O₃ (RE=rare earth elements) and SiO₂@Gd₂O₃:Ln³⁺ (Ln=Eu, Tb, Dy, Sm, Er, Ho) particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence spectra as well as lifetimes were used to characterize the resulting SiO₂@RE₂O₃ (RE=rare earth elements) and SiO₂@Gd₂O₃:Ln³⁺ (Eu³⁺, Tb³⁺, Dy³⁺, Sm³⁺, Er³⁺, Ho³⁺) samples. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 380 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (40 nm for two deposition cycles). Under the excitation of ultraviolet, the Ln³⁺ ion mainly shows its characteristic emissions in the core-shell particles from Gd₂O₃:Ln³⁺ (Eu³⁺, Tb³⁺, Sm³⁺, Dy³⁺, Er³⁺, Ho³⁺) shells.     

Ternary rare-earth titanium antimonides: Phase equilibria in the RE-Ti-Sb (RE=La, Er) systems and crystal structures of RE2Ti7Sb12 (RE=La, Ce, Pr, Nd) and RETi3(SnxSb1-x)4 (RE=Nd, Sm)

Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 °C. In the La-Ti-Sb system, the previously known compound La₃TiSb₅ was confirmed and the new compound La₂Ti₇Sb₁₂ (own type, Cmmm, Z=2, a=10.5446(10) Å, b=20.768(2) Å, and c=4.4344(4) Å) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La₂Ti₇Sb₁₂ consists of a complex arrangement of TiSb₆ octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi₃(Sn_xSb_1−x)₄ for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) Å, b=10.0846(7) Å, and c=24.2260(16) Å for NdTi₃(Sn_0.1Sb_0.9)₄; a=5.7590(4) Å, b=10.0686(6) Å, and c=24.1167(14) Å for SmTi₃(Sn_0.1Sb_0.9)₄). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets.     

A comparative study of the magnetic properties and phase separation behavior of the rare earth cobaltates, Ln0.5Sr0.5CoO3 (Ln=rare earth)

A comparative study of the magnetic properties of a few members of the Ln_0.5Sr_0.5CoO₃ family with different radii of the A-site cations, 〈r_A〉, in the range 1.19-1.40 Å has been carried out. The apparent T_c (where the magnetization undergoes an abrupt increase) decreases markedly with 〈r_A〉 as well as the size-disorder arising from the mismatch in the size of the A-site cations. The value of the magnetization at low temperatures decreases markedly with decrease in 〈r_A〉 or increase in size-disorder, suggesting that the relative proportion of the ferromagnetic (FM) species decreases relative to that of the paramagnetic (PM) species. Such a variation of the FM/PM ratio with composition and temperature is evidenced from the Mössbauer spectra of La_0.5Sr_0.5CoO₃ as well. The variation of the FM/PM ratio with 〈r_A〉 and size-disorder, as well as a local-probe study using ⁵⁹Co Nuclear magnetic resonance spectroscopy suggest that electronic phase separation is an inherent feature of the Ln_0.5Sr_0.5CoO₃ type cobaltates, with the nature of the different magnetic species in the phase-separated system varying with 〈r_A〉 and size disorder.     

Preparation and photoluminescence properties of RE:Na3La9O3(BO3)8 (RE=Er, Yb) crystals

Using Na₂CO₃-H₃BO₃-NaF as fluxes, transparent RE:Na₃La₉O₃(BO₃)₈ (abbr. RE:NLBO, RE=Er, Yb) crystals have been grown by the top seed solution growth (TSSG) method. The X-ray powder diffraction analysis shows that the RE:NLBO crystals have the same structure with NLBO. The element contents were determined by molar to be 0.64% Er³⁺ in Er:NLBO, 2.70% Yb³⁺ in Yb:NLBO, respectively. The polarized absorption spectra of RE:NLBO have been measured at room temperature and show that both Er:NLBO and Yb:NLBO have a strong absorption bands near 980 nm with wide FWHM (Full Wave at Half Maximum) (21 nm for Er:NLBO and 25 nm for Yb:NLBO). Fluorescence spectra have been recorded. Yb:NLBO has the emission peaks at 985 nm, 1028 nm and 1079 nm and the emission peak of Er:NLBO is at 1536 nm. Spectral parameters have been calculated by the Judd-Ofelt theory for Er:NLBO and the reciprocity method for Yb:NLBO, respectively. The calculated values show that Er:NLBO is a candidate of 1.55 μm laser crystals and Yb:NLBO is a candidate for self-frequency doubling crystal.     

Structure and physical properties of rare-earth zinc antimonides REZn1-xSb2 (RE=La, Ce, Pr, Nd, Sm, Gd, Tb)

The ternary rare-earth zinc antimonides REZn_1-xSb₂ (RE=La, Ce, Pr, Nd, Sm, Gd, Tb) were prepared by heating at 1050 °C followed by annealing at 600 °C. For all members, single-crystal X-ray diffraction studies indicated that the Zn deficiency is essentially fixed, corresponding to the formula REZn_0.6Sb₂, with no appreciable homogeneity range. These compounds adopt the HfCuSi₂-type structure (Pearson symbol tP8, space group P4/nmm, Z=2). Single-crystal electrical resistivity measurements confirmed the occurrence of an abrupt resistivity decrease near 4 K for RE=Ce, and a less pronounced one for RE=La, Pr, and Gd. Except for the ferromagnetic Ce (T_c=2.5 K) and antiferromagnetic Tb (T_N=10 K) members, all remaining compounds exhibit no long-range magnetic ordering down to 2 K, instead showing temperature-independent (RE=La), van Vleck (RE=Sm), or Curie-Weiss paramagnetism (RE=Pr, Nd, Gd).     

Synthesis of zirconium titanate with an ordered M-fergusonite (beta) structure

We report a new zirconium titanate compound (Zr,Ti)O₂ with 27.5-35 mol% titania (TiO₂) formed from the oxides at 35-38 kbar, 1400-1500 °C. Crystal structure investigations at atmospheric conditions with powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed a monoclinic structure related to that of M-fergusonite (beta). Unit-cell dimensions (from 27.5 to 35 mol% TiO₂): a=7.267(20)-7.340(2) Å, b=10.435(3)-10.429(1) Å, c=5.023(11)-5.040(1) Å, β=136.45(12)-137.55(1)°, V=262.44(92)-260.40(12) Å³, Z=4. Rietveld refinement (R_F=1.55) of a sample with 32.8 mol% TiO₂ indicates that site A is 8-fold coordinated, mostly occupied by Zr, while site B has 6-fold average coordination, occupied by Ti and Zr. Site B is at least partly ordered, as indicated by superstructure reflections 0 0 1 and −2 0 1 detected with TEM, reducing the space group from C2/c to C2. Pronounced streaking of selected diffraction spots is linked to the boundaries of lamellar domains in twin orientation, with twin planes either (200) or (20−2). Adjacent lamellae differ slightly in composition, causing subtle asymmetry of the twin diffraction patterns.     

Rare earth metal rich magnesium compounds RE4NiMg (RE=Y, Pr-Nd, Sm, Gd-Tm, Lu)—Synthesis, structure, and hydrogenation behavior

The rare earth metal rich compounds RE₄NiMg (RE=Y, Pr-Nd, Sm, Gd-Tm, Lu) were synthesized from the elements in sealed tantalum tubes in an induction furnace. All compounds were investigated by X-ray diffraction on powders and single crystals: Gd₄RhIn type, space group F4¯3m, Z=16, a=1367.6(2) pm for Y₄NiMg, a=1403.7(3) pm for Pr₄NiMg, a=1400.7(1) pm for Nd₄NiMg, a=1386.5(2) pm for Sm₄NiMg, a=1376.1(2) pm for Gd₄NiMg, a=1362.1(1) pm for Tb₄NiMg, a=1355.1(2) pm for Dy₄NiMg, a=1355.2(1) pm for Ho₄NiMg, a=1354.3(2) pm for Er₄NiMg, a=1342.9(3) pm for Tm₄NiMg, and a=1336.7(3) pm for Lu₄NiMg. The nickel atoms have trigonal prismatic rare earth coordination. These NiRE₆ prisms are condensed via common edges to a three-dimensional network which leaves voids for Mg₄ tetrahedra and the RE1 atoms which show only weak coordination to the nickel atoms. The single crystal data indicate two kinds of solid solutions. The RE1 positions reveal small RE1/Mg mixing and some compounds also show Ni/Mg mixing within the Mg₄ tetrahedra. Y₄NiMg and Gd₄NiMg have been tested for hydrogenation. These compounds absorb up to eleven hydrogen atoms per formula unit under a hydrogen pressure of 1 MPa at room temperature. The structure of the metal atoms is maintained with only an increase of the lattice parameters (ΔV/V≈22%) if the absorption is done at T<363 K as at higher temperature a decomposition into REH₂-REH₃ hydrides occurred. Moreover, the hydrogenation affects drastically the magnetic properties of these intermetallics. For instance, Gd₄NiMg exhibits an antiferromagnetic behavior below T_N=92 K whereas its hydride Gd₄NiMgH₁₁ is paramagnetic down to 1.8 K.     

Ternary silicides M2Cr4Si5 (M=Ti, Zr, Hf): filled variants of the Ta4SiTe4 structure type

The isostructural ternary silicides M₂Cr₄Si₅ (M=Ti, Zr, Hf) were prepared by arc-melting of the elemental components. The single-crystal structure of Zr₂Cr₄Si₅ was determined by X-ray diffraction (Pearson symbol oI44, orthorhombic, space group Ibam, Z=4, a=7.6354(12) Å, b=16.125(3) Å, c=5.0008(8) Å). Zr₂Cr₄Si₅ adopts the Nb₂Cr₄Si₅-type structure, an ordered variant of the V₆Si₅-type structure. It consists of square antiprisms that have Zr and Cr atoms at the corners and Si atoms at the centers; they share opposite faces to form one-dimensional chains _∞¹[Zr_4/2Cr_4/2Si] surrounded by additional Si atoms and extending along the c direction. In a new interpretation of the structure, additional Cr atoms occupy interstitial octahedral sites between these chains, clarifying the relation between this structure and that of Ta₄SiTe₄. The formation of short Si-Si bonds in Zr₂Cr₄Si₅ is contrasted with the absence of Te-Te bonds in Ta₄SiTe₄. The compounds M₂Cr₄Si₅ (M=Ti, Zr, Hf) exhibit metallic behavior and essentially temperature-independent paramagnetism. Bonding interactions were analyzed by band structure calculations, which confirm the importance of Si-Si bonding in these metal-rich compounds.     

Structure and magnetic properties of rare-earth chromium germanides RECrxGe2 (RE=Sm, Gd-Er)

The ternary rare-earth chromium germanides RECr_xGe₂ (RE=Sm, Gd-Er) have been obtained by reactions of the elements, either in the presence of tin or indium flux, or through arc-melting followed by annealing at 800 °C. The homogeneity range is limited to 0.25?x?0.50 for DyCr_xGe₂. Single-crystal and powder X-ray diffraction studies on the RECr_0.3Ge₂ members revealed that they adopt the CeNiSi₂-type structure (space group Cmcm, Z=4, a=4.1939(5)-4.016(2) Å, b=16.291(2)-15.6579(6) Å, c=4.0598(5)-3.9876(2) Å in the progression for RE=Sm to Er), which can be considered to be built up by stuffing transition-metal atoms into the square pyramidal sites of a “REGe₂” host with the ZrSi₂-type structure. (The existence of YbCr_0.3Ge₂ is also implicated.) Only the average structure was determined here, because unusually short Cr-Ge distances imply the development of a superstructure involving distortions of the square Ge net. Magnetic measurements on RECr_0.3Ge₂ (RE=Gd-Er) indicated that antiferromagnetic ordering sets in below T_N (ranging from 3 to 17 K), with additional transitions observed at lower temperatures for the Tb and Dy members.     

Surface chemistry and optical property of TiO2 thin films treated by low-pressure plasma

The low temperature RF plasma treatment was used to control the surface chemistry and optical property of TiO₂ thin films deposited by RF magnetron sputtering with a very good uniformity at 300 °C substrate heating temperature. The XRD pattern indicates the crystalline structure of the film could be associated to amorphous structure of TiO₂ in thin film. The plasma treatment of TiO₂ film can increase the proportion of Ti³⁺ in Ti2p and decrease in carbon atoms as alcohol/ether group in C1s at the surface. The optical transmittance of the film was enhanced by 50% after the plasma treatment. The surface structure and morphology remain the same for untreated and low-pressure plasma-treated films. Therefore, increase in the optical transmission could be due to change in surface chemistry and surface cleaning by plasma treatment.     

Argon matrix effect on the geometry and infrared spectrum of H2CMH2 (M = Ti, Zr, Hf): A theoretical study

Within the framework of polarizable continuum model with integral equation formalism (IEF-PCM), an argon matrix effect on the geometry and infrared frequencies of the agostic H₂CMH₂ (M = Ti, Zr, Hf) methylidene complexes was investigated at B3LYP level of theory with the 6-311++G(3df,3pd) basis set for C, H, and Ti atoms and Stuttgart/Dresden ECPs MWB28 and MWB60 for the Zr and Hf atoms. At the B3LYP/IEF-PCM level of theory, H₂CTiH₂ was optimized to an energy minimum having a pyramidal structure. The calculated dipole moment of this structure is 3.06 D. The B3LYP/IEF-PCM simulations gave the three complexes’ agostic angle ∠HCM (°), distance r(H?M) (Å), and CM bond length r(CM) (Å) as follows: ∠HCTi = 87.4, r(H?Ti) = 2.079, r(CTi) = 1.803; ∠HCZr = 89.3, r(H?Zr) = 2.243, r(CZr) = 1.956; ∠HCHf = 94.7, r(H?Hf) = 2.343, r(CHf) = 1.972. As a comparison, the B3LYP simulations gave the values as follows: ∠HCTi = 91.5, r(H?Ti) = 2.150, r(CTi) = 1.811; ∠HCZr = 92.9, r(H?Zr) = 2.299, r(CZr) = 1.955; ∠HCHf = 95.6, r(H?Hf) = 2.352, r(CHf) = 1.967. As far as the MH₂ symmetric and asymmetric stretching and CH₂ wagging frequencies are concerned, the IEF-PCM calculated values are in better agreement with the experimental argon matrix ones than those calculated based on a gas phase model.     

Structure and magnetic properties of RE2Cu2Cd

The ternary intermetallic compounds RE₂Cu₂Cd (RE=Y, Sm, Gd-Tm, Lu) were synthesized by induction-melting of the elements in sealed tantalum tubes. The samples were characterized by X-ray powder diffraction. The structure of Gd₂Cu₂Cd was refined from single crystal X-ray diffractometer data: Mo₂FeB₂ type, space group P4/mbm, a=756.2(3), c=380.2(3) pm, wR2=0.0455, 321 F² values, 12 variables. The structures are 1:1 intergrowth variants of slightly distorted CsCl and AlB₂ related slabs of compositions RECd and RECu₂. The copper and cadmium atoms build up two-dimensional [Cu₂Cd] networks (257 pm Cu-Cu and 301 pm Cu-Cd in Gd₂Cu₂Cd) which are bonded to the rare earth atoms via short RE-Cu contacts (290 pm in Gd₂Cu₂Cd). Temperature dependent susceptibility measurements of RE₂Cu₂Cd with RE=Gd, Tb, Dy, and Tm show experimental magnetic moments which are close to the free RE³⁺ ion values. The four compounds show ferromagnetic ordering at T_C=116.7(2), 86.2(3), 48.4(1), and 14.5(1) K, respectively, as confirmed by heat capacity measurements. Dy₂Cu₂Cd shows a spin reorientation at T_N=16.9(1) K.     

The (100) orientation evolution and temperature-dependent electrical properties of Bi(Zn1/2Ti1/2)O3–PbTiO3 ferroelectric films

The 0.2Bi(Zn_1/2Ti_1/2)O₃–0.8PbTiO₃ (0.2BZT–0.8PT) ferroelectric thin film was successfully fabricated on Pt(111)/Ti/SiO₂/Si substrates by a sol–gel method. The result indicates that the film exhibits the (100) preferred orientation and has a relatively dense and uniform microstructure with a thickness of ~230 nm. The formation mechanism of the oriented films was ascribed to the growth of the (100) oriented PbO layer at ~450 °C during a layer-by-layer crystallization process. Temperature-dependent electrical properties of the 0.2BZT–0.8PT films were investigated, showing that the film has a potential for high temperature applications.     

Effects of Mg doping on the properties of highly transparent conductive and near infrared reflective Zn1−xMgxO:Ga films

Highly transparent conductive and near infrared (IR) reflective Gallium-doped ZnMgO (Zn_1−xMg_xO:Ga) films with Mg content from 0 to 10 at% were deposited on glass substrate by DC reactive magnetron sputtering. X-ray diffraction shows all the ZnMgO:Ga films are polycrystalline and have wurtzite structure with a preferential c-axis orientation. Hall measurements indicate that the resistivity of these films obviously increases with the Mg concentration increasing. The average transmittance of Zn_1−xMg_xO:Ga films is over 90% in the visible range. All the Zn_1−xMg_xO:Ga films have low transmittance and high reflectance in the IR region.     

Preparation, characterization, magnetic susceptibility (Eu, Gd and Sm) and XPS studies of Ln2ZrTiO7 (Ln=La, Eu, Dy and Gd)

Bulk and nanosized pyrochlore materials Ln₂ZrTiO₇ (Ln=La, Eu, Dy, Gd and Sm) have been prepared by the sol-gel method. All the samples were characterized by powder X-ray diffraction, Raman and X-ray photoelectron spectroscopy. Magnetic susceptibility (χ) measurements of Gd₂ZrTiO₇, Sm₂ZrTiO₇ and Eu₂ZrTiO₇ were carried out by vibrating sample magnetometer in the temperature range 2-320 K. The variation of χ⁻¹ (or χ) with temperature of Gd₂ZrTiO₇, Sm₂ZrTiO₇ and Eu₂ZrTiO₇ follows the Curie law, intermediate formula and the Curie-Weiss law, respectively. From the linear portion of χT vs. T⁻¹ plot of Eu₂ZrTiO₇ from 2 to 15 K, the classical nearest neighbor exchange (J^cl) and dipolar interactions (D_nn) are obtained. The XPS of Ln₂ZrTiO₇ (Ln=La, Eu, Dy and Gd) gave characteristic peaks for Ln, Ti, Zr and O. The satellite peaks are observed only for 3d La of La₂ZrTiO₇.