Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

The effect of stress on the dielectric constants of Bi4Ti3O12 films

Both experiment and theory have shown that the stress has a notable impact on the polarization of Nd-doped Bi₄Ti₃O₁₂ films. In this paper, thermodynamic theory is used to study the effect of stress on the dielectric constants of Bi₄Ti₃O₁₂ films at room temperature with a two-dimensional model. Results indicate that the change of the dielectric constant for a-phase induced by the lattice distortion is far greater than that for c-phase. Considering the domain reorientation, the external tensile stress may lead to an obvious decrease in the effective dielectric constant of Bi₄Ti₃O₁₂ films.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Anisotropic grain growth of Bi4Ti3O12 in molten salt fluxes

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were obtained by the molten salt synthesis method in NaCl-KCl and Na₂SO₄-K₂SO₄ fluxes, using an amorphous Bi₄Ti₃O₁₂ precursor and a mechanically mixed Bi₂O₃-TiO₂ mixture as the starting materials. It was found that the synthesizing temperature, salt species and starting materials could significantly affect the crystallization habit and morphology of Bi₄Ti₃O₁₂ platelets. Under the same processing conditions (i.e. in Na₂SO₄-K₂SO₄ flux at 1000 °C), the Bi₄Ti₃O₁₂ platelets synthesized from the Bi₂O₃-TiO₂ mixture generally showed a smaller particle size than those synthesized using the amorphous Bi₄Ti₃O₁₂ precursor. The Bi₄Ti₃O₁₂ platelets prepared in the chloride flux were faceted along either (0 0 1) or (1 1 2) planes, while those prepared in the sulfate flux were solely (0 0 1) faceted. The former system also had smaller particle size than the latter. Furthermore, the salt content and the addition of plate-like Bi₄Ti₃O₁₂ seeds in the amorphous Bi₄Ti₃O₁₂ precursor showed a strong influence on the particle size of the synthesized Bi₄Ti₃O₁₂ platelets. The particle size of Bi₄Ti₃O₁₂ platelets prepared in the sulfate flux decreased as the mole ratio of the sulfate salts to Bi₄Ti₃O₁₂ was increased from 7.9 to 23.7. And the addition of 10 wt.% plate-like Bi₄Ti₃O₁₂ seeds into the amorphous Bi₄Ti₃O₁₂ precursor led to a significant increase in the particle size of the resulting Bi₄Ti₃O₁₂ platelets.     

Optical characterization of BaSm2Ti4O12 thin films by spectroscopic ellipsometry

We performed spectroscopic ellipsometric measurement to characterize BaSm₂Ti₄O₁₂ (BST) thin films grown on Pt/Ti/SiO₂/c-Si substrate by rf magnetron sputtering. The six BST films were prepared at various deposition temperatures and thermal annealing times. The resulting refractive indices and extinction coefficients of the BST films show only slight change by the deposition temperature but a significant change after thermal annealing, implying the importance of the post annealing process. The increase of the refractive index can be understood by the higher density of the BST films caused by the crystallization after annealing process.     

Variations of microstructures and electrical properties of Bi4Ti3O12/SrTiO3/(La0.5, Sr0.5)CoO3/MgO epitaxial thin films by annealing

Epitaxial thin films of a heterostructure with Bi₄Ti₃O₁₂(BIT)/SrTiO₃(ST) were successfully grown with a bottom electrode consisting of La_0.5Sr_0.5CoO₃(LSCO) on MgO(001) substrates using pulsed laser deposition. The grown BIT and ST (001) planes were parallel to the growth surface with the orientation relationship of BIT <110>//ST <010>. In the as-deposited film, the BIT (001) plane appeared to expand to relieve a lattice mismatch with the ST (001) plane. However, annealing for 20-40 min induced the BIT (001) plane to contract horizontally with its c-axis expanding, which was associated with a local perturbation in the layer stacking of the BIT structure. This structural distortion was reduced in the film annealed for 1 h, with restoration of the periodicity of the layer stacking. Correspondingly, the dielectric constant of the as-deposited film was increased from 292 to 411 by annealing for 1 h. In parallel, the film was paraelectric but became more ferroelectric, with the remanent polarization and the coercive field changing from 0.1 μC/cm² and 14 kV/cm to 1.7 μC/cm² and 69 kV/cm, respectively.     

Elastic modulus and hardness of CaTiO3, CaCu3Ti4O12 and CaTiO3/CaCu3Ti4O12 mixture

Three ceramic systems, CaTiO₃ (CTO), CaCu₃Ti₄O₁₂ (CCTO) and intermediate nonstoichiometric CaTiO₃/CaCu₃Ti₄O₁₂ mixtures (CTO.CCTO), were investigated and characterized. The ceramics were sintered at 1100 °C for 180 min. The surface morphology and structures were investigated by XRD and SEM. Elastic modulus and hardness of the surfaces were studied by instrumented indentation. It was observed that CCTO presented the higher mechanical properties (E = 256 GPa, hardness = 10.6 GPa), while CTO/CCTO mixture showed intermediate properties between CTO and CCTO.     

Ferroelectric Bi3.25La0.75Ti3O12 thin films on a conductive Sr4Ru2O9 electrode obtained by pulsed laser deposition

Strontium ruthenate and Bi_3.25La_0.75Ti₃O₁₂ (BLT) layers were grown on Si(100) substrate using pulsed laser deposition technique. Starting from a Sr₂RuO₄ target, we obtained single phase films composed of Sr₄Ru₂O₉; on these strontium ruthenate electrodes, textured and non-textured BLT were grown at 700 °C. Structural characterizations of these double layers were done by X-ray diffraction, scanning electron microscopy, normal and high-resolution transmission electron microscopy. The Van der Pauw's resistivity measurements indicate that Sr₄Ru₂O₉ can be used as a back electrode. The temperature dependence of the resistivity at low temperatures is , which corresponds to a variable-range hopping mechanism.     

Effect of yttrium doping on the dielectric properties of CaCu3Ti4O12 thin film produced by chemical solution deposition

Pure and yttrium substituted CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0, 0.02, 0.1) thin films were prepared on boron doped silica substrate employing chemical solution deposition, spin coating and rapid thermal annealing. The phase and microstructure of the sintered films were examined using X-ray diffraction and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using electrochemical impedance spectroscopy. Highly ordered polycrystalline CCTO thin film with bimodal grain size distribution was achieved at a sintering temperature of 800 °C. Yttrium doping was found to have beneficial effects on the dielectric properties of CCTO thin film. Dielectric parameters obtained for a CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0.02) film at 1 KHz were k ∼ 2700 and tan δ ∼ 0.07.     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.     

Synthesis of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.     

Topochemical synthesis of plate-like Na0.5Bi0.5TiO3 templates from Bi4Ti3O12

Plate-like templates for the development of grain oriented microstructures are required for lead-free piezoelectric ceramics with directionality of properties. Plate-like Na_0.5Bi_0.5TiO₃ templates with perovskite structure were synthesized by the Topochemical Microcrystal Conversion (TMC) method from bismuth layer-structured ferroelectric compound Bi₄Ti₃O₁₂. The TMC-derived NBT templates, with diameters of 5-15 µm and an average thickness of 0.7 µm, maintained the morphology of Bi₄Ti₃O₁₂ precursors, showing a high degree of preferred pseudocubic < 001> orientation. The Na_0.5Bi_0.5TiO₃ particles prepared could serve as good templates for the preparation of grain oriented lead-free NBT-based piezoelectric ceramics.     

Dependence of Zr content on electrical properties of Bi3.15Nd0.85Ti3-xZrxO12 thin films synthesized by chemical solution deposition (CSD)

The Bi_3.15Nd_0.85Ti_3-xZr_xO₁₂ (BNTZ) thin films with Zr content (x = 0, 0.05, 0. 1, 0.15, and 0.2) were prepared on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition (CSD) technique. The crystal structures of BNTZ films were analyzed by X-ray diffraction (XRD). The effects of Zr contents on the ferroelectric, dielectric properties, and leakage current of BNTZ films were thoroughly investigated. The XRD results demonstrated that all the films possessed a single phase bismuth-layered structure and exhibited the highly preferred (117) orientation. Among these films, the film with Zr content x = 0.1 held the maximum remanent polarization (2P_r) of 50.21 μC/cm² and a low coercive field (2E_c) of 210 kV/cm.     

第一性原理对CaTiO3和CaCu3Ti4O12的对比研究

通过Ca替换CaCu_3Ti_4O_(12)晶胞中的所有Cu,建立了包含TiO6八面体扭转的CaTiO3;通过Cu替换CaTiO32×2×2超胞中3/4的Ca,建立了不包含CuO_4正方形的CaCu_3Ti_4O_(12)。采用Materials Studio软件的CASTEP模块,对比了上述晶体和标准晶体成键状况、能带结构、态密度及介电函数,分析了TiO6八面体扭转和CuO_4正方形的影响,发现了Cu-O键或CuO_4正方形对CaCu_3Ti_4O_(12)光频介电常数的关键性作用。研究结果提供了通过内禀机制优化CaCu_3Ti_4O_(12)材料介电性能的新途径。     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Size effects of polycrystalline lanthanum modified Bi4Ti3O12 thin films

The film thickness dependence on the ferroelectric properties of lanthanum modified bismuth titanate Bi_3.25La_0.75Ti₃O₁₂ was investigated. Films with thicknesses ranging from 230 to 404 nm were grown on platinum-coated silicon substrates by the polymeric precursor method. The internal strain is strongly influenced by the film thickness. The morphology of the film changes as the number of layers increases indicating a thickness dependent grain size. The leakage current, remanent polarization and drive voltage were also affected by the film thickness.     

Spectroscopic properties of red Bi4Ge3O12 by vertical Bridgman method

Red Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by vertical Bridgman (VB) method. The structure of this crystal was determined by XRD. The absorption and emission spectra of the red BGO in visible and near infrared region (NIR) were measured at room temperature. The emission intensity of the red BGO is weaker than that of ordinary BGO at about 500 nm. Interestingly, the red BGO shows a significant emission band centered at about 1495 nm. The red BGO faded and its properties recovered after ultraviolet (UV) irradiation or annealing.     

Enhancement of fatigue endurance and retention characteristic in Bi3.25Eu0.75Ti3O12 thin films

The effects of moderate annealing temperature (600–800 °C) on the microstructure, fatigue endurance, retention characteristic, and remnant polarization (2P_r) of Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films prepared by metal-organic decomposition (MOD) were studied in detail. 2P_r (66 µC/cm² under 300 kV/cm), fatigue endurance (3% loss of 2P_r after 1.2 × 10¹⁰ switching cycles), and retention characteristic (no significant polarization loss after 1.8 × 10⁵s) for BET thin film annealed at 700 °C are better than those for thin films annealed at other temperature. The mechanisms concerning the dependence of microstructure and ferroelectric properties on the annealing temperature were discussed.     

Dielectric properties of sol-gel derived Ta2O5 thin films

The dielectric constant and the dielectric loss of tantalum pentoxide (Ta₂O₅) thin films, produced by sol-gel spin-coated process on Corning glass substrates, have been investigated in the frequency range of 20-10⁵ Hz and the temperature range of 183-403 K, using ohmic Al electrodes. The frequency and temperature dependence of relaxation time has also been determined. The capacitance and loss factor were found to decrease with increasing frequency and increase with increasing temperature. The activation energy values were evaluated and a good agreement between the activation energy values obtained from capacitance and dielectric loss factor measurements were observed.