Origin of improved tunability and loss in N2 annealed barium strontium titanate films

Barium strontium titanate (BSTO) thin films were deposited on Pt(111) by high throughput evaporative physical vapor deposition and then annealed at 650 °C for 30 min under N2 atmosphere. Using advanced transmission electron microscopy, energy-dispersive x-ray spectroscopy and electron energy-loss spectroscopy, we directly show that not only does N substitute for O in the BSTO lattice but that it also compensates for Ti3+ ions, suppressing conductivity, thereby reducing dielectric loss and enhancing dielectric tunability. However, this effect is negated near the film edge where we speculate that exposed Pt acts as a reservoir of adsorbed/absorbed O and alters the local N2 concentration during annealing

Microstructure Evolution of In Situ Pulsed-Laser Crystallized Pb(Zr0.52Ti0.48)O3 Thin Films

Integration of lead zirconate titanate (PZT) films with temperature-sensitive substrates (CMOS, polymers) would benefit from growth at substrate temperatures below 400°C. In this work, in situ pulsed-laser annealing [Rajashekhar et al. (2013) Appl. Phys. Lett., 103 [3] 032908] was used to grow crystalline lead zirconate titanate (PbZr0.52Ti0.48O3) thin films at a substrate temperature of ~370°C on PbZr0.30Ti0.70O3-buffered platinized silicon substrates. Transmission electron microscopy analysis indicated that the films were well crystallized into columnar grains, but with pores segregated at the grain boundaries. Lateral densification of the grain columns was significantly improved by reducing the partial pressure of oxygen from 120 to 50 mTorr, presumably due to enhanced adatom mobility at the surface accompanying increased bombardment. It was found that varying the fractional annealing duration with respect to the deposition duration produced little effect on lateral grain growth. However, increasing the fractional annealing duration led to shift of 111 PZT X-ray diffraction peaks to higher 2θ values, suggesting residual in-plane tensile stresses in the films. Thermal simulations were used to understand the annealing process. Evolution of the film microstructure is described in terms of transient heating from the pulsed laser determining the nucleation events, while the energy of the arriving species dictates grain growth/coarsening

Local stabilisation of polar order at charged antiphase boundaries in antiferroelectric (Bi_0.85Nd_0.15)(Ti_0.1Fe_0.9)O₃

Observation of an unusual, negatively-charged antiphase boundary in (Bi<sub>0.85</sub>Nd<sub>0.15</sub>)(Ti<sub>0.1</sub>Fe<sub>0.9</sub>)O<sub>3</sub> is reported. Aberration corrected scanning transmission electron microscopy is used to establish the full three dimensional structure of this boundary including O-ion positions to ~ ± 10 pm. The charged antiphase boundary stabilises tetragonally distorted regions with a strong polar ordering to either side of the boundary, with a characteristic length scale determined by the excess charge trapped at the boundary. Far away from the boundary the crystal relaxes into the well-known Nd-stabilised antiferroelectric phase

Characterizing oxygen atoms in perovskite and pyrochlore oxides using ADF-STEM at a resolution of a few tens of picometers

We present an aberration corrected scanning transmission electron microscopy (ac-STEM) analysis of perovskite (LaFeO3) and pyrochlore (Yb2Ti2O7 and Pr2Zr2O7) oxides and demonstrate that both the shape and contrast of visible atomic columns in annular dark-field (ADF) images are sensitive to the presence of nearby atoms of low atomic number (e.g. oxygen). We show that point defects (e.g. oxygen vacancies), which are invisible – or difficult to observe due to limited sensitivity – in x-ray and neutron diffraction measurements, are the origin of the complex magnetic ground state of pyrochlore oxides. In addition, we present a method by which light atoms can be resolved in the quantitative ADF-STEM images. Using this method, we resolved oxygen atoms in perovskite and pyrochlore oxides and propose this method to be suitable for other materials containing both light and heavy elements

Multi-material additive manufacture and microwave-assisted sintering of a metal/ceramic metamaterial antenna structure

Multi-material metal/ceramic 3D structures comprising of metallic silver and ultra-low sintering temperature silver molybdenum oxide ceramics, have been additively manufactured and hybrid densified using microwave-assisted sintering for the first time. Optimum densification conditions at 440 °C / 1 h, resulted in relative permittivity, εr = 10.99 ± 0.04, dielectric losses, tanδ = 0.005 ± 0.001 and microwave quality factor, Q × f = 2597 ± 540 GHz. Applying 2 kW microwave energy at 2.45 GHz for 60 min, was proven sufficient, to densify the metallic Ag infilling electrodes, without causing any macroscopic defects. A fully functional multi-layered antenna structure with a metamaterial artificial magnetic conductor was designed, dual-printed and densified, to showcase the potential of combining multi-material additive manufacturing with microwave-assisted sintering

Multi-material additive manufacturing of low sintering temperature Bi2Mo2O9 ceramics with Ag floating electrodes by selective laser burnout

Additive manufacturing (AM) of co-fired low temperature ceramics offers a unique route for fabrication of novel 3D radio frequency (RF) and microwave communication components, embedded electronics and sensors. This paper describes the first-ever direct 3D printing of low temperature co-fired ceramics/floating electrode 3D structures. Slurry-based AM and selective laser burnout (SLB) were used to fabricate bulk dielectric, Bi2Mo2O9 (BMO, sintering temperature = 620–650°C, εr = 38) with silver (Ag) internal floating electrodes. A printable BMO slurry was developed and the SLB optimised to improve edge definition and burn out the binder without damaging the ceramic. The SLB increased the green strength needed for shape retention, produced crack-free parts and prevented Ag leaching into the ceramic during co-firing. The green parts were sintered after SLB in a conventional furnace at 645°C for 4 h and achieved 94.5% density, compressive strength of 4097 MPa, a relative permittivity (εr) of 33.8 and a loss tangent (tan δ) of 0.0004 (8 GHz) for BMO. The feasibility of using SLB followed by a post-printing sintering step to create BMO/Ag 3D structures was thus demonstrated

High electromechanical response in the non morphotropic phase boundary piezoelectric system PbTiO3-Bi(Zr1/2Ni1/2)O-3

There is a general perception that a large piezoelectric response in ferroelectric solid solutions requires a morphotropic/polymorphic phase boundary (MPB/PPB), i.e., a composition driven interferroelectric instability. This correlation has received theoretical support from models which emphasize field driven polarization rotation and/or interferroelectric transformations. Here, we show that the ferroelectric system ( 1 − x ) PbTi O 3 − ( x ) Bi ( Zr 1 / 2 Ni 1 / 2 ) O 3 (PT-BNZ), which shows d 33 ( ∼ 400 p C / N ) comparable to the conventional MPB/PPB systems, does not belong to this category. In the unpoled state the compositions of PT-BNZ showing large d 33 exhibit a coexistence of tetragonal and cubiclike (CL) phases on the global length scale. A careful examination of the domain strucures and global structures (both in the unpoled and poled states) revealed that the CL phase has no symptom of average rhombohedral distortion even on the local scale. The CL phase is rather a manifestation of tetragonal regions of short coherence length. Poling increases the coherence length irreversibly which manifests as poling induced CL → P 4 m m transformation on the global scale. PT-BNZ is therefore qualitatively different from the conventional MPB piezoelectrics. In the absence of the composition and temperature driven interferroelectric instability in this system, polarization rotation and interferroelectric transformation are no longer plausible mechanisms to explain the large electromechanical response. The large piezoelectricity is rather associated with the increased structural-polar heterogeneity due to domain miniaturization without the system undergoing a symmetry change. Our study proves that attainment of large piezoelectricity does not necessarily require interferroelectric instability (and hence morphotropic/polymorphic phase boundary) as a criterion

Local structure, pseudosymmetry, and phase transitions in Na1/2Bi1/2TiO3-K1/2Bi1/2TiO3 ceramics

The structural behavior of ceramic solid solutions (1 - x)Na1/2Bi1/2TiO3-xK(1/2)Bi(1/2)TiO(3) (NBT-KBT) was studied using high-resolution powder diffraction and transmission electron microscopy. A temperature-independent morphotropic phase boundary (MPB) separating NBT-like pseudorhombohedral (R) and KBT-like pseudotetragonal (T) phases was observed at x approximate to 0.2. For x 0.2 exhibit a tetragonal-like distortion; however, complex splitting of reflections in XRD patterns suggests that the actual symmetry is lower than tetragonal. For 0.2 0.5 the structure becomes untilted. In-phase tilting evolves above the ferroelectric transition and occurs around a nonpolar (a or b) axis of the average T structure. The onset of polar order has no significant effect on the coherence length of in-phase tilting, which suggests only weak coupling between the two phenomena. The average symmetry of the T phase is determined by the effective symmetry (Imm2) of assemblages of coherent in-phase tilted nanodomains. Near the MPB, the coexistence of extended R-and T-like regions is observed, but lattice distortions within each phase are small, yielding narrow peaks with a pseudocubic appearance in XRD. The temperature of the FE phase transition exhibits a minimum at the MPB. The structured diffuse scattering observed in electron diffraction patterns for all the compositions suggests that polar order in NBT-KBT solid solutions is modulated away from the average displacements refined using powder diffraction data.open13

Microstructure evaluation of titanate based layered perovskites: Constrained vs. free sintering

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