Domain Structure-Second Harmonic Generation Correlation in Potassium Niobate Thin Films Deposited on a Strontium Titanate Substrate

The experimental measurement of second harmonic generation (SHG) and theoretical correlation of the SHG output to domain microstructure is presented for ferroelectric KNbO₃ (110) thin films on a SrTiO₃ (100) substrate. From X-ray diffraction, four possible domain variants in the film growth plane were determined to be KNbO₃ [1 1 0]∥SrTiO₃ [001], [00 1 ], [010], or [0 1 0] denoted as variants X +, X −, Y +, and Y −, respectively. From theoretical modeling of the SHG output from the film, the ratios of nonlinear coefficients d_o/d₃₂ and d ₂₄/d₀ in the film were determined to be 2.19 ± 0.12 and 0.46 ± 0.26, respectively, in good agreement with the bulk KNbO₃ crystals. The term d₀ is defined as d₁₅+ (d₃₁+ d₃₃)/2 . The SHG can also distinguish between X+ and X– , as well as Y+ and Y– , domains, which was not possible by X-ray diffraction. The ratio of net area fraction (| A ^X+− A ^X−|/| A ^Y+− A ^Y−|) was determined to be 2.76 ± 1.06 in the probe area (2.25π mm²) where A ^x+, A ^x-, A ^Y+, and A ^Y− are the area fractions of domain variants X+, X−, Y+ , and Y− , respectively, in the film growth plane.     

Decomposition of Mullite by Silica Volatilization

Thermal decomposition of mullite into corundum was investigated using a high-temperature X-ray single-crystal camera equipped with a gas-flame furnace and by scanning electron microscopy and electron probe microanalysis (EPMA). When heated to ∼1750°C, mullite decomposed to corundum by the liberation of the SiO₂ component with topotaxial relations of:

• (1) 

  (310)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (2) 

  (130)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (3) 

  (110)_mull∥(001)_cor; [001]_mull∥[110]_cor

Thus, it was considered that, when mullite decomposed into corundum, their oxygen close-packed planes were almost preserved. The SEM photographs showed that the crystals of the developed corundum are prismatic and ∼5 μm wide. The EPMA showed that the phase boundary between mullite and developed corundum is discontinuous.     

Transformation of X-Phase SiAlON to Mullite

The transformation of X-phase SiAlON (a composition of approximately Si₃Al₆O₁₂N₂) to 3/2 mullite (3Al₂O₃·2SiO₂) plus vitreous silica (SiO₂) at temperatures >1200°C has been studied in polycrystalline ceramics via transmission electron microscopy. The transformation of X-phase SiAlON to mullite is observed to be topotactical. Analyses of electron-diffraction patterns and lattice-fringe images reveal the following orientation relationship between X-phase SiAlON (X) and mullite (Mu): (110)_Mu∥ (100)_X and [001]_Mu∥ [010]_X. The observed orientation relationship between mullite and X-phase SiAlON and the close similarities between both structures-especially the occurrence of the same type of octahedral chains-suggest that these types of structural units are preserved during the transformation process. Excess noncrystalline SiO₂ is exsolved between the mullite crystallites and is transported to the sample surface in later transformation stages.     

Crystallographic Domain Structure of an Epitaxial (Pr0.7Ca0.3)MnO3 Thin Film Grown on a SrTiO3 Single Crystal Substrate

We characterized the structure of the crystallographic domain of a (Pr_0.7Ca_0.3)MnO₃ (PCMO ( x =0.3)) thin film epitaxially grown on a (001)SrTiO₃ (STO) single-crystal substrate. We found that the domain structure exhibited an atomically smooth coherent interface with the STO substrate with no misfit dislocations. The crystallographic relationships between the domains and the substrate in their planes were interpreted to be PCMO ( x =0.3)[110][001]//STO[100][010] and PCMO ( x =0.3)[001][1-10]//STO[100][010]. The domain structure of PCMO ( x =0.3)[110][1-10]//STO[100][010] has less possibility of having the larger anisotropic strain energy found in a monoclinically distorted pseudo-cubic perovskite unit cell of PCMO ( x =0.3). This epitaxial growth structure is totally different from the previously reported PCMO ( x =0.5) epitaxial thin-film structure on STO substrate. Our observations suggested that an x value change strongly influences the structure of epitaxial PCMO thin films.     

Optical and X-Ray Single Crystal Studies of the Monoclinic ⇌ Tetragonal Transition in ZrO2

The monoclinic ⇌ tetragonal phase transition in ZrO₂ single crystals was studied at temperature by transmission optical microscopy and X-ray diffraction techniques. A series of timelapse photographs illustrated the relations between the events that occur during the transition. The events themselves were recognized by direct observation using a high-temperature microscope stage and by scrutiny of several high-temperature Laue photographs. During heating the monoclinic phase transforms to the tetragonal by the motion of an interface parallel to the (100) _m plane; simultaneous twinning also occurs behind the advancing interface. The tetragonal phase is usually twinned on the (1 2) _bct or ( 12) _bct plane, and the extent of twinning is influenced by the heating rate. Cooling transforms the untwinned tetragonal form into a twinned monoclinic form with the orientation of the monoclinic twins parallel to the trace of the (001) _m plane when observations are made in the (100) _m plane. Transformation of a twinned tetragonal crystal results in twins on the {110} _m and {001} _m planes. Orientation relations in the ZrO₂ transformation are: (100) _m ‖(110) _bct , [010] _m ‖[001] _bct , and by the virtue of twinning, (100) _m ‖(110) _bct , [001] _m ‖[001] _bct . During cooling the same topotaxial relations are maintained.     

Sequential Precipitation of MgAl2O4 on Mg1-x CaxAl2O4 in Hot-Pressed MgO Single Crystals

In a hot-pressed and deformed MgO single crystal, precipitates of Mg_1-xCa_xAl₂O₄ spinel upon which MgAl₂O₄ spinel subsequently precipitated were observed and analyzed using transmission electron microscopy and scanning electron microscopy. This behavior is related to the respective solubility limits of CaO and Al₂O₃ in MgO at the hot-pressing temperature and may be aided by impurity segregation to the dislocations. The spinel selectively precipitated at the nodes of a dislocation network which was formed during [001] hot-pressing deformation, as a result of the reaction b₃= b₁+ b₂= (1/2) [011] + (1/2)     = [001]. The dislocation is sessile, and the precipitates have a <100>_matrix≨ <100>_spinel coherent relationship.     

Fabrication of Transparent Tellurite Glasses Containing Potassium Niobate Crystals by an Incorporation Method

To fabricate transparent oxide glasses containing ferroelectric KNbO₃ crystals, a new method in which KNbO₃ particles are directly incorporated into TeO₂─K₂O─Nb₂O₅ glasses has been developed. Transparent TeO₂-based glasses containing KNbO₃ crystals with a diameter of ∼ 10 μm have been first successfully fabricated by adjusting temperature and time for incorporation. A small difference in the refractive indexes, n , between TeO₂-based matrix glasses ( n = 2.0) and incorporated KNbO₃ crystals ( n = 2.21) is a significant reason for the transparency. This new method is applicable for the fabrication of new transparent glasses containing other functional materials with high refractive indexes.     

Oriented Structure and Crystallography of Directionally Solidified LaB6—ZrB2 Eutectic

Directional solidification of LaB₆—ZrB₂, by use of an electron beam heating technique, yielded oriented ZrB₂ fibers in a LaB₆ matrix. The average diameter of the ZrB₂ fibers was ∼0.2–1.2 µm, with fiber lengths up to 100 µm. Primary platelike LaB₆ dendrites formed upon the solidification of an ingot with a composition of LaB₆—18 wt% ZrB₂. LaB₆ was the first phase to nucleate when eutectic growth occurred, and ZrB₂ showed nonfaceted growth. For the ingot solidified with planar growth the orientation relations of the phases were as follows: growth direction, [001]_LaB6∥[00.1]_ZrB2; interfacial plane, (11.0)_LaB6∥(11.0)_ZrB2.     

Formation Mechanisms of Platelet Sr3Ti2O7 Crystals Synthesized by the Molten Salt Synthesis Method

The molten salt synthesis (MSS) method is utilized to synthesize the anisotropic platelet Sr₃Ti₂O₇ (S3T2) single-crystal particles. The aim of this study is to identify the essence of platelet Sr₃Ti₂O₇ crystal growth and guide the synthesis of anisotropic platelet SrTiO₃ crystals as well as various technologically important materials. Based on the results of X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy, the formation mechanism of platelet Sr₃Ti₂O₇ crystals conforms to a nucleation–structure rearrangement–dissolution–diffusion in situ epitaxial growth mechanism model. First, SrCO₃ reacts with TiO₂ to form submicrometer SrTiO₃ nuclei. Then, most of the nuclei surrounded by salt ions aggregate and rearrange to form a large SrTiO₃ matrix. The structural rearrangement and the subsequent in situ epitaxial growth processes control the morphology, composition, and size of the final Sr₃Ti₂O₇ crystals. In the synthesis process, the conversion between SrTiO₃ and Sr₃Ti₂O₇ is as follows: and the crystallographic orientation relationship between Sr₃Ti₂O₇ and SrTiO₃ in the interface is (100)_S3T2//{100}_ST, (010)_S3T2//{010}_ST, and (001)_S3T2//{001}_ST.     

Anisotropic Fracture Behavior in Ferroelectric Relaxor PZN–4.5%PT Single Crystals

The anisotropic fracture behavior in unpoled and poled (1− x )Pb(Zn_2/3Nb_1/3)− x PbTiO₃ ( x =0.045) (PZN–4.5%PT) single-crystal relaxor ferroelectrics cut along the crystal planes, [010] and [001], was characterized. The crack tip toughness ( K _tip) determined from Vickers indentations was compared with the R -curve behavior measured using the single-edge V-notch beam (SEVNB) method. Several of the SEVNB fracture experiments resulted in cracks forming and propagating under mixed mode loading ( K _I and K _II) along the [110] crystal plane. Other specimens formed cracks at 0° along the [010] plane. To assess the anisotropic fracture behavior, the local and global critical energy release rates were determined using Stroh's formalism.     

Growth Sequence of Gadolinium-Iron Garnet Crystals in Molten PbO-B2O3, Solutions

Gadolinium-iron garnet crystals grown from low-volatility molten PbO-B₂O₃ solutions exhibit macroscopic dendritic growth patterns indicative of their growth sequence and mechanism. There exists a growth anisotropy preferring the [001] direction from which (100) and (010) axial-plane dendrites radiate. The equilibrium {211} and {110} faces grow from intermediate branch dendrites which are attached to the (100) and (010) dendrites.     

High-Resolution Electron Microscopy of the Silicon Carbide/Aluminum Carbide Interface

The interface of single-crystal SiC and Al brazed at 1273 K is investigated by high-resolution electron microscopy. The orientation relationship of SiC to the Al₄C₃ reaction layer that forms between the SiC and the Al can be expressed as (0001)_SiC∥(0001)_Al4C₃ and [11∼00]_SiC∥[11∼00]_Al4C₃. Furthermore, a very thin (two tetrahedral layers thick) transition phase and misfit dislocations are observed between the SiC and Al₄C₃ lattices. The structure of the transition phase is discussed based on the high-resolution electron microscopy, the stacking of the (Al,Si)C₄ tetrahedral layers, and the charge balance. The same reaction product, with the same orientation relationship, is observed at the interface of a polycrystalline SiC and Al brazed joint.     

Deformation Microstructure in (001) Single Crystal Strontium Titanate by Vickers Indentation

Recent interests on the plastic deformation of strontium titanate (SrTiO₃) are derived from its unusual ductile-to-brittle-to-ductile transition (DBDT). The transition is divided into three regimes (A, B, and C) corresponding to the temperature range of 113–1053 K (−160° to 780°C), 1053 to ∼1503 K (780° to ∼1230°C), and ∼1503–1873 K (∼1230° to 1600°C), discovered by Sigle and colleagues in the MPI-Stuttgart. We report the dislocation substructures in (001) single crystal SrTiO₃ deformed by Vickers indentation at room temperature, studied by scanning and transmission electron microscopy. Dislocation dipoles of screw and edge character are observed and confirmed by inside–outside contrast using ± g -vector by weak-beam dark field imaging. They are formed by edge trapping, jog dragging, and cross slip pinching-off. Similar to dipole breaking off in deformed sapphire (α-Al₂O₃) at 1200°C and γ-TiAl intermetallic at room temperature, the dipoles pinch off at one end, and emit a string of loops at trail. Two sets of slip systems {110}〈     〉 and {100}〈011〉 are activated under both 100 g and 1 kg load. The suggestion is that plastic deformation has reached the stage II work hardening, which is characterized by multiplication of dislocations through cross slip, interactions between dislocations, and operating of multiple slip systems.     

Crystallography of the Tetragonal to Monoclinic Transformation in MgO-Partially-Stabilized Zirconia

The structure of monoclinic ZrO₂ particles dispersed in MgO-partially-stabilized zirconia has been examined systematically using transmission electron microscopy and electron micro-diffraction. In both particles transformed athermally and those transformed under stress, the product of the martensitic tetragonal to monoclinic transformation comprises parallel variants of the monoclinic structure. The monoclinic domains extend either parallel or normal to the original precipitate habit plane and, to within the accuracy of the technique, adjacent pairs are twin related. For particles with domains parallel to the particle habit plane the boundary between variants is (001)_m and the orientation relationship between tetragonal and monoclinic lattices is such that (001)_m‖ (001)_t and [100]_m‖ [100]_t. In particles with transverse domains, the domain boundaries are parallel to (100)_m, and the orientation relationship is given by (100)_m‖ (100)_t and [001]_m‖ [001]_t. In each case the lattice correspondence implied between parent and product lattices is such that the c _m axis is parallel to the C _m axis. The microcracking associated with transformed particles appears closely related to the substructure adopted by the particles and the origin of this microcracking is briefly discussed.     

Microstructure and Dielectric Properties of Textured SrTiO3 Thin Films

We investigate the relationship between microstructure and dielectric properties of textured SrTiO₃ thin films deposited by radio-frequency magnetron sputtering on epitaxial Pt electrodes on sapphire substrates. The microstructures of Pt electrodes and SrTiO₃ films are studied by transmission electron microscopy, atomic force microscopy, and X-ray diffraction. SrTiO₃ films grown on as-deposited and annealed Pt electrodes, respectively, consist of a mixture of (111)- and (110)-oriented grains. Temperature-dependent dielectric measurements show that differences in texture and microstructure are reflected in the Curie–Weiss behavior of the SrTiO₃ films. Phenomenological models that account for the effects of thermal mismatch strain on the dielectric behavior are developed for different film textures. The models predict that at a given temperature, paraelectric (111)-oriented films of SrTiO₃ on tensile substrates will have a higher Curie–Weiss temperature and a greater dielectric constant than (110)-oriented films or bulk SrTiO₃. The experimental dielectric behavior is compared with the predictions from theory, and different contributions, such as interfacial layers, film stress, and microstructure, to the Curie–Weiss behavior are discussed.     

Precipitation Studies in the System WC-ZrC

The solubility of WC in ZrC varied from 25 mol% at 1800°C to 65 mol% at 2550°C. There was no detectable solubility of ZrC in WC in the same temperature range. Tungsten carbide precipitates from supersaturated WC-ZrC solutions as rods. The crystallographical relation between the precipitated phase and the matrix established by electron diffraction techniques is: [100]_wc|[110]_ZrC and [010]_wc|[011]_zrc. The interfacial planes were (001) for WC and (111) for ZrC. The hardness of the solid solution of 55 mol% WC and 45 mol% ZrC increased ∼ 10% after it was annealed at 1900°C.     

Influence of Ionic Charge on Diffusion in the Surface Layer of Magnesia

The diffusion of ⁵⁷Co isotope on the MgO (100) surface was investigated by the edge-source method. The surface diffusion parameter, αD_sδ, where α is the segregation factor, D_s the surface diffusion coefficient, and δ the thickness of the high-diffusivity layer, was determined over the temperature region 750° to 1250°C. An Arrhenius plot shows a break at ∼1100°C. Below this temperature ionic or localized transport predominates and above it nonlocalized transport seems to predominate. The divalent Co ion diffuses faster than the trivalent Cr ion in the surface layer. The apparent activation energies for the localized surface diffusion of ⁵⁷Co and ⁵⁹Cr are 59±12 and 110±12 kj/mol, respectively.     

Study of the elastic properties of glycine phosphite crystals (Gly·h3PO3) by Brillouin scattering

The results concerning the elastic properties of glycinium phosphite (GPI) crystals obtained by Brillouin scattering method are reported. The temperature measurements of the relative change AVN of the phase velocity for acoustic modes propagating in q = [100], q = [010], q = [110] and q = [011] directions have been performed in the temperature range 300 K - 170 K. Obtained results confirm the existence of the ferroelectric phase transition (P2₁/a - P2₁) at 224 K.     

Synthesis of Highly Oriented Lead Zirconate–Lead Titanate Film Using Metallo-organics

Crack-free Pb(Zr,Ti)O₃ (PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO₃ (100), and Pt/Ti/SiO₂/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H₂O─-O₂ gas mixture was found to be effective not only for low-temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single-phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO₂/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO₂/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm², and a coercive field of 54 kV/cm.     

Microstructure/Process Relations in Sol-Gel-Prepared KnbO3 Thin Films on (100) MgO

Epitaxial (110) orthorhombic KNbO₃ thin films were prepared using alkoxide solutions. Single-phase films were produced with stoichiometric sols while slight variations in stoichiometry (52/48 Nb/K or 48/52 Nb/K) created residual second phases. Nucleation and growth of KNbO₃, as a function of process conditions were monitored by observing the KNbO₃ rosettes produced from niobium-rich solutions. Methanolic solutions produced films with the highest rosette density and the highest amount of KNbO₃. Hydrolysis of the sol aided the crystallization of the KNbO₃ phase but also promoted the formation of second phases. Hydrolysis at 0°C reduced second-phase formation.