Computer modelling of point defects in ABO3 perovskites and MgO

We present results for basic intrinsic defects: F-type electron centers (O vacancy which trapped one or two electrons) and hole polarons bound to Mg or K vacancy in ionic MgO and partly covalent KNbO₃ perovskite, respectively. We demonstrate that a considerable covalency of the perovskite chemical bonding makes the F-type centers therein much more similar to defects in partly-covalent quartz-type oxides rather than the conventional F centers in alkali halides and ionic MgO. Both one-site (atomic) and two-site (molecular) polarons are expected to coexist in KNbO₃ characterized by close absorption energies. Our calculations confirm existence of the self-trapped electron polarons in KNbO₃, KTaO₃, BaTiO₃, and PbTiO₃ crystals. The self-trapped electron is mostly localized on B-type ion due to a combination of breathing and Jahn–Teller modes of nearest six oxygen ion displacements. The relevant lattice relaxation energies are typically 0.2–0.3 eV, whereas the optical absorption energies 0.7–0.8 eV, respectively. According to our calculations, the absorption energy of a bound electron polaron in KNbO₃ by 0.1 eV exceeds that for the self-trapped electron polaron and equals 0.88 eV.     

Quantum chemical modelling of polarons and perovskite solid solutions

Following our previous study [J. Phys.: Condens. Matter 10 (1998) 6271] of a single Nb impurity and Nb clusters in KTaO₃, we present results of the calculations for a series of perovskite KNb_xTa_1−xO₃ (KTN) solid solutions (x=0, 0.125, 0.25, 0.75, 1). The quantum chemical method of the intermediate neglect of the differential overlap (INDO) combined with the large unit cell (LUC) periodic model is used. According to the INDO calculations, Nb impurity becomes off-center in KTaO₃ already at the lowest studied concentrations (x=0.125), in a good agreement with XAFS measurements. We compare our results with previous ab initio FP-LMTO calculations. Quantum chemical calculations confirm the existence of self-trapped electrons in KNbO₃; the corresponding lattice relaxation energy is 0.21 eV. We estimate the optical absorption energy to be 0.78 eV. An electron in the ground state occupies a t_2g orbital of the Nb⁴⁺ ion. Its orbital degeneracy is lifted by a combination of the breathing and Jahn–Teller (JT) modes when four nearest equatorial O atoms are displaced by 1.4% a_o outwards and two oxygens shift 1% inwards along the z axis.     

Influence of substrate on the pulsed laser deposition growth and microwave behaviour of KTa0.6Nb0.4O3 potassium tantalate niobate ferroelectric thin films

Thin films of potassium tantalate niobate KTa_0.6Nb_0.4O₃ (KTN) were grown by pulsed laser deposition on five different substrates suitable for microwave devices: (100)MgO, (100)LaAlO₃, (1–102)sapphire (R-plane), (0001)sapphire (C-plane) and alumina. The high volatility of potassium at the film growth temperature required the addition of an excess of potassium to the ablation target. For optimized deposition conditions, Rutherford backscattering showed that the KTN films had a 1: 1 atomic ratio for K:(Nb + Ta). As grown KTN thin films were single-phase, without any particular orientation on sintered alumina, whereas an epitaxial growth with the (100) orientation was achieved on (100)MgO and (100)LaAlO₃ with a mosaicity Δω_(100)KTN close to 0.7°–1.5° and  0.4°–0.9°, respectively, attesting a high crystalline quality. In contrast, growth of KTN on R-plane sapphire results in a texture with the (100) orientation and the presence of the (110) orientation as a secondary one. The room temperature measurements carried out on Au interdigited capacitors patterned on KTN coated (100) LaAlO₃ and sapphire led at 1 GHz to an agility ΔC / C  4.6% and  7.2%, respectively, for a moderate applied field of 15 kV cm^− 1. Stubs patterned on the same systems led to an agility ΔF_r / F_r of  2.2% and 4.2%, respectively, for F_r = 7 GHz and the same applied field.     

Influence of disorder on electronic structure and magnetic properties in Fe-rich Fe–Si alloys

We present the results of ab initio calculations of the spin-polarized electronic structure of disordered bcc and fcc Fe_1 − xSi_x alloys from dilute solid solutions of Si on iron up to FeSi intermetallic compound composition (x=0.01..0.5) and ordered intermetallic phases FeSi in B20 structure and Fe₃Si in DO₃ structure. The self-consistent calculations were performed with the coherent potential approximation within the Korringa–Kohn–Rostoker method (KKR–CPA) for disordered case and by using the tight-binding linear muffin–tin orbital (TB LMTO) method for intermetallic compounds. In the last case the supercell approach has been utilized in order to take into account the structural defects for this ordered phase. In particular, we have performed a series of calculations in the BCC Fe_1 − xSi_x alloys with x=0.01, 0.015, 0.1, 0.15, 0.25.     

A comparative study of the atomic and electronic structure of F centers in ferroelectric KNbO3: Ab initio and semi-empirical calculations

The linear muffin-tin-orbital method combined with density functional theory (in a local density approximation) and the semi-empirical method of the intermediate neglect of the differential overlap (INDO) based on the Hartree-Fock formalism are used for the supercell study of the F centers (O vacancy with two electrons) in cubic and orthorhombic ferroelectric KNbO₃ crystals. The two electrons are found to be considerably delocalized even in the ground state of the defect. Their wave functions extend over the two Nb atoms closest to the O vacancy and over other nearby atoms. Thus, the F center in KNbO₃ resembles much more electron defects in the partly covalent SiO₂ crystal (the so-called E₁′ center) rather than usual F centers in ionic crystals like MgO and alkali halides. This covalency is confirmed by the analysis of the electronic density distribution. The absorption energies were calculated by means of the INDO method using the ΔSCF scheme after a relaxation of atoms surrounding the F center. For the orthorhombic phase three absoprtion bands are predicted, the first one is close to that observed experimentally under electron irradiaton.     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

A theoretical study on the second-order nonlinear optical susceptibilities of lithium formate monohydrate crystal, HCOOLi·H2O

Ab initio calculations of the first hyperpolarizabilities of (HCOOLi·H₂O)_2n supermolecules, as the building-blocks of lithium formate monohydrate (LFM) crystal with extended system, were performed for the first time. The dependence of the static β_ijk⁰ values on chain length was explored, and the frequency dependence of β_ijk(−2ω;ω,ω) was measured, and the influences of electron correlation and basis set on β_ijk⁰ were evaluated. Finally, we predicted the second-order nonlinear optical coefficients of LFM crystal. The β_ijk⁰ value of (HCOOLi·H₂O)_2n is linearly dependent on the chain length of supermolecule, which is quite unusual for an extended system connected by the O–Li bonds with ionic characters. Although the static component of β_zzz⁰ tensor is the static largest in these three components under study, the absolute value of frequency-dependent β_zyy(−2ω;ω,ω) element, transforming the smallest into the largest, is the most sensitive to frequency. After the fundamental wavelength is smaller than 500 nm, it is found that the β_ijk(−2ω;ω,ω) value is resonantly enhanced to a great extent due to the double frequency lies in the region of resonance. In addition, the β_zxx⁰ value goes from negative to positive with changes of electron correlation and basis set. Obviously, it is very necessary to take into account the effect of electron correlation, if the hyperpolarizability tensor components must be accurately calculated. Moreover, it is also very important whether it is adopted a complete basis set with diffuse and polarization functions. The calculated nonlinear coefficients at high level suggest that the scaled set reported by Robert seem more reasonable.     

Chemical vapour deposition of praseodymium oxide films on silicon: influence of temperature and oxygen pressure

Metal-organic chemical vapour deposition (MOCVD) of various phases in PrO_x system has been studied in relation with deposition temperature (450–750 °C) and oxygen partial pressure (0.027–100 Pa or 0.2–750 mTorr). Depositions were carried out by pulsed liquid injection MOCVD using Pr(thd)₃ (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) precursor dissolved in toluene or monoglyme. By varying deposition temperature and oxygen partial pressure amorphous films or various crystalline PrO_x phases (Pr₂O₃, Pr₇O₁₂, Pr₆O₁₁) and their mixtures can be grown. The pure crystalline Pr₂O₃ phase grows only in a narrow range of partial oxygen pressure and temperature, while high oxygen pressure (40–100 Pa) always leads to the most stable Pr₆O₁₁ phase. The influence of annealing under vacuum at 750 °C on film phase composition was also studied. Near 90% step coverage conformity was achieved for PrO_x films on structured silicon substrates with aspect ratio 1:10. In air degradation of Pr₂O₃ films with transformation to Pr(OH)₃ was observed in contrast to Pr₆O₁₁ films.     

Fracture-resistant ultralloys for space-power applications: Normal-spectral-emissivity and electron-emission studies of tungsten, rhenium, hafnium-carbide alloys at elevated temperatures

A series in this journal on high-temperature properties of “fracture-resistant ultralloys for space-power systems” preceded the present paper: the antecedent publications covered tungsten(W), rhenium(Re) alloys with and without thoria(ThO₂) (W, 23Re; W, 27Re; W, 30Re and W, 30Re, 1ThO₂). This paper reports radiative and thermionic effects of hafnium carbide(HfC) and Re variation in W alloys: normal spectral emissivity(ε_λ) is used in pyrometry to determine the true temperature of a surface. Effective work function (φ_e) is an important consideration in the selection of the electrode materials for high-temperature thermionic energy converters in space-power applications. The _0.535μ, ε_0.65μ and φ_e trends of W, Re, 0.35HfC with 5–20% Re were measured in the range of 1700–2500K. The results indicate that ε_λ decreases with increasing temperatures and Re contents. The presence of HfC produced higher ε_λ values than those of sintered materials with comparable W,Re alloy contents. The results also indicate that φ_e increases with rhenium contents. This can be explained as growth of the potential barrier at the metal, vacuum boundary associated with a volume effect—the decrease in the lattice constant of W.     

Diffusion barrier properties of sputtered TaNx between Cu and Si using TaN as the target

TaN_x films sputtered from a TaN target were used as diffusion barriers between Cu thin films and Si substrates. Material characteristics of TaN_x films and metallurgical reactions of Cu/TaN_x/Si systems annealed in the temperature range 400–900 °C for 60 min were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, cross-sectional transmission electron microscopy, and sheet resistance measurements. We found that the deposition rate decreased with increasing bias. TaN, β-Ta, and Ta₂N phases appeared and/or coexisted in the films at specific biases. A step change in N/Ta ratio was observed whenever a bias was applied to the substrate. After depositing a copper overlayer, we observed that the variation percentage of sheet resistance for Cu (70 nm)/TaN_x (25 nm, x=0.37 and 0.81)/Si systems stayed at a constant value after annealing up to 700 °C for 60 min; however, the sheet resistance increased dramatically after annealing above 700 and 800 °C for Cu/TaN_0.37/Si and Cu/TaN_0.81/Si systems, respectively. At that point, the interface was seriously deteriorated and formation of Cu₃Si was also observed.     

Chemical vapour deposition of molybdenum carbides: aspects of phase stability

Thin films of different molybdenum carbides (δ-MoC_1−x, γ′-MoC_1−x and Mo₂C) have been deposited from a gas mixture of MoCl₅/H₂/C₂H₄ at 800°C by CVD. The H₂ content in the vapour has a strong influence on the phase composition and microstructure. Typically, high H₂ contents lead to the formation of nanocrystalline δ-MoC_1−x films while coarse-grained γ′-MoC_1−x is formed with an H₂-free gas mixture. This phase has previously only been synthesized by carburization of Mo in a CO atmosphere and it has therefore been considered as an oxycarbide phase stabilized by the presence of oxygen in the lattice. Our results, however, show that γ′-MoC_1−x films containing only trace amounts of oxygen can be deposited by CVD. Stability calculations using a FP-LMTO method confirmed that the γ′-MoC_1−x phase is stabilized by oxygen but that the difference in energy between e.g. δ-MoC_0.75 and oxygen-free γ′-MoC_0.75 is small enough to allow the synthesis of the latter phase in the absence of kinetic constraints. Annealing experiments of metastable δ-MoC_1−x and γ′-MoC_1−x films showed two different reaction products suggesting that kinetic effects play an important role in the decomposition of these phases.     

Enhanced piezoelectric properties of potassium niobate single crystals with fine engineered domain configurations

Potassium niobate (KNbO₃) single crystals were grown by a top seed solution growth (TSSG) method. At first, the electric field was applied along [0 0 1]_c (cubic notification system) direction of KNbO₃ crystals to induce the engineered domain configurations into KNbO₃ crystals. Prior to domain engineering, the piezoelectric properties of [0 0 1]_c oriented KNbO₃ single-domain crystals were measured. These measured values were completely consistent with the calculated apparent d₃₁ and d₃₂. Finally, the engineered domain configurations were induced into KNbO₃ crystals. As a result, piezoelectric properties increased with decreasing domain sizes of the engineered domain configuration.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Dielectric and piezoelectric properties of sol–gel derived Ca doped PbTiO3

Synthesis of Ca doped PbTiO₃ powder by a chemically derived sol–gel process is described. Crystallization characteristics of different compositions Pb_1−xCa_xTiO₃ (PCT) with varying calcium (Ca) content in the range x = 0–0.45 has been investigated by DTA/TGA, X-ray diffraction and scanning electron microscopy. The crystallization temperature is found to decrease with increasing calcium content. X-ray diffraction reveals a tetragonal structure for PCT compositions with x ≤ 0.35, and a cubic structure for x = 0.45. Dielectric properties on sintered ceramics prepared with fine sol–gel derived powders have been measured. The dielectric constant is found to increase with increasing Ca content, and the dielectric loss decreases continuously. Sol–gel derived Pb_1−xCa_xTiO₃ ceramics with x = 0.45 after poling exhibit infinite electromechanical anisotropy (k_t/k_p) with a high d₃₃ = 80 pC/N, ′ = 298 and low dielectric loss (tan δ = 0.0041).     

On the formation of radiation-induced defects in fluoroaluminate glasses

The spectra of electron paramagnetic resonance (EPR) of fluoroaluminate glass (FAG-36) based on mineral usovite Ba₂CaMgAlF₁₄ were studied. The paramagnetic centers responsible for EPR signals were induced by ion bombardment of the substrates prepared from this glass. The N⁺, O⁺, Ar⁺ and Pb + ions with energy E = 150 keV were used. The integrated dose D was 2 × 10¹⁶ ions/cm². It is shown by means of isochronal anneal experiments and computer simulation of the EPR spectra that they contain four components: broad Gaussian line (GL) with g = 2.016 and σ oscillating in the range 30–40; two anisotropic spectra with g_z = 2.016, g_y = 2.009; g_x = 2.001 (FA₁) and g_z = 2.045; g_y = 2.010; g_x = 1.98 (FA₂) as well as narrow isotropic line of Lorentzian shape with g = 2.0025 and ΔH = 0.6 mT. The comparison of obtained results with literature data for γ-irradiated fluoride glasses and ion-implanted oxide glasses of different compositions permitted to conclude that GL is due to hole defects typical of fluoride glasses and localized on several anions (fluorines and oxygen(s)); anisotropic FA₁- and FA₂-spectra are attributed to molecular 0₂⁻-ions, and narrow isotropic signal is supposedly assigned to big molecular ions (O₂O⁻, 0₄⁻ , CO⁺, CO⁻) located in voids of damaged implantation layer.     

Measurement of continuous damage parameter

The present paper introduces several measuring methods of continuous damage parameter derived by the classical definition D = 1 − (A_e/A_a): (1) The measuring method on the basis of D = 1 − (E'/ E); (2) The measuring method on the basis of D = 1 − (ε₁/ε₂); (3) The measuring method on the basis of D = −Δρ_o/ρ_o, (4) The measuring method on the basis of D = A_d/A_a, and comments on these measuring methods.