Effects of Co and Ni addition on reactive diffusion between Sn–3.5Ag solder and Cu during soldering and annealing

The reactive diffusion between Sn–Ag solders and Cu was experimentally examined during soldering and isothermal annealing. Three sorts of solders with compositions of Sn–3.5Ag, Sn–3.5Ag–0.1Ni and Sn–3.5Ag–0.1Co were used for the experiment. Each solder was soldered on a Cu plate at 523 K (250 °C) for 1–60 s in a pure nitrogen gas, and then the solder/Cu diffusion couple was isothermally annealed at 423 K (150 °C) for 168–1008 h. Due to soldering, only Cu₆Sn₅ is formed at the interface in each diffusion couple. On the other hand, Cu₃Sn is produced between Cu₆Sn₅ and Cu owing to the isothermal annealing. The composition of Cu₆Sn₅ is (Cu_0.8Ni_0.2)₆Sn₅ and (Cu_0.93Ni_0.07)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Ni)/Cu diffusion couple, and it is (Cu_0.9Co_0.1)₆Sn₅ and (Cu_0.99Co_0.01)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Co)/Cu diffusion couple. Different rate-controlling processes were suggested for the (Sn–3.5Ag)/Cu, (Sn–3.5Ag–0.1Ni)/Cu and (Sn–3.5Ag–0.1Co)/Cu diffusion couples. Finally, thermodynamic models were herein adopted to explore influences of the additives on the thermodynamic interaction of the component elements and the driving force for the growth of intermetallics.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

First investigations on twin-rolled Zr59Cu20Al10Ni8Ti3 bulk amorphous alloy by mechanical spectroscopy

Zr₅₉Cu₂₀Al₁₀Ni₈Ti₃ is one among compositions of ZrCu-based alloys giving bulk amorphous material by cooling from the melt. Twin-roll casting enabling samples suitable for our inverted torsion pendulum has been processed in strips of about 0.60 mm thick.

Low temperature IF measurements have been conducted on a specimen from room temperature to −120 °C at different heating and cooling rates. IF spectra exhibit peaks at around −40 °C (cooling) and −10 °C (heating) which are sensitive to heating rates and to the number of cycle (heating and cooling). DSC measurements have also been performed to help interpret the phenomena linked to the IF peaks.     

Alkoxide route to La0.5Sr0.5CoO3 epitaxial thin films on SrTiO3

An all alkoxide based sol–gel route was investigated for preparation of epitaxial La_0.5Sr_0.5CoO₃ (LSCO) films on 100 SrTiO₃ (STO) substrates. Films with 20–30 to 80–100 nm thickness were prepared by spin-coating 0.2–0.6 M (metal) solutions on the STO substrates and heat treatment to 800 °C at 2 °C min^− 1, 30 min, in air. The films were epitaxial with a cube-on-cube alignment and the LSCO cell was strained to match the STO substrate of 3.905 Å closely; a and b = 3.894 Å and 3.897 Å for the 20–30 and 80–100 nm films, respectively. The c-axis was compressed to 3.789 Å and 3.782 Å for the 20–30 and 80–100 nm films, respectively, which resulted in an almost unchanged cell volume as compared to polycrystalline film and nano-phase powders prepared in the same way. The SEM study showed mainly very smooth, featureless surfaces, but also some defects. A film prepared in the same way on an -Al₂O₃ substrate was dense and polycrystalline with crystallite sizes in the range 10–50 nm and gave cubic cell dimensions of a_c = 3.825 Å. The conductivity of the ca 30–40 nm thick polycrystalline film was 1.7 mΩcm, while the epitaxial 80–100 nm film had a conductivity of around 1.9 mΩcm.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Epitaxy of atomically flat CaF2 films on Si(1 1 1) substrates

The growth of CaF₂ films with a thickness of approximately 3–4 nm on well-oriented Si(1 1 1) substrates by molecular beam epitaxy at temperatures between 410 and 560 °C were investigated by ex vacuo atomic force microscopy. Layer-by-layer growth producing atomically flat CaF₂ surfaces has been observed in a very narrow growth temperature window between approximately 430 and 470 °C. Perfect triangular shaped islands of one CaF₂ layer height are found on the surface with all corners aligned with the Si directions, indicating a pure B-stacking of the CaF₂ film. Surprisingly, also the substrate steps have been overgrown without visible defects. Below 410 °C, two different island orientations revealed a mixture of A- and B-stacking areas in the films. Above 520 °C non-wetting of the CaF interface layer leads to epitaxial films with a rough surface morphology.     

Compressive fracture of Zr55Al10Ni5Cu30 bulk amorphous alloy at high temperatures

The fracture behavior of the Zr₅₅Al₁₀Ni₅Cu₃₀ bulk amorphous alloy under uniaxial compression at high temperatures has been investigated. At room temperature, the fracture occurred along the maximum shear plane which declined by 45° to the direction of the applied load, and a crack with serrated edge appeared on the ridge of the veins at the fracture surface for the Zr₅₅Al₁₀Ni₅Cu₃₀ bulk amorphous alloy. At high temperatures, the compressive fracture surface of the Zr₅₅Al₁₀Ni₅Cu₃₀ bulk amorphous alloy became much rougher than that at room temperature and steps appeared on the fracture surface. With increasing temperature, a different pattern from the vein-like morphology appeared on the fracture surface, which is very similar to the lava-flow. This type of fracture pattern is most likely due to the adiabatic heating created by plastic flow.     

Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

Synthesis, phase transformation and dielectric properties of sol–gel derived Bi2Ti2O7 ceramics

Sol–gel derived Bi₂Ti₂O₇ ceramic powders have been prepared from methoxyethoxides of bismuth and titanium (molar ratio of Ti/Bi = 1.23 and water/alkoxides = 1.31). The Bi₂Ti₂O₇ phase was stable at a low temperature (700 °C), but it then transformed into mixed phases of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ at 850–1150 °C. The single phase of Bi₂Ti₂O₇ reoccurred at 1200 °C. Dielectric properties and ferroelectric behavior of samples sintered at 1150 and 1200 °C were examined. Under frequency of 1 MHz, samples sintered at 1150 and 1200 °C had a dielectric constant of 101.3 and 104.2, and a loss tangent of 0.0193 and 0.0145, respectively. Only the sample sintered at 1150 °C showed ferroelectric behavior, where remanent polarization is 3.77 μC cm⁻² and coercive field is 24 kV cm⁻¹. Thus, the Bi₂Ti₂O₇ did not exhibit ferroelectricity, but the mixed phase of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ did.     

Thermomechanical processing and transport current density of Ag-sheathed (Tl,Cr)Sr2(Ca0.9,Pr0.1)Cu2O7 superconductor tapes

Powders with nominal composition (Tl,Cr_0.15)Sr₂(Ca_0.9,Pr_0.1)Cu₂O₇ (Tl-1212) and T_c90 K were used to fabricate Ag-sheathed superconducting tapes employing the powder-in-tube (PIT) method. The tapes were subjected to intermediate mechanical rolling or pressing. Conditions that enhance the transport critical current density (J_c) of the tapes were investigated. Optimum annealing temperature and period together with uniaxial pressing are necessary to increase J_c of the Tl-1212/Ag tapes. Annealing at 910 °C for 0.5–1 h enhanced the 1212 phase formation and improved intergranular connectivity between grains, as well as to provide healing for the fractured structure caused by deformation process. A relatively longer annealing time at higher temperature gave rise to secondary phases and resulted in the decrease of J_c. Mechanical uniaxial pressing greatly densified the tapes core and thus led to closer contact between grains. At liquid nitrogen temperature and zero field, J_c of the pressed tapes annealed at 910 °C for 1 h is 3060±127 A cm⁻². The initial drastic drop of J_c in low fields (<0.06 T) indicates the performance of the tapes is limited by weak links. No significant anisotropic transport properties were observed in applied magnetic field. This is due to the absence of texturing in the tapes as the grains are randomly oriented revealed through SEM micrographs.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Deposition and dielectric properties of CaCu3Ti4O12 thin films on Pt/Ti/SiO2/Si substrates using pulsed-laser deposition

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates using pulsed-laser deposition technique. The crystalline structure and the surface morphology of the CCTO thin films were greatly affected by the substrate temperature and oxygen pressure. Thin films with a (2 2 0) preferential orientation were obtained at the substrate temperature above 700 °C and oxygen pressure above 13.3 Pa. The 480-nm thin films deposited under 720 °C and 26.6 Pa have a fairly high dielectric constant of near 2000 at 10 kHz and room temperature. The values of the dielectric constant and loss and their temperature-dependence under different frequency are comparable with those obtained in the epitaxial CCTO films grown on oxide substrates.     

Impedance spectroscopy study of RuO2/SrTiO3 thin film capacitors prepared by radio-frequency magnetron sputtering

Thin film capacitors of SrTiO₃ with RuO₂ top and bottom electrodes on Si substrates were prepared by radio-frequency magnetron sputtering at substrate temperatures 500 and 700 °C and at various oxygen partial pressures. The thickness of the dielectric layer was varied between 200 and 900 nm. The impedance spectra of these samples could be interpreted with an equivalent circuit comprising a resistance and two RC-parallel elements in series. The dielectric permittivity _r of the bulk grains, as extracted from the high-frequency semicircle in the Cole–Cole plot, was in the range 300–600. High oxygen contents lead to high values of _r but also increase the grain boundary resistance.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Electrochromic properties of nanocrystalline MoO3 thin films

Electrochromic MoO₃ thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO₃ thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO₄/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO₃ thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.     

Changes in the real structure and magnetoresistance of Co90Fe10/Cu and Co90Fe10/Cu85Ag10Au5 multilayers after annealing

Annealing of the (1.1 nm Co₉₀Fe₁₀/2.2 nm Cu)×20 and (1.1 nm Co₉₀Fe₁₀/2.2 nm Cu₈₅Ag₁₀Au₅)×20 multilayers at 235 °C improved their magnetoresistance as compared to the virgin samples. Annealing at higher temperatures resulted in degradation of the magnetoresistance effect. This observation raised the motivation of a detailed structural study using small-angle X-ray scattering, wide-angle X-ray diffraction, electron diffraction and transmission electron microscopy with the aim to link the structural changes in the system to the changes in the magnetoresistance. The structure studies have shown that the maximum of the magnetoresistance observed after annealing at 235 °C is related to the separation of Co₉₀Fe₁₀ and Cu, which are partly intermixed at interfaces after the deposition process. The decay of the GMR effect at higher annealing temperatures is caused by an increase of the interface roughness, which led in the Co₉₀Fe₁₀/Cu multilayers to occurrence of non-continuous interfaces and to short-circuiting of magnetic layers. In the Cu₈₅Ag₁₀Au₅ multilayers, the combination of small-angle X-ray scattering and wide-angle X-ray diffraction has shown that Cu₈₅Ag₁₀Au₅ did not form an alloy with the nominal composition: Only a part of Au and Ag was dissolved in the copper structure; the remainder of Ag and Au formed precipitates.     

Effect of PWVA/Sb2O3 complex inhibitor on the corrosion behavior of carbon steel in 55%LiBr solution

The inhibition performance of PWVA/Sb₂O₃ complex inhibitor on carbon steel was studied in 55%LiBr + 0.07 mol L⁻¹ LiOH solution. Results indicated that the complex inhibitor decreased both anodic and cathodic polarization current density and widened the passive potential region of carbon steel in test solution and can be classified as mixed inhibitor. The complex inhibitor exhibited excellent inhibition performance on carbon steel when the concentrations of PWVA and Sb₂O₃ were 300 and 200 mg L⁻¹, respectively. With the solution temperature increasing from 145 to 240 °C, the corrosion rates of carbon steel increased from 4.71 to 120.66 μm y⁻¹. In solution containing the complex inhibitor, the relationship between relative coverage ratio of inhibitor on carbon steel surface and inhibition efficiency at 145 °C was obtained as the equation μ = 0.94η, it was a direct proportion. This result proved that the complex inhibitor inhibited the corrosion of carbon steel by geometric blocking effect. When solution temperature was 160 °C, the adsorption Gibbs free energy of PWVA and Sb₂O₃ on carbon steel were −49.59 and −44.29 kJ mol⁻¹, respectively. It indicated that the adsorption processes of PWVA and Sb₂O₃ on carbon steel surface were spontaneous processes. As a strong oxidant, PWVA facilitated the compact passive film comprising of FeO, Fe₂O₃ and Fe₃O₄ forming on the surface and itself was reduced to heteropoly blue. Sb₂O₃ adsorbed on carbon steel surface formed an adsorption film. PWVA and Sb₂O₃ behaved synergistic effect. The corrosion resistance performance of carbon steel in 55%LiBr + 0.07 mol L⁻¹ LiOH solution was improved by PWVA/Sb₂O₃ complex inhibitor.     

Cracking behavior of oxide scale formed on Ti3SiC2-based ceramic

The cyclic oxidation and acoustic emission (AE) tests were carried out for studying cracking behavior of oxide scales formed on Ti₃SiC₂-based ceramic at 1100 °C. A duplex oxide scale with an outer layer of pure TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed. The oxide scale did not spall from substrate during the cyclic oxidation at 1100 °C for 360 times. However, a great number of micro-cracks penetrating whole inner oxide layer were detected. AE test showed that the oxide scale did not crack during the isothermal oxidation at 1100 °C for 1 h, however, the scale cracked during the cooling stage. Comparing the growth rate and thickness between the oxide layers formed during the isothermal oxidation and cyclic oxidation, respectively, indicated that cracks in the inner oxide layer served as paths mainly for outward diffusion of titanium and for inward diffusion of oxygen, resulting in increased growth rate of the outer oxide layer. Because of entire and compact TiO₂ consisted of outer oxide layer, and low thermal stress resulting from small mismatch of thermal expansion coefficients between the oxides and the substrate, Ti₃SiC₂ exhibited excellent cyclic oxidation resistance at 1100 °C for 360 cycles.     

Influencing factors on the pyroelectric properties of Pb(Zr,Ti)O3 thin film for uncooled infrared detector

Zr-rich PZT thin films were synthesized by metallorganic decomposition and their dielectric and pyroelectric properties were investigated with different ratios of zirconium/titanium and poling condition. All the films became effectively (1 1 1) textured and well crystallized at the annealing temperature of 700 °C. With increasing Zr content, coercive field increased and voltage dependent capacitance curve appeared asymmetrical, indicating the presence of antiferroelectric phase, PbZrO₃, in film composition. The pyroelectric coefficient in the practically applicable temperature ranges of 20–60 °C was found to be maximum for the thin film with 0.85 mol of zirconium in PZT. Further increase in zirconium content led to severe deterioration in pyroelectric properties. The values of pyroelectric coefficient and figures of merit were greatly influenced by poling direction and temperature. The result was explained in terms of electric phase and state of polarization in film.