The Influence of Bi Doping on the In Situ Growth of TlBa2Ca2Cu3O9 High-Tc Films

The in situ process—laser ablation in combination with thermal evaporation of Tl₂O—has turned out to be a preparation method for single-phase and epitaxial TlBa₂Ca₂Cu₃O₉ (1223) thin films with T _c values up to 109 K. It was found by several groups that a partial substitution of Tl by Bi simplifies the phase development of the 1223 compound in the usual two-step process. We have investigated the influence of the Bi doping on the in situ growth. X-ray measurements show that the films consisted mainly of the 1223 compound. In 300-nm thin films there was no evidence of a Bi amount in the crystal structure, but thinner films (80 nm) show a small amount of Bi. We concluded that Bi doping supports the phase development of the 1223 compound only in an early stage of the film growth. The Bi-doped films have higher T _c values up to 114 K, higher j _c values up to 6 × 10⁵ A/cm² (77 K, 0 T), and lower surface resistances of 56 m (77 K, 87 GHz) than the undoped films.     

Film thickness dependence of critical current density for YBa2Cu3O7 films post-annealed at a low oxygen partial pressure

The variation of critical current density at 77 K as a function of film thickness was studied for YBa₂Cu₃O₇ films on (100) LaAlO₃ substrates. Film thicknesses were in the range 0.2–1.6m. The films were deposited by co-evaporation and post-annealed under conditions which have previously resulted in high-quality films (750°C and an oxygen partial pressure of 29 Pa). The critical current density at 77 K exceeds 1 MA cm^–2 for the thinner films, and decreases with increasing film thickness in excess of about 0.4m. The decrease is in rough agreement with a switch fromc-axis toa-axis growth at about this critical thickness. A good anticorrelation was found between room temperature resistivity and critical current density at 77 K. The results are compared to those obtained before by post-annealing at 850°C in 1 atm of oxygen.     

Transport properties of textured Bi2Sr2CaCu2O8+y, thin films

Superconducting films of the high-T _c compound Bi₂Sr₂CaCu₂O_8+y , have been grown on (111)-oriented gadolinium gallium garnet substrates by a liquid-phase technique. The films show a very high degree of preferential orientation with thec-axis perpendicular to the substrates. The onset of the resistive transition was 85 K while zero resistance was obtained at 78 K. Results concerning the critical current properties of the films are described. Measurements of the paraconductivity effects on the electrical resistivity above the superconducting transition due to thermodynamic fluctuations are also reported.Supported by Ansaldo S.p.A Divisione Ansaldo Ricerche, Via Corso Perrone 25, I-16100 Genova, Italy.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_SiH4=0.8 Torr, the resistivity gradually increased, but for P_SiH4=1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Fabrication and Transport Properties of MgB2 Thin Films and Tunnel Junctions

We report on fabrication and characterization of MgB₂ thin films and tunnel junction structures. The MgB₂ films were prepared on Al₂O₃, Si, glass, and plastic foil substrates by either vacuum codeposition of boron and magnesium, or high-temperature magnesium annealing of boron films. The crystalline structure of our films depended directly on the method of preparation. The films prepared by codeposition and postannealed in Ar atmosphere were amorphous with nanocrystal inclusions and were characterized by very smooth surfaces. On the other hand, the boron-precursor films annealed in magnesium vapor were rough, polycrystalline with approximately 1-m-diameter single-crystal blocks. Because of their surface quality, the amorphous films were used for preparation of point contact junctions and for optical characterization. The point-contact spectra of tested junctions exhibited a two-gap structure. The MgB₂ polycrystalline films was used for bulk transport studies. The best films were characterized by the critical temperature T _c of up to 39 K and the current density j _c at 4.2 K of about 10⁷ A/cm².     

Reproducibility of transition temperature and critical current density of thin films of YBa2Cu3O7 on (100) LaAlO3

Submicrometer epitaxial films of YBa₂Cu₃O₇(YBCO) on (100) LaAlO₃ were made by coevaporation and furnace annealing. Samples from more than a dozen runs are used in this study. The zero resistance transition temperature (T _c) is high (89 or 90 K) if the film composition is phase pure (Ba/Y=2, Cu/Y=3) or if it is enriched in Ba and Cu. For these compositions the critical current density (J _c) at 77 K has an average value of 2×10⁵ A cm^–2, with a tendency for decreasingJ _c with increasing film thickness (0.2 to 0.8m). Variations inJ _c are not correlated with deviations from ideal stoichiometry. Steeper slopes of the resistance-temperature curves above 100 K and lower values of the room-temperature resistivity are associated with high values ofJ _c. If the film composition is enriched in Y relative to Ba and Cu,T _c decreases by several degrees.     

The As-prepared surfaces of C-axis-oriented Nd1Ba2Cu3Oy thin films characterized using scanning probe microscopes

Recently, superconducting Nd₁Ba₂Cu₃O_y (Ndl23) thin films with high superconducting transition temperature (T _c) have been successfully fabricated at our institute employing the standard laser ablation method. In this paper, we report the results of surface characterization of the Nd123 thin films using an ultrahigh vacuum scanning tunneling microscope/spectroscopy (UHV-STM/STS) and an atomic force microscope (AFM) system operated in air. Clear spiral pattern is observed on the surfaces of Nd123 thin films by STM and AFM, suggesting that films are formed by two-dimensional island growth mode. Contour plots of the spirals show that the step heights of the spirals are not always the integer or half-integer number of thec-axis parameter of the structure. This implies that the surface natural termination layer of the films may not be unique. This result is supported byI-V STS measurements. The surface morphology of the Nd123 thin films is compared with that of thec-axis-oriented Y₁Ba₂Cu₃S_y thin films. Surface atomic images of the as-prepared Nd123 thin films are obtained employing both STM and AFM. STS measurements show that most of the surfaces are semiconductive. The results of STS measurements together with the fact that we are able to see the surface atomic images using scanning probe microscopes suggest that exposure to air does not cause serious degradation to the as-prepared surfaces of Nd123 thin films.     

Effect of Ca Substitution on the Superconductivity of La2.5Y0.5CaBa3(Cu0.88Fe0.12)7Oz

The structural and superconducting properties of single-phase La_2.5–y Y_0.5Ca_1+y Ba₃ (Cu_0.88Fe_0.12)₇O _z (LYCaBCuFe) (y= 0.0–1.0) compounds with triple perovskite structure are investigated using X-ray diffraction, resistivity, a.c. susceptibility, and oxygen content measurements. Increasing Ca substitution for La resulted in a decrease in unit cell axes and volume. T _c ^R=0 shows a marginal increase from 31 K to 37 K for y = 0.0–0.21 and thereafter it decreases with increasing y leading to zero T _c ^R=0 at y 0.84. This shows that the suppression of T _c from 80 K to 31 K by Fe doping at x = 0.12 La_2.5Y_0.5CaBa₃(Cu_1–x Fe _x )₇O _z cannot be compensated by appropriate hole doping with Ca in LaYCaBCuFe.     

High Critical Current Density YBa2Cu3Ox Tapes Using the RABiTs Approach

Progress in the fabrication of epitaxial, high-J _c, biaxially aligned YBCO thick films on Rolling-assisted biaxially textured substrates (RABiTs) is reported. RABiT substrates comprise a biaxially textured metal substrate with epitaxial oxide buffer layers suitable for growth of superconductors. Oxide buffer layers have been deposited using three techniques: laser ablation, electron-beam evaporation, and sputtering. Epitaxial YBCO films grown using laser ablation on such substrates have critical current densities approaching 3 × 10⁶ A/cm² at 77 K in zero field and have field dependences similar to epitaxial films on single crystal ceramic substrates. Critical current densities in excess of 0.2 MA/cm² have been obtained on stronger, nonmagnetic substrates. In addition, samples with J _e of 12.5 kA/cm² at 77 K have been fabricated. The highest strain tolerence obtained so far is 0.7% in compression and 0.25% in tension. Deposited conductors made using this technique offer a potential route for the fabrication of long lengths of high-J _c wire capable of carrying high currents in high magnetic fields and at elevated temperatures.     

Critical current density and microstructure of YBa2Cu3O7 thin films post-annealed at a low oxygen partial pressure

Post-annealing of thin films of YBa₂Cu₃O₇ (YBCO) has been performed at 29 Pa and 750°C. For films 0.6 m thick, a critical current density >1 MA cm^–2 is obtained at 77 K, with a sharp eddy current response at 25 MHz. Microstructural investigation of these films by crosssectional and planar transmission electron microscopy reveals that the YBCO film has thec-axis normal to the plane of the substrate in a continuous sheet of varying thickness, frequently covering the entire thickness of the film. Mutually perpendicular rods with thec-axis in the plane of the LaAlO₃ substrate are also seen. The microstructure and critical current density of these films are compared with those of previously reported films post-annealed in atmosphericpressure oxygen.     

Preparation of La0.8Sr0.2Cr0.97V0.03O3 − δ films for solid oxide fuel cell application

La_0.8Sr_0.2Cr_0.97V_0.03O_3 − δ (LSC) is commonly studied as a ceramic interconnect material as well as a coating material for metallic interconnects for solid oxide fuel cell applications. However, it is difficult to sinter this type of material to high density. In order to overcome this problem and to study the material in form of a thin film we have used Pulsed Laser Deposition to obtain a dense, uniform film with the right stochiometry. Investigation of preparation-parameter dependence of the LSC films deposited on a stainless steel substrate during pulsed-laser deposition was carried out. The LSC films were deposited with KrF excimer laser (248 nm) on a stainless steel substrate at different oxygen pressure and substrate temperatures. The substrate temperature (873-1073 K) and the oxygen background pressure (5-20 Pa) were varied in order to obtain optimal growth conditions. The surface morphology and structural information of the films were obtained using scanning electron microscope (SEM) and X-ray diffraction, respectively. Under the optimal preparation-parameter conditions: substrate temperature of 1023 K and an oxygen pressure of 10 Pa the structure of the film agreed with the target structure and the SEM micrographs show that the surfaces are homogeneous, smooth, crack-free and dense.     

Superconductivity of Ba1 ? xKxBiO3 (0.35 < x < 1) Synthesized by the High Pressure and High Temperature Technique

Ba_{1 – x} K _x BiO₃ (BKBO) samples with 0.35 < x < 1 were synthesized by the high pressure and high temperature technique. XRD analysis showed that the BKBO samples were single phase for the whole range of the potassium doping concentration. The change of superconducting transition temperature, T _c, as well as lattice parameters have been investigated upon doping concentration. As the K doping concentration (x) increases from x = 0.37, T _c decreases from 30.4 K to almost zero at x = 0.74. However, in some BKBO samples without including any barium in the starting composition (x = 1), which is denoted as KBO samples, superconductivity is observed with T _c as high as 9 K with partial substitutions of Bi at the K site. Depending on the synthesis condition of the KBO samples, T _c and lattice parameters were different from sample to sample. Compared with other superconducting bismuthates, the evolution of T _c by potassium doping in the cubic BKBO system is discussed in terms of its electronic band structure.     

Structural and thermal characterization of La5Ca9Cu24O41 thin films grown by pulsed laser deposition on (1 1 0) SrTiO3 substrates

In the present study stoichiometric, b-axis oriented La₅Ca₉Cu₂₄O₄₁ thin films were grown by pulsed laser deposition on (1 1 0) SrTiO₃ substrates in the temperature range 600-750 °C. High resolution transmission electron microscopy was employed to investigate the growth mechanism and the epitaxial relationship between the SrTiO₃ substrates and the La₅Ca₉Cu₂₄O₄₁ films grown at 700 °C. The 3-ω method was used to measure the cross-plane thermal conductivity of La₅Ca₉Cu₂₄O₄₁ films in the temperature range 50-350 K. The observed glass-like behavior is attributed to atomic-scale defects, grain boundaries and an interfacial layer formed between film and substrate.     

Microstructure and nano-scratch behaviors of La0.7Sr0.3MnO3 films

The La_0.7Sr_0.3MnO₃ (LSMO) films were prepared at various substrate temperatures on si(100) by DC magnetron sputtering method. The microstructure and nano-scratch behaviors of the films were investigated. The results indicate that the films are single phase with perovskite distorted cubic structure and the texture orientation changes obviously with the increase of substrate temperature. A smooth and dense nanocrystalline LSMO film is obtained at high substrate temperature. The (110) preferred orientation growth is beneficial to the improvement of nano-scratch resistance of the films. The friction coefficient between the films and the diamond tip depends on the critical load (L_c). Elastic deformation is the dominant deformation mechanism and the friction coefficient is about 0.08-0.14 for all the films when the loading normal load is less than L_c. When the loading load is larger than L_c, the delamination or detachment of the films occur and the friction coefficient increases abruptly near the L_c. The films deposited at 480 °C and 680 °C possess higher L_c which is about 77 mN due to lower hardness. The suitable decrease in hardness can enhance cohesion strength and scratch resistance of the films.     

Growth and structure characterization of epitaxial Bi2Sr2Co2Oy thermoelectric thin films on LaAlO3 (001)

Epitaxial Bi₂Sr₂Co₂O_y thin films with excellent c-axis and ab-plane alignments have been grown on (001) LaAlO₃ substrates by chemical solution deposition using metal acetates as starting materials. Microstructure studies show that the resulting Bi₂Sr₂Co₂O_y films have a well-ordered layer structure with a flat and clear interface with the substrate. Scanning electron microscopy of the films reveals a step-terrace surface structure without any microcracks and pores. At room temperature, the epitaxial Bi₂Sr₂Co₂O_y films exhibit a resistivity of about 2 mΩ cm and a seebeck coefficient of about 115 μV/K comparable to those of single crystals.     

Zero resistance at 117 K in Bi1.6Pb0.4Sr2Ca2Cu2+xOy compounds

In the Pb-doped Bi-Sr-Ca-Cu-O system, optimization of the composition and heat treatment conditions at which a greater amount of the high-T _c phase forms has been reported in our early paper [1], where the temperature of zero resistance was 107K. Recently, we have achieved zero resistance at 117 K and observed an a.c. susceptibility step at around 150 K by changing the Cu composition in the Bi^1.6Pb^0.4Sr²Ca²Cu^2+x O ^y system (x=0, 0.4, 0.8, 1.2, and 1.6).     

Microstructural study of YBa2Cu3O7/SrTiO3/YBa2Cu3O7 heteroepitaxial trilayer films grown on (100) SrTiO3 substrates

Detailed transmission electron microscopic study has been carried out on heteroepitaxial YBa₂Cu₃O₇/SrTiO₃/YBa₂Cu₃O₇ trilayer thin films grown on (100)SrTiO₃ substrates prepared by DC and RF magnetron sputtering. The microstructural results showed the existence of somea-axis-oriented YBCO grains 20–90 nm wide in thec-axis-oriented YBCO matrix. Some of thea-axis grains in the lower YBCO thin film layer have protruded into the above SrTiO₃ layer, which may cause short circuit between the two YBCO superconducting layers. This is unsuitable for the application of trilayer thin films for microelectronic devices. The defects on the surface of the substrates would also influence the growth quality of the YBCO thin films.     

Effect of annealing on characteristics of Ni48Fe12Cr40/Ni80Fe20 bilayer films deposited on Si(1 0 0)/SiO2 by electron beam evaporation

Ni₄₈Fe₁₂Cr₄₀(7 nm)/Ni₈₀Fe₂₀(40 nm) bilayer films and Ni₈₀Fe₂₀(40 nm) monolayer films were deposited at ambient temperature on Si(1 0 0)/SiO₂ substrates by electron beam evaporation. The effect of annealing on the structure, composition, magnetization and magnetoresistance of the Ni₄₈Fe₁₂Cr₄₀/Ni₈₀Fe₂₀ bilayer films was investigated. The structure of the Ni₄₈Fe₁₂Cr₄₀/Ni₈₀Fe₂₀ bilayer films remains stable for annealing temperature up to 280 °C. For the as-deposited bilayer film the introducing of the Ni₄₈Fe₁₂Cr₄₀ underlayer promotes both the [1 1 1] texture and grain growth in the Ni₈₀Fe₂₀ layer. The annealing promotes the grain growth of the Ni₄₈Fe₁₂Cr₄₀/Ni₈₀Fe₂₀ bilayer films when the annealing temperature exceeds 280 °C. After annealing at a temperature over 280 °C, Cr atoms inside the Ni₄₈Fe₁₂Cr₄₀ layer diffuse into the Ni₈₀Fe₂₀ layer and segregate on the surface of the Ni₈₀Fe₂₀ layer. The Ni₄₈Fe₁₂Cr₄₀ underlayer as a seed layer can enhance the anisotropic magnetoresistance ratio of the Ni₈₀Fe₂₀ layer at a annealing temperature up to 280 °C compared with Ni₈₀Fe₂₀ monolayer film. After annealing at a temperature over 280 °C, however, the anisotropic magnetoresistance ratio of the Ni₈₀Fe₂₀ monolayer films exceeds that of the Ni₄₈Fe₁₂Cr₄₀/Ni₈₀Fe₂₀ bilayer films. For all annealing temperatures, the coercivities of the Ni₄₈Fe₁₂Cr₄₀/Ni₈₀Fe₂₀ bilayer films are smaller than those of the Ni₈₀Fe₂₀ monolayer films.     

Surface resistance of large-area Tl2Ba2CaCu2O8 thin films at microwave and millimeter wave frequencies measured by three noncavity techniques

The surface resistanceR _s of Tl₂Ba₂CaCu₂O₈ films fabricated on LaAlO₃ wafers up to 3 inches (7.6 cm) in diameter through a post-deposition anneal process was measured over the frequency range 5.55–94.1 GHz by the following techniques: 5.55 and 27.5 GHz high-temperature superconductor (HTS)-sapphire resonators, 10 GHz parallel plate resonator, and 94.1 GHz scanning confocal resonator.R _s was found to exhibit a quadratic dependence on frequencyf at 77 K:R _s f ^2.0±0.1. The highest-quality films yieldR _s =145±15 at 10 GHz and 77 K. Scanning confocal resonator mapping ofR _s across a 2-inch (5.1 cm) diameter wafer yielded a base value forR _s of 16±1 m at 77 K and 94.1 GHz (equivalent to 180±10 at 10 GHz) and good uniformity inR _s across the wafer. HTS-sapphire resonator measurements ofR _s for fifteen 1.2 cm square parts cut from a 3-inch diameter wafer yieldedR _s values scaled to 10 GHz of 196±10 at 80 K. Similar values were measured for Tl₂Ba₂CaCu₂O₈ films prepared on both sides of a 2-inch diameter wafer.Rs values at 10 GHz and 80 K of 147–214 were maintained over the course of 40 independent and successive deposition runs and corresponding anneals under nominally identical film fabrication conditions. Surface resistance at 5.55 GHz remained below 80 for maximum rf magnetic fields up to 85 Oe at 4.2 K and 7 Oe at 80 K, respectively. Results are compared with predictions of the two-fluid model. The relative advantages and disadvantages of the different techniques for measuring surface resistance are discussed.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.