Metal organic chemical vapor deposition of superconducting YBa2Cu3O7-x thin films

The discovery of YBCO superconductors has stimulated a great deal of scientific and technological research into thin films of these materials. Because the MOCVD technique is known to produce high quality films in the III/V and II/VI material groups, our approach has been to apply the method to superconducting thin films. Thin films were grown in a vertical high speed (0–2000 rpm) rotating disk reactor. The source materials were metalβ-diketonates kept at temperatures in excess of 100° in order to obtain growth rates of 0.3 to 0.5μm/hr. The precursors were transported to the chamber with a nitrogen carrier and injected separately in order to avoid any gas phase reactions. The chamber pressure was maintained at 76 Torr with an oxygen partial pressure of 38 Torr. A resistance heater was used to keep the substrate temperature at 500° YBa₂Cu₃O_7-x films were deposited simultaneously on a variety of substrates such as (100) MgO, (1-102) sapphire, (100) SrTiO₃ and (100) YSZ. Full XPS spectra were collected for the binary oxides. The scans demonstrate the existence of Y₂O₃, BaO, and CuO with the correct valence state for the metallic species. Energy dispersive analysis of x-ray (EDAX) was used to determine film compositions by comparing EDAX spectral intensity to a known superconducting standard. Appropriate changes were made in the precursor flows to correct the stoichiometry. The as-grown films were dark brown and semi-transparent. Cross-sectional SEM photomicrographs revealed an ordered columnar structure. After annealing at 950–980° however, the films on (100) SrTiO₃ appeared dull black and opaque. The surface morphology exhibited smooth large plate-like grains. X-ray data clearly display an orthorhombic phase, with c-axis perpendicular to the substrate surface. Four point resistance measurements for films on (100) SrTiO₃ show the onset of superconductivity at 90 K with a complete loss of resistance at 88 K. This sharp (≤2K) transition shows the high quality of these MOCVD grown YBCO films and are the first reported results from a large area (2 × 50 mm substrates) commercial reactor.     

Microwave performance-property relationships of YBa2Cu3O7-δ thin films grown on LaAlO3 (001) substrate

We report correlations between growth parameters, structure and microwave performance for YBa₂Cu₃O7-δ (YBCO) thin films. Two series of YBCO thin films were grown byin-situ laser ablation. The first series were deposited at 100 mTorr oxygen pressure with a laser fluence of 2.9 Joule/cm², the second series were deposited at 600 mTorr of oxygen and a higher laser fluence of 5 Joule/cm². Microwave performance of these films was evaluated using a 5.6 GHz resonator. In both series, we found that films with higherT _c , narrower x-ray rocking curve width, and sharper electron channeling pattern tend to have higher microwave resonator Qs. Optimal film growth conditions were infered from this systematic study. Films grown at higher oxygen pressure have smoother surfaces and fewer second phases.     

Interfacial properties of YBa2Cu3O7−x thin films on AI2O3 substrates prepared by pulsed laser deposition

The interfaces of YBa₂Cu₃O_7−x (YBCO) superconducting thin films grown on (1 102) r-plane A1₂O₃ by pulsed laser deposition have been investigated by a transmission electron microscopy and an Auger electron spectroscopy depth profile. We used the PrBa₂Cu₃O_7−x (PBCO) buffer layer to prevent the interdiffusion and compared the interfaces of YBCO/A1₂O₃ and YBCO/PBCO/A1₂O₃. The intermediate layer in the YBCO film deposited on bare sapphire is visible between the film and the substrate but no boundary layer in the film grown on PBCO buffered sapphire was observed directly by the cross-section image of TEM. The thickness of the intermediate layer in the film on bare sapphire is about 30 nm. This result of TEM observation is consistent with that of AES depth profile.     

High Tc superconducting linear array ir detectors using YBa2Cu3O7-δ thin films

8-element linear array IR detectors based on high Tc superconducting films have been fabricated. The thin films were deposited by magnetron sputtering onZrO ₂ substrates and patterned by standard photolithographic technique forming microbridge structure. An average detectivity of 1.85 × 10⁹ cmHz ^1/2 W^?1 with a variance of less than 20% in the detector-to-detector detectivity of the array has been obtained at the operating temperature of 84K. A bolometric response mechanism has been discussed.     

Large critical current densities in YBa2Cu3O7-x thin films formed by plasma-enhanced metalorganic chemical vapor deposition at reduced temperature

YBa₂Cu₃O_7-x (YBCO) superconducting thin films with a critical current density exceeding 1 x 10⁶ A/cm² at 77.7 K were prepared by a plasma-enhanced metalorganic chemical vapor deposition (PE-MOCVD) process. The thin films (130 nm thick) were formed in-situ on LaAlO₃ substrates at a temperature of 670‡ C in 2 Torr partial pressure of activated N₂O. Resistivity and magnetic susceptibility measurements of the as-deposited films show a sharp superconducting transition temperature of 89.8 K. Critical current densities were measured by the dc transport method with a patterned bridge of 120 × 40 Μm. Both x-ray diffraction and high resolution electron microscopy measurements indicate that films grew epitaxially with the c-axis perpendicular to the surface of the substrate.     

Magnetic flux pinning in epitaxial YBa2Cu3O7−δ thin films

The influence of microstructure on the critical current density of laser ablated YBa₂Cu₃O_7−δ thin films has been examined. Scanning tunneling microscopy was used to examine the morphologies of YBa₂Cu₃O_7−δ films and the morphology data were then correlated with measurements of the critical current density. The films were found to grow by an island nucleation and growth mechanism. The critical current densities of the films are similar to those of films with screw dislocation growth, indicating that screw dislocation growth is not necessary for good pinning. The data suggest that the critical current density in applied magnetic field may be higher in films with higher densities of growth features.     

LaNiO3 and Cu3Ge contacts to YBa2Cu3O7-x films

Metallization of high-T_c superconductors using low resistivity metal oxides and Cu-Ge alloys has been investigated on high quality pulsed laser deposited epitaxial YBa₂Cu₃O_7-x (YBCO) films. Epitaxial LaNiO₃ (LNO) thin films have been grown on YBCO films at 700°C using pulsed laser deposition. The specific resistivity of LNO was measured to be 50 μΩ-cm at 300K which decreases to 19 μΩ-cm at 100K indicating good metallicity of the LNO films. The contact resistance of LNO-YBCO thin film interface was found to be reasonably low (of the order of 10^-4Ω-cm² at 77K) which suggests that the interface formed between the two films is quite clean and LNO can emerge as a promising metal electrode-material to YBCO films. A preliminary investigation related to the compatibility of Cu₃Ge alloy as a contact metallization material to YBCO films is discussed. The usage of other oxide based low resistivity materials such as SrRuO₃ (SRO) and SrVO₃ (SVO) for metallization of high-T_c YBCO superconductor films is also discussed.     

Growth orientation and superconducting properties of YBa2Cu3OT-8 films prepared by the low-fluorine sol-gel process

YBa2Cu3O7-δ(YBCO) films were deposited on (100)-oriented LaAlO3 (LAO) single crystal substrates by the dip-coating process using low-fluorine solution. Their microstructures were characterized with the aid of X-ray diffractometry, scanning electron microscopy and high-resolution transmission electron microscopy. Their supercon-ducting properties were measured by the standard four-probe method. The experiment results show that the film obtained under high enough humidity conditions exhibits better c-axis texture and superconducting properties than the film under a relatively low humidity conditions. Based on the classical nucleation and chemical reaction thermodynamics theory, the underlying crystalline and growth mechanisms of YBCO films under certain humidity conditions are explained in combination with our experimental results. It is suggested that the unreacted intermediate phases such as BaF2 and CuO aggregated in the YBCO grain boundary will cause lattice distortion in the YBCO matrix and further induce the formation of a-axis oriented YBCO grains as crystallization proceeds. Therefore, it is believed that the relative content of water vapor within the heat-treatment atmosphere plays quite an important role in the preparation of c-axis oriented YBCO film with good superconducting properties.     

Effect of substrate smoothness on the microstructure of YBa9n2Cu3O7−x/Y2O3/YBa2Cu3O7−x trilayers

Transmission electron microscopy was used to analyze the microstructure of YBa₂Cu₃O_7−x/Y₂O₃/YBa₂Cu₃O_7−x trilayer structures deposited by off-axis sputtering on MgO substrates with varying degrees of roughness. Substrate surface hillocks with a peak-to-valley height of about 4.5 nm were found to contribute to strain that extended through the film and disrupted the smoothness of the Y₂O₃ layer. In some cases, these hillocks served as nucleation sites for yttria precipitates. Such defects may seriously jeopardize the realization of weak-link Josephson junctions.     

Characterization and antibacterial capabilities of nanocrystalline CdS thin films prepared by chemical bath deposition

Antibacterial capabilities of nanocrystalline cadmium sulfide (CdS) thin films have been developed against Gram-positive and Gram-negative bacteria in dark and sunlight at 60 °C. For this purpose, a strain of Gram-positive Staphylococcus aureus, and two strains of Gram-negative bacteria (Pseudomonas aeruginosa, and Escherichia coli) were used. The nanocrystalline CdS thin films have been prepared using a chemical bath deposition (CBD) method at different thicknesses (50, 80 and 100 nm). The different deposition parameters including the speed of rotation of substrate, temperature of chemical bath, pH of solution and time of the deposition were optimized. The Polyvinylpyrrollidone (PVP) was successfully used as capping agent in order to stop the agglomeration in the CdS thin films. It was found that, CdS thin films have remarkable antibacterial activity in dark and sunlight and it could be applied as antimicrobial agent in medical field. In order to confirm the crystalline structure of CdS thin films, the polycrystalline nature of the deposited CdS thin films with hexagonal structure was obtained. Furthermore, the structural parameters including lattice parameters, cell volume, the space group, average grain size, dislocation density and the strain have been calculated. The topography and surface roughness of the CdS thin films have been studied before and after the bacteriostatic effect using Scanning Electron Microscopy (SEM). Furthermore, the compositions of nanocrystalline CdS thin films have been evaluated using Energy Dispersive X-ray emission (EDX) and a Transmission Electron Microscope (TEM). Based on the optical measurements in the range of 300–2500 nm, the band gap energy of the prepared CdS thin films was found to be 2.4 eV.     

Effects of annealing on nanocrystalline Bi2S3 thin films prepared by chemical bath deposition

Nanocrystalline Bi₂S₃ thin films are deposited on tin chloride treated glass substrate from the solution containing bismuth nitrate, triethanolamine (TEA) and thioacetamide (TAM) at a bath temperature 318 K. The prepared films are subsequently annealed at different temperatures for studying the effect of thermal treatment on the structural, surface morphology, optical and electrical properties of the films. The X-ray diffraction studies affirmed that the deposited films are orthorhombic structures with average crystallites size of 14 nm to 28 nm. The scanning electron microscopy (SEM) images revealed that the films comprise of grains of spherical shape of unequal size. It is also observed that the small particles aggregate together to form a larger cluster. The average grain sizes determined from the TEM images are smaller than the crystallites size obtained from the XRD studies. The optical band gap of the films has been estimated to be 2.24–2.05 eV for the as-prepared and annealed films, respectively. The electrical conductivity of the as prepared Bi₂S₃ films at room temperature is found to be in the order of 10⁻³ Ω⁻¹ m⁻¹.     

Synthesis and characterization of Pb(Zr0.54Ti0.46)O3 thin films on (100)Si using textured YBa2Cu3O7−δ and yttria-stabilized zirconia buffer layers by laser physical vapor deposition technique

We have fabricated high-quality <001> textured Pb(Zr_0.54Ti_0.46)O₃ (PZT) thin films on (00l)Si with interposing <001> textured YBa₂Cu₃O_7−δ (YBCO) and yttria-stabilized zirconia (YSZ) buffer layers using pulsed laser deposition (KrF excimer laser, λ, = 248 nm, τ = 20 nanosecs). The YBCO layer provides a seed for PZT growth and can also act as an electrode for the PZT films, whereas YSZ provides a diffusion barrier as well as a seed for the growth of YBCO films on (001)Si. These heterostructures were characterized using x-ray diffraction, high-resolution transmission electron microscopy, and Rutherford backscattering techniques. The YSZ films were deposited in oxygen ambient (∼9 × 10⁻⁴ Torr) at 775°C on (001)Si substrate having <001>YSZ // <001>Si texture. The YBCO thin films were deposited in-situ in oxygen ambient (200 mTorr) at 650°C. The temperature and oxygen ambient for the PZT deposition were optimized to be 530°C and 0.4-0.6 Torr, respectively. The laser fluence to deposit this multilayer structure was 2.5-5.0 J/cm². The <001> textured perovskite PZT films showed a dielectric constant of 800-1000, a saturation polarization of 37.81 μC/cm², remnant polarization of 24.38 μC/cm² and a coercive field of 125 kV/cm. The effects of processing parameters on microstructure and ferroelectric properties of PZT films and device implications of these structures are discussed.     

Study of the optical features of YBa2Cu3O7-x films by SEW spectroscopy

The results of YBa₂Cu₃O_7-x films on SrTiO₃ investigation by far infrared surface electromagnetic waves (SEW) amplitude and phase spectroscopy at temperatures 80–350 K are presented. Strong SEW absorption at frequency 142 cm^?1 has been observed. The origin of the observed absorbtion is proposed to be concerned with slab- phonons in YBa₂Cu₃O_7-x. The optical constants of the films have been obtained. Also has been determined, that only the imaginary part of the SEW refraction index changes when the film transits into superconducting state, while the real part remains unchanged.     

MgO和STO基片上制备YBCO高温超导薄膜生长研究

用AFM和XRD研究在MgO和STO基片上外延生长2-200nm的YBCO高温超导薄膜的生长机制。采用倒筒式直流溅射装置,首次实现单轴驱动双轴旋转技术,本质上实现同时在MaO基片和STO基片上沉积同一均匀厚度的YBCO薄膜。     

Preparation and characterization of thin films of MgO,Al2O3 and MgAl2O4 by atomic layer deposition

MgO, Al₂O₃ and MgAl₂O₄ thin films were deposited on silicon substrates at various temperatures by the atomic layer deposition (ALD) method using bis(cyclopentadienyl)magnesium, triethylaluminum, and H₂O and were characterized systematically. High-quality polycrystalline MgO films were deposited for a substrate temperature above 500°C, and amorphous thin films were deposited around 400°C. The deposited Al₂O₃ and MgAl₂O₄ thin films were characterized as amorphous in structure. Applicability of ALD to complex oxides is discussed.     

Preparation and characterization of ZnS thin films prepared by chemical bath deposition

Zinc sulfide thin films were prepared by chemical bath deposition technique using zinc sulfate (ZnSO₄·7H₂O) and thiourea [SC(NH₂)₂] as sources of Zn²⁺ and S^2– ions, and ammonia (NH₃) and hydrazine hydrate (N₂H₄) as complexing agents. The structural, stoichiometric proportion, morphology and optical properties of the ZnS thin films were investigated as a function of thiourea and ammonia concentrations using X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and UV-visible spectrophotometry measurements. The deposition mechanism is discussed. The results reveal that the ZnS films exhibit poor crystallinity. The ammonia concentration had an obvious effect on the surface morphology, optical properties and deposition mechanism. The S/Zn atomic ratio and optical bandgap of the ZnS thin films first increased and then decreased with increasing ammonia or thiourea concentration.     

Dislocations and flux pinning in YBa2Cu3O7

The dislocation structures of bulk textured and epitaxial thin film YBa₂Cu₃O₇ superconductors are examined. Correlations between increases in flux pinning and dislocation densities are noted. A model for flux pinning by individual dislocations is presented. This gives a treatment of strain induced effects and effects of normal state region interactions. It is shown that the values of pinning predicted are in line with experimental observations.     

Orientation texture in YBa2Cu3O7−δ films synthesized from amorphous precursors

The metalorganic decomposition technique was utilized in the fabrication of YBa₂Cu₃O_7−δ films with preferred orientation on (100) MgO and (100) SrTiO₃ substrates. The processing parameters such as film thickness, firing treatment, and substrate modifications were controlled to obtain a high degree of three-dimensional preferred growth in the films. Results indicate that three-dimensional film preferred growth diminishes with increasing film thickness. Preferential growth in YBa₂Cu₃O_7−δ films is enhanced with increasing firing temperature and reduced oxygen partial pressure due to enhanced atom mobility. Epitaxial growth of YBa₂Cu₃O_7−δ films has been achieved on both lattice mismatched (MgO) and on lattice matched (SrTiO₃) substrates. Epitaxial growth is promoted by lattice matched substrates at lower film firing temperatures. An attempt is made to understand the development of YBa₂Cu₃O_7−δ film preferential growth via the epitaxial grain growth mechanism.     

Comparison of the surface morphology and microstructure of in situ and ex situ derived YBa2Cu3O7−x thin films

The surface morphology and microstructure of in situ and ex situ derived YBa₂Cu₃O_7−x (YBCO) thin films have been investigated. In situ films were deposited by single-target off-axis sputtering and three-target co-sputtering. Ex situ films were derived by metalorganic deposition (MOD) of trifluoroacetate precursors. Surface defects resulting from mixed a-axis and c-axis orientation as well as secondary phases have been identified in these films. Despite these defects, films with excellent electrical properties have been formed. However, defects interfere with film patterning and the fabrication of multi-layered structures. Several secondary phase precipitates have been identified, including CuO, Y₂O₃, Cu-Ba-O, and Y₂Cu₂O₅. Secondary phases resulting from a lack of stoichiometry can be eliminated by direct composition control in the MOD and three-target sputtering techniques, and by composition control through the application of an externally applied magnetic field in single-target off-axis sputtering. Secondary phases caused by contamination were also identified: Cr-Ba-O in off-axis sputtering, resulting from contamination by the oxidized heater block; and BaSO₄ in MOD, resulting from gas phase impurities. These results suggest that cation composition control is not sufficient to prevent the formation of secondary phases and that small levels of contamination may prevent phasepure material from being formed.     

PLD法制备高介电调谐率的纳米晶BZT薄膜

用脉冲激光沉积工艺制备了Ba(ZrxTi1-x)O3(x=0.25,0.30简称BZT25和BZT30)介电薄膜。在650℃原位退火10 min,薄膜为(111)取向柱状生长的晶粒,取向度分别为0.45和0.75。BZT25和BZT30薄膜的平均晶粒尺寸分别为50 nm和60 nm。在室温、1 MHz和3×105 V/cm条件下,BZT25的最大εr和调谐率分别达到563和65%,BZT30的最大εr和调谐率分别达到441和57%。薄膜为(111)取向生长,主要是基于薄膜与底电极Pt界面层立方相结构Pt3Ti的诱导,即(111)Pt3Ti和(111)BZT的晶格匹配。