MgO单晶基片上YBCO高温超导薄膜的制备

在2英寸MgO(001)单晶基片上,采用直流溅射法,通过基片高温退火,成功制备了性能优越的YBa2C3O7-δ(YBCO)双面超导薄膜,能够满足超导滤波器的设计要求。X射线衍射(XRD)分析表明经过退火的基片上生长的YBCO薄膜与基片有单一的外延取向关系;用原子力显微镜(AFM)和高能电子衍射(RHEED)分析高温退火对基片表面状况的改变。结果表明制备的YBCO薄膜具有很好的超导电性,薄膜临界电流密度Jc(77K,0T)≈2.5×106A/cm2,微波表面电阻Rs(10GHz,77K)≈0.16mΩ。     

热处理对MgO基片的表面形貌以及对CeO_2和Tl-2212薄膜生长的影响

研究了MgO基片在高温退火时表面形貌和表面结构的变化,以及它对CeO2缓冲层和Tl-2212超导薄膜生长的影响。原子力显微镜(AFM)研究表明,在流动氧环境中1100℃温度下退火,MgO的表面首先由未退火时的皱褶形貌,演化为光滑表面,随着退火时间的延长,表面形貌最终演化为具有光滑基底的独立生长峰结构。XRD测试表明,通过高温热处理可以大幅度提高MgO基片表面结晶的完整性。在1100℃温度下热处理8小时的MgO基片上可以生长出具有高度c轴取向的CeO2(001)缓冲层。然后在此缓冲层上制备了厚度为500nm的外延Tl-2212超导薄膜,其临界转变温度(Tc)达到108.6K,液氮温度下临界电流密度(Jc)为2.8mA/cm2,微波表面电阻Rs(77K,10GHz)约为360.9μΩ。     

Improved initial epitaxial growth of superconducting YBa2Cu3O7 thin films on Y–ZrO2 substrates with a La1.85Sr0.15CuO4 buffer layer

Epitaxial thin films of YBa₂Cu₃O₇ (YBCO) have been deposited on Y–ZrO₂ (YSZ) substrates by means of the pulse laser deposition technique. It has been found that the initial epitaxy of YBCO thin films grown on YSZ can be significantly improved by using La_1.85Sr_0.15CuO₄ (LSCO) as a buffer layer. X-ray diffraction measurements show that the epitaxial YBCO films have single in-plane orientation with YBCO [100]LSCO [100] and LSCO [100]YSZ [110]. The real-time resistance measurements reveal that with LSCO buffer layers the initial formation of the YBCO ultra-thin films changes from the island growth to the layer-by-layer growth.     

High critical current density YBa2Cu3O7−δ tapes prepared by the surface-oxidation epitaxy method

YBa₂Cu₃O_7−δ (YBCO) films with high critical current density (J_c) were successfully fabricated on nickel tapes buffered with epitaxial NiO. NiO was prepared on the textured nickel tape by the surface-oxidation epitaxy (SOE) method. We have reported so far a critical temperature (T_c) of 87 K and J_c=4–6×10⁴ A/cm² (77 K, 0 T) for the YBCO films on NiO/Ni tapes. To enhance the superconducting properties of the YBCO films on the SOE-grown NiO, depositions of thin oxide cap layers such as YSZ, CeO₂, and MgO on NiO were investigated. These oxide cap layers were epitaxially grown on NiO and provided the template for the epitaxial growth of YBCO films. Substantially improved data of T_c=88 K and J_c=3×10⁵ A/cm² (77 K, 0 T) and 1×10⁴ A/cm² (77 K, Hc, 4 T) were obtained for YBCO film on NiO, by using a MgO cap layer with a thickness of 50 nm. The method described in this paper is a simple way to produce long YBCO tape conductors with high-J_c values.     

Observation of defects and growth orientations of YBa2Cu3Ox thin films with YSZ buffer layers on Si

We have investigated defects and in-plate orientations of YBa₂Cu₃O_x thin films prepared by pulsed laser deposition (PLD) with YSZ as a buffer layer. The films showed c-axis oriented growth with the transition temperature T_co up to 87 K. Several types of defects including thermally induced cracks, grain boundaries and outgrowths were observed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The grain boundary provided a favorable path for crack propagation. The outgrowths nucleated on the YSZ surface grew with stoichiometric composition. According to X-ray diffraction (XRD) and HRTEM studies the YSZ buffer layer grew with the orientation relationship, YSZ110//Si110 and YSZ(001)//Si(001) up to the YBCO/YSZ interface. The superconducting YBCO films on top grew mainly with YBCO100//Si110 and YBCO(001)//Si(001), with some minor portions of YBCO110//Si110 and YBCO(001)//Si(001).     

The effect of Ag or Au overlayers on underlying YBa2Cu3O7 thin films

Although Ag and Au are commonly used to provide low-resistance contacts to YBa₂Cu₃O₇ (YBCO), their effect on the electrical properties of the underlying YBCO has been largely neglected. Epitaxial YBCO thin films on LaAlO₃ substrates were used in this study. Thin (50 nm) and thick (1 μm) layers of Ag or Au were deposited as overlayers, and in some cases annealed in oxygen at 550–650°C. Compared to samples with no metal overlayers, for both Ag and Au the normal-state parameters changed (resistivity, its temperature coefficient, and the transition width), whereas the transition temperature and critical current density remained unaltered. These results are encouraging for the use of these metals as contacts and/or conducting overlayers on YBCO.     

YBa_2Cu_3O_(7-δ)薄膜制备工艺对体系结构和性能的影响研究

采用起始原料无氟的工艺和含氟的Ba-TFA工艺制备YBa2Cu3O7-δ(YBCO)前驱体溶胶,在LAO(001)基板上制得YBCO凝胶膜,热处理后都可以获得表面光滑、无裂缝的YBCO薄膜。薄膜的性能利用X-射线衍射(XRD),扫描电镜(SEM)以及光电子谱(XPS)等手段进行测试,结果表明:无氟工艺制备的薄膜由于热处理过程中生成了BaCO3相而严重地影响到薄膜的超导性能,而Ba-TFA法所获得的薄膜则表现出了良好外延生长,临界转变温度Tc=89K,转变温度宽度△Tc<1 K,临界电流密度Jc=2.8MA/cm2。     

Nb/Au/(1 1 0)YBa2Cu3O7−δ Josephson junctions: evidence against atomic scaled “corner junctions”

We report on I–V characteristics for in situ formed Nb/Au/(1 1 0)YBa₂Cu₃O_7−δ (YBCO) Josephson junction, where the homoepitaxial (1 1 0)YBCO film shows ultra-smooth surface morphology. The field dependence of critical supercurrent I_c shows anisotropic large junction behavior with normal Fraunhofer patterns expected from BCS model of d_x²−y² wave superconductors. This strongly suggests that the Nb/Au/(1 1 0)YBCO junctions cannot be regarded as atomic scaled corner junctions, in contrast with (0 0 1)/(1 1 0)YBCO grain boundary junctions to show “π-junction” with a pronounced dip near zero fields in field modulation of I_c.     

High quality epitaxial YBCO(F) films directly deposited on sapphire

High-quality epitaxial YBa₂Cu₃O_7−δ (F) films were grown directly on r-plane (1 02) sapphire by a pulsed laser deposition technique using a multiphase fluorinated target. X-ray diffraction data showed that the film is highly c-axis oriented and in-plane aligned. The c-axis and in-plane mosaic spread are 1.1° and 2.4°, respectively. The microwave surface resistance measured by a con-focal resonator configuration is 56 mΩ at 94.1 GHz at 77 K which is the best reported value for a YBCO film on sapphire.

The improved film quality is attributed to the fluorine which is transported from the target to the growing surface of the film where it acts as an etching and/or catalytic agent to preferentially remove defects and second phase impurities and to promote better in-plane epitaxy.     

High TcYBa2Cu3O7−δ superconducting transition-edge microbolometers

High T_c superconducting thin film YBa₂Cu₃O_7−δ (YBCO) bolometers have been fabricated on various substrates such as MgO, LaAlO₃, YSZ and Si using laser ablation technique. Performance of these IR bolometers operating with a Joule-Thomson refrigerator has been investigated. Measurements of the responsivity and low frequency noise near T_c in the current biased YBCO bolometers show that reliable devices can be fabricated. Measured noise equivalent power (NEP), for YBCO/YSZ bolometer, reaches 6 × 10⁻¹⁰W/Hz^1/2 at 165 Hz and has a responsivity of 60 V/W with a blackbody source. This performance is comparable to that of the optimized pyroelectric detectors. The characteristics of YBCO films deposited on Si substrates reveal that superconducting thin film multi-elements or focal plane array with silicon integrated readout circuit are feasible. Such bolometers exhibit NEP of 7 × 10⁻⁹W/Hz^1/2, and significant improvement appears possible. Electrical measurements show no noticeable film degradation after the bolometer is exposed to atmosphere for three months.     

Deposition of MgO films by pulsed mid-frequency magnetron sputtering

MgO films were deposited by pulsed mid-frequency magnetron sputtering from metallic targets in the mixture of Ar and O₂ gas. The surface morphology, crystalline structure, and optical properties were characterized by using atomic force microscopy (AFM), X-ray diffraction (XRD), and spectroscopic ellipsometry, respectively. The secondary electron emission coefficients of MgO films were measured by using a self-made apparatus in He gas. A pronounced hysteresis phenomenon of target voltage, current, and deposition rate with increasing and decreasing O₂ flow rate was observed. The structure of films deposited at a metallic mode changes from Mg phase to the mixed Mg and MgO phase, and the films have a very rough surface. All the films deposited at oxide mode have high transparency and smooth surface, and show (2 2 0) preferred orientation growth. The refractive index and extinction coefficient at a wavelength of 670 nm for MgO films deposited at oxide mode with a O₂ flow rate of 3 sccm are 1.698 and 1.16×10⁻⁴, respectively. The secondary emission coefficient at a E/p of 57.8 V/(cm Torr) for MgO films deposited at a O₂ flow rate of 3 sccm is 0.16, which is higher than that of MgO films deposited by e-beam evaporation.     

Laser ablated bismuth cuprate thin films preparation and effect of oxygen nonstoichiometry upon superconductivity

Thin films of Bi₂Sr₂CaCu₂O₈ and (Bi, Pb)₂Sr₂Ca₂Cu₃O₁₀ have been prepared on monocrystalline (100) MgO substrates, using a laser ablation method with post annealing treatment. The influence of substrate temperature and oxygen pressure during deposition were investigated. SEM observations, EDS analysis, electric and magnetic measurements have been used to characterize the films. Superconducting “2212” films, with T_c(R = 0) at 80–83 K and J_c (50 K) up to 5 × 10⁵ A/cm², have been currently achieved, while Pb-doped “2223” films exhibit T_c as high as 110 K with J_c = 5 × 10⁴ A/cm² at 77 K. The effect of annealing at low temperature (350°C) in an argon flow has been studied for the 2212 phase, it shows the influence of the oxygen non-stoichiometry, i.e. of the hole carrier density upon T_c's which can be measured up to 89 K (zero resistance).     

Fabrication of YBCO／YSZ and YBCO／MgO thick films using electrophoretic deposition with top-seeded melt growth process

Superconducting thick films were grown on single crystals MgO and YSZ by electrophoretic deposition with Y_2BaCuO_5(Y211) addition. YBCO thick films were then accomplished by sintering the precursor films above the peritectic temperature. Single crystals of MgO (3×3×0.5 mm^3) were used as top-seed to control crystal structure of the thick films. As shown by scanning electron microscopy, the morphologies of YBCO/YSZ and YBCO/MgO thick films are spherulitic texture and platelet type. The critical temperature is ～89 K for the YBCO/YSZ thick film; the onset transition temperature is 86.4 K and the transition width is ～3 K for YBCO/MgO thick film. The critical current densities (as determined by Bean model) are, in A/cm^2, 3870 (77 K) for YBCO/YSZ thick films and 2399 (77 K) for YBCO/MgO thick films, which are comparable to the best J_c reported of the thick films prepared by the same method.     

Trajectory-property relationships in MOD-derived YBCO films

A study of the physical and chemical changes during processing in MOD-derived YBCO films was performed. Fully processed films were 70–85% of theoretical density. The sintering rate increased substantially in the compositional range F/Ba = 1.8–1.5. The activation energy for sintering decreased above a P(H₂O) dependent threshold temperature. XRD indicated this temperature/composition threshold also corresponded to YBCO nucleation, suggesting ex situ YBCO forms in contact with a melt. The ramp rate and P(H₂O) were used to control F/Ba trajectories, which were correlated to performance. The nucleation of YBCO was strongly dependent on processing conditions. Nucleation temperature was varied by at least 60 °C in the study. The optimal YBCO nucleation temperature in the 300–800 nm films was around 725 °C. a-axis grains dominated the microstructures of films where YBCO nucleated at <700 °C. Large second phases, but no a-axis grains, were found when the nucleation temperature was >750 °C.     

TEM investigation of YBa2Cu3O7 thin films on SrTiO3 bicrystals

YBa₂Cu₃O₇ films in c-axis orientation on bicrystalline SrTiO₃ substrates are investigated by TEM. The films and the substrates are examined in cross-section and in plane view. The grain boundary of the bicrystal substrate contains (110) faceted voids, but is otherwise straight on a nanometer scale. Contrary to this, the film grain boundary is not straight grain boundary can be up to 100 nm for a 100 nm thick film. The deviation from the intended position of the YBCO grain boundary can already occur at the film/substrate interface where it can be as much as ±50 nm.     

低能离子对高温超导YBa_2Cu_3O_(7-δ)薄膜的表面改性和机理

低能氩离子束轰击并后退火处理的离子束表面改性,会影响高温超导薄膜的表面结构和超导特性,但是其中的深刻微观机理不清楚.本文通过连续改变离子束轰击时间,系统研究了离子束表面改性对于超导膜结构和临界电流密度的影响.通过扫描电子显微镜、X射线衍射、J_(c-scanning)测试表征样品的结构特性和超导特性,并得出内应变、氧空位缺陷等参量.研究表明,经过表面改性的钇钡铜氧(YBa_2Cu_3O_(7-δ),YBCO)薄膜,随轰击时间增加表面形貌会变得更加均匀致密,a轴晶粒消失,并且临界电流密度有了显著的提高.由化学键收缩配对模型分析得出,临界电流密度的提高与薄膜内应变增大和引发的局部YBCO结构中Cu—O键收缩有关.     

Structural properties of high-quality sputtered Fe films on Al2O3(1120) and MgO(001) substrates

High-quality thin Fe films were deposited on MgO(001) and Al₂O₃(1120) substrates in the thickness range from 7 to 50 nm. The structural properties have been studied by out-of-plane and in-plane X-ray scattering experiments. From the out-of-plane measurements the electron density profile was determined together with interface and surface roughness parameters. Fe on Al₂O₃ grows along the [110]-direction with a structural coherence length comprising about the total film thick ness and a very small mosaicity. From in-plane scattering experiments a three-domain structure was observed. On MgO(001) substrates Fe grows in the [001]-direction, with the Fe [100]-axis parallel to the MgO [110]-axis. On both substrates, the Fe films exhibit a very small surface and interface roughness, indicative for a high quality of the sputtered samples.     

面内和面外取向对RBa_2Cu_3O_z薄膜热稳定性影响的研究

采用高温金相显微镜,实时观察RBa2Cu3Oz(RBCO,R代表稀土元素)薄膜的熔化过程.结合X射线衍射(XRD)极图的分析,对不同面内取向和面外取向的RBCO薄膜熔化行为进行横向比较,研究了RBCO微结构对于其热稳定性的影响,并用半共格界面能理论很好地解释了XRD分析和实时观察熔化过程的实验结果.对不同面内取向YBa2Cu3Oz(YBCO)薄膜的研究结果表明,空气中0°晶粒的热稳定性优于45°晶粒;此外还研究了c轴取向的SmBa2Cu3Oz(SmBCO)薄膜的热稳定性,结果表明微量a轴晶粒对SmBCO薄膜的熔化行为以及其热稳定性有明显影响.     

Structural investigation of YBCO films and bicrystal grain boundary junctions

Summary We present a structural analysis of YBCO superconducting thin films fabricatedin situ by Inverted Cylindrical Magnetron (ICM) sputtering on commercial SrTiO₃ single-crystal and bicrystal substrates. A detailed structural characterization of the superconductor films was performed by using single-crystal X-ray diffractometry confirming that YBCO films have a strongc-axis orientation of the grains with a small mosaic spread. In the films grown on bicrystal substrates we observed a strong correlation with the lattice structure of the substrate. In addition, a surface analysis of the region across the grain boundary edge has been performed by using scanning electron microscopy. Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.