European Journal of Scientific Research ISSN 1450-216X Vol.29 No.4 (2009), pp. 438-446 EuroJournals Publishing, Inc.

. 2009 http://www.eurojournals.com/ejsr.htm

Superconducting Properties of BSCCO Thin Films by Pulsed Laser Deposition

A.N. Jannah Faculty of Applied Sciences, University Technology MARA 72000, Kuala Pilah, Negeri Sembilan, Malaysia E-mail: nurjannah@ns.uitm.edu.my Tel: 06-4821235, 016-6740026 S.A. Halim Superconductor and Thin Films Laboratory, Department of Physics Faculty of Science & Environmental, University Putra Malaysia 43400 Serdang, Selangor, Malaysia H. Abdullah Dept.of Electrical, Electronic and System Engineering Faculty of Engineering and Built Environment Universiti Kebangsaan Malaysia, Malaysia Abstract Thin films of Bi(Pb)-Sr-Ca-Cu-O have been grown epitaxially in c-axis orientation on (100) MgO by pulsed laser deposition from 2223 target. The substrate temperature was 500C and the oxygen partial pressure during the deposition was ~2 x 10-3 mbar using the second harmonics of an Nd:YAG pulse laser beam. The main properties of BSCCO thin films obtained by laser ablation followed by a post-deposition oxygen annealing treatment were investigated by X-ray diffraction, scanning electron microscopy, atomic force microscopy and four-probe resistivity measurements. The high-temperature annealing treatment was also found to be the important parameter for obtaining superconducting transitions. The effect of annealing treatment on the structure and quality of as-deposited and annealed thin films of BSCCO are reported and discussed, as well of the sintered pellets used as targets. Keywords: Pulsed Laser Deposition, MgO, BSCCO, thin film.

1. Introduction
Since the discovery of the first high-temperature superconductor (HTS) (Maeda et al, 1988) a significant effort has been put into the research on and realization of textured and epitaxial HTS films. This effort is motivated largely by the potential applications of thin films in a number of cryoelectronic devices and by the possibility of using epitaxial single or multiplayer HTS films to study new physical properties of these unique layered materials. However, the future application of HTSs in cryoelectronic devices which are capable of operating at temperatures between typically 20 K and 77 K will strongly depend on the development of a reproducible deposition technology or high-quality single and

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multilayer HTS thin films. Typical applications areas included metrology and electronic instrumentation, radioastronomy and environmental spectroscopy (atmosphere and space), neurology and medical diagnostics, electronic warfare (radar, ECM, magnetic anomaly detection), nondestructive materials evaluation (NDE-NDT), telecommunications, ultrafast digital signal and data processing. In this work, it has been found that thermal treatment parameters such as annealing time and annealing temperature play an important role in the formation of high Tc phases (Li et al, 1997, Hakuraku et al, 1993). X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and resistivity measurements on the BSCCO thin films grown by means of PLD were discussed.

2. Previous Research
Thin films of the BiSrCaCuO family have been grown by single-target pulsed laser deposition by Viret et al (1993). The post annealing (ex situ) technique normally leads to very granular films. For Bi2Sr2CaCu2O8+ (2212) films prepared in this way, the resistivity drops abruptly at temperatures in the range 80-85 K. Post-annealed Bi2Sr2Ca2Cu3O10+ (2223) films could only be obtained in a very narrow annealing temperature window. They all contained the secondary 2212 phase and therefore displayed a two-step resistivity drop at 110 K and 80 K. All the ex situ films display a resistive tail at lower temperatures due to their granularity. In situ crystallized films have very flat surfaces but have poorer superconducting properties than ex situ films. The resistive transitions are broader, but there is no resistive tail at lower temperatures. This behaviour could be due to inhomogeneities in the oxidation process during deposition. The deposition conditions for optimizing the in situ formation of the 2223 phase may need to be closely defined. Kula et al have reported the investigation of the 110 K Bi2Sr2CaCu3Ox phase formation in superconducting thin films of Bi-based cuprates in 1991. The films were dc magnetron sputtered from single Bi(Pb)-Sr-Ca-Cu-O targets of various stoichiometries, and subsequently annealed in air at high temperatures. It has been found that the films, fully superconducting above 100 K could be reproducibly fabricated on various dielectric substrates from Pb-rich targets by optimizing annealing conditions for each initial Pb/Bi ratio. Heavy Pb doping considerably accelerated formation of the 110K phase reducing the film annealing time to less than 1 hour. Films containing, according to the x-ray measurement more than 90% of the 110 K phase were obtained on MgO subtrates, after sputtering from Bi2Pb2.5Sr2Ca2.15Cu3.3Ox target and annealing in air for 1 hour at 870C. The films were c-axis oriented, with 4.5 K wide superconducting transition, and zero resistivity at 106 K. Their critical current density was 2 102 A/cm2 at 90 K, and above 104 A/cm2 below 60 K. The growth of the 110 K phase on epitaxial substrates, such as CaNdAlO4 and SrTiO3, was considerably deteriorated, and the amount of this phase was always lower than 50%. Superconductive Bi2Sr2CuO6+x (Bi-2201) thin films were prepared on MgO (100) substrates by laser ablation using a KrF excimer laser beam and the 4th harmonics of an Nd:YAG pulse laser beam (Uchiyama and Wang, 2000). A stoichiometric non substituted Bi-2201 target was used. In the case of using the Nd:YAG pulse laser, as-deposited Bi-2201 thin films showed high crystallinity, metallic normal-conductivity till a onset of the critical temperature and Tc0 ~ 4 K. The R-T characteristics were changed drastically for slightly different PO2, that is, the superconductivity of Bi-2201 thin films was very sensitive to PO2. It was seen that the preparation by 4th YAG laser ablation was, even if under the optimum doping, difficult to obtain high Tc0. Bi2Sr2CanCun+1Oy (n 0; BSCCO) thin film is fabricated via two different processes using an ion beam sputtering method i.e. co-deposition and layer-by-layer deposition (Mori et al, 1996). A single phase of Bi2212 can be fabricated via the co-deposition process, while it cannot be obtained by the layer-by-layer process. Ultra-low growth rate in ion beam sputtering system brings out the difference in Bi element adsorption between the two processes and results in only 30% adsorption against total incident Bi amount by layer-by-layer deposition, in contrast to enough Bi adsorption by co-deposition. Re-evaporation in the form of Bi atoms or Bi2O3 molecules easily bring out the

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deficiency of Bi atoms in thin film due to the long sputtering time of the layer-by-layer deposition. Bi deficiency leads to compositional deviation on the substrate surface, and to the formation of impurity compounds. It was found that the Bi2212 structure is difficult to construct at such a low growth rate in the layer-by-layer deposition. Kim et al, 1988, deposited thin films of Bi-Sr-Ca-Cu-O on (100) cubic zirconia by laser ablation from a bulk superconducting target of nominal composition BiSrCaCu2Ox had investigated by dc resistance and magnetically modulated microwave absorption measurements. The latter technique reveals important features regarding the phase purity of superconducting samples that are masked in the dc resistance measurements. It has shown that the film quality is affected by the substrate temperature and the annealing process. Observations of magnetic field effects using the MAMMA technique show that the films are oriented with the c-axis perpendicular to the film plane. Thick c-oriented films of single-phase Bi2Sr2CaCu2Oy (Bi-2212) were prepared on (100) MgO substrates by employing a partial melting method (Wang et al, 1995). The effect of quenching on Tc0 obtained by resistance was studied and the highest Tc0 obtained by resistance measurement was 92 K, whereas 93.2 K was achieved by AC susceptibility measurements. The best results for the critical current density Jc, measured in zero magnetic field, were 1.3 x 103 A cm-2 at 77 K and 7 x 103 A cm-2 at 53 K. Near Tc the temperature dependence of Jc can be described by Jc ~ (1 T/Tc)2. At temperatures T Tc the dependence of Jc on temperature can be described by a homogenous superconductor flux creep model. The effect of the growth rate on the Bi2Sr2CaCu2Oy (Bi2212) thin film quality on MgO substrate have been investigated by Qi et al (2001) at several growth rate from 0.175 to 3 nm/min. The maximal step height on the film surface is improved from about 100 to 6 nm by the reduction of growth rate to 0.5 nm/min and simultaneously the superconducting critical temperature attaining to a zero resistance Tc (R = 0),is also improved from 50 to 63 K. The surface morphologies of the upmost Bi-superconducting thin films with the intermediate layers on MgO substrate is also studied in contrast to that deposited directly on the MgO substrate.

3. Research Method
Deposition The substrate is positioned ~5.0 cm from the target and heated at 500C. The chamber were pumped to 1 x 10-4 mbar before deposition and it was kept at 2 x 10-3 mbar (O2 environment) during the ablation. Thin films were deposited on MgO single crystal (100) oriented substrate by laser ablation the sintered Bi(Pb)-Sr-Ca-Cu-O pellets. The pellets were obtained by calcining mixtures of Bi2O3, PbO, CaCO3, SrCO3 and CuO, with the aim that the Pb partial substitution of Bi should promote the growth of the BSCCO 2223 high Tc phase. The as-deposited Bi(Pb)-Sr-Ca-Cu-O film were annealed in a tube furnace under oxygen flow at the temperatures between 820C to 850C for 2 hours with heating rate 3C/min; and cooling rate of 2C /min. The annealing temperature was varied in order to obtain the best annealing sequence. Morphological and structural analysis of thin films produced were performed by an SEM, X-ray diffractometer and AFM. The electrical properties of the bulk and film were measured using a four point probe system.

4. Results and Discussion

Target Surface modifications on irradiated target always take place in the PLD process in periodic structure such as ripples, ridges and cones. Figure 1 shows the formation of surface morphology on a rotational target irradiated by low fluence laser.

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Figure 1: Scanning electron micrograph of the laser impact on the superconducting Bi(Pb)-Sr-Ca-Cu-O target (1) before irradiation (2) after irradiation for the rotating target, (3) after irradiation for the fixed target (crater).

(a) 3 2 1

A similar behaviour was previously discussed (Fogarassy et al, 1989). Microstructure observation was done by using Leo VPSEM scanning electron microscopy (SEM). The SEM micrograph of fractured surface for the pellet are shown in Figure 2. SEM studies have shown that the surface morphology of the sample comprises of platelets having an average size 10m with uniform and homogenous microstructure. The platelet-type-features of the morphology are believed to be due to the 110 K phase (Sharma et al, 1995). The electrical resistivity of the pellet was measured by a standard d.c four point-probe method to ascertain the superconducting transition temperature Tc. The resistance versus temperature for the target is presented in Figure 3. A Tc onset of 110K, corresponding essentially to the high temperature phase 2223, is observed, and zero resistance temperature higher than 102 K is achieved.
Figure 2: SEM micrograph of sample Bi(Pb)SrCaCuO pellet.

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Figure 3: R-T curve showing resistance of Bi1.6Pb0.4Sr2Ca2Cu3Oy pellet.
0.004 0.0035 Resistivity ( ohm ) 0.003 0.0025 0.002 0.0015 0.001 0.0005 0 20 70 120 170 220 270 Temperature ( Kelvin )

Thin Film X-ray diffraction measurements were taken using a CuK source. Figure 4 shows X-ray diffraction patterns of Bi(Pb)-Sr-Ca-Cu-O film deposited 30 minutes on MgO single crystal and annealed at 800C-850C. It shows that as-deposited film did not shows any significant crystallinity from the XRD spectrum. When annealing process is applied, there is a slight (00l) preferred orientation, indicating that the a and b axes lie along the substrate surface, whereas the c axis is perpendicular to the surface. The diffraction patterns of sample in Figure 4 show a series of strong peaks at 2 = 23.2, 29.0, 35.0, 47.3 and 60.1. Small features at the base of some peaks indicate the presence of small amounts of the 2201 phase. The XRD peaks became significantly stronger and sharper by post-annealing. The peaks of the film exhibit a mixed of the 2212 and 2201 phases. Peaks with () are from the substrate and the structure at the base of the MgO reflection is due to the absorption edges of MgO (Bowman et al, 1991).

Superconducting Properties of BSCCO Thin Films by Pulsed Laser Deposition

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Figure 4: X-ray diffraction patterns of Bi-Sr-Ca-Cu-O film on (100) MgO a) as-deposited and annealed at b) 820C c)840 C d) 850C for 2 hours in oxygen flow.
counts/s

MgO (100) (008) (0010) (0012) o (0016) (0020) annealed at 850oC

annealed at 840oC

annealed at 820oC as deposited

O

2Theta

A typical resistivity curve measured on the film deposited for 30 minutes as shown in Figure 5, displays a broad transition followed by a long tail at lower temperatures. These tails lead to zero resistivities at temperature around 60 K. The typical morphology of the annealed film is shown in Figure 6. The crystallites have typical sizes of 3m. The upper layer of the film consists of small Cuenriched needles and long crystals. Platelets are observed at some parts of the film. These could be due to the presence of 2212 and 2223 phases.
Figure 5: R-T curve of a Bi-Sr-Ca-Cu-O thin film deposited 30 minutes on (100) MgO annealed at 850C for 2 hours in oxygen flow.
0.16

0.14

0.12

Resistivity ( ohm )

0.1

0.08

0.06

0.04

0.02

0 0 -0.02 50 100 150 200 250 300 350

Temperature ( Kelvin )

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Figure 6: SEM micrograph of a Bi(Pb)-Sr-Ca-Cu-O film deposited 30 minutes and annealed at 850 C.

Figure 7: FM image of the Bi(Pb)SrCaCuO thin films deposited for 30 minutes and annealed at 880C

The surface morphology of Bi(Pb)SrCaCuO thin films deposited for 30 minutes and annealed at 880C was carried out by using AFM as shown in Figure 7. The mean surface roughness, Ra, of the samples were measured with scanning areas of 80 x 80m2. Mean deviation,Ra values and the root mean square deviation value (RMS) from AFM images are 263.5 nm and 372.4 nm respectively. The film showed a rough surface. This mode may be correlated to the existence of clusters in the plasma.

5. Summary
Superconducting films of Bi(Pb)-Sr-Ca-Cu-O have been fabricated from BSCCO pellet of 2223 phase by laser deposition with annealing process. Annealing at 850C for 2 hours improved the superconducting properties of the film. The XRD patterns and Tc measurement with zero resistivity temperature at about 60 K indicate that the film were mainly grown in 2212 phase, with 2223 phase which is detected in small structures on the film surface. X-ray diffraction data show the films to be caxis oriented. The annealing process was very effective to increase a zero-resistivity temperature. To improve the epitaxy of these films the conditions of growth have to be improved.

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6. Acknowledgement
The financial support of the ministry of science and technology, under the IRPA vote 54952 is gratefully acknowledged.

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