Effect of deposition temperature on the growth of Y1Ba2Cu3O7−x thin film by aerosol assisted chemical vapor deposition using liquid solution sources

We have investigated the effect of the deposition temperature on the growth of Y₁Ba₂Cu₃O_7−x (YBCO) thin film using liquid solution sources on MgO (100) single crystalline substrate and have characterized the superconducting properties. The YBCO films were prepared by aerosol assisted chemical vapor deposition (AACVD). Single solution source of Y, Ba, and Cu β-diketonates dissolved in tetrahydrofuran (THF) was used as precursor. This precursor was passed through an ultrasonic aerosol generator and transported into a hot-wall CVD reactor using Ar as reactant gas (400 secm). The substrate was placed normal to the gas stream and the substrate temperature was varied from 760 to 860 °C. Deposition was carried out in oxygen atmosphere maintaining total pressure of 3.2 Torr inside the chamber. Deposition time was also varied from 10 to 30 min. The grown YBCO thin films were highly oriented to (001) orientation perpendicular to the substrate. The film deposited at 815 °C had a sharp transition to superconducting state about 87 K. The activation energy estimated from the Arrhenius plot is ∼19.14 kJ/mol at the deposition temperature of 815 °C.     

Superheating nature coupled with Mg-doping effect of high thermal stable NdBa2Cu3O7-δ film

NdBa₂Cu₃O_7-δ thin film deposited on a MgO substrate has been verified to remain solid above its peritectic melting temperature (T_p). Such a superheating nature is attributed to its low energy surface and epitaxial interface with substrate. Here, combining superheating nature with doping effect, we report a novel structure, Mg-doped NdBa₂Cu₃O_7-δ film with YBa₂Cu₃O_7-δ buffer layer for the first time. Remarkably, this film presents a higher thermal stability level than heretofore possible when acting as a seed for preparing SmBa₂Cu₃O_7-δ bulks by melt growth, enduring a temperature of 1128°C, 43 K above its T_p for 1 hour. The utilization of such a high T_max in melt growth is beneficial to the fabrication of large-sized and high-performance bulk in terms of effectively broadening the growth window and suppressing the heterogeneous nucleation. More importantly, some high thermal stability required technological applications, such as batch growth and failed bulk recycling, are likely to be realized by this novel Mg-doped NdBa₂Cu₃O_7-δ film seed. Finally, we show how the observed metastable phase is linked to the distinctive film architecture.     

Significant Improvement of Superconducting Properties in Nano‐NiFe2O4‐Doped Y–Ba–Cu–O Single‐Grain Superconductor

Introduction of refined second‐phase particles in superconducting YBa₂Cu₃O_7?x (Y‐123) matrix is known to be an effective route to improve the δl‐type pinning and the performance of Y–Ba–Cu–O (YBCO) single‐grain superconductors, while the δT_c‐type pinning induced by spatial fluctuations in matrix composition is also important and contributes to the in‐field J_c performance and high‐field applications of bulk superconductors. In this communication, chemical doping of nano‐sized NiFe₂O₄ (mean size 50 nm) in single‐grain YBCO superconductor is performed using a novel top‐seeded infiltration growth (TSIG) technique based on a solid source pellet (SSP) of nano‐Y₂O₃ + BaCuO₂. The results indicate that, significant improvement of bulk performances including levitation force (33.93 N) and trapped field (0.3628 T) has been observed in the 0.2 wt% nano‐NiFe₂O₄‐doped sample, which are much higher than the undoped sample (28.81 N and 0.2754 T). T_c measurement indicates that, a decreased onset T_c of about 87.5 K and a broadened transition width of about 5 K are observed in the NiFe₂O₄‐doped sample, indicating appearance of weak superconducting regions in superconducting matrix caused by Ni and Fe substitutions in Y‐123 crystal lattice. This study supplies a practical approach to increase the YBCO bulk performance significantly.     

Surface engineering of the flexible metallic substrate by SDP-Gd-Zr-O layer for IBAD-MgO templates

Tuning substrate properties is an effective methodology to modulate the texture development of MgO films deposited by ion beam-assisted deposition (IBAD) process for epitaxial oxide films. Herein, a solution deposition planarization (SDP) technique is employed to deposit Gd-Zr-O layer for engineering surface properties of the flexible metal substrate. The correlation between the Gd-Zr-O thin film microstructure and the IBAD-MgO texture is investigated. The coordinated study on atomic force microscopy (AFM) and reflection high-energy electron diffraction (RHEED) reveal that the grain coarsening during high-temperature sintering negatively influences the texture formation of IBAD-MgO. Moreover, the chemical environment of the atoms on the surface of Gd-Zr-O seed layer also plays a critical role, which is normally overlooked. The X-ray photoelectron spectroscopy (XPS) analysis indicates that the carbon residue and intermediate phase result in the poor texture of the IBAD-MgO. This phenomenon is related to the partial decomposition and synthesis reactions due to the lower sintering temperature or reduced surface to volume ratio. We demonstrate the high-quality texture of IBAD-MgO layer, deposited on mono-coated thick Gd-Zr-O film, by using optimal heat-treatment conditions. The cross-sectional TEM images present the dense Gd-Zr-O film with Gd₂Zr₂O₇ nanograins. The multifunctionalities, such as planarization, a barrier layer, and seed layer, of Gd-Zr-O layers are realized in full-stacked CeO₂/LaMnO₃/IBAD-MgO/SDP-Gd-Zr-O/C276 samples. This work demonstrates a route for simplifying the architecture of 2G-HTS using Gd-Zr-O layer and explores the effect of the surface properties on texture formation in IBAD-MgO layer.     

Interface reaction-governed heteroepitaxial growth of YBa2Cu3O7-δ film on CeO2-buffered technical substrate

Due to the high growth rate and environmental-friendly, fluorine-free metal-organic decomposition routes (FF-MOD) have attracted more attention for growth of high-quality YBa₂Cu₃O_7-δ (YBCO) films. Few works have been performed when using technical substrates. In this study, correlation among the sintering process, microstructure, and superconductivity of the YBCO was systematically established on the technical substrates capped with CeO₂ layer. We found that the optimal process conditions are mainly related to the enhanced transient liquid phase and BaCeO₃. Combined X-ray diffraction and scanning electron microscopy analyses indicate that high-quality growth of YBCO film is a trade-off of two different competition phenomena during sintering: (a) the presence of enhanced transient liquid phase, (b) the formation of BaCeO₃ at the interface. The former is beneficial to YBCO epitaxial growth/structure rearrangement, while the latter should be suppressed in view of minimizing YBCO partial decomposition triggered by the interfacial reaction. Moreover, we confirmed that both two aforementioned phenomena are somehow associated with the cross-linkage between the sintering temperature and pO₂ during the YBCO conversion. According to this systemic study, the key parameters are defined to avoid the BaCeO₃ formation prior to the YBCO orientation nucleation. Structure and superconductivity of the YBCO film were also investigated. Remarkably, a high J_c value of 3.69 mA/cm² (77 K, sf) was obtained in the YBCO film grown on the CeO₂ technical substrate deposited under optimized deposition conditions, which is rather comparable with that on the LaAlO₃ single crystal. TEM cross-sectional observation reveals that the enhanced J_c (B) properties of the YBCO film are mainly contributed by high density of short stacking faults. This work demonstrates the feasibility of FF-MOD to fabricate high-performance YBCO films on the CeO₂-buffered technical substrate.     

A Novel Top‐Seeded Infiltration Growth Technique for Fabricating Y–Ba–Cu–O Single‐Grain Superconductor Nano‐Composites

Top‐seed infiltration and growth technique (TSIG) is proposed to fabricate Y–Ba–Cu–O (YBCO) single‐grain superconductor nano‐composites, in which a solid source composition of nano‐Y₂O₃ + BaCuO₂ and a liquid source composition of Y₂O₃ + 10BaO + 16CuO are employed. As can be seen, this novel technique uses just one source of precursor powder of BaCuO₂, so it is more simplified and efficient. Microstructural observation indicates that fine Y₂BaCuO₅ (Y‐211) inclusions with a size from dozens of nanometers to about one hundred nanometers are successfully introduced in YBa₂Cu₃O_7?x (Y‐123) superconducting matrix, which can act as more effective pinning centers for improving the bulk performance. Superconducting property measurement shows that, a maximum trapped field of 0.36044 T is present at the center of the sample after magnetization by a permanent magnet (B = 0.5 T). These results prove that our proposed TSIG technique is a practical method for fabricating YBCO bulk superconductor nano‐composites with high performance.     

Statistical evaluation of the mechanical properties of partially oxygenated YBCO,oxygenated YBCO and oxygenated YBCO(Ag) single grains

It is of great significance to enhance the mechanical properties in single grain YBCO bulk superconductors, as mechanical failure limits the suitability of these materials for high-field applications. The influence of the microstructure on the mechanical properties of YBCO bulk materials was studied in 11 partially oxygenated YBCO, 11 oxygenated YBCO, and 10 oxygenated YBCO(Ag) melt-processed bulk single grains in a statistically significant way using Brazilian testing. Surprisingly, the oxygenation cracks evolving during the tetragonal to orthorhombic phase transition do not influence the average tensile strength of YBCO bulk single grains, with compaction cracks and pores as the main microstructural flaws responsible for mechanical failure. The mechanical properties of bulk YBCO single grains even improve following oxygenation, as indicated by an increase in Weibull modulus. An addition of 10 wt% Ag₂O to YBCO increases the average tensile strength and the Weibull modulus further, making the material mechanically more robust. However, an overlap in the measured tensile strengths of oxygenated YBCO and oxygenated YBCO(Ag) bulk materials reveals that not all silver-containing samples have better mechanical properties compared to oxygenated YBCO bulk samples.     

Impact of SnS Buffer Layer at Mo/Cu2ZnSnS4 Interface

Cu₂ZnSnS₄ (CZTS) compound is a promising candidate for thin‐film solar cells since its constituents are earth abundant and nontoxic. One of the major challenges to obtain a high‐quality CZTS absorber is to overcome the interfacial mismatch and formation of secondary phases between the CZTS and Mo substrate during the sulfurization process. Generally, the CZTS decomposed into Cu₂S, ZnS, and SnS phases during sulfurization, and high‐density voids and cracks were observed. These micro‐ or macroreactions changed the stoichiometry of CZTS. In this paper, we present the insertion of a SnS buffer layer at Mo/CZTS interface to inhibit the undesired reaction and improve the thin‐film quality. The insertion of the thin SnS buffer layer prevented the CZTS absorber to contact directly with Mo and suppressed the present of secondary phases, pores and cracks. Crack‐free and smooth morphology was obtained. The cell efficiency was significantly improved.     

Fabrication and Characterization of Anode‐Supported Low‐Temperature SOFC Based on Gd‐Doped Ceria Electrolyte

Large‐size, 9.5 cm × 9.5 cm, Ni‐Gd_0.1Ce_0.9O_1.95 (Ni‐GDC) anode‐supported solid oxide fuel cell (SOFC) has been successfully fabricated with NiO‐GDC anode substrate prepared by tape casting method and thin‐film GDC electrolyte fabricated by screen‐printing method. Influence of the sintering shrinkage behavior of NiO‐GDC anode substrate on the densification of thin GDC electrolyte film and on the flatness of the co‐sintered electrolyte/anode bi‐layer was studied. The increase in the pore‐former content in the anode substrate improved the densification of GDC electrolyte film. Pre‐sintering temperature of the anode substrate was optimized to obtain a homogeneous electrolyte film, significantly reducing the mismatch between the electrolyte and anode substrate and improving the electrolyte quality. Dense GDC electrolyte film and flat electrolyte/anode bi‐layer can be fabricated by adding 10 wt.% of pore‐former into the composite anode and pre‐sintering it at 1,100 °C for 2 h. Composite cathode, La_0.6Sr_0.4Fe_0.8Co_0.2O₃, and GDC (LSCF‐GDC), was screen‐printed on the as‐prepared electrolyte surface and sintered to form a complete single cell. The maximum power density of the single cell reached 497 mW cm^–2 at 600 °C and 953 mW cm^–2 at 650 °C with hydrogen as fuel and air as oxidant.     

YBa2Cu3O7-x薄膜的制备与半导体性能的研究

采用高温固相反应制备φ60mmYBa2Cu3O7-x－（YBCO）靶材;通过直流磁控溅射后退火制备具有不同过滤层（SiO2/Si,ZrO2/SiO2/Si)的薄膜,对于Si为衬底的YBa2Cu3O7-x薄膜,当x＞0．5时,薄膜的导电性由超导态转向半导体状态,进行了X射每衍射（XRD）分析,电阻温度系数（TRC）和Hall系数测试,并进行Raman散射的微观分析实验,认为半导体薄膜可用作室温工作的红外测辐射热计（Bolometer)灵敏元。     

Fabrication and properties of ZnO/GaN heterostructure nanocolumnar thin film on Si (111) substrate

Zinc oxide thin films have been obtained on bare and GaN buffer layer decorated Si (111) substrates by pulsed laser deposition (PLD), respectively. GaN buffer layer was achieved by a two-step method. The structure, surface morphology, composition, and optical properties of these thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, infrared absorption spectra, and photoluminiscence (PL) spectra, respectively. Scanning electron microscopy images indicate that the flower-like grains were presented on the surface of ZnO thin films grown on GaN/Si (111) substrate, while the ZnO thin films grown on Si (111) substrate show the morphology of inclination column. PL spectrum reveals that the ultraviolet emission efficiency of ZnO thin film on GaN buffer layer is high, and the defect emission of ZnO thin film derived from Zn_i and V_o is low. The results demonstrate that the existence of GaN buffer layer can greatly improve the ZnO thin film on the Si (111) substrate by PLD techniques.     

Epitaxial growth of LaMnO3 thin films on different single crystal substrates by polymer assisted deposition

Structure of epitaxial LaMnO₃ thin films grown on different single crystal substrates by unconventional polymer assisted deposition (PAD) method was investigated. Epitaxial films were prepared from lanthanum manganite water based solutions deposited by spin coating on single crystal MgO (001), SrTiO₃ (001) and SrTiO₃ (110) substrates, and the influence of substrate type on the film structure was analysed. Better uniformity of the epitaxial LaMnO₃ films on SrTiO₃ substrates was obtained, but a non-stoichiometric La_1-xMnO₃ phase was formed after the heat treatment at 750 °C. In addition, the prepared thin films were multiple annealed at different temperatures up to 900 °C, in order to investigate importance of post-annealing treatment. Epitaxial nature of the prepared films was preserved after annealing at up to 900 °C and the structure rearrangement through formation of cell closer to bulk stochiometric LaMnO₃ phase was observed.     

Preferentially oriented BaTiO3 thin films deposited on silicon with thin intermediate buffer layers

Barium titanate (BaTiO₃) thin films are prepared by conventional 2-methoxy ethanol-based chemical solution deposition. We report highly c-axis-oriented BaTiO₃ thin films grown on silicon substrates, coated with a lanthanum oxynitrate buffer layer of 8.9 nm. The influence of the intermediate buffer layer on the crystallization of BaTiO₃ film is investigated. The annealing temperature and buffer layer sintering conditions are optimized to obtain good crystal growth. X-ray diffraction measurements show the growth of highly oriented BaTiO₃ thin films having a single perovskite phase with tetragonal geometry. The scanning electron microscopy and atomic force microscopy studies indicate the presence of smooth, crack-free, uniform layers, with densely packed crystal grains on the silicon surface. A BaTiO₃ film of 150-nm thickness, deposited on a buffer layer of 7.2 nm, shows a dielectric constant of 270, remnant polarization (2P_r) of 5 μC/cm², and coercive field (E_c) of 60 kV/cm.     

Ferroelectric and structural instability of (Pb,Ca)TiO3 thin films prepared in an oxygen atmosphere and deposited on LSCO thin films which act as a buffer layer

Structural, microstructural and ferroelectric properties of Pb_0.90Ca_0.10TiO₃ (PCT10) thin films deposited using La_0.50Sr_0.50CoO₃ (LSCO) thin films which serve only as a buffer layer were compared with properties of the thin films grown using a platinum-coated silicon substrate. LSCO and PCT10 thin films were grown using the chemical solution deposition method and heat-treated in an oxygen atmosphere at 700 °C and 650 °C in a tube oven, respectively. X-ray diffraction (XRD) and Raman spectroscopy results showed that PCT10 thin films deposited directly on a platinum-coated silicon substrate exhibit a strong tetragonal character while thin films with the LSCO buffer layer displayed a smaller tetragonal character. Surface morphology observations by atomic force microscopy (AFM) revealed that PCT10 thin films with a LSCO buffer layer had a smoother surface and smaller grain size compared with thin films grown on a platinum-coated silicon substrate. Additionally, the capacitance versus voltage curves and hysteresis loop measurement indicated that the degree of polarization decreased for PCT10 thin films on a LSCO buffer layer compared with PCT10 thin films deposited directly on a platinum-coated silicon substrate. This phenomenon can be described as the smaller shift off-center of Ti atoms along the c-direction 〈001〉 inside the TiO₆ octahedron unit due to the reduction of lattice parameters. Remnant polarization (P_r) values are about 30 μC/cm² and 12 μC/cm² for PCT10/Pt and PCT10/LSCO thin films, respectively. Results showed that the LSCO buffer layer strongly influenced the structural, microstructural and ferroelectric properties of PCT10 thin films.     

Low‐Temperature Control of Twins and Abnormal Grain Growth in BaTiO3

The microstructure of polycrystalline barium titanate (BaTiO₃) thin films processed with a liquid‐phase can be controlled by the crystallographic orientation of the underlying sapphire substrate. During postdeposition crystallization, the tendency for {111} twin nucleation, which drives subsequent abnormal grain growth, depends upon the specific sapphire facet. Specifically, tilting away from the close‐packed c‐plane modifies the orientation, morphology, and relative amount of an interfacial BaAl₂O₄ second phase. These factors control the density of twin formation, and thus overall grain size of the crystallized BaTiO₃. As the substrate orientation transitions from c‐plane, to r‐plane, to a‐plane, the twin density is reduced, the average grain size decreases systematically from 270 to 130 nm, and the grain structure becomes overall more homogeneous. This twinning mechanism and abnormal grain growth occur by 900°C, several hundred degrees lower than reported previously.     

Effects of Bismuth Oxide Buffer Layer on BiFeO3 Thin Film

Bismuth ferrite (BiFeO₃) thin films with Bi₂O₃ buffer layers were prepared on Si/SiO₂/TiO₂/Pt substrates by sol–gel‐derived spin‐coating method. The structural and electrical properties of BiFeO₃ was effectively improved by adding a Bi₂O₃ buffer layers either at Pt/BiFeO₃ interface or on BiFeO₃ surface, also strongly depending on the positions and the annealing conditions of buffer layers. A 500°C‐annealed Bi₂O₃ buffer layer could act as a Bi source for compensating Bi volatilization and a diffusion barrier for species from BiFeO₃. A near stoichiometric BiFeO₃ with less defects and substrate contamination was obtained by employing a 500°C‐annealed Bi₂O₃ buffer layer in between Pt substrate and BiFeO₃. The structure change in BiFeO₃ led by such a buffer layer should result from the interfacial constraint between buffer layer and BiFeO₃. Furthermore, this crystalline BiFeO₃ specimen exhibited a highly (100)‐textured, where this preferred orientation was attributed to the accumulation of Bi at Pt/BFO interface. Therefore, the Pt/500°C‐annealed Bi₂O₃/BiFeO₃/Pt thin film exhibited the good ferroelectric and magnetic properties. As compared to the usual method for controlling BiFeO₃ composition by adding excess Bi, this study indicates the more advantages using a Bi₂O₃ buffer layer.     

Improved mechanical properties through recycling of Y-Ba-Cu-O bulk superconductors

The success rate of the growth of single grain Y–Ba–Cu–O (YBCO) bulk superconductors, applied typically as trapped field magnets, by melt processing techniques is often rather low. To ensure that the rare earth elements used in these materials are not wasted, and to improve the economics of production, therefore, an effective way of recycling such “failed” samples is essential for the long-term sustainability of the bulk process. In the present paper, a detailed study of the microstructural and mechanical properties of recycled YBCO samples has been made and their properties compared to those of primary grown samples. Recycled YBCO samples exhibit trapped magnetic fields of ～ 70 – 80 % of those observed in primary grown samples. Microstructural investigations reveal a significant reduction in the porosity and a simultaneous improvement in the distribution of Y₂BaCuO₅ second phase inclusions throughout the microstructure of recycled, single grain YBCO samples. This means that, while the superconducting properties of the recycled samples are generally inferior to those of primary grown samples, somewhat surprisingly the mechanical properties such as flexural strength, hardness and tensile strength of the recycled samples can be improved. The recycled YBCO samples studied here exhibited an average flexural strength of 75 MPa, which is almost 50 % higher compared to primary grown YBCO, which has significant implications for their use in practical applications that involve large mechanical forces, such as levitation. Good correlations were observed between the microstructural parameters and measured mechanical properties in both primary grown and recycled YBCO samples.     

Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate

The BiFeO₃ (BFO) thin film was deposited by pulsed-laser deposition on SrRuO₃ (SRO)-buffered (111) SrTiO₃ (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.     

Solvothermal synthesis and thermoelectric properties of indium telluride nanostring-cluster hierarchical structures

A simple solvothermal approach has been developed to successfully synthesize n-type α-In₂Te₃ thermoelectric nanomaterials. The nanostring-cluster hierarchical structures were prepared using In(NO₃)₃ and Na₂TeO₃ as the reactants in a mixed solvent of ethylenediamine and ethylene glycol at 200°C for 24 h. A diffusion-limited reaction mechanism was proposed to explain the formation of the hierarchical structures. The Seebeck coefficient of the bulk pellet pressed by the obtained samples exhibits 43% enhancement over that of the corresponding thin film at room temperature. The electrical conductivity of the bulk pellet is one to four orders of magnitude higher than that of the corresponding thin film or p-type bulk sample. The synthetic route can be applied to obtain other low-dimensional semiconducting telluride nanostructures.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.