Advanced ion beam technology for versatile oxide thin film formation

Various oxide films, such as SnO₂, In₂O₃, Al₂O₃, SiO₂, ZnO, and Sn-doped In₂O₃ (ITO) have been deposited on glass and polymer substrates by advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry, crystallinity, and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. IBSD method has been carried out for understanding the growth mode of the films on glass and polymer substrate. Relationships between microstructure and electrical properties in ITO films on polymer and glass substrates were intensively investigated by changing ion energy, reactive gas environment, substrate temperature, etc. Smooth-surface ITO films (R_rms ⩽ 1 nm and R_p−v ⩽ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. In the case of Al₂O₃ and SiO₂ films, the oxygen and moisture barrier properties were also improved by IAR surface treatment. The experimental results of the oxide films prepared by the ion beam technologies and its applications will be represented in detail.     

Reduction of thin-film ceria on Pt(111) by supported Pd nanoparticles probed with resonant photoemission

Local defects present in CeO_2 ? x films result in a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. Previous studies of the Ce 3d region with XPS have shown that depositing metal nanoparticles on ceria films causes further reduction, with an increase in Ce³⁺ concentration. Here, we compare the use of XPS and resonant photoemission spectroscopy (RESPES) to estimate the concentration of Ce³⁺ and Ce⁴⁺ in CeO_2 ? x films grown on Pt (111), and the variation of this concentration as a function of Pd deposition. Due to the nature of the electronic structure of CeO_2 ? x, resonant peaks are observed for the 4d–4f transitions when the photon energy matches the resonant energy; (hν = 121.0 eV) for Ce³⁺ and (hν = 124.5 eV) for Ce⁴⁺. This results in two discrete resonant photoemission peaks in valence band spectra. The ratio of the difference of these peaks with off-resonance scans gives an indication of the relative contribution of Ce³⁺. Results from RESPES indicate reduction of CeO_2 ? x on deposition of Pd, confirming earlier findings from XPS studies.     

Aqueous polymer–nitrate solution deposition of YBCO films

High critical current density YBa₂Cu₃O_7?x (YBCO) films were prepared by solution deposition of aqueous non-fluorine precursors. Non-fluorine polymer-assisted deposition (PAD) processes utilizing rheology modifiers and chelating agents were used to produce 50 nm films with a critical current density (J_c) over 3 MA/cm² and 400 nm films with J_c > 1 MA/cm²_. T_c measurements indicated that films have T_c values near 90 K. The total heat treatment time to produce these high performance films was less than 4 h. Rheology modifiers such as polyvinyl alcohol (PVA) and hydroxyethyl cellulose (HEC) were used to increase the thickness of deposited films independent of the solution cation concentration. Chelating agents such as polyethylene glycol (PEG) and sucrose increased the barium ion solubility. Nitrate crystallization during deposition was controlled through rapid drying with vacuum and coating with hot solutions.     

Structural and vibrational properties of PVT grown Bi2Te3 microcrystals

High-quality Bi₂Te₃ microcrystals have been grown by physical vapor transport (PVT) method without using a foreign transport agent. The microcrystals grown under optimal temperature gradient are well facetted and they have dimensions up to ～100 μm. The phase composition of grown crystals has been identified by X-ray single crystal structure analysis in space group R3?m, a=4.3896(2) Å, b=30.5019(10) Å, Z=3 (R=0.0271). Raman microspectrometry has been used to describe the vibration parameters of Bi₂Te₃ microcrystals. The FWHM parameters obtained for representative Raman lines at 61 cm^?1 and 101 cm^?1 are as low as 3.5 cm^?1 and 4.5 cm^?1, respectively.     

Reduced crystallization time of YBCO in a fluorine-free MOD process using uv-lamp irradiation

We have studied the crystallization time dependence of the epitaxial YBCO films (t = 0.8 μm) grown on CeO₂-buffered SrTiO₃ substrates by fluorine-free metal–organic deposition using uv-lamp irradiation (uv-MOD). As increasing the time (T₀) for heat treatment at the reaction temperature (760 °C) from 0 to 90 min, J_c and the YBCO 0 0 l XRD intensity are steeply increased and reach their maximum values at T₀ = 10 min. This suggests that the heat treatment required for YBCO crystallization is significantly shortened in uv-MOD compared to conventional all-pyrolytic F-free MOD processes, which consume T₀ = 90–150 min for crystallizing 0.4–0.5-μm-thick films. Scanning electron microscope measurement revealed a drastic change in surface morphology between T₀ = 8 and 10 min, showing a good correspondence to the J_c and XRD data which suggest that the epitaxial growth reaches the film surface at the very early stage in the heat treatment.     

Modified Lanthanum Zirconium Oxide buffer layers for low-cost,high performance YBCO coated conductors

The pyrochlore Lanthanum Zirconium Oxide, La₂Zr₂O₇ (LZO), has been developed as a potential replacement barrier layer in the standard RABiTS three-layer architecture of physical vapor deposited CeO₂ cap/YSZ barrier/Y₂O₃ seed on Ni–5%W metal tape. The main focus of this research is to ascertain whether: (i) we can further improve the barrier properties of LZO; (ii) we can modify the LZO cation ratio and still achieve a high level of performance; and (iii) it is possible to reduce the number of buffer layers. We report a systematic investigation of the LZO film growth with varying compositions of La:Zr ratio in the La₂O₃–ZrO₂ system. Using a metal–organic deposition (MOD) process, we have grown smooth, crack-free, epitaxial thin films of La_xZr_1?xO_y (x = 0.2–0.6) on standard Y₂O₃ buffered Ni–5W substrates in short lengths. Detailed XRD studies indicate that a single epitaxial LZO phase with only (0 0 1) texture can be achieved in a broad compositional range of x = 0.2–0.6 in La_xZr_1?xO_y. Both CeO₂ cap layers and MOD–YBCO films were grown epitaxially on these modified LZO barriers. High critical currents per unit width, I_c of 274–292 A/cm at 77 K and self-field were achieved for MOD–YBCO films grown on La_xZr_1?xO_y (x = 0.4–0.6) films. These results indicate that LZO films can be grown with a broad compositional range and still support high performance YBCO coated conductors. In addition, epitaxial MOD La_xZr_1?xO_y (x = 0.25) films were grown directly on biaxially textured Ni–3W substrates. About 3 μm thick YBCO films grown on a single MOD–LZO buffered Ni–3W substrates using pulsed laser deposition show a critical current density, J_c, of 0.55 MA/cm² (I_c of 169 A/cm) at 77 K and 0.01 T. This work holds promise for a route for producing simplified buffer architecture for RABiTS based YBCO coated conductors.     

Assessment of the link between quantitative biexponential diffusion-weighted imaging and contrast-enhanced MRI in the liver

PurposeTo investigate if intravoxel incoherent motion (IVIM) modeled diffusion-weighted imaging (DWI) can be linked to contrast-enhanced (CE-)MRI in liver parenchyma and liver lesions.MethodsTwenty-five patients underwent IVIM-DWI followed by multiphase CE-MRI using Gd-EOB-DTPA (n = 20) or Gd-DOTA (n = 5) concluded with IVIM-DWI. Diffusion (D_slow), microperfusion (D_fast), its fraction (f_fast), wash-in-rate (R_early) and late-enhancement-rate (R_late) of Gd-EOB-DTPA were calculated voxel-wise for the liver. Parenchyma and lesions were segmented. Pre-contrast IVIM was compared 1) between low, medium and high R_early for parenchyma 2) to post-contrast IVIM substantiated with simulations 3) between low and high R_late per lesion type.ResultsD_fast and f_fast increased (P < 0.001) with 25.6% and 33.8% between low and high R_early of Gd-EOB-DTPA. D_slow decreased (− 15.0%; P < 0.001) with increasing R_early. Gd-DOTA demonstrated similar observations. f_fast (+ 10%; P < 0.001) and D_fast (+ 6.6%; P < 0.001) increased after Gd-EOB-DTPA, while decreasing after Gd-DOTA (− 4.2% and − 5.7%, P < 0.001) and were confirmed by simulations. For focal nodular hyperplasia lesions (n = 5) D_fast and f_fast increased (P < 0.001) with increasing R_late, whereas for hepatocellular carcinoma (n = 4) and adenoma (n = 7) no differences were found.ConclusionMicroperfusion measured by IVIM reflects perfusion in a way resembling CE-MRI. Also IVIM separated intra- and extracellular MR contrast media. This underlines the potential of IVIM in quantitative liver imaging.     

Microstructural properties of plasma-enhanced chemical vapor deposited WNx films using WF6–H2–N2 precursor system

A WF₆–H₂–N₂ precursor system was used for plasma-enhanced chemical vapor deposition (PECVD) of WN_x films. We examined the microstructural changes of the WN_x films depending on N₂/H₂ flow-rate ratio and post-annealing (600–800 °C for 1 h). As the N₂/H₂ flow rate was increased from 0 to 1.5, as-deposited WN_x films exhibited various different crystalline states, such as nanocrystalline and/or amorphous structure comprising W, WN, and W₂N phases, a fine W₂N granular structure embedded in an amorphous matrix, and a crystalline structure of β-W₂N phase. After post-annealing above 600 °C, crystalline recovery with phase separation to β-W₂N and α-W was observed from the WN_x films deposited at an optimized deposition condition (flow-rate ratio = 0.25). From this PECVD method, an excellent step coverage of ∼90% was obtained from the WN_x films at a contact diameter of 0.4 μm and an aspect ratio of 3.5.     

Colossal magnetoresistance effect in epitaxially grown La2/3Ca1/3MnO3 perovskite-like manganite thin films

We report in this work, study on colossal magnetoresistance (CMR) effect in epitaxial La_2/3Ca_1/3 MnO₃ thin films grown on SrTiO₃ (0 0 1) substrates by pulsed laser deposition (PLD) technique. The films were grown on as-received SrTiO₃ substrates and on SrTiO₃ substrates prepared by HF etching (Koster et al., Appl. Phys. Lett. 73 (1998) 2920; V. Leca et al., Wet etching methods for perovskite substrates, University of Twente, MESA+ Research Institute, Low Temperature Division). Two of the samples were annealed in different conditions to investigate the films heat treatment effect on electric and magnetic properties. Electrical resistance was done using the four-probe method at temperatures in the range of 2–375 K without a magnetic field and in an external field of 5 T applied in the film plane. Resistance-magnetic field (R vs. H) at 77 K for the two annealed samples was done in a 5 T sweep magnetic field. The surface morphology and structural information of the films were obtained using atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. Secondary ion mass spectroscopy (SIMS) analysis was performed on the annealed samples to investigate any possible chemical reaction between La_2/3Ca_1/3MnO₃ thin films and SrTiO₃ substrate.     

Optical parameters of In–Se and In–Se–Te thin amorphous films prepared by pulsed laser deposition

The thin films of materials based on In–Se are under study for their applicability in photovoltaic devices, solid-state batteries and phase-change memories.The amorphous thin films of In₂Se_3−xTe_x (x=0–1.5) and InSe were prepared by pulsed laser deposition method (PLD) using a KrF excimer laser beam (λ=248 nm, 0.5 J cm⁻²) from polycrystalline bulk targets. The compositions of films verified by energy-dispersive X-ray analysis (EDX) were close to the compositions of targets. The surfaces of PLD films containing small amount of droplets were viewed by optical and scanning electron microscopy (SEM).The optical properties (transmittance and reflectance spectra, spectral dependence of index of refraction, optical gap, single-oscillator energy, dispersion energy, dielectric constant) of the films were determined.The values of index of refraction increased with increasing substitution of Te for Se in In₂Se₃ films, the values of the optical gap decreased with increasing substitution of Te for Se in In₂Se₃ films.     

Effect of the composition on the superconducting properties of IBAD-MgO SmBCO coated conductors with superconducting film directly deposited on epi-MgO layer

Sm_1+xBa_2?xCu_3+yO_7?δ (SmBCO) films were directly deposited on the epi-MgO/IBAD-MgO/Y₂O₃/Al₂O₃/Hastelloy template by co-evaporation using the evaporation using drum in dual chambers (EDDC) system without the buffer layer in order to investigate the effect of the composition ratios on superconducting property, microstructure and texture of SmBCO film. The films with gradient composition ratios of Sm:Ba:Cu were deposited using a shield with an opening which was placed between the substrate and the boats. The highest I_c of 52 A (corresponding to J_c = 1.6 MA/cm² and a thickness of 800 nm) was observed at 77 K in self field at a composition x = 0.01–0.05 and y = ?0.23 to ?0.46. When the composition ratio is outside this range, the I_c value rapidly decreased. The superconducting critical current was highly dependent on the composition ratio. As the composition ratio is farther away from that of the highest I_c, the SmBCO (1 0 3) peak intensity increased and the amount of a-axis oriented parts increased. A dense microstructure with round-shape grains was observed in the region showing the highest I_c. The optimum composition ratio can be found by analyzing films deposited with variable deposition rates of each depositing element.     

Surface X-ray diffraction analysis of Fe nanostructured films grown on c(2 × 2)-N/Cu(100)

We report the results of a Surface X-Ray Diffraction (SXRD) study of Fe nanostructured films deposited on c(2 × 2)-N/Cu(100) at room temperature (RT), with Fe coverage Θ_Fe = 0.5 ML and Θ_Fe = 1 ML. The c(2 × 2)-N/Cu(100) surface is an example of self-organised system, that can be used for growth of arrays of metal nano-islands and organic molecules assemblies. We chose two different values of N coverage, Θ_N = 0.3 ML and Θ_N = 0.5 ML, the second value corresponding to N saturation. We monitored the presence of surface diffraction peaks in hk scans and we performed Crystal Truncation Rods (CTR) analysis with ROD fitting programme. In the case of Θ_N = 0.5 ML, i.e. at saturation coverage, the CTR could be fitted with one surface domain with p4gm(2 × 2) symmetry. In the surface cell adopted, N atoms occupy four-fold hollow sites, with Fe (intermixed with Cu) giving rise to a “clock” reconstruction previously observed on iron nitride films obtained by co-deposition and annealing. This result is an indirect confirmation of N surface segregation on top of the Fe films, occurring during the growth at RT. When subsaturation N coverage (Θ_N = 0.3 ML) is used as a substrate for Fe deposition, the best results could be obtained with a model where two surface domains are present: the first one corresponds to a surface cell with Fe sitting in four-fold hollow sites on bare Cu areas, with possible interdiffusion in the second lattice. The second domain is assigned to growth of Fe on the N-covered square islands occurring once the bare Cu areas are fully covered. The SXRD analysis on N-covered surface domains shows that the mechanism of reconstruction and of N segregation on top layer is already active at RT for all N-coverage values.     

Chemical bath deposition of SnO2 and Cd2SnO4 thin films

A new approach of chemical bath deposition (CBD) of SnO₂ thin films is reported. Films with a 0.2 μm thickness are obtained using the multi-dip deposition approach with a deposition time as little as 8–10 min for each dip. The possibility of fabricating a transparent conducting oxide layer of Cd₂SnO₄ thin films using CBD is investigated through successive layer deposition of CBD-SnO₂ and CBD-CdO films, followed by annealing at different temperatures. High quality films with transmittance exceeding 80% in the visible region are obtained. Annealed CBD-SnO₂ films are orthorhombic, highly stoichiometric, strongly adhesive, and transparent with an optical band gap of ～4.42 eV. Cd₂SnO₄ films with a band gap as high as 3.08 eV; a carrier density as high as 1.7 × 10²⁰ cm^?3; and a resistivity as low as 1.01 × 10^?2 Ω cm are achieved.     

Epitaxial alloyed films out of the bulk stability domain: Surface structure and composition of Ni3Al and NiAl films on a stepped Ni(1 1 1) surface

We have studied by Spot Profile Analysis Low Energy Electron Diffraction (SPA-LEED) and Auger Electron Spectroscopy (AES) Ni–Al alloyed layers formed by annealing, around 780 K, Al deposits on a stepped Ni(1 1 1) surface. The surface structure and composition of the thin epitaxial Ni₃Al and NiAl films, obtained respectively below and above a critical Al initial coverage θ_c, differ markedly from those of corresponding bulk alloys.The Ni₃Al ordered films form in a concentration range larger than the stability domain of the L1₂ Ni₃Al phase. The NiAl films present a marked distortion with respect to the lattice unit cell of the B2 NiAl phase, which slowly decreases when the film thickness increases.It also appears that the value of θ_c depends on the morphology of the Ni(1 1 1) substrate, increasing from θ_c = 4.5 ML for a flat surface to θ_c = 10 ML for a surface with a miscut of 0.4°. This could be directly related to the presence of steps, which favour Ni–Al interdiffusion.     

Ionic conductivity and phase transition in Pb4.8Bi1.6Na3.6(PO4)6, an apatite-type compound

Bismuth sodium lead phosphate, Pb_4.8Bi_1.6Na_3.6(PO₄)₆, a compound having an apatite structure, was obtained via a solid-state reaction. Determination of the structure by X-ray diffraction on a single crystal gave the following results: hexagonal, P6₃/m, a = 9.6545(11) Å, c = 7.1457(5) Å, R = 0.03 and R_w = 0.09. The presence of Bi³⁺ and Pb²⁺ ions, carrying a lone electron pair, at (6h) sites helped to stabilize the apatite structure in spite of the anionic vacancies in the center of the tunnel. The compound was characterized by chemical analysis, differential thermal analysis, thermal expansion of the cell, and infrared, impedance and ²³Na NMR spectroscopy. The thermal behavior revealed two breaks attributed to order–disorder transitions. One of them was ascribed to a reordering of cations from the (6h) site to the center of the tunnel. Conductivity was dominated by hopping mechanisms.     

Crystal growth and structural properties of the spinel-type Li1 + xMn2 − xO4 (x = 0.10, 0.14)

Single crystals of the lithium-rich lithium manganese oxide spinels Li_1 + xMn_2 − xO₄ with x = 0.10 and 0.14 have been successfully synthesized in high-temperature molten chlorides at 1023 K. The single-crystal X-ray diffraction study confirmed the cubic Fd3¯m space group and the lattice parameters of a = 8.2401(9) Å for x = 0.10 and a = 8.2273(10) Å for x = 0.14 at 300 K, respectively. The crystal structures have been refined to the conventional values R = 3.7% for x = 0.10 and R = 3.1% for x = 0.14, respectively. Low-temperature single-crystal X-ray diffraction experiments revealed that these single crystal samples showed no phase transition between 100 and 300 K. The electron-density distribution images in these compounds by the single-crystal MEM analysis clearly showed strong covalent bonding features between the Mn and O atoms due to the Mn–3d and O–2p interaction.     

High performance GdBa2Cu3O7−z film preparation by non-fluorine chemical solution deposition approach

Biaxially textured GdBa₂Cu₃O_7?z (GdBCO) films with T_c above 93 K have been prepared on (0 0 l) LaAlO₃ substrate by self-developed non-fluorine polymer-assisted chemical solution deposition (PA-CSD) approach. The GdBCO films show smooth and crack-free morphology. Many nanoscale particles with homogeneous distribution are observed in the GdBCO films, which have not been observed yet in the YBa₂Cu₃O_7?z (YBCO) films prepared by the same processing technique. Besides a high J_c (77 K, 0 T) of 2.28 MA/cm², the optimized GdBCO films show a better J_c–B behavior and an improved high-field J_c, compared to the YBCO films.     

Thickness dependence of Ic and Jc of LTG-SmBCO coated-conductor on IBAD-MgO tapes

We have reported SmBa₂Cu₃O_y (SmBCO) films on single crystalline substrates prepared by low-temperature growth (LTG) technique. The LTG-SmBCO films showed high critical current densities in magnetic fields compared with conventional SmBCO films prepared by pulsed laser deposition (PLD) method. In this study, to enhance critical current (I_c) in magnetic field, we fabricated thick LTG-SmBCO films on metal substrates with ion-beam assisted deposition (IBAD)-MgO buffer and estimated the I_c and J_c in magnetic fields.All the SmBCO films showed c-axis orientation and cube-on-cube in-plane texture. T_c of the LTG-SmBCO films were 93.1–93.4 K. J_c and I_c of a 0.5 μm-thick SmBCO film were 3.0 MA/cm² and 150 A/cm-width at 77 K in self-field, respectively. Those of a 2.0 μm-thick film were 1.6 MA/cm² and 284 A/cm-width respectively. Although I_c increased with the film thickness increasing up to 2 μm, the I_c tended to be saturated in 300 A/cm-width. From a cross sectional TEM image of the SmBCO film, we recognized a-axis oriented grains and 45° grains and Cu–O precipitates. Because these undesired grains form dead layers, I_c saturated above a certain thickness. We achieved that I_c in magnetic fields of the LTG-SmBCO films with a thickness of 2.0 μm were 88 A/cm-width at 1 T and 28 A/cm-width at 3 T.     

Internal evaluation of impregnation treatment of waterlogged wood; relation between concentration of internal materials and relaxation time using magnetic resonance imaging

The purpose of this study is to clarify the degree of impregnation resulting from treatment of internal waterlogged wood samples using MRI. On a 1.5 T MR scanner, T₁ and T₂ measurements were performed using inversion recovery and spin-echo sequences, respectively. The samples were cut waterlogged pieces of wood treated with various impregnation techniques which were divided into different concentrations of trehalose (C₁₂H₂₂O₁₁) and polyethylene glycol (PEG; HO-(C₂H₄O)_n-H) solutions. Then these samples underwent impregnation treatment every two weeks. From the results, we found that the slope of the T₁-concentration curve using linear fitting showed the value of the internal area for PEG to be higher than the external area; internal, − 2.73 ms/wt% (R² = 0.880); external, − 1.50 ms/wt% (R² = 0.887). Furthermore, the slope of the T₁-concentration curve using linear fitting showed the values for trehalose to have almost no difference when comparing the internal and the external areas; internal, − 2.79 ms/wt% (R² = 0.759); external, − 3.02 ms/wt% (R² = 0.795). However, the slope of the T₂-concentration curve using linear fitting for PEG showed that there was only a slight change between the internal and the external areas; internal, 0.26 ms/wt% (R² = 0.642); external, 0.18 ms/wt% (R² = 0.920). The slope of the T₂-concentration curve did not show a change in linear relationship between the internal and the external areas; internal, 0.06 ms/wt% (R² = 0.175); external, − 0.14 ms/wt% (R² = 0.043). In conclusion, using visualization of relaxation time T₁, it is possible to obtain more detail information noninvasively concerning the state of impregnation treatment of internal waterlogged wood.     

Structure and magnetic properties of co-sputtered Co–C thin films

We studied the structure and magnetic properties of co-sputtered Co_1−xC_x thin films using a transmission electron microscope (TEM) and a SQUID magnetometer. These properties were found to depend critically on deposition temperature, T_S, and composition, x. Generally, phase separation into metallic Co and graphite-like carbon phases proceeds with increasing T_S and decreasing x. Plan view and cross-sectional TEM images of the films prepared showed that Co grains about 10–20 nm in diameter and 30–50 nm in height are three-dimensionally separated by graphite-like carbon layers 1–2 nm thick. Optimum magnetic properties with saturation magnetization of 380 emu/cc and coercivity of 400 Oe were obtained for a film with x=0.5 and T_S=350°C.