The influence of YSZ interlayer on microstructures and dielectric properties of BST thin films prepared by RF magnetron sputtering

(Ba_{1 − x} Sr _x )TiO₃ (BST) thin films were deposited on Pt/Ti/SiO₂/Si and YSZ/Pt/Ti/SiO₂/Si substrates by radio frequency (RF) magnetron sputtering. The influence of YSZ interlayer on microstructures and dielectric properties of BST thin films were investigated by X-ray diffraction, atomic force microscopy, scanning electron microscopy and dielectric frequency spectra. It was found that the preferred orientation of BST thin films could be tailored by insertion of YSZ interlayer and adjusting the thickness of YSZ interlayer. The BST thin films deposited on YSZ interlayer exhibited a more compact and uniform grain structure than that deposited directly on Pt electrode. Dielectric measurement revealed that the BST thin films deposited on 10 nm YSZ interlayer have the largest dielectric constant and a low dielectric loss tangent. The enhanced dielectric behavior is mainly attributed to the YSZ interlayer which serves as an excellent seeding layer to enhance the crystallization of subsequent BST films layer, and a smaller thermal stress field built up at the interface between YSZ interlayer and BST film layer.     

YSZ thin films deposited by e-beam technique

YSZ thin films were grown evaporating cubic and tetragonal phase ZrO₂ stabilized by 8 wt.% of Y₂O₃ (8% of YSZ) ceramic powders by using e-beam deposition technique. Operating technical parameters that influence thin film properties were studied. The influence of substrate crystalline structure on growth of deposited YSZ thin film was analyzed there. The YSZ thin films (1.5-2 μm of thickness) were deposited on three different types of substrates: Al₂O₃, optical quartz (SiO₂), and Alloy 600 (Fe-Ni-Cr). The dependence of substrate temperature, electron gun power, and phase of ceramic powder on thin film structure and surface morphology was investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The substrate temperature was changed in the range of 20-600° C (during the YSZ thin film deposition) and its influence on the crystallinity of deposited YSZ thin films was analyzed. It was found that electron gun power and substrate temperature has the influence on the crystallite size, and texture of YSZ thin films. Also, the substrate has no influence on the crystal orientation. The crystallite size varied between 20 and 40 nm and increased linearly changing the substrate temperature. The crystal phase of evaporated YSZ powder has the influence on the structure of the deposited YSZ thin films.     

Reactive sputtering of titanium and properties of titanium suboxide films for photochemical applications

The effect of oxygen partial pressure on the deposition rate, crystalline structure and optical absorption of thin film titanium suboxides prepared by the reactive sputtering of a titanium metal target is given. A wide variety of films ranging from metallic through semiconducting to dielectric specimens were deposited in a reproducible manner simply by controlling the oxygen content in the sputtering plasma atmosphere. In addition, polycrystalline stable semiconducting TiO₂ electrodes were deposited onto heated glass substrates. The spectral response was investigated; a main absorption edge of about 410 nm was obtained. The design of a special substrate table with a unique mask changer that allowed for the fabrication of different geometrical film patterns is also given.     

High-power impulse magnetron sputtering of Ti-Si-C thin films from a Ti3SiC2 compound target

We have deposited Ti-Si-C thin films using high-power impulse magnetron sputtering (HIPIMS) from a Ti₃SiC₂ compound target. The as-deposited films were composite materials with TiC as the main crystalline constituent. X-ray diffraction and photoelectron spectroscopy indicated that they also contained amorphous SiC, and for films deposited on inclined substrates, crystalline Ti₅Si₃C_x. The film morphology was dense and flat, while films deposited with direct-current magnetron sputtering under comparable conditions were rough and porous. We show that, due to the high degree of ionization of the sputtered species obtained in HIPIMS, the film composition, in particular the C content, depends on substrate inclination angle and Ar process pressure.     

High textured AlN thin films grown by RF magnetron sputtering; composition, structure, morphology and hardness

High quality thin aluminum nitride (AlN) films have been deposited onto a silicon (1 0 0) substrate by radio frequency magnetron sputtering of a pure Al target using different gas (Ar, N₂) mixtures. The depositions were carried out at substrate temperatures varying from room temperature (plasma heating) up to 400°C. The crystalline structures were investigated by X-ray diffractometry (XRD) revealing a pronounced texture of the deposited films. Some of the compounds investigated were deposited onto a thin buffer layer of pure Al. The film surface morphology was investigated by Atom Force Microscopy (AFM) (SPM-9500J3 from Shimadzu Co), and was found to depend distinctively upon the different deposition conditions. Generally, two kinds of structures were found—a columnar one, which was densely packed or organized in planar parallel sheets, and a flat structure, (typical for mono-crystals), with rms roughness below 0.2 nm. In this paper, the influence of argon added to the sputtering gas environment on the film properties is investigated and discussed. The depth elemental distributions were calculated using 2.4 MeV ⁴He⁺ Rutherford Backscattering Spectrometry (RBS). Finally, the mechanical characteristics were described using hardness tests.     

Preparation of Double Perovskite Ca2NiWO6 as a Buffer Layer for YBa2Cu3O7−δ Coated Conductors

Ca₂NiWO₆ films were deposited on the Y-stabilized ZrO₂ (100) (YSZ) single crystalline substrates by pulsed laser deposition process. X-ray diffraction reveals that the Ca₂NiWO₆ film is coherently strained due to the small lattice mismatch between Ca₂NiWO₆ and YSZ substrate. With this c-axis orientated Ca₂NiWO₆ film as buffer layer, YBa₂Cu₃O_7?δ film has been successfully prepared by pulsed laser deposition. The subsequently deposited YBa₂Cu₃O_7?δ film has a preferred c-axis orientation and a smooth surface. The temperature dependence of resistance indicates a superconducting critical temperature higher than 82 K. Our results demonstrate that the double perovskite Ca₂NiWO₆ is a promising buffer layer candidate for coated conductors.     

Influence of deposition parameters on preferred orientation of RF magnetron sputtered BST thin films

Ba_0.65Sr_0.35TiO₃ (BST) thin films have been deposited by radio frequency magnetron sputtering. The effects of the deposition parameters on the crystallization and microstructure of BST thin films were investigated by X-ray diffraction and field emission scanning electron microscopy, respectively. The crystallization behavior of these films was apparently affected by the substrate temperature, annealing temperature and sputtering pressure. The as-deposited thin films at room temperature were amorphous. However, the improved crystallization is observed for BST thin films deposited at higher temperature. As the annealing temperature increased, the dominant X-ray diffraction peaks became sharper and more intense. The dominant diffraction peaks increased with the sputtering pressures increasing as the films deposited at 0.37–1.2 Pa. With increasing the sputtering pressure up to 3.9 Pa, BST thin films had the (110) + (200) preferred orientation. Possible correlations of the crystallization with changes in the sputtering pressure were discussed. The SEM morphologies indicated the film was small grains, smooth, and the interface between the film and the substrate was sharp and clear.     

Crystallographic properties of four-fold grain K3Li2Nb5O15 thin films

The structural properties of a potassium lithium niobate (KLN; K₃Li₂Nb₅O₁₅) thin film deposited by rf-magnetron sputtering on a Pt/Ti/SiO₂/Si(100) substrate were investigated. The crystalline structures of the Pt under layer and KLN thin films were examined using θ-2θ, θ-rocking, and mesh scan X-ray diffraction (XRD). The XRD results revealed that the Pt under layer was a strong (111) direction orientated poly crystal. Unlike the Pt under layer film, the KLN(001) peak was found to consist of two separate peaks, one with a broad full width half maximum (FWHM) and the other with a narrow FWHM, indicating that the KLN film had a single crystalline structure. The surface and cross-section morphology were investigated using a scanning electron microscope (SEM). Accordingly, from the results of the SEM and XRD experiments, it was concluded that the KLN film was composed of small single crystals, which had a four-fold symmetry morphology with a c-axis normal to the substrate.     

RF sputtered piezoelectric zinc oxide thin film for transducer applications

This paper demonstrates the substrate dependency of the c-axis zinc oxide growth in radio-frequency sputtering system. Different deposition conditions were designed to study the influences of Si, SiO₂/Si, Au/Ti/Si, and Au/Ti/SiO₂/Si substrates on the piezoelectric and crystalline qualities of the ZnO thin films. Experimental results showed that the multilayer of Au/Ti/SiO₂/Si-coated silicon substrate provided a surface that facilitated the growth of ZnO thin film with the most preferred crystalline orientation. The 1.5 μm-thick thermally grown amorphous silicon dioxide layer effectively masked the crystalline surface of the silicon substrate, thus allowing the depositions of high-quality 20 nm-thick titanium adhesion layer followed by 150 nm-thick of gold thin film. The gold-coated surface allowed deposition of highly columnar ZnO polycrystalline structures. It was also demonstrated that by lowering the deposition rate at the start of sputtering by lowering RF power to less than one-third of the targeted RF power, a fine ZnO seed layer could be created for subsequent higher-rate deposition. This two-step deposition method resulted in substantially enhanced ZnO film quality compared to single-step approach. The influence of stress relaxation by annealing was also investigated and was found to be effective in releasing most of the residual stress in this layered structure.     

The problems of native SiO2 layer removing for epitaxial growth of YSZ film on Si

The preparation processes of epitaxially grown YSZ (Yttrium stabilized ZrO₂) buffer layers on silicon (100) wafers were investigated. The “etching” procedure, at which the thin (∼5 nm) SiO₂ native amorphous layer from the Si surface was reduced to volatile SiO by deposition of a few nm thick Zr layer and subsequent annealing at low pressure, was monitored by mass spectrometer. The subsequent YSZ layer was deposited by evaporation or RF sputtering technique and examined by XRD and TEM observations. The results show that the epitaxy of YSZ layer is strongly influenced by efficiency of amorphous SiO₂ reduction at Si surface.     

Crystallization control of the amorphous buffer layer in hydrogenated nanocrystalline silicon

Hydrogenated nanocrystalline silicon film have been deposited by RF sputtering in a pure hydrogen plasma at a substrate temperature of 150°C. The unintentionally grown amorphous buffer layer was almost completely crystallized at an annealing temperature as low as 150°C. By combining infrared absorption measurements and electron microscopy observations, the critical role of dihydride species, SiH₂, in the crystallization process have been clearly evidenced and discussed.     

Temperature dependence of InN film deposition by an RF plasma-assisted reactive ion beam sputtering deposition technique

Indium nitride (InN) films were deposited on Si(100) substrates using a radiofrequency (RF) plasma-assisted reactive ion beam sputtering deposition technique at various substrate temperatures. The X-ray diffraction patterns of the InN films suggest that the InN films deposited at substrate temperatures up to 370 °C were cubic crystalline InN; and at 500 °C, the InN film was hexagonal crystalline InN. In a scanning electron microscope image of the InN film surface, facets of cubic single-crystalline InN grains were clearly observed on the InN film deposited at 370 °C. The inclusion of metallic indium appeared on the InN film deposited at 500 °C.     

Effect of barrier layers on the properties of indium tin oxide thin films on soda lime glass substrates

In this paper, the electrical, structural and optical properties of indium tin oxide (ITO) films deposited on soda lime glass (SLG) haven been investigated, along with high strain point glass (HSPG) substrate, through radio frequency magnetron sputtering using a ceramic target (In₂O₃:SnO₂, 90:10 wt.%). The ITO films deposited on the SLG show a high electrical resistivity and structural defects compared with those deposited on HSPG due to the Na ions from the SLG diffusing to the ITO film by annealing. However, these properties can be improved by intercalating a barrier layer of SiO₂ or Al₂O₃ between the ITO film and the SLG substrate. SIMS analysis has confirmed that the barrier layer inhibits the Na ion's diffusion from the SLG. In particular, the ITO films deposited on the Al₂O₃ barrier layer, show better properties than those deposited on the SiO₂ barrier layer.     

Growth and characterization of high-quality δ-Bi2O3 thin films grown by carbothermal evaporation

We have succeeded in the heteroepitaxial growth of a single-crystal thin film of δ-Bi₂O₃, which is stable at room temperature, on a YSZ substrate by carbothermal evaporation. The deposited film has no rotational in-plane domain, and the deposited film has a single crystalline phase. The film thickness is approximately 1.1 μm, and the interface of the film and the YSZ substrate is smooth. The results in this study indicate that carbothermal evaporation is suitable for the deposition of δ-Bi₂O₃ thin films. Further, it can be speculated that interfacial stress is crucial in the stabilization of the δ phase, indicating that the deposition as a thin film may play a role in the stabilization of δ-Bi₂O₃.     

Studies on the target conditioning for deposition of LiCoO2 films

Deposition of good quality thin films of Lithium Cobalt Oxide (LiCoO₂), by sputtering is preceded by target conditioning, which dictates the surface composition, morphology and electrochemical performance of the deposited film. Sputtering from a virgin target surface, results in films with excess of the more reactive elements. The concentration of these reactive elements in the films decreases until the system reaches a steady state after sufficient sputtering from the target. This paper discusses the deposition kinetics in terms of target conditioning of LiCoO_2. The composition, morphology and texturing of deposited film during various hours of sputtering were analyzed using X-ray photoelectron spectroscopy (XPS) and Field Emission Scanning electron microscopy (FESEM). The compositional stability is not observed in the films formed during the initial hours of sputtering from the fresh target, which becomes stable after several hours of sputtering. The Li and Co concentration in the films deposited subsequently is found to be varying and possible causes are discussed. After the compositional stability is reached, electrochemical analysis of LiCoO₂ thin films was performed, which shows a discharge capacity of 129 μAh/cm².     

Structures and properties of the Al-doped ZnO thin films prepared by radio frequency magnetron sputtering

Al-doped ZnO thin films were deposited by radio frequency magnetron sputtering using a ZnO target with 2 wt.% Al₂O₃. The structures and properties of the films were characterized by the thin film X-ray diffraction, high resolution transmission electron microscopy, Hall system and ultraviolet/visible/near-infrared spectrophotometer. The Al-doped ZnO film with high crystalline quality and good properties was obtained at the sputtering power of 100 W, working pressure of 0.3 Pa and substrate temperature of 250 °C. The results of further structure analysis show that the interplanar spacings d are enlarged in other directions besides the direction perpendicular to the substrate. Apart from the film stress, the doping concentration and the doping site of Al play an important role in the variation of lattice parameters. When the doping concentration of Al is more than 1.5 wt.%, part of Al atoms are incorporated in the interstitial site, which leads to the increase of lattice parameters. This viewpoint is also proved by the first principle calculations.     

Formation of semitransparent CuAlSe2 thin films grown on transparent conducting oxide substrates by selenization

Wide band-gap semiconductors have been studied for applications as buffer layers in thin film solar cells and as top cell in tandem devices. CuAlSe₂ (CAS) thin films were deposited onto bare and two different transparent conducting oxide (TCO)-coated glass substrates, In₂O₃:Sn (ITO) and ZnO:Al (AZO), by a two stage process consisting on the selenization of metallic precursor layers. Homogeneous and crystalline formation of CAS thin films is not trivial and it is strongly influenced by selenization conditions, type of substrate and the film thicknesses. Under certain conditions, polycrystalline CuAlSe₂ thin films with chalcopyrite structure and preferential orientation along the (112) plane were obtained onto bare glass susbtrates. However, formation and crystallization of homogeneous CAS thin films was promoted by transparent conducting oxides (ITO and AZO)-coated glass substrates and take place in a wide range of thicknesses and Se amounts with high degree of reproducibility. TCO-coated substrates promoted larger grains when the CAS compound was formed. The band-gap energy, preferential orientation, crystallite size and the average surface roughness varied depending on the film thickness and type of substrate.     

Oxidation and reduction behavior of Ni and NiO layers sputter deposited onto yttrium-stabilized zirconia single crystals

Thin single-crystal yttrium-stabilized zirconia (YSZ) substrate was prepared by indentation fracture and mechanical polishing. The specimen was analyzed in detail by transmission electron microscopy (TEM). The (110) edge surface was faceted, in contrast to the smooth (001) edge surface, and the facet surfaces were identified as {111}-type planes. Good cross-sectional TEM specimens comprised of crystalline Ni and NiO layers deposited on YSZ edge surface could be prepared by sputtering of a Ni support grid using Ar⁺ ion milling and subsequent re-deposiotion on the smooth (001) fracture surface of the YSZ specimen. The epitaxial growth of a pure Ni layer on the YSZ edge planes occurred during ion milling in vacuum. However, subsequent ion milling of the specimen after exposure in air for several minutes resulted in the formation of a NiO layer on top of the first Ni layer. Reduction of the NiO layer was confirmed by electron energy-loss spectroscopy after annealing at 973 K in a vacuum of 1.2 × 10⁻⁵ Pa. This Ni layer was re-oxidized upon annealing in air at 1073 K for 1 h. The deposition behavior of the Ni and NiO layers was discussed on the basis of the surface oxidation of Ni layer.     

Comparative study of zinc oxide and aluminum doped zinc oxide transparent thin films grown by direct current magnetron sputtering

Pure and aluminum (Al) doped zinc oxide (ZnO and ZAO) thin films have been grown using direct current (dc) magnetron sputtering from pure metallic Zn and ceramic ZnO targets, as well as from Al-doped metallic ZnAl2at.% and ceramic ZnAl2at.%O targets at room temperature (RT). The effects of target composition on the film's surface topology, crystallinity, and optical transmission have been investigated for various oxygen partial pressures in the sputtering atmosphere. It has been shown that Al-doped ZnO films sputtered from either metallic or ceramic targets exhibit different surface morphology than the undoped ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (002). More significantly, Al-doping leads to a larger increase of the optical transmission and energy gap (E_g) of the metallic than of the ceramic target prepared films.     

Topography and microstructure of Cu-Sn coatings deposited by magnetron sputtering

The topographical and microstructural features of Cu-Sn coatings deposited by magnetron sputtering using alloy target of Cu-7.8%Sn and Cu-74%Sn onto ferritic stainless steel substrates with a temperature gradient were investigated by means of optical and scanning electron microscopy.Depending on the substrate temperature the alloy film forms by a vapour → solid process or a vapour → liquid process with solidification after substrate cooling. In between a mixed mechanism of vapour → liquid → solid occurs during condensation in the temperature ranges 990–1170 K and 460–790 K for coatings deposited by sputtering of Cu-7.8%Sn and Cu-74%Sn targets respectively.The copper-rich condensate formed in the temperature range 370–1220 K consists of a single-phase α solid solution of tin in copper. Its lattice parameter decreases with increasing temperature mainly because of the decreasing tin content.The film obtained by sputtering a Cu-74%Sn target has a two-phase η′-Cu₆Sn₅ plus tin structure independently of the deposition temperature.