Synthesis of epitaxial BaZrO3 thin films by chemical solution deposition

This work reports on the low temperature preparation and characterization of BaZrO₃ (BZO) epitaxial thin films by chemical solution deposition (CSD). The X-ray θ-2θ scan and φ-scan measurements have demonstrated that the BZO films exhibit cube-on-cube epitaxy on (100) MgO substrates, with the full width at half maximum (FWHM) for the ω-scan and φ-scan of 0.35° and 0.46°, respectively. The SEM and AFM analyses revealed that the morphology of the films is strongly correlated with annealing temperature. The root mean square roughness for the film annealed at 600 °C is 3.63 nm, while for the film grown at 1000 °C is 5.25 nm.     

Dielectric properties of (Ba,Ca)(Zr,Ti)O3/CaRuO3 heterostructure thin films prepared by pulsed laser deposition

(Ba_0.90Ca_0.10)(Zr_0.25Ti_0.75)O₃ (BCZT) thin films were grown on Pt/Ti/SiO₂/Si substrates without and with a CaRuO₃ (CRO) buffer layer using pulsed laser deposition (PLD). The structure and surface morphology of the films have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). At room temperature and 1 MHz, the dependence of dielectric constant and tunability of the films with electric field were investigated; the dielectric constant and tunability are 725 and 47.0%, 877 and 50.4%, respectively, for the BCZT film on Pt/Ti/SiO₂/Si substrates without and with the CRO buffer layer at 400 kV/cm. The tunability of the BCZT/CRO heterostructure thin films on Pt/Ti/SiO₂/Si substrates was higher than that of the BCZT thin films on Pt/Ti/SiO₂/Si substrates. The high constant likely results from the oxide electrode (CRO).     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.     

Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

Integration of stacked capacitor module with ultra-thin ferroelectric SrBi2Ta2O9 film for high density ferroelectric random access memory applications at low voltage operation

The crystallization route of thin SrBi₂Ta₂O₉ (SBT) films deposited on Pt(100 nm)/Ti(10 nm)/SiO₂/Si substrate is investigated at different annealing temperatures by atomic force microscopy (AFM) and X-ray diffractometry (XRD). To evaluate the SBT film properties for low voltage operation and for high storage density (>16 MBit), SBT is deposited at different film thicknesses. Furthermore, the performance of a Pt/SBT/Pt capacitor on a barrier-/contact-layer/polysilicon-plug architecture suitable for stacked capacitor memories is investigated by transmission electron microscopy (TEM)/energy dispersive X-ray analysis (EDX) and electrical measurements. It is shown that an oxidized and highly resistive contact layer can be recovered by electrical pulses. Finally, a process solution for a successful integration of 38 nm thin SBT films into this structure is provided.     

A simple approach of preparing amorphous SiOx film on aluminum substrate

A kind of silicon oxide (SiO_x) film was grown on aluminum substrate by low temperature-atmospheric pressure chemical vapor deposition (CVD). The film thickness, changed with the procession temperature and time, and source gaseous ratio, were studied. The optimized procession parameters were determined. The film section morphology was investigated by the scanning electronic microscopy (SEM) and result shows that the SiO_x film is bound firmly to the aluminum substrate without any crack or gap. The reason of the excellent combination was also discussed. The X-ray diffraction technology (XRD) and transmission electronic diffraction technology (TED) demonstrate that the SiO_x film is basically amorphous with a little crystalline area in it.     

Pulsed laser deposition optical waveguiding Bi3TiNbO9 thin films on fused silica

The layered-perovskite ferroelectric Bi₃TiNbO₉ (BTN) optical waveguiding thin films have been prepared on fused silica substrates by pulsed laser deposition (PLD). X-ray θ-2θ scans revealed that the films are single-phase perovskite and highly (00l) textured. The wavelength dependence of the transmittance of the films was determined. We obtained an average transmittance of 75% in the wavelength range of 400-1100 nm and the band gap E_g=3.55 eV. The optical waveguiding properties of the films were characterized by using prism-coupling method. The distinct m lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the BTN films waveguide have been observed. The cross sectional morphology of the film was studied by scanning electron microscopy (SEM).     

Synthesis of GaN nanorods by ammoniating Ga2O3 films on TiO2 (rutile) layer deposited on Si(111) substrates

GaN nanorods have been synthesized by ammoniating Ga₂O₃ films on a TiO₂ middle layer deposited on Si(111) substrates. The products were characterized by X-Ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transformed infrared spectra (FTIR) and high-resolution transmission electron microscopy (HRTEM). The XRD analysis indicates that the crystallization of GaN film fabricated on TiO₂ middle layer is rather excellent. The FTIR, SEM and HRTEM demonstrate that these nanorods are hexagonal GaN and possess a rough morphology with a diameter ranging from 200 nm to 500 nm and a length less than 10 μm, the growth mechanism of crystalline GaN nanorods is discussed briefly.     

Nanocomposites alumina/Pt produced by PVD and thermal oxidation methods used in catalytic applications

The work was focused on the deposition of Al₂O₃+Pt composite in the form of a nanofilm adherent to the substrate with good surface development and catalytic properties on the surface of 0H20J5 foil. With this end in view, a special carousel fixture for fixing the corrugated and flat foil and then coating with Al and Pt from two magnetron sources, in order to obtain a nanofilm of Al+Pt composite, was designed. A Pt/Al laminate layer was also produced by depositing Pt first and then Al, and the other way round. The layer systems obtained this way were subject to oxidation for 48 h at 860 °C and under Ar+O₂. The surface examined has shown that the process of oxidation produces the compact sublayer of columnar crystals (whiskers) well adherent to the substrate from which the needle-like whiskers are growing. Structures of whiskers form a laminar system with a catalytic element having a very-well developed surface. Structure analyses revealed that the films obtained comprised mostly α and θ Al₂O₃ phases and missed a Pt crystalline phase. The film morphology on the basis of oxide-film sections examined by TEM showed that the α Al₂O₃ structure was generated mostly deep in oxide films and was integrated with the foil. A microanalysis showed that it was uniformly distributed in its entirety in the Pt-composite based layers; however, in the case of laminate the surface of whiskers was coated. It was found from the comparison of the laminar system activity that the composite layers revealed much better catalytic properties at lower temperature than the laminate layers.     

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.     

Deposition and structural properties of RF magnetron-sputtered ZnO thin films on Pt/Ti/SiNx/Si substrate for FBAR device

This work investigates high-quality bottom electrode and piezoelectric film used in a thin-film bulk acoustic resonator (TFBAR) device. The titanium (Ti) seeding layer and platinum (Pt) bottom electrode were deposited on silicon substrates by DC sputtering using a dual-gun system. Zinc oxide (ZnO) was then deposited onto the Pt bottom electrode by RF magnetron sputtering. Field-emission scanning electron microscopy (SEM), atom force microscopy (AFM) and the four-point probe method showed that the Pt bottom electrode deposited on the Ti seeding layer exhibited favorable characteristics, such as a crystallite size of less than 10 nm, a surface roughness of 0.69 nm and a sheet resistance of 2.27 Ω/□. The ZnO thin film with a highly c-axis-preferred orientation (FWHM = 0.28°) and a roughness of 6.22 nm was investigated by X-ray diffraction (XRD) and AFM analysis, respectively. The bottom electrode with a low resistance and the highly crystalline ZnO thin film will contribute significantly to the favorable characteristics of the FBAR devices.     

Growth of pseudocubic perovskite-type SrRuO3 thin films on quartz substrate using pulsed laser deposition method

Strontium ruthenium oxide (SrRuO₃) thin films have been grown using pulsed laser deposition technique on silicon, Pt coated silicon and quartz substrates. The effect of substrate temperatures on the structural, microstructure, and electrical properties of the SrRuO₃ films on quartz substrate has been investigated using XRD, SEM, AFM and four-probe method, respectively. The lowest resistivity at room temperature for the SrRuO₃ thin film on quartz substrate has been achieved at substrate temperature of 700 °C. Furthermore, the comparisons of SrRuO₃ thin films deposited on various substrates have been done with respect to structural, microstructural and electrical properties. XRD patterns exhibit that all thin films are a single phase, pseudo-cubic perovskite structure. Study of surface morphology shows that grain size and roughness varies with respect to substrate. It is observed that SrRuO₃ thin films yield larger grain size and root mean square roughness on Pt/Si substrate. Investigation of electrical properties shows that SrRuO₃ thin films can serve the purpose of the bottom electrode in dielectric and ferroelectric devices.     

Influence of substrate temperature on structural,optical, and electrical properties of flash evaporated CuIn0.81Al0.19Se2 thin films

Chalcopyrite copper indium aluminum diselenide (CuIn_0.81Al_0.19Se₂) compound is prepared by direct reaction of high purity elemental copper, indium, aluminum and selenium in their stoichiometric proportion. Structural and compositional characterizations of pulverized material confirm the formation of a single phase, polycrystalline nature. CuInAlSe₂ (CIAS) thin films are deposited on organically cleaned soda lime glass substrates using flash evaporation technique by varying the substrate temperatures in the range from 423 K to 573 K. Influence of substrate temperature observed by X-ray diffraction (XRD), scanning electron microscope (SEM), optical and electrical measurement. CIAS Films grown at different substrate temperatures are polycrystalline in nature, exhibiting a chalcopyrite structure with lattice parameters a = ∼0.576 nm and c = ∼1.151 nm. The crystallinity in the films increases with increasing substrate temperature up to 473 K, and tend to degrade at higher substrate temperatures. Optical band gap is in the range of 1.20 eV–1.38 eV and the absorption coefficient is close to 10⁵ cm⁻¹. Electrical characterization reveals p-type conductivity and the structural, morphological and optical properties indicate potential use of CIAS thin films as an absorber layer for thin film solar cell applications.     

ZnO thin films deposited by a CVT technique in closed ampoules

ZnO thin films were prepared on quartz glass, Si (100), and sapphire (001) substrates by a chemical vapour transport (CVT) technique. During the growing processes, the source and substrate temperatures were maintained at 1000 °C and 600 °C, respectively. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements showed that the crystalline qualities of ZnO thin films were sensitively dependent on substrates. ZnO thin film deposited on sapphire substrate exhibited the best morphology with the largest crystallite size of more than 20 μm. Meanwhile, the XRD patterns showed that ZnO thin film deposited on sapphire substrate was strongly c-axis preferred-oriented with high crystalline quality. The optical properties of ZnO thin films were investigated by photoluminescence (PL) spectroscopy at room temperature (RT). The results suggested that the optical properties of ZnO thin films were highly influenced by their crystalline qualities and surface morphologies.     

Microstructure of thin film platinum electrodes on yttrium stabilized zirconia prepared by sputter deposition

(111) oriented thin film Pt electrodes were prepared on single crystals of yttrium-stabilized zirconia (YSZ) by sputter deposition of platinum. The electrodes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), atomic force microscopy (AFM) and by profilometry. SEM images of the as-sputtered platinum film show a compact amorphous Pt film covering uniformly the substrate. Upon annealing at 1123 K, gaps and pores at the interface develop leading to a partial dewetting of the Pt film. Increasing the annealing temperature to 1373 K transforms the polycrystalline Pt film into single crystalline grains exhibiting a (111) orientation towards the substrate.     

Microstructure, domain structures and ferroelectric properties in (Pb0.8,La0.1,Ca0.1)TiO3/Pb(Zr0.2,Ti0.8)O3 bilayered thin film

Ferroelectric (Pb_0.8,La_0.1,Ca_0.1)TiO₃/Pb(Zr_0.2,Ti_0.8)O₃ (PLCT/PZT) bilayered thin film was prepared on Pt(111)/Ti/SiO₂/Si(100) substrate by RF magnetron sputtering technique. Pure perovskite crystalline phase, determined by X-ray diffraction, was formed in the PLCT/PZT bilayer. The bilayered film exhibited a very dense and smooth surface morphology with a uniform grain size distribution. The ferroelectric domain structures were investigated by a combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively). It is demonstrated by both VPFM and LPFM observations that out-of-plane and in-plane lamellar ferroelectric domains coexist in the bilayered thin film. The PLCT/PZT bilayered film possesses good ferroelectric properties with relatively high spontaneous polarization (2P_s = 82 µC/cm²) and remnant polarization (2P_r = 26.2 µC/cm²).     

Structure evolution and ferroelectric properties of Bi3.4Yb0.6Ti3O12 thin films crystallized under a moderate temperature

Ytterbium-doped Bi₄Ti₃O₁₂ (Bi_3.4Yb_0.6Ti₃O₁₂, BYT) ferroelectric thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by chemical solution deposition (CSD). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to identify the crystal structure, the surface and cross-section morphology of the deposited ferroelectric films. Structure evolution and ferroelectric properties of the as-prepared thin films annealed under different temperatures (600 °C-750 °C) were studied in detail. Additionally, the mechanism concerning the dependence of electrical properties of the BYT ferroelectric thin films on the annealing temperature was discussed.     

Residual stresses and Raman shift relation in anatase TiO2 thin film

Anatase TiO₂ film (100-1000 nm thick) grown on glass, sapphire (0001), and Si (100) substrates by pulsed dc-magnetron reactive sputtering were evaluated for stress and strain analysis using Raman spectroscopy and curvature measurement techniques. The X-ray analysis revealed that films prepared for this study were purely anatase, and the measurements indicate that the film exhibit that (101) is the preferred growth orientation of the crystallites, especially for the film thicker than 100 nm. Curvature measurements and Raman spectroscopy, with 514.5 nm excitation wavelength, phonon line shift were used for stress analysis. A comparison between Raman lineshapes and peak shifts yields information on the strain distribution as a function of film thickness. The measurements of residual stresses for crystalline anatase TiO₂ thin film showed that all thin film were under compressive stress. A correlation between Raman shifts and the measured stress from the curvature measurements was established. The behavior of the anatase film on three different substrates shows that the strain in film on glass has a higher value compared to the strain on sapphire and on silicon substrates. The dominant 144 cm^− 1E_g mode in anatase TiO₂ clearly shifts to a higher value by 0.45-5.7 cm^− 1 depending on the type of substrate and film thickness. The measurement of the full width at half maximum values of 0.59-0.80 (2θ°) for the anatase (101) peaks revealed that these values are greater than anatase powder 0.119 (2θ°) and this exhibits strong crystal anisotropy with thermal expansion.     

Epitaxial growth and properties of cubic Zn0.7Mg0.3O films on TiN-buffered Si(100) substrates by in situ pulsed laser deposition

A novel cubic Zn_0.7Mg_0.3O film on silicon substrate is conducted by KrF excimer pulsed-laser ablation system. By introducing a thin TiN buffer, layer-by-layer growth of cubic Zn_0.7Mg_0.3O film epilayer has been realized. The overall growth process was monitored in situ by reflection high-energy electron diffraction (RHEED) method. It was found that the crystallinity and surface morphology of the Zn_0.7Mg_0.3O films were strongly affected by the TiN buffer layer. The Zn_0.7Mg_0.3O film obtained at an optimal buffer layer exhibited high quality and good surface. For the metal-insulator-metal (MIM) structure of Pt/Zn_0.7Mg_0.3O (200 nm)/TiN (20 nm)/Si (400 μm) prepared at the optimal growth conditions achieved a very low leak current density of ∼10⁻⁶ A cm⁻² at an electric field of 9 × 10⁵ V cm⁻¹ and the permittivity (?_r) of about 8.1, agreed well with that of acquired MgO film and MgO single crystal.     

Effect of lead on formation and dielectric tunability of (Pbx,Sr1? x )0.85Bi0.1TiO3 thin films

(Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin films with the perovskite phase structure were prepared on an ITO glass substrate by sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and an impedance analyzer were respectively used in order to characterize the phase status, morphology and dielectric properties of the thin films. The results show that during the formation process of (Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin films, the nucleus of the perovskite phase are initially formed and then congregated. These aggregated nucleus are then transformed as the perovskite-phase crystalline in the thin film. Finally, the crystalline phase grows and separates gradually to form the perfect crystalline-phase structure. The content of the perovskite phase formed in the thin film under rapid thermal process (RTP) is more than that formed under traditional heat treatment with kinetic equilibrium. This is due to the high active decomposed ions that form the perovskite phase directly when heat-treated by RTP. The formation of the perovskite phase therefore overcomes a much lower barrier under RTP than that under traditional calcinations. The structure of the perovskite phase has a close relation to the ratio of Pb/Sr in the system because of the radius difference between Pb²⁺ and Sr²⁺. The transformation temperature between the cubic and the tetragonal structures of the perovskite phase increases with increasing Pb²⁺ content because the radius of Pb²⁺ is larger than that of Sr²⁺. It appears at room temperature when the content of Pb²⁺/Sr²⁺ is about 40/60 in the thin film. Meanwhile, the tetragonality of the perovskite phase is increased when Pb²⁺ ions increase due to its high polarization. The higher tunability of the (Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin film is exhibited when the film composition is close to the transformation point between the paraelectric and ferroelectric phases. Pb²⁺ ions show a dominant factor to affect the Curie point of the system and then changing tunability. Translated from Journal of Inorganic Materials, 2006, 21(2): 466–472 [译自: 无机材料学报]