Effect of post-deposition annealing on phase formation and properties of RF magnetron sputtered PLZT thin films

In this work, we report the preparation of lanthanum-modified lead zirconate titanate (PLZT) thin films by RF magnetron sputtering on platinized silicon (Pt/Ti/SiO₂/Si) substrate. Sputtering was done in pure argon at 100 W RF power without external substrate heating. X-ray diffraction studies were performed on the films to study the effect of post-deposition furnace annealing temperature and time on the perovskite phase formation of PLZT. Annealing at 650 °C for 2 h was found to be optimum for the preparation of PLZT films in pure perovskite phase. The effect of different annealing conditions on surface morphology of the films was examined using AFM. The dielectric, ferroelectric and electrical properties of these films were also investigated in detail as a function of different annealing conditions. The pure perovskite film exhibits better properties than the other films which have some fraction of unwanted pyrochlore phase. The remanent polarization for pure perovskite film was found to be ∼29 μC/cm² which is almost double compared to the films having mixed phases. The dc resistivity of the pure perovskite film was found to be 7.7 × 10¹⁰ Ω cm at the electric field of ∼80 kV/cm.     

RF sputtered PLZT thin film on Pt/Ti electrode

PLZT (7.5/65/35) thin films were deposited by rf magnetron sputtering on single crystal Si substrates using an oxide sintered target with excess PbO. The effects of postannealing and bottom Pt/Ti electrodes on the thin film crystal structures and ferroelectric properties were studied. Film deposited at 200°C or below crystallizes to a perovskite phase after annealing treatment at 550°C or above, and the crystal structure depends on the annealing treatment. The best crystal structures and electronic properties were obtained when the thin films were annealed at 600°C to 650°C for 1 h in O₂. For the Pt/Ti two-layer bottom electrode, the thickness of the Ti layer has a dominant effect. When the Ti layer was too thick or too thin, the PLZT thin film structures consist mainly of pyrochlore phases. However, using an appropriate Ti layer thickness, PLZT thin films having good crystal structures and ferroelectric properties can be obtained, with typical remanent polarization value of 220 mC/m² and coercive field strength of 6.5 MV/m     

BaPbO3 conductive coating layers on platinized Si substrate for the growth of PbZr1−xTixO3 thin films

Barium metaplumbate (BaPbO₃, BPO) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol–gel method and a rapid thermal annealing (RTA) process. X-ray diffraction (XRD) was used to characterize the crystalline structure of the resultant films. It was shown that the formation of perovskite BPO greatly depends on the lead concentration and the final annealing temperature. In terms of the semi-quantitative energy dispersion spectrum (EDS) analysis, the ratio of Pb/Ba in the BPO ceramic films increases as the final heating temperature increases. Using BPO as buffer layers, PZT thin films with a pure perovskite structure were grown at a very low temperature of 500 °C by the sol–gel technique and the RTA process. The remanent polarization of Pt/PZT/BPO/Pt ferroelectric capacitors is about 17 μC/cm² at an applied voltage of 3 V.     

Preparation and characterization of highly (1 1 1)-oriented (Pb,La)(Zr,Ti)O3 thin films by sol-gel processing

Lanthanum modified lead zirconate titanate (Pb_0.91La_0.09)(Zr_0.65Ti_0.35)O₃ (PLZT) ferroelectric thin films were grown on Pt/Ti/SiO₂/Si(1 0 0) and fused quartz substrates using a sol-gel method with rapid thermal annealing processing. The results showed that the highly (1 1 1)-oriented pervoskite PLZT thin film growth on Pt/Ti/SiO₂/Si(1 0 0) substrates. The electrical measurements were conducted on PLZT films in metal-ferroelectric-metal capacitor configuration. The PLZT thin films annealed at 600 °C showed well-saturated hysteresis loops with remanent polarization and coercive electric field values were 10.3 μC/cm² and 36 kV/cm, respectively, at an applied field of 300 kV/cm. At 100 kHz, the dielectric constant and dielectric loss of the film are 682 and 0.021, respectively. The PLZT thin film on fused quartz substrate, annealed at 600 °C, exhibited good optical transmittance, the band gap of optical direct transitions is 3.89 eV.     

铅过量PLZT铁电薄膜的制备及其电学性质研究

采用Sol Gel法 ,在Pt TiO2 Si基片上制备了具有不同铅过量 (0— 2 0mol% )的PLZT铁电薄膜。分析了薄膜的晶相结构 ,研究了铅过量对PLZT铁电薄膜的介电性能和铁电性能的影响。结果表明 ,各薄膜均具有钙钛矿型结构 ,且各薄膜均呈 (110 )择优取向。PLZT铁电薄膜的介电性能和铁电性能随铅过量的变化而改变。铅过量为 10mol%的薄膜具有最佳的的介电性能和铁电性能。     

Deposition of silicon films in presence of nitrogen plasma—A feasibility study

A design, development and validation work of plasma based ‘activated reactive evaporation (ARE) system’ is implemented for the deposition of the silicon films in presence of nitrogen plasma on substrate maintained at room temperature. This plasma based deposition system involves evaporation of pure silicon by e-beam gun in presence of nitrogen plasma, excited by inductively coupled RF source (13.56 MHz). The activated silicon reacts with the ionized nitrogen and the films get deposited on silicon substrate. Different physical and process related parameters are changed. The grown films are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and ellipsometry. The results indicate that the film contains silicon nitride and a phase of silicon oxy nitride deposited even at room temperature. This shows the feasibility of using the ARE technique for the deposition of silicon films in nitrogen plasma.     

Studies of BaTiO3 thin films on different bottom electrode

BaTiO₃ (BT) thin films were prepared on Pt/Ti/SiO₂/Si and Ru/Ti/SiO₂/Si substrates by a modified sol-gel technique. The microstructure of the films was characterized by atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy. The results showed that BT thin films crystallized with perovskite structure. Compared to BT film on Pt/Ti/SiO₂/Si substrate, BT thin film deposited on Ru electrode has similar dielectric constant, while it has higher dielectric loss. C–E curve for BT film on Pt/Ti/SiO₂/Si was more symmetrical around zero-bias field than C–E curve for BT film on Ru/Ti/SiO₂/Si substrate. The tunability was 52.02% for BT film on Pt electrode, which was 33.42% on Ru electrode, at 275 kV/cm and room temperature. The leakage current density of BT on Pt electrode was about an order of magnitude lower than BT film on Ru electrode at the applied electrical field below 150 kV/cm. The leakage conduction mechanism was investigated.     

Fabrication of thin film TiO2 nanotube arrays on Co–28Cr–6Mo alloy by anodization

Titanium oxide (TiO₂) nanotube arrays were prepared by anodization of Ti/Au/Ti trilayer thin film DC sputtered onto forged and cast Co–28Cr–6Mo alloy substrate at 400 °C. Two different types of deposited film structures (Ti/Au/Ti trilayer and Ti monolayer), and two deposition temperatures (room temperature and 400 °C) were compared in this work. The concentrations of ammonium fluoride (NH₄F) and H₂O in glycerol electrolyte were varied to study their effect on the formation of TiO₂ nanotube arrays on a forged and cast Co–28Cr–6Mo alloy. The results show that Ti/Au/Ti trilayer thin film and elevated temperature sputtered films are favorable for the formation of well-ordered nanotube arrays. The optimized electrolyte concentration for the growth of TiO₂ nanotube arrays on forged and cast Co–28Cr–6Mo alloy was obtained. This work contains meaningful results for the application of a TiO₂ nanotube coating to a CoCr alloy implant for potential next-generation orthopedic implant surface coatings with improved osseointegrative capabilities.     

Preparation of Pb0.98La0.02(Zr0.65Ti0.35)O3 films and their fine patterning

The photosensitive lanthanum-doped lead zirconate titanate (PLZT) gel films were prepared by chemical modification with acetylacetone (AcAcH), and their fourier transform infrared (FT-IR) spectra and ultraviolet visible (UV-Vis) spectra were measured. The results show that the chelate rings of AcAcH with Ti or Zr are formed in the PLZT gel films. With irradiation of UV light, the chelate rings are photolyzed, and lead to a change of the solubility of the PLZT gel films in methanol. Transmission electron microscope (TEM) observations show that the perovskite phase is crystallized in PLZT thin film after heat treatment at 700 °C, whose grain sizes are less than or equal to 60 nm. The PLZT thin films exhibited hysteresis loops and good fatigue properties.     

A new and rapid process for production of solution-derived (Pb, La)(Zr, Ti)O3 thin films and powders

A simple and rapid process for synthesizing (Pb,La)(Zr,Ti)O₃ (PZT, PLZT, and PLT) precursor solutions has been developed. This process, termed the “basic route to PLZT” (or BRP) process, offers several advantages over standard methods, including rapid solution synthesis (<10 min), use of commercially available materials, film production under ambient conditions, ease of lanthanum dissolution at high concentrations (<1 min), and no heating requirements during solution synthesis. The PLZT precursor solution synthesis involves dissolution of lead acetate (or acetyl acetate) in pyridine followed by addition of a pre-dissolved mixture of titanium and zirconium iso-propoxide in toluene. The lanthanum source can then be added and, depending on the precursor, total synthesis time was <10 min. The preferred lanthanum starting material is a highly soluble bis(iso-propyl)aryloxide complex; however, this compound is extremely air and water sensitive. The compositions investigated in this study include PZT 40/60, PLZT 3/30/70, 5/30/70, and 10/40/60, and PLT films with 10–20 mol % La. All films were crystallized at 650 19°C and exhibit ferroelectric properties comparable to films produced by other techniques which require higher crystallization temperatures. This revised version was published online in November 2006 with corrections to the Cover Date.     

The ferroelectric and optical properties of (Pb0.92La0.08)(Zr0.65Ti0.35)O3 thin films deposited by radio-frequency magnetron sputtering

Ferroelectric (Pb_0.92La_0.08)(Zr_0.65Ti_0.35)O₃ (PLZT) films have been prepared on Pt/Ti/SiO₂/Si and fused quartz substrates using radio-frequency (rf) magnetron sputtering at a deposition temperature of 650°C. X-ray diffraction analysis shows that the PLZT thin films on platinized silicon are polycrystalline with (100)-preferential orientation. A Al/PLZT/Pt capacitor has been fabricated and it shows that the films have excellent ferroelectric character, with saturation polarization (P _s), remanent polarization (P _r) and coercive field (E _c) of 32.8μC/cm², 24.3μC/cm² and 142 kV/cm, respectively. The PLZT thin films exhibit good insulating property and the leakage current density of the films on platinized silicon is only about 0.86 × 10⁻⁷ A/cm² at 200 kV/cm. By the optical transmission spectra measurements, the energy gap (E _g) of the PLZT films on fused quartz is found to be about 3.54 eV. The optical constants (n and k) of the films in the wavelength range of 250–900 nm are obtained by a Filmetrics F20 reflectance spectrometer.     

Effects of bias voltage on the microstructure and mechanical properties of (Ti,Al,Cr)N hard films with N-gradient distributions

(Ti,Al,Cr)N hard reactive films were deposited on high speed steel substrates by multi-arc ion plating (MAIP) technology using pure Cr and Ti-50Al(at.%) alloy targets. The partial pressure of N₂ was raised step by step in each deposition process. The surface morphology, the cross-sectional morphology of fracture sample, the surface compositions and the phase structure of the (Ti,Al,Cr)N films were investigated by scanning electronic microscope (SEM) and X-ray diffraction (XRD). The dense columnar microstructure was obtained in all of the (Ti,Al,Cr)N films, though micro-droplets evidently existed on the surface of the films. The micro-hardness of the film surface, the adhesive strength of the film/substrate and the thermal shock resistance were investigated. The results revealed the effects of bias voltage on the composition, phase structure, and mechanical properties. The improved balanced properties of a micro-hardness of about 50 GPa, an adhesive strength larger than 200 N and a thermal shock resistance of 7-8 cycles were reached at a bias voltage of 150 V. The present super-hard (Ti,Al,Cr)N films with N-gradient distribution may be an actual substitution of TiN, (Ti,Al)N, (Ti,Cr)N and single-layer (Ti,Al,Cr)N hard films.     

Phase evolution in solution deposited Pb-deficient PLZT thin films

Initial crystallization of Pb-deficient, lanthanum modified lead zirconate titanate (PLZT) layers followed by post-crystallization phase conversion can be used to obtain high quality PLZT thin films. However, phase evolution in Pb-deficient PLZT thin films is not well understood. To characterize phase evolution in these films, we developed a new in situ, high-temperature X-ray diffraction (XRD) measurement approach for slow heating rates. The well-characterized Pb-excess PLZT composition was used for comparison and to validate the new XRD setup described herein. During crystallization of Pb-deficient thin films, a Pb-rich/La-poor perovskite phase and Pb-poor/La-rich fluorite phase were observed to form simultaneously. The fluorite phase was observed to partially transform into a secondary perovskite phase at higher temperatures. The results obtained are discussed in view of the current understanding of phase evolution in these materials. The details of the new in situ XRD technique are also presented.     

Dual DC magnetron cathode co-deposition of (Al,Ti) and (Al,Ti,N) thin films with controlled depth composition

In this work (Al,Ti) and (Al,Ti,N) films with composition gradient in depth starting either with pure Al or pure Ti were deposited on Si, glass and Au at room temperature in a DC magnetron discharge without bias. The plasma parameters, for both custom made cathodes, were determined and the process was real-time controlled to obtain in the plasma the necessary deposition changes in relative metal abundances to get the desired depth profile composition on the films. In this work the process was designed to get a constant gradient for the composition depth profile. The morphology of the films was analysed by SEM while the composition gradients were measured by SIMS, XPS and RBS, confirming preset nominal depth composition profile of the films.To obtain (Al,Ti,N) thin films with gradient depth composition, N₂ must be supplied to the discharges. The plasma behaviour is modified in the presence of N₂ and the influence on the film characteristics is studied using the same techniques referred above.The (Al,Ti) and (Al,Ti,N) film properties are compared. We succeed in validating the coating technique opening new application possibilities.     

Effects of a PbTiO3 insertion layer on the morphological and electromechanical characteristics of sol-gel-driven 0.2PZN-0.8PZT piezoelectric films for energy harvesters

This study investigated the morphological and electromechanical characteristics of 0.2PZN-0.8PZT films fabricated using a PbTiO3 layer. Crack-free 1-microm-thick films with a pure perovskite phase were obtained on Pt/Ti/SiO2/Si substrates using a modified sol-gel deposition method. A highly dense and smooth morphology and a high piezoelectric coefficient (d33) of 230 pC/N were observed in a 0.2PZN-0.8PZT film with a PbTiO3 insertion layer after annealing at 750 degrees C. The as-produced sol-gel-driven 0.2PZN-0.8PZT thin films are attractive for application to piezoelectrically operated microelectronic actuators, sensors, or energy harvesters due to their low facility cost, smooth surface, and excellent electromechanical characteristics.     

Thermal reliability of n-GaAs/Ti/Pt/Au Schottky contacts with thin Ti films for reduced gate resistance

The thermal stability of Ti/Pt/Au Schottky contacts on n-GaAs with Ti films 0–60 nm is investigated. The contacts with Ti films as small as 10 nm remain thermally stable with annealing up to 400°C. The changes induced by thermal treatment in the electrical characteristics of the contacts are correlated with the Rutherford backscattering and microscopic analysis of the annealed samples. It shows profuse interdiffusion and interfacial reaction with 300°C anneal for the GaAs/Pt/Au system. It has been found that introducing the Ti film between GaAs and Pt/Au, the interdiffusion of Pt and Au is also prevented. These results are useful for reducing the gate metallisation resistance of metal semiconductor field effect transistors.     

Preparation of strontium titanate thin films by mirror-confinement-type electron cyclotron resonance plasma sputtering

Using mirror-confinement-type electron cyclotron resonance (ECR) plasma sputtering method, strontium titanate (SrTiO₃) thin films have been prepared on Si and Pt/Ti/SiO₂/Si substrates at a low substrate temperature (below 450 K) in a low pressure (2.7×10⁻² Pa) environment of pure Ar and Ar/O₂ mixture. Prepared film surfaces were very smooth regardless of high deposition rate (8.5 nm/min). The composition ratio Sr/Ti of Sr to Ti in the films varied with the distance between the target and the substrate. All as-deposited films on Si substrates were found to be amorphous and were crystallized by post-deposition annealing using an electric furnace at 650 K, i.e. approximately 250 K lower than annealing for films obtained by conventional RF magnetron sputtering. Post-deposition annealing of these films using millimeter-wave radiation decreased the crystallization temperature to a value of 550 K. Furthermore, all as-deposited films on Pt/Ti/SiO₂/Si substrates by a plasma of Ar and O₂ gas mixture were found to be crystallized regardless of no substrate heating.     

Two-step growth of high-quality nano-diamond films using CH4/H2 gas mixture

Diamond films with fine grain size and good quality were successfully deposited on pure titanium substrate using a novel two-step growth technique in microwave plasma-assisted chemical vapor deposition (MWPCVD) system. The films were grown with varying the methane (CH₄) concentration at the stage of bias-enhanced nucleation (BEN) and nano-diamond film deposition. It was found that nano-diamond nuclei were formed at a relatively high methane concentration, causing a secondary nucleation at the accompanying growth step. Nano-diamond film deposition on pure titanium was always very hard due to the high diffusion coefficient of carbon in Ti, the big difference between thermal expansion coefficients of diamond and Ti, the complex nature of the interlayer created during diamond deposition, and the difficulty in achieving very high nucleation density. A smooth and well-adhered nano-diamond film was successfully obtained on pure Ti substrate. Detailed experimental results on the synthesis, characterization and successful deposition of the nano-diamond film on pure Ti are discussed.     

The effects of oxygen partial pressure on BST thin films deposited on multilayered bottom electrodes

Ba_0.5Sr_0.5TiO₃ (BST) thin films have been deposited by r.f. magnetron sputtering on silicon and platinum-coated silicon substrates with different buffer and barrier layers. BST films deposited on Si/SiO₂/SiN/Pt and Si/SiO₂/Ti/TiN/Pt multilayer bottom electrode have been used for the fabrication of capacitors. XRD and SEM studies were carried out for the films. It was found that the crystallinity of the BST thin film was dependent upon oxygen partial pressure in the sputtering gas. The role of multilayered bottom electrode on the electrical properties of Ba_0.5Sr_0.5TiO₃ films has been also investigated. The dielectric properties of BST films were measured. The results show that the films exhibit pure perovskite phase and their grain sizes are about 80–90 nm. The dielectric properties of the BST thin film on Si/SiO₂/Ti/TiN/Pt electrode was superior to that of the film grown on Si/SiO₂/SiN/Pt electrode.     

On the preparation of PLZT thin films grown by pulsed laser deposition

Polycrystalline PLZT thin films have been grown onto glass slides substrate, from a sintered stoichiometric 9/65/35 commercial target, by using a Nd:YAG laser (1064 nm, 7 ns, 10 Hz). The substrate temperature and oxygen pressure were varied during the deposition, as was the post-deposition annealing temperature in order to achieve stoichiometric films with a perovskite structure and with a composition near the ratio 9/65/35. Perovskite PLZT is formed around the substrate temperature of 500°C and oxygen pressure of ∼0.5 mbar after annealing at 580°C during 90 min. The pyrochlore structure, on the other hand, is always formed in the films during the deposition. However, this structure disappear for annealing temperatures above 550°C, for the films grown at oxygen pressure in the range 0.5–1 mbar and temperature deposition above 450°C. The degree of crystallinity and the structure present in the films is correlated with the deposition conditions. The influence of post-deposition annealing conditions on the formation of perovskite PLZT structure and optical transparency of the films is also discussed.