On the correlation between crystallinity of platinum bottom electrode and that of MOD derived PZT thin films

Growth of well(111)-oriented Pt and Pt/Ti films on SiO₂/Si(111) substrates and crystallinity of PZT films grown on the Pt(111)/SiO₂/Si(111) and Pt(111)/Ti/SiO₂Si(111) substrates have been investigated. It was found by X-ray diffraction analysis that well (111)-oriented Pt film with a best full-width at half maximum (FWHM) of 0.28° was grown by the DC sputtering method. PZT films were prepared by metallo-organic decomposition (MOD) on Pt(111)-coated SiO₂Si(111) substrates. The crystallinity of the PZT films improved as the FWHM of the Pt(111) diffraction peak decreased. The best FWHM obtained for a PZT film grown on a Pt(111)/Ti/SiO₂/Si(111) substrate was 0.33°.     

Structural Variation of the BaTi4O9 Thin Films Grown by RF Magnetron Sputtering

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using rf magnetron sputtering and the structure of the thin films were then investigated. For the films grown at low temperature (≤350°C), an amorphous phase was formed during the deposition, which then changed to the BaTi₅O₁₁ phase when the annealing was conducted below 950°C. However, when the annealing temperature was higher than 950°C, a BaTi₄O₉ phase was formed. On the contrary, for the films grown at high temperature (>450°C), small BaTi₄O₉ grains were formed during the deposition, which grew during the annealing. The homogeneous BaTi₄O₉ thin films were successfully grown on Pt/Ti/SiO₂/Si substrate when they were deposited at 550°C and subsequently rapid thermal annealed at 900°C for 3 min.     

The FRL-FRH phase transition in PZT 95/5 thin film

The PZT 95/5 thin film was prepared on Pt/Ti/ SiO₂Si substrate by sol-gel method. The behavior of F_RL-F_RH phase transition was investigated in the thin film. The change of the remanent spontaneous polarization during the F_RL-F_RH phase transition is 0.6 μc/cm².     

PASSIVATION OF COPPER BY LOW TEMPERATURE ANNEALING OF Cu/Mg/SiO2 BILAYERS

Annealed thin films of Cu/Mg/SiO₂ are studied as possible conductors for microelectronics. Rutherford backscattering and sheet resistance measurements show that vacuum annealing at 350-400°C results in transport of Mg from the buried layer to the surface of the copper where it reacts with impurities to form a thin surface layer of MgO. Such films are then exceedingly resistant to further oxidation. These films have a resistivity of 2·μω-cm and are adherent to the SiO₂ substrate. However, at temperatures 450-500°C there is a reaction between Mg and the SiO₂ substrate releasing free Si into the copper.     

Effects of Thermal Annealing on the Structure of Ferroelectric Thin Films

The effects of thermal annealing on the structure of polycrystalline Pb(Zr_0.3Ti_0.7)O₃ (PZT) ferroelectric thin films prepared by chemical solution deposition on Pt/TiO _x electrode stacks were studied using scanning electron microscopy, transmission electron microscopy (TEM), and grazing incidence X-ray specular and diffuse reflectivity of synchrotron radiation. The stratified multilayered structure and element diffusions in the sample were characterized by TEM. Global statistical structural parameters including the density, surface or interface roughness and thickness of each layer in the samples were obtained from fitting the X-ray specular reflectivity using a homogeneous stratified multilayer model of PZT/Pt/TiO _x /SiO₂. The results showed that the PZT surface and PZT/Pt interface roughness changed slightly during thermal annealing in oxygen at 700°C. By contrast, the density increase of the PZT ceramic and density decrease of the Pt-bottom electrode during annealing were observed. A high density value of the PZT ceramic film after the annealing was found, up to 99.8% of the theoretical value of the corresponding bulk ceramics. The density changes of the PZT and Pt layers were further confirmed by X-ray diffuse reflectivity. The influences of the annealing treatment on the density changes of the PZT and Pt layers were attributed to the further densification of the PZT ceramic and incorporation of light elements such as Zr, Ti and O from the neighboring layers into the Pt layer, respectively, as discussed in correlation with the TEM analyses.     

Influence of annealing atmosphere on the structure, resistivity and transmittance of InZnO thin films

Dependence of the electrical and optical properties of In₂O₃–10 wt% ZnO (IZO) thin films deposited on glass substrates by RF magnetron sputtering on the annealing atmosphere was investigated. The electrical resistivities of indium zinc oxide (IZO) thin films deposited on glass substrate can be effectively decreased by annealing in an N₂ + 10% H₂ atmosphere. Higher temperature (200 °C) annealing is more effective in decreasing the electrical resistivity than lower temperature (100 °C) annealing. The lowest resistivity of 6.2 × 10⁻⁴ Ω cm was obtained by annealing at 200 °C in an N₂ + 10% H₂ atmosphere. In contrast, the resistivity was increased by annealing in an oxygen atmosphere. The transmittance of IZO films is improved by annealing regardless of the annealing temperature.     

Phase transitions of antiferroelectric lead zirconate thin films in high electric field

Phase transitions in antiferroelectric lead zirconate thin films were studied at room temperature and at 77 K. The lead zirconate films were prepared on Pt coated Si substrates by a reactive magnetron co-sputtering mthod followed by a rapid thermal annealing process at 700 °C. An electric field induced antiferroelectric — ferroelectric phase transition was observed at room temperature with a maximum polarization value of 70 μC/cm². The average field required to induce the ferroelectric state and that for the reversion to the antiferroelectric state were 294 kV/cm and 179 kV/cm respectively. At 77 K a metastable ferroelectric — ferroelectric transition was observed with a maximum polarization of 58 μC/cm². These transitions were found to be coincident with those of lead zirconate single crystals.     

退火工艺对Pb(Zr_(0.55)Ti_(0.45))O_3铁电薄膜结晶取向的影响

用射频磁控溅射法在Pt(111)/Ti/SiO2/Si上成功的制备了Pb(zr0.55Ti0.45)O3(PZT)铁电薄膜,通过传统退火(CFA)和快速退火(RTA)不同的退火方式,获得了(100)和(111)择优取向的铁电薄膜。对薄膜电学特性的测试表明,薄膜的织构对其电学性能有很大影响,(111)取向的薄膜与(100)取向的薄膜相比,剩余极化Pr和矫顽场Ec较大,但抗疲劳特性却较差。     

Deposition of Pb(Zr,Ti)O3 Thin Films by Metal-Organic Chemical Vapor Deposition Using β-diketonate Precursors at Low Temperatures

Lead zirconate titanate (PZT) thin films were deposited by metal-organic chemical vapor deposition (MOCVD) using β-diketonate precursors and 0₂ at temperatures below 500°C on variously passivated Si substrates. PZT thin films could not be deposited on bare Si substrates, owing to a serious diffusion of Pb into the Si substrate during deposition. Pt/SiO₂/Si substrates could partially block the diffusion of Pb, but a direct deposition of PZT thin films on the Pt/SiO₂/Si substrates resulted in a very inhomogeneous deposition. A TiO₂ buffer layer deposited on Pt/SiO₂/Si substrates could partially suppress the diffusion of Pb and produce homogeneous thin films. However, the crystallinity of PZT thin films deposited on the TiO₂-buffered Pt/SiO₂/Si substrate was not good enough, and the films showed random growth direction. PZT thin films deposited on the PbTiO₃-buffered Pt/SiO₂/Si substrates had good crystallinity and a- and c-axis oriented growth direction. However, the PZT thin film deposited at 350°C showed fine amorphous phases at the grain boundaries, owing to the low chemical reactivities of the constituent elements at that temperature, but they could be crystallized by rapid thermal anneaiing (RTA) at 700°C. PZT thin film deposited on a 1000-å PbTiO₃,-thin-film-buffered Pt/SiO₂/Si substrate at 350°C and rapid thermally annealed at 700°C for 6 min showed a single-phase perovskite structure with a composition near the morphotropic boundary composition.     

Synthesis of Highly Oriented Lead Zirconate–Lead Titanate Film Using Metallo-organics

Crack-free Pb(Zr,Ti)O₃ (PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO₃ (100), and Pt/Ti/SiO₂/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H₂O─-O₂ gas mixture was found to be effective not only for low-temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single-phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO₂/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO₂/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm², and a coercive field of 54 kV/cm.     

底电极原位退火与沉积温度对PZT薄膜性能影响研究

采用磁控溅射工艺,在Pt/Ti底电极上沉积锆钛酸铅(PZT)薄膜,研究了原位退火温度与底电极沉积温度对溅射PZT薄膜结晶取向、微观结构、介电性能、铁电性能及疲劳性能的影响。X射线衍射(XRD)和扫描电子显微镜(SEM)分析结果表明,随着电极沉积温度升高,Pt晶粒尺寸增大,随着退火温度升高,PZT薄膜致密性变差。对室温制备的Pt/Ti底电极进行200 ℃原位退火30 min后,易于促进PZT薄膜沿(100)择优取向,而高温制备或经高温退火处理的Pt/Ti底电极更有利于PZT薄膜的(111)晶向生长。电学性能分析表明,室温制备的Pt/Ti底电极在经200 ℃原位退火30 min后,其PZT薄膜介电性能最优,同时展现较高的剩余极化强度和最小的矫顽场强,经历10⁸次极化翻转后,初始极化下降仅为11％。     

Titanium Diffusion into (K0.5Na0.5)NbO3 Thin Films Deposited on Pt/Ti/SiO2/Si Substrates and Corresponding Effects

Lead-free (K_0.5Na_0.5)NbO₃ (KNN) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol–gel processing method, and titanium diffusion from the substrates into the KNN films under different thermal treatment conditions were investigated by the secondary ion mass spectroscopy depth profile and X-ray photoelectron spectroscopy surface analysis. Titanium diffusion was evident in all the KNN thin films, which was further aggravated not only by increasing the annealing temperature, but also surprisingly by higher ramping rate attributed to the resulting larger grain boundaries. The pronounced effects of the titanium diffusion and the resulting substitution of Ti⁴⁺ for Nb⁵⁺ with different valence states on the composition, structure, and electrical properties of the KNN thin films are analyzed and discussed. The results showed that the Ti diffusion from the substrate played a crucial role in affecting the structure and electrical properties of the ferroelectric KNN thin films deposited on Pt/Ti/SiO₂/Si substrate.     

Microstructure and ferroelectric properties of sol–gel graded PZT (40/52/60) and (60/52/40) thin films

Graded Pb(Zr_x,Ti_1−x)O₃ films with Zr compositions varied across the thickness direction were deposited on Pt/Ti/SiO₂/Si substrate using a conventional spin-coating method. The up- and down-graded PZT films exhibited the perovskite polycrystalline structure. Microstructure investigations of the films showed a dense texture and successive layers of different compositions. The relative permittivities of the up- and down-graded PZT films measured at 1 kHz and room temperature were 1846 and 1019, respectively. Good dielectric and ferroelectric properties as well as the low-temperature processing suggested that the compositionally graded PZT films were promising for memory device applications.     

Enhanced dielectric tunability properties of Ba(ZrxTi1−x)O3 thin films using seed layers on Pt/Ti/SiO2/Si substrates

The compositionally graded and homogeneous Ba(Zr_xTi_1−x)O₃ (BZT) thin films were fabricated on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si and Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method, respectively. These films crystallized into a single perovskite phase. The BZT thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates had a highly (1 0 0) preferred orientation and exhibited a preferred (1 1 0) orientation when the thin films were deposited on Pt/Ti/SiO₂/Si substrates. The LNO and Ba(Zr_0.30Ti_0.70) served as seed layer on Pt/Ti/SiO₂/Si substrates and analyze the relationship of seed layer, microstructure and dielectric behavior of the thin films. The compositionally graded thin films from BaTiO₃ to BaZr_0.35Ti_0.65O₃ were fabricated on LNO/Pt/Ti/SiO₂/Si substrates. The tunability behavior of compositionally graded films was analyzed in order to produce optimum effective dielectric properties. The dielectric constant of BaZr_xTi_1−xO₃ compositionally graded thin films showed weak temperature dependence. This kind of thin films has a potential in a fabrication of a temperature stable tunable device.     

The effect of the hydrothermal treatment with aqueous NaOH solution on the photocatalytic and photoelectrochemical properties of visible light-responsive TiO2 thin films

The effect of the hydrothermal treatment with aqueous NaOH solution on the photoelectrochemical and photocatalytic properties of visible light-responsive TiO₂ thin films prepared on Ti foil substrate (Vis-TiO₂/Ti) by a radio-frequency magnetron sputtering (RF-MS) deposition method has been investigated. The hydrothermally treated Vis-TiO₂/Ti electrodes exhibited a significant increase in their photocurrent under UV and visible light irradiation as compared to untreated Vis-TiO₂/Ti electrode. SEM investigations revealed that the surface morphology of Vis-TiO₂/Ti are drastically changed from the assembly of the TiO₂ crystallites to the stacking of nanowires with diameters of 30–50 nm with increasing hydrothermal treatment time (3–24 h), accompanying the increase in their surface area. The separate evolution of H₂ and O₂ from water under solar light irradiation was successfully achieved using the Vis-TiO₂/Ti/Pt which is hydrothermally treated for 5 h, while the H₂ evolution ratio was 15 μmol h⁻¹ in the early initial stage, corresponding to a solar energy conversion efficiency of 0.23%.     

Textured ferroelectric SbNbO4 thin films deposited by ion-beam sputtering

In this letter, we report on the first synthesis of oriented SbNbO₄ ferroelectric thin films on Pt coated silicon substrates. Textured SbNbO₄ thin films are formed by rapid thermal annealing of films deposited by Ar⁺ ion-beam sputtering at room temperature. The films are characterized by X-ray diffraction spectra. Ferroelectric P-E loops are measured and dielectric properties are studied at low frequency. The effect of Pt electrodes on the formation of ferroelectric SbNbO₄ thin films is discussed.     

Temperature dependence of electrical and electromechanical properties of Pb(Mg1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thin films

The electrical and electromechanical properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PNN–PZT, PMN/PNN/PZT = 20/10/70) on Pt/Ti/SiO₂/Si substrates by chemical solution deposition was investigated. The PMN–PNN–PZT films annealed at 650 °C exhibited slim polarization hysteresis curves and a high dielectric constant of 2100 at room temperature. A broad dielectric maximum at approximately 140–170 °C was observed. The field-induced displacement was measured by scanning probe microscopy, the bipolar displacement was not hysteretic, and the effective piezoelectric coefficient (d₃₃) was 66 × 10⁻¹² m/V. The effective d₃₃ decreased with temperature, but the value at 100 °C remained 45 × 10⁻¹² m/V.     

Pulsed laser deposition of Sm modified PbTiO3 ferroelectric thin films

Sm modified PbTiO³ thin films have been prepared by pulsed laser deposition on Pt/TiO₂/SiO₂/(100)Si substrates. It has been found that the Sm concentration of the films remains close its concentration in the target, however, a Pb loss exists during the deposition process. To compensate for the Pb loss we used Pb rich targets and an oxygen pressure of 0.1 mbar. Films deposited at 530°C are crystalline and preferentially oriented with the [100] film direction perpendicular to the substrate surface. In comparison to bulk ceramics, the films have a tetragonal distortion lower than that expected from their Sm concentration. This is likely due to the influence of the substrate. The films prepared are ferroelectric with aP_r = 3.2 μC/cm².     

Dependence of the properties of compositionally graded Pb(Zr,Ti)O3 ferroelectric films of the bottom electrode

Compositionally graded Pb(Zr_,Ti)O₃ thin films were prepared on the Pt(1 1 1)/Ti/SiO₂/Si, LNO/Si(1 0 0) and LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates by a modified sol–gel method and rapid heat-treatment. The composition depth profile of a typical up-graded film was determined using a combination of auger electron spectroscopy and Ar-ion etching. The crystallographic orientation and the microstructure of the resulting graded PZT thin films on the different substrates were characterized by XRD. The dielectric and ferroelectric properties of the graded PZT films were discussed. The graded PZT films on LNO/Pt/Ti/SiO₂/Si and LNO/Si(1 0 0) substrates have larger dielectric constant and remnant polarizations compared to that grown on Pt/Ti/SiO₂/Si substrates.     

Lead Zirconate Titanate Thin Films by Aerosol Plasma Deposition: Microstructure Analysis

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) thin films were grown on silicon 〈100〉 substrate by aerosol plasma deposition (APD) using solid-state-reacted powder containing donor oxide Nb₂O₅ when keeping the substrate at room temperature and 200°C. Crystalline phases of the deposited films have been analyzed via X-ray diffractometry (XRD), and microstructure via scanning and transmission electron microscopy (SEM and TEM). Cross-sectional TEM revealed that the microstructure comprised several layers including the deposited PZT film and the platinum-electrode-and-titanium-buffered layers on SiO₂–Si substrate. The Pt-electrode layer contained (111)_Pt twinned columnar grains with a slight misorientation and forming low-angle grain boundaries among them. The PZT layer contained randomly oriented grains embedded in an amorphous matrix. Some of the PZT grains, oriented with the zone axis Z = [[Twomacr]11]_PZT parallel to Z = [111]_Pt, were grown epitaxially on the Pt layer by sharing the (111)_PZT plane with the (111)_Pt twinned columnar Pt crystals. However, the existence of such an orientation relationship was confined to several nanosize grains at and near the PZT-Pt interface, and no gross film texture has been developed. An amorphous grain boundary phase, generated by pressure-induced amorphisation (PIA) in the solid state, was identified by high-resolution imaging. Its presence is taken to account for the densification of the PZT thin films via a sintering mechanism involving an amorphous phase on deposition at 25° and 200°C.