Electrical properties of paraelectric PLT(28) thin films deposited by dc magnetron sputtering

Abstract

Paraelectric [Pb, La]TiO₃ (PLT, La = 28 mol%) thin films were prepared by dc magnetron sputtering using a multi-element metal target. In order to crystallize the as-deposited PLT thin films into the cubic perovskite structure, a heat treatment was applied at annealing temperatures ranging between 450 and 750°C. The electrical measurements such as dielectric properties, polarization-electric field (P-E), and current-voltage (I–V) were investigated with the change of annealing temperature. The dielectric constant and dissipation factor of paraelectric PLT film annealed at 750°C were 1216 and 0.018, respectively. The charge storage density was approximately 12.5 μC/cm². The leakage current density in PLT film annealed at 650°C was around 0.1 μA/cm² at the electric field of 0.25 MV/cm.     

Characterization of the CeO2 thin films for insulation layer and Pt/SrBi2Ta2O9/CeO2/Si MFISFET structure

Abstract

CeO₂ and SrBi₂Ta₂O₉ (SBT) thin films for MFISFET (metal-fcrroelectrics-insulator-semiconductor field effect transistor) were deposited by rf sputtering and pulsed laser deposition method, respectively. The effects of oxygen partial pressure during deposition for CeO₂ films were investigated. The oxygen partial pressure significantly affected the preferred orientation, grain size and electrical properties of CeO₂ films. The CeO₂ thin films with a (200) preferred orientation were deposited on Si(100) substrates at 600°C. The films deposited under the oxygen partial pressure of 50 % showed the best C-V characteristics among those under various conditions. The leakage current density of films showed order of the 10^?7～10^?8 A/cm² at 100 kV/cm. The SBT thin films on CeO₂/Si substrate showed dense microstructure of polycrystalline phase. From the C-V characteristics of MFIS structure composed of the SBT film annealed at 800°C, the memory window width was 0.9 V at ±5 V. The leakage current density of Pt/SBT/CeO₂/Si structure annealed at 800°C was 4×10^?7 A/cm² at 5 V.     

Chemical Vapor Deposition of Ru Bottom Electrode for Ferroelectric Bi4 − x La x Ti3O12 Capacitors

Ruthenium films formed by metalorganic chemical vapor deposition were investigated, taking account of the application to the bottom electrode of ferroelectric capacitors. Ruthenium films were deposited using a liquid-type source of Ru[EtCp]₂ in a cold-wall type reactor with infrared lamps. A smooth and flat Ru film was successfully formed on a SiO₂-covered Si substrate without a seed layer. As the deposition temperature increased to 400°C, the crystallinity of the Ru film improved and the film exhibited high c-axis orientation. After forming a Bi_{4 ? x} La _x Ti₃O₁₂ (BLT) film by a sol-gel technique, a Pt/BLT/Ru capacitor was fabricated on the Ru film. Good hysteresis loops with 2P _r = 20 μC/cm² and 2V _c = 3.4 V were successfully obtained and the ferroelectric property did not depend on the deposition temperature of Ru in the temperature range from 325°C to 400°C. On the contrary, the leakage current density was significantly suppressed down to 1/100 as the deposition temperature of Ru increased from 325°C to 400°C.     

Recent progress in sputtering PZT thin films for ferroelectric memories

Abstract

This paper describes amorphous Pb(Zr, Ti)O₃ (PZT) thin films deposited by cosputtering Pb(Zr_0.5 Ti_0.5)O₃ and PbO targets. By optimizing the amount of the excess Pb and the deposition temperature, PZT thin films with a single perovskite phase were obtained successfully on Ir substrates and Pt substrates at 520°C. 250-nm-thick PZT films crystallized by rapid thermal annealing (RTA) at 600°C for 20 s exhibited excellent ferroelectric properties: a coercive voltage of 1.0 V, a remanent polarization density of about 40 μC/cm², and a polarization switching endurance over 1x109 cycles. Although a heat treatment in a reductive ambient causes degradation of ferroelectric properties of PZT thin films, their degraded ferroelectric properties can be easily recovered from by a 1-min RTA in an oxygen at 400°C.     

PATTERNED HIGH FREQUENCY THICK FILM MEMS TRANSDUCER

ABSTRACT

Ferroelectric properties of BiFeO₃ (BFO) thin films epitaxially grown on SrRuO₃ (SRO)/(001)SrTiO₃ (STO) structure were investigated. First, bottom SRO electrodes were deposited on STO substrates by metalorganic chemical vapor deposition (MOCVD) or by sputtering. Then, BFO thin films were deposited on SRO/STO structures by chemical solution deposition. X-ray diffraction analysis showed that the SRO films deposited by both methods grew epitaxially on STO substrates as a single phase perovskite structure, but the out-of-plane lattice parameters of SRO were different, that is, they were 0.396 nm in MOCVD and 0.399 nm in sputtering. The leakage current densities were higher than 1 A/cm² at room temperature in BFO films on both MOCVD-and sputtered-SRO, but the current density in the film on sputtered SRO decreased to 2 × 10^?4 A/cm² at 80 K. The remanent polarization of approximately 50 μC/cm² was observed at 80 K in the BFO thin film on sputtered-SRO/STO.     

Advances in processing and properties of perovskite thin-films for FRAMs,DRAMs, and decoupling capacitors

Abstract

Highly oriented, dense, and crack-free ferroelectric and paraelectric thin-films on three inch diameter Pt/Ti/Si₃N₄/Si (100) substrates were obtained by polymeric sol-gel processing. Ferroelectric PZT thin-films were fabricated at temperatures as low as 550°C within 15 minutes by rapid thermal annealing. The films heat treated at 700°C for 5 minutes were single grain thick and exhibited P_r, P_sp, and E_c in the ranges of 29–32 μC/cm², 44–53 μC/cm², and 50–60 kV/cm, respectively, and high speed switching times below 5 ns on 30×30 μm² electrodes. A switching time of 2.7 ns was observed on 19×19 μm² area electrodes at a field of 200 kV/cm. Results of low and high field characterization on paraelectric PLT thin-films which were conventionally heat treated indicated that it has an excellent potential for use in ULSI DRAMs and as decoupling capacitors. These films showed a high charge storage density (15 μC/cm²) and a low leakage current (0.5 μA/cm²) at a field of 200 kV/cm. Also, the charging time for a capacitor area of 1 μm² at 200 kV/cm was estimated to be 0.10 ns.     

Morphology of PZT-PMN Films Grown from Airflow

Lead zirconate titanate-lead magnesium niobate (PZT-PMN) films with thicknesses in the range 5 to 200 μm were fabricated by deposition from airflow at room temperature. Precursor powders of PZT and PMN were mixed in a ball mill and entrained in an airflow generated by a commercial jet-mill (Micron-Master 02-506). Films were grown at a rate of 1 μm/minute onto the Ni and tungsten carbide substrates exposed to the air-powder mixture. Unfired, poled PZT-PMN films provided an audio acoustic response and form translucent 20–30 μm thick layers. Full density of the air-flow deposited materials has been achieved at temperatures 450°C lower than that typical for ball milled bulk PZT-PMN ceramics. After sintering for 2 hours at 850°C PZT-PMN ceramics with relative density of 99.5%, ? ～ 2170, tan δ ～ 0.009 @1 kHz and acceptable piezoelectric properties was obtained. Films sintered 2 hours at 1000°C showed remnant polarization P _r = 26 μC/cm², P _s = 36 μC/cm² @95 kV/cm, and 50 Hz ac electric breakdown field as high as 120–170 kV/cm. Unusual grain morphology governs improved sinterability and enhanced properties of ferroelectric ceramics. Optical and AFM micrographs revealed needle-like grains preferentially oriented parallel to the air-powder stream. As-deposited films were found to be very non-uniform across the thickness: glass-like and with tensile strain on the contact surface. This strain is released and film microcrystalline structure becomes uniform in annealed film.     

Effect of crystalline phases on the ferroelectric properties of HoMnO3 thin films

Ferroelectric HoMnO₃ thin films were deposited on the Si (100) substrates at 700°C for 2 h by metal–organic chemical vapor deposition. When the films were post-annealed at 800°C for 1 h in air, the single phase of hexagonal HoMnO₃ was detected, and the remnant polarization (Pr) and coercive field (Ec) were decreased due to the decrease of c-axis orientation. With an increase of annealing time, the crystalline phase of HoMnO₃ was changed from the single hexagonal to the mixtures of the hexagonal and orthorhombic phases of HoMnO₃, and/or HoMn₂O₅. Leakage current density was related with charge valence of Mn ion and surface roughness of thin film. Pr of hexagonal HoMnO₃ thin films with high c-axis orientation was 136 nC/cm² and the leakage current density was 10^?6 A/cm².     

Ferroelectric SrBi2Ta2O9 thin films deposited by liquid injection MOCVD using novel bimetallic alkoxide precursor

Abstract

The ferroelectric SBT films were deposited on Pt/Ti/SiO₂/Si substrates by liquid injection metalorganic chemical vapor deposition (MOCVD) with single-mixture solution of Sr[Ta(OEt)₅(dmae)]₂ and Bi(C₆H₅)₃. The Sr/Ta and Bi/Ta ratio in SBT films depended on deposition temperature and mol ratio of precursor in the single-mixture solution. At the substrate temperature of 400°C, Sr/Ta and Bi/Ta ratio were close to 0.4 and 1 at precursor mol ratio of 0.5～1.0. As-deposited film was amorphous. However, after annealing at 750°C for 30 min in oxygen atmosphere, the diffraction patterns indicated polycrystalline SBT phase. The remanent polarization (Pr) and coercive field (Ec) of SBT film annealed at 750°C were 4.7 μC/cm²and 115.7 kV/cm at an applied voltage of 5 V, respectively. The SBT films annealed at 750°C showed practically no polarization fatigue up to 10¹⁰ switching cycles.     

The electrical properties of Ba1-x SrxTiO3 thin films grown by sputter deposition

Abstract

Ba_1-x Sr_xTiO₃ (BST) thin films were deposited by reactive rf-magnetron sputtering onto Si substrates. The influence of the deposition parameters such as temperature and oxygen ambient on the dielectric constant of the films is presented. BST films deposited at 450°C and optimum conditions exhibited a dielectric constant of approximately 200 at frequencies as high as 1GHz. In addition, the films were found to have leakage current densities of <0.1μAmp/cm² at fields of 5×10⁵V/cm. An extrapolated lifetime greater than 10 years was obtained from stress tests at elevated temperatures and fields. These films compared favorably with published data.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Dielectric characteristics investigation of (Ba0.7Sr0.3)(Ti0.9Zr0.1)O3 ferroelectric thin films

By the radio frequency (RF) magnetron sputtering methods, (Ba_0.7Sr_0.3)(Ti_0.9Zr_0.1)O₃ (BSTZ) ferroelectric thin films were deposited on the Pt/Ti/SiO₂/Si(100) substrates. The crystal structural and microstructure of these thin films were analyzed by means of the XRD, SEM, and AFM. Moreover, the dielectric characteristics were also investigated by the C-V and J-E analyses. The optimal deposition parameters for these BSTZ thin films were: RF power is 160 W, oxygen concentration is 25%, substrate temperature is 580°C, and chamber pressure is 0.075 mPa. Under these optimal deposition conditions, the (111) and (110) oriented polycrystalline of the BSTZ thin films grow easily. And under a bias voltage of 0.5 MV/cm, the dielectric constant and leakage current density of the BSTZ thin films are 191 and 3×10^?8 A/cm², respectively. In addition, under various measured temperatures (0 ～ 80°C) and frequencies (100 kHz ～ 1 MHz), all the dielectric constants remain almost unchanged. Compared to BSTZ thin films reported previously, in this study, the deposited thin films have the advantage of lower leakage current and hence are suitable for the applications of dynamic random access memory.     

Electrical characterizations of MgTiO3 thin films grown on Si

Abstract

We have analyzed MgTiO₃ thin films grown on the Si substrate with/without SiO₂ using pulsed laser deposition (PLD). We find that MgTiO₃ thin films start to crystallize at 600°C, causing electrical instabilities in the MIS capacitors above this temperature. Detailed analysis by XRD technique reveals that structural differences of MgTiO₃ thin films were not obvious below 600°C, whereas the electrical characteristics changes as a function of deposition temperature and the presence of thermally grown SiO₂. We observe that the decrease of deposition temperature results in the increase of leakage current and anomalous positive charge (APC) density. These drawbacks were effectively suppressed by growing 100A SiO₂ layer on the Si substrate prior to the deposition of MgTiO₃ thin films.     

Ferroelectric properties of plzt thin films prepared by mocvd

Abstract

Lanthanum-modified lead zirconate titanate (PLZT) thin films have been grown on Pt/SiO₂/Si substrate at 650[ddot]C by metalorganic chemical vapor deposition. The relative dielectric constant increased as the La content was increased up to about 5 atomic percent (at%). The remanent polarization and coercive field decreased from 30 to 20 μC/cm² and from 53 to 30 kV/cm, respectively, with increasing La content in the range of 0–13 at%. The leakage current of PLZT film was 3 × 10^?9 A/cm² at an applied voltage of 3 V. The degradation of switched charge density of PLZT film was not observed even at 2 × 10¹¹ cycles.     

Influence of the growth temperature on the epitaxial quality of PbTiO3 films deposited in-situ by sputtering

Abstract

Thin films of lead titanate were prepared in-situ on SrTiO₃ substrates using radio-frequency magnetron sputter deposition. The epitaxial quality of the films has been studied as a function of the substrate temperature. Stoichiometric films have been obtained in the temperature range [550°C, 600°C]. The films deposited in the equilibrium zone have a high degree of c-axis oriented epitaxial crystalline structure as shown by X-ray diffraction in the 2θ/θ, θ, and ? scans configuration as well as by electron channeling pattern. The optimum conditions for growing epitaxial PbTiO₃ layers were determined. The crystallinity of films deposited at 550°C is suprior to those deposited at 600°C. The PbTiO₃ films grown at 550°C have a rocking curve full width at half maximum (FWHM) of 0.2°; Normaski optical and atomic force microscopy show that the surface is apparently free of grain boundaries and very smooth. The refractive index of these films has been evaluated from transmission spectra; it is very close to the bulk material value.     

Effect of Buffer Layer on the Properties of Laser Ablated PZT Thin Films

Lead zirconate titanate (PbZr _x Ti_1?x O₃) or PZT ceramics are a class of piezoelectric materials that are currently experiencing widespread use in industry as electromechanical devices. PtSi/ZnO/PZT thin films were deposited by pulsed laser deposition at relatively low substrate temperature. The PZT thin films on PtSi substrates and on ZnO buffer layer were deposited at substrate temperature 300°C. The composition analysis shows that the film deposited at low temperature is stoichiometric. The films exhibit ferroelectric nature with coercive field of 19.6 kV/cm for 800 nm thick film. The leakage current density of the films shows a good insulating behavior.     

Preparation of Bi4Ti3O12 thin films by electron cyclotron resonance sputtering

Abstract

Ferroelectric Bi₄Ti₃O₁₂ thin films were deposited on Pt-coated oxidized Si substrate by electron cyclotron resonance (ECR) sputtering using ceramic targets. Crystal structure and dielectric properties of the films were investigated as functions of sputtering conditions such as substrate temperature and sputtering gas. Using a target with excess Bi content compared to stoichiometric composition was required to compensate Bi re-evaporation from the substrate and to obtain a perovskite single phase at 600°C. (117)-oriented films exhibited ferroelectric hysteresis loops. The remanent polarization and coercive field of the films were 9.8 μC/cm² and 180 kV/cm, respectively.     

Fundamental characteristics of DRAM capacitor application of PLZT ultrathin films prepared by MOCVD

Lanthanum-modified lead zirconate titanate (PLZT) thin films (50 nm to 200 nm) were deposited on Pt/SiO₂/Si substrate by metal-organic chemical vapor deposition (MOCVD). The electrical properties of the films were investigated as a function of the La content or the substrate temperature. Ferroelectric PZT(0/50/50) films were obtained at substrate temperatures as low as 500 °C; their electrical characteristics improved with increasing substrate temperature. La exhibited adequate solid solution in the PZT above 650 °C. PLZT(15/45/55) films with a thickness of 100 nm were found to have good properties for application to the capacitors of dynamic random access memory (DRAM), namely, an effective charge density of 80 fF/μm², a permittivity of 1000, an SiO₂ equivalent thickness of 0.4 nm, and a leakage current density of 5 × 10⁻⁸ A/cm. Addition of La to PZT was effective in reducing the leakage current with an increase in the registration rate. RuO₂ and/or IrO₂ bottom electrodes for ferroelectric PLZT films were also investigated. The RuO₂ films were found effective as diffusion barriers for PLZT and MgO. Significant interdiffusion at RuO₂/Si and RuO₂/SiO₂ interfaces occurred during the deposition of PLZT films. Annealing of the RuO₂ film considerably depressed interface reactions. © 1998 Scripta Technica. Electr Eng Jpn, 122(1): 25–36, 1998     

Filament-assisted pulsed laser deposition of epitaxial PbZrxTi1−xO3 films: Morphological and electrical characterization

Abstract

A modification of the conventional pulsed laser deposition technique was employed, whereby a low energy electron emitting filament was placed between the target and the substrate (-20 V filament/substrate bias) in order to produce reactive species (O_2- and O_?) during deposition. Using this modification, epitaxial thin films of PbZr_xTi_1?xO3 (PZT, 0 ≤ × ≤ 0.6) were prepared in situ on virgin (100) MgO and (100) Pt/(100) MgO substrates at a substrate temperature of 550°C and in an oxygen ambient (0.3 Torr). The topography of films prepared without a filament on virgin MgO were porous and composed of grains of about 1000 Å in diameter. As the emission current was increased from 0 to 400 μA, the grain size decreased to less than 100 Å with a concomitant decrease in the porosity. The nucleation of crystallites of other orientations was observed at emission currents greater than about 500 μA. Trilayer structures (Pt/PZT/Pt/<100>MgO) were fabricated for electrical measurements. Non-filament-assisted PZT cells usually failed because of a high probability of conductive paths through the PZT layer. Filament-assisted films were much less prone to this problem. Typical remanent polarizations and coercive fields were 15–20 μC/cm² and 30–50 kV/cm, respectively.     

Preparation of Si-Added SrBi2Ta2O9 Ferroelectric Thin Films by RF Magnetron Sputtering

Si-added SrBi₂Ta₂O₉ (SBT) ferroelectric films were prepared by RF magnetron sputtering on a Pt/Ti/SiO₂/Si (100) structure. The films were deposited at temperatures below 100°C for surpressing Bi evaporation, and crystallized at 800°C in air. A typical composition was Sr_0.79Bi_2.37Ta_2.00Si_0.2O_x. The remanent polarization value (2Pr) of the Si-added SBT film was 16 μC/cm². The Si atom addition was found to be effective in improvement of the fatigue and leakage current of SBT ferroelectric films. The leakage current density was further improved by annealing in the high-pressure oxygen ambient at 7 atms.