Electrically tunable Ag(Ta,Nb)O3 thin film structures on oxide substrates

Abstract

We report on design, fabrication, and comparative test of three different types of voltage-variable interdigital capacitors made on ferroelectric Ag(Ta,Nb)O₃ films deposited on MgO and A1₂O₃ substrates. X-ray diffraction patterns show that ATN films pulsed laser deposited on MgO(001) and Al₂O₃(0112) single crystals have preferential (00/) and (0kk) orientation. Capacitance and loss tangent in interdigital capacitors were measured as the functions of frequency and applied dc voltage bias. Loss tangent was as low as 0.0025 and 0.0034 and AT-factor (tunability/tanδ) was around 26.2 and 20.0 for MgO and A1₂O₃, respectively, @ ± 40 V (maximum electric field 200 kV/cm), 300 K, and 1 MHz. Both of polarization and steady leakage currents were observed in the current-time domain measurements. 0.1 pF interdigital capacitors have pA leakage current level @ ± 40 V.     

Mod processing of epitaxial ferroelectric films

Abstract

Ferroelectric thin films have been receiving great attention for the applications in emerging areas. The MOD(Metal-Organic Deposition) processing could be successfully applied for processing the well controlled epitaxial ferroelectric films at relatively low temperatures. Examples are K(Ta, Nb)O₃ and LiNbO₃ film processings. Epitaxial films of K(Ta, Nb)O₃ could be synthesized by the reaction control of metal alkoxides on Pt(100)/MgO(100) substrates. The structures of the precursor solutions were analyzed to control the crystallization. The chemically modified metal alkoxide precursor with a chelate ligand could be utilized for micro-patterned LiNbO₃ epitaxial films using ultra-violet irradiation. The combination of micro-patterning will afford the novel break-through to the development of the integrated functional materials.     

Comparative Characteristics of Na0.5K0.5NbO3 Films on Pt by Pulsed Laser Deposition and Magnetron Sputtering

Ferroelectric Na_0.5K_0.5NbO₃ (NKN) thin films were grown on the Pt₈₀Ir₂₀ polycrystalline substrates by pulsed laser deposition (PLD) and radio frequency-magnetron sputtering (RF) technique using the same stoichiometric Na_0.5K_0.5NbO₃ ceramic target. X-ray diffraction proved both PLD- and RF-made Na_0.5K_0.5NbO₃/Pt₈₀Ir₂₀ films are single phase and have preferential c-axis orientation. Temperature dependence of dielectric permittivity reveals the presence of two phase transitions around 210 and 410°C. Capacitance vs. applied voltage C-V @ 100 kHz, I-V, and P-E hysteresis characteristics recorded for the vertical capacitive structures yielded loss tanδ = 0.026 and 0.016, tunability about 44.5 and 30% @ 100 kV/cm, Ohmic resistivity 6.7 × 10¹² Ω·cm and 0.2 × 10¹² Ω·cm, remnant polarization 11.7 and 9.7 μC/cm², coercive field 28.0 and 94.6 kV/cm for PLD- and RF-films, respectively. Piezoelectric test carried out in hydrostatic conditions showed piezoelectric coefficient d _H = 21 for PLD-NKN and 15 pC/N for RF-NKN film.     

Ferroelectric Na0.5K0.5NbO3 thin films by pulsed laser deposition

Abstract

Highly c-axis oriented single phase Na_0.5K_0.5NbO₃ (NKN) thin films have been deposited onto polycrystalline Pt₈₀lr₂₀ substrates and SiO₂/Si(001) wafers using pulsed laser ablation of stoichiometric ceramic target. Strong self-assembling of NKN films along the [001] direction has been observed. Properties of NKN/Pt thin film structures have been successfully tailored by oxygen pressure control from the ferroelectric state, characterized by the remnant polarization of 12 uC/cm², dielectric constant ? ～ 520 and tan δ ～ 0.024 @ 100 kHz, to superparaelectric state with tan δ as low as 0.003 and ? = 210 with very small 1.7% dispersion in the frequency domain 0.4–100 kHz and less than 10% variation in the temperature range 77–415 K. NKN films grown onto SiO₂/Si(001) substrates show quadrupled super-lattice structure along c-axis, loss tan δ less than 0.01, and ? ～ 110 @ 1 MHz. C-V measurements for Au/NKN (270nm)/SiO₂/Si MFIS-diode structure yield memory window of 3.26 V at the programmable voltage of 8 V.     

Chemical solution processing of sr2(nb,ta)2o7 thin films

Abstract

Sr₂(Nb,Ta)₂O₇ thin films have been synthesized by chemical solution deposition. Homogeneous and stable Sr₂(Nb,Ta)₂O₇ precursor solutions with various Nb/Ta ratios were prepared by controlling the reaction of metal alkoxides in ethanol with a key additive of 2-ethoxyethanol. The crystallization temperature of the perovskite-type Sr₂(Nb,Ta)₂O₇ slabs structure decreased with increasing Nb substitution in amount. The crystallization temperature of Sr₂(Nb_0.2Ta_0.8)₂O₇ films on Pt/Ti/SiO₂/Si and Pt/Ir/Ti/SiO₂/Si substrates was above 800°C. On the other hand, by using Pt(100)/MgO(100) as a substrate, Sr₂(Nb,Ta)₂O₇ thin films crystallized into the Sr₂(Nb,Ta)₂O₇ phase at 700°C.     

Ferroelectric switching and fatigue behavior for PZT/YBCO thin film heterostructures

Abstract

The dielectric and ferroelectric properties for Au/Pb(Zr,Ti)O₃/YBa₂Cu₃O_7?x heterostructures at low temperatures are reported. The fatigue behavior and the ferroelectric switching effect for the structures are also investigated. The PZT/YBCO thin film heterostructures were deposited on MgO(100) substrates by laser ablation. The ferroelectric and dielectric properties and optical response of the oriented PZT films with different thicknesses have been studied over the temperature range from 20 K to 300 K. The dielectric loss of the structure was found to decrease by an order of magnitude when the YBCO bottom electrode became superconducting. A very low fatigue rate of the structure has also been obtained below T _c of YBCO layer.     

Temperature-Stable Super High Permittivity Dielectric Ceramics Based on (Ag1 − x Na x )(Nb1 − y Ta y )O3 System

The dielectric properties of (Ag_{1 –x} Na _x )(Nb_{1 –y} Ta _y )O₃ were studied in this paper. The molar ratios of Ag/Na and Nb/Ta were quite important to adjust dielectric properties of the system. The ceramic material with high permittivity and low dielectric loss can be obtained in the cases where Ag/Na ratio is 3/2 and Nb/Ta ratio is 3/2. In addition, the dielectric loss was reduced by preparing the precursor in advance.     

MOCVD preparation of SBTN thin films from two organometallic sources bottles

Abstract

SrBi₂(Ta_0.7Nb_0.3)₂O₉ (SBTN) films were first prepared on (111)Pt/Ti/SiO₂/Si substrates by MOCVD from only two organometallic source bottles. Bi(CH₃)₃ and the mixture of Sr[Ta(O°C₂H₅)₆]₂ and Sr[Nb(O°C₂H₅)₆]₂ were used as source materials. High compositional reproducibility was obtained; the Nb/(Ta+Nb) ratio was the same as the mixing ratio of the source. Sr/(Ta+Nb) and Bi/(Ta+Nb) ratios can be controlled by the reactor pressure and the input gas flow rate ratio of the source gases. Almost single phase of SBTN was obtained for the film deposited at 500°C and the following heat-treated at 800°C in O₂ atmosphere. Pr and Ec values of 330 nm-thick SBTN film were 8.5 μC/cm² and 91 kV/cm, respectively and were larger than those of SrBi₂Ta₂O₉ film. There was no degradation after 5x10¹⁰ cycles polarization switching.     

Effects of nitridation treatments for SBT/Ta2O5 stack gate capacitors

Abstract

In this study, effects of ICP nitride treatments on characteristics of ferroelectric gate stack capacitor were investigated for FET type ferroelectric memory applications. Pt/SBT(200nm)/Ta₂O₅(20nm)/ Nitride/Si (MeFINS) structure capacitors show wide ΔV (memory window) of 1.06V under ±3V operation, while Pt/SBT(200nm)/ Ta2O₅(20nm)/Si (MeFIS) capacitors without nitride treatments exhibit memory window of 0.60V. At the same time, an accumulation capacitance of the MeFINS structure device is higher than that of the MeFIS structure capacitor. This result implies that the ICP nitride treatment successfully suppresses a formation of low dielectric constant interfacial SiO_x layer and alleviates a series capacitance problem.     

Preparation of SrBi2(Ta,Nb)2O9 thin films by rf sputtering for ferroelectric memory production

Abstract

Ferroelectric SrBi₂(Ta, Nb)₂O₉ (SBTN) thin films were prepared by rf magnetron sputtering utilizing a multi-chamber type production tool (ULVAC CERAUS ZX1000). Accurate and dynamic compositional control results in excellent ferroelectric performances such as large 2Pr up to 15μC/cm², fatigue free at least 10⁹ cycles as well as good uniformity and process repeatability. These results indicate that the SBTN sputtering process is promising for ferroelectric memory production.     

Chemical processing and properties of Sr2(Ta,Nb)2O7 thin films

Abstract

The crystallographic orientation, microstructure and electrical properties of Sr₂(Ta, Nb)₂O₇ thin films strongly depended on the composition (Ta:Nb). Post-annealing at 850°C was effective for the improvement of some properties. The thin films with relatively Nb-rich compositions, such as Sr₂(Ta_0.6Nb_0.4)₂O₇ and Sr₂(Ta_0.5Nb_0.5)₂O₇, showed the (0k0) preferred orientation. The Sr₂(Ta_0.5Nb_0.5)₂O₇ thin film had a lamination layer structure after the post-annealing at 850°C for 6 min in oxygen. The characteristic microstructure originated in the crystallographic orientation of (0k0), which is the cleavage plane, and influenced electrical properties. The dielectric constant little change with the composition, however, the P-E hysteresis properties improved with the Nb content.     

Polycrystalline SrBi2Ta0.8Nb1.2O9 thin films

Abstract

The growth, microstructure and micro-Raman properties of SrBi₂Tao_0.8Nb_1.2O₉ (SBTN) thin films deposited on Si(100) substrates using pulsed laser deposition (PLD) technique were studied at various substrate temperatures. Films were characterized using X-ray diffraction(XRD), atomic force microscopy(AFM), energy dispersive X-ray analysis (EDAX) and micro-Raman studies. AFM studies indicated that the average grain size of the films increased between 0.08 μm to 0.1 μm with the increasing growth temperatures. Micro-Raman studies of SBTN films revealed the fact that shifting of Raman modes corresponds to the BO₆ (where B' Ta/Nb) octahedral symmetry, to higher frequencies, is in accordance with the different masses of the B site atoms and the force constants involved due to Nb doping at Ta sites.     

Piezoelectric properties and domain structure of the orthorhombic (K,Na,Li)(Nb,Ta,Sb)O3 single crystal

ABSTRACT

In this work, (K,Na,Li)(Nb,Ta,Sb)O₃ (KNLNTS) crystal is in the orthorhombic phase at room temperature. The orthorhombic-tetragonal phase transition temperature is 50.0°C, and the Curie temperature T_C of the tetragonal-cubic phase transition temperature is 253.8°C. The crystal is poled, the defects were “pinned” in specific position, and has positive effect in domain wall motions and better ferroelectric property (P_r is 6.49 µC/cm², E_c is 6.66 kV/cm). The domain configrations of the crystal were studied by means of a polarizing light microscopy (PLM), with poling along [100]_C direction.     

Development of Low Temperature Al2O3 MOCVD for Ferroelectric Film Passivation on 8″ Wafers

A long-term consideration in the application of ferroelectrics in device production is hydrogen-induced failures. Subsequent to ferroelectric formation, post-capacitor processes of inter-level dielectric layers contain hydrogen and are performed at elevated temperatures. Free hydrogen may react with the ferroelectric oxides, reducing portions of the dielectric layer and creating leakage paths. For optimum ferroelectric film performance, protection against hydrogen infusion is needed. In part, a design solution to this problem is to employ an Al₂O₃ hydrogen diffusion barrier in the device structure. We have focused on MOCVD of the barrier layer using an array of precursors—including trimethylaluminum (TMAl) and aluminum iso-propoxide (Al i-Pr) among others. We have successfully lowered the Al₂O₃ deposition temperature from 600°C to 350°C without sacrificing film quality or deposition rate. We have produced Al₂O₃ MOCVD films in a SpinCVD? cluster tool rotating disk low-pressure reactor. The Al₂O₃ films are uniform and reproducible. The MOCVD process provides uniform precursor and temperature distributions necessary for coverage over topology in stacked architectures. This paper describes the MOCVD process and resultant film properties.     

Growth and characterization of epitaxial SrBi2Ta2O9 films on (110) SrTiO3 substrates

Abstract

SrBi₂Ta₂O₉ (SBT) is an attractive material for nonvolatile ferroelectric memory applications. In this paper we report on the deposition of highly epitaxial and smooth SrBi₂Ta₂O₉ films on (110) SrTiO₃substrates. The films were grown by pulsed laser deposition at temperatures ranging from 600 to 800°C and at various laser fluences from a Bi-excess SBT target. The background oxygen pressure was maintained at 28 Pa during the film deposition. Structural characterization of the films was performed by x-ray diffraction. Atomic force microscopy was used to investigate morphology and growth of the films. The films grew with preferred (115) or (116) orientation. The roughness was of the order of unit cell height. The films display a growth pattern resulting in corrugated film morphology.     

Laser ablation preparation and property of bismuth-layer-structured SrBi2Ta2Ta2O9 and Bi4Ti3O12 ferroelectric thin films

Abstract

Bismuth-layer-structured ferroelectric thin films, SrBi₂Ta₂O₉ and Bi₄Ti₃O₁₂, have been prepared by laser ablation method on both Pt sheets and Si wafers at low temperatures of 400 ～ 500°C. These thin films have been characterized by XRD, XPS, AFM, C-V, D-E hysteresis and J-V measurement. SrBi₂Ta₂O₉ thin films have a good (105) preferential orientation, and Bi₄Ti₃O₁₂ thin films have (117) and c-axis orientation on these substrates. Ferroelectric film-SiO₂-Si structures show good C-V hysteresis curve owing to Si surface potential controlled by the D-E hysteresis. D-E hysteresis is obtained in Bi₄Ti₃O₁₂ thin film prepared on Pt sheet, and the remnant polarization and the coercive force are 7.5 μC/cm² and 72 kV/cm, respectively.     

Hysteresis caused by defects in buffer layer of metal-ferroelectric-insulator-semiconductor (MFIS) devices

Abstract

We have investigated the roles of buffer layer in the Pt/SBT-Y₂O₃/p-Si (MFIS) capacitors. We found that the insertion of Y₂O₃ buffer layer prevents the charge injection from the Si substrate to ferroelectric layer. However, negative charges with the effective density of 3.21×10¹²/cm² were generated due to the additional process step for Y₂O₃ deposition. We suggested that the asymmetrical increase of a memory window is due to the domain pinning caused by negative charges in buffer layer. In addition, we reported that the mobile positive charges in ferroelectric layer can induce the shift of the hysteresis loops depending on the gate-bias polarity and a ramp rate during the capacitance-voltage (C-V) measurement. Since Y₂O₃ buffer layer minimize the charge injection, the shift of the hysteresis loops was asymmetrical.     

Improvement in the electrical properties of ferroelectric SrBi2Ta2O9 capacitors by electron beam irradiation on precursor films

Abstract

Ferroelectric SrBi₂Ta₂O₉ (SBT) capacitors were fabricated by the Electron-Beam-Induced Patterning process and their electrical properties were evaluated in detail. In this process, the dose of an electron beam irradiated on precursor films had a great influence on the electrical properties of the SBT capacitors. The appropriate electron dose significantly improved the electrical properties of the SBT capacitors although the excess electron dose made severe deterioration in the properties. The SBT capacitors fabricated with the optimum electron dose, 1.5 mC/cm² for Sr:Bi:Ta = 0.8:2.2:2.0 solutions, exhibited excellent ferroelectric properties: a remanent polarization of 11.5 μC/cm², a coercive field of 40 kV/cm, a leakage current of 8×10^?8 A/cm²@ 1V and fatigue-free up to 1010 cycles. It seems that such improvements were caused by the adjustment of Bi contents in the films and the modification or the decompositon of precursors before heat treatment by electron beam irradiation.     

Room temperature and 77K dielectric properties of acetate-derived PZT,PLZT, PSZT and PBZT thin films

Abstract

Ferroelectric thin films in the PZT, PLZT, PBZT (lead barium zirconate titanate) and PSZT (lead stannate zirconate titanate) compositional systems were prepared from as-received acetate precursors. Multiple-layer thin films were fabricated via a spin coating technique and sintered at 650 – 700°C for two to three minutes per layer, yielding an overall thickness of 0.45um. The dielectric and ferroelectric hysteresis loop properties of these films were measured at room temperature and 77K. The results show that the thin films experience a substantial loss (-80% avg.) in dielectric permittivity at 77K and a significant increase in P_R, E_c and electrical breakdown strength. The phase transformation trends on cooling from room temperature to 77K were from SFE (slim-loop FE)-to-FE and AFE-to-FE. Compositions in these systems show promise for potential low temperature applications.     

Effects of Substrate and Annealing Temperatures on the Characteristics of SrBi4Ti4O15 Thin Films

In this study, radio frequency (RF) sputtering was used as the method and the layer-structured bismuth compound of SrBi₄Ti₄O₁₅ + 4 wt% Bi₂O₃ ferroelectric ceramic was used as the target to deposit the SrBi₄Ti₄O₁₅ (SBT) thin films. The addition of excess Bi₂O₃ content in the target ceramic was used to compensate the vaporization of Bi₂O₃ during the sintering and deposition processes. SBT ferroelectric thin films were deposited on Pt/Ti/SiO₂/Si under optimal RF magnetron sputtering parameters with different substrate temperatures for 2 h. After that the SBT thin films were post-heated using rapid temperature annealing (RTA) method. The dielectric and electrical characteristics of the SBT thin films were measured using metal-ferroelectric-metal (MFM) structure. From the physical and electrical measurements of X-ray diffraction pattern, scanning electronic microscope (SEM), I-V curve, and C-V curve, we had found that the substrate temperature and RTA-treated temperature had large influences on the morphology, the crystalline structure, the leakage current density, and the dielectric constant of the SBT thin films.