Strong thickness dependence of aurivillius phase formation in SrBi2Ta2O9 thin films

Sr_0.7Bi_2.4Ta₂O₉ (SBT) thin films were studied for the dependence of Aurivillius phase formation kinetics on their film thickness. SBT thin films were fabricated using a sol-gel process and spin coating, and their thickness was varied controlling the number of spin coating. The films were first heated at a low temperature for the complete crystallization of amorphous film to fluorite phase and then further heated at different elevated temperatures for the phase transformation to Aurivillius for 40 min. It was found that the phase transformation kinetics apparently increased with thickness up to ∼390 nm, and then it sharply decreased at higher values. The Aurivillius crystal size decreased and the density of crystals increased with the increase of film thickness up to ∼390 nm, implying increasing number of nuclei due to the reduced energy barrier for nucleation. Above the critical value both the size and density of crystals decreased. It is suggested that up to ∼390 nm the tensile strain energy in the films, which was stored by the shrinkage of thin films during the removal of remaining organic components from sol-gel chemistry, plays a major role for determining the phase transformation kinetics and above the critical value SBT films act as a free bulk material without substrate constraints.     

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.     

Studies on Laser Ablated SrBi 2 Ta 2 O 9 and Sr 0.8 Ca 0.2 Bi 2 Ta 2 O 9 Ferroelectric Thin Films

Ferroelectric thin films of SrBi 2 Ta 2 O 9 (SBT) and (Sr 0.8 Ca 0.2 )Bi 2 Ta 2 O 9 (SCBT) were grown on platinized silicon substrates by using pulsed laser deposition technique. The effect of annealing temperature on the structural and electrical properties of the films was studied. Films were grown at 200 mTorr oxygen pressure with a constant substrate temperature at 500°C and annealed at different temperatures ranging from 700-800 °C in an oxygen ambient. X-ray diffraction data showed that as-grown films were crystalline nature. Atomic force micrographs showed that the grain size and surface roughness increased with increase in annealing temperature. The SBT films annealed at 800 °C showed ferroelectric properties with remanent polarization of 9.1 w C/cm 2 and coercive field of nearly 72 kV/cm. Whereas the SCBT films showed maximum remanent polarization of 7.3 w C/cm 2 with higher coercive field of 86 kV/cm. The higher coercive field in case of SCBT is attributed to the higher electronegativity of partially substituted Ca at Sr site. The dielectric constant increased with increase in annealing temperature and was attributed to the higher grain size.     

New top and bottom electrodes for SrBi2Ta2O9 ferroelectric capacitors

Abstract

SBT is a candidate as the ferroelectric material for large scale FeRAMs with the great advantages of less fatigue and better squareness in its P-E hysteresis curves, while SBT has the disadvantages of higher crystallization temperature that results in difficulties realizing a stacked structure cell and greater damage to its ferroelectric properties from forming gas annealing. This paper presents new top and bottom electrodes to eliminate these disadvantages for SBT. The remanent polarization decreases only slightly after forming gas annealing with the top electrodes of partially oxidized Ru. Ru-O top electrodes show no bubbles or peeling after forming gas. In order to achieve the stacked structure cell for SBT capacitors, a new diffusion barrier was developed. This new diffusion barrier withstands the high temperature annealing that is required to crystallize SBT films. With the new diffusion barrier hysteresis curves could be obtained with electrical connections through Si substrates.     

Defect Chemistry of SrBi2Ta2O9 and Ferroelectric Fatigue Endurance

The defect chemistry and charge transport properties of doped and undoped SrBi₂Ta₂O₉ (SBT) were studied by making 4-point dc equilibrium electrical conductivity, thermopower, ionic transport number, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) measurements. Results of high temperature equilibrium dc conductivity, thermoelectric power, and transport number measurements as a function of oxygen activity in the temperature range 650–725°C revealed that undoped SBT displays a broad centrally located plateau of ionic conductivity with an activation energy of mobility of 0.94 eV and a prominent upturn at high oxygen activity, caused by p-type conductivity. The effects of acceptor and donor dopants are consistent with a 1–2% net acceptor excess in the undoped compound. It has been observed that there is substantial (several percent) cation place exchange between the Sr²⁺ and Bi³⁺ in SBT. It is proposed that the net acceptor excess in undoped SBT consists of disordered Sr²⁺ substituting for Bi³⁺ in the fluorite-like bismuth oxide layers which are locally compensated by oxygen vacancies. The formation of the net donor excess by disordered Bi³⁺ substituting for Sr²⁺ in the perovskite-like layers does not manifest itself as n-type conductivity behavior, because the band gap is large and the mobility is highly thermally activated. The superior intrinsic ferroelectric fatigue endurance of SBT is attributed to the lack of mobile charged defects in the perovkite-like layers which create the ferroelectric response of the compound. The metallic bismuth presence on the surface of undoped SBT, as revealed by qualitative XPS measurements, is believed to result from long exposure to the highly reducing conditions in the XPS system.     

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.     

Preparation of SrBi 2 Ta 2 O 9 Ferroelectric Thin Films by RF Magnetron Sputtering

Ferroelectric SrBi 2 Ta 2 O 9 (SBT) thin films were deposited by RF magnetron sputtering on a Pt/Ti/SiO 2 /Si(100) structure. The deposition temperature of the film was varied from RT (room temperature) to 600C. It was found that the SBT films were crystallized at temperatures between 500C and 600C, which was much lower than the annealing temperature (700C to 800C) of the RT-deposited film. The maximum remnant polarization value (2Pr) of the SBT film was 15 w C/cm 2 , which was deposited at 575C.     

Thickness dependent morphology and electrical characteristics of SrBi2Ta2O9 deposited by metal organic decomposition

Abstract

The dependence of morphology of SrBi₂Ta₂O₉ (SBT) deposited by Metal Organic Decomposition (MOD) on film thickness and annealing temperature during the crystallization anneal was investigated. From Atomic Force Microscope (AFM) images of these films it can be seen that nucleation and grain growth strongly depends on SBT thickness which also affects the electrical characteristics of the correspondent Pt/SBT/Pt-capacitors. In this work results of a morphological study of SBT films with thicknesses between 40 and 110nm and annealing temperatures between 650°C and 725°C will be presented.     

Integration of H2 barriers for ferroelectric memories based on SrBi2Ta2O9 (SBT)

Abstract

In this study, integration of an hydrogen barrier into a FeRAM process flow is investigated. It is reported in the literature that ferroelectric properties can be maintained after hydrogen annealing by using IrO_x as a top electrode [16][17][18]. Advantage of materials like IrO_x is less catalytic activity compared to Pt. However, we found that IrO_x is not a promising candidate for top electrode barrier. (Pt)/IrO_x/SBT/Pt capacitors are prone to shorting or exhibit high leakage. IrO_x films are very easily reduced by reducing ambient which will result in peeling off. Also, IrO_x films tend to oxidize Ti or TiN layers immediately. Therefore, other barrier materials or layer sequences like Ir/IrO_x have to be considered.

For protection of the entire capacitor an Encapsulation Barrier Layer (EBL) is required. In this study, LPCVD SiN is used. LPCVD SiN is a standard material in CMOS technology. Production tools are available and it is well known as hydrogen barrier. By modifying the deposition process and using a novel process sequence, no visual damage of the capacitors after SiN-deposition and FGA is seen. Also, no degradation of electrical properties after capacitor formation as well as after SiN-deposition and FGA is observed. However, after metal 1 and metal 2 processing, 2P_r values at 1.8V are reduced from 12μC/cm²to 2μC/cm². Polarization at 5.0V is not affected.     

Development of a new annealing process to allow new top electrode materials for SrBi2Ta2O9 capacitors

Abstract

Using the Rapid Thermal Annealing (RTA) process, a technique has been established to obtain SrBi₂Ta₂O₉ (SBT) films which showed well-shaped hysteresis curves without a postannealing process after top electrode deposition, maintaining high remanent polarization (Pr) values. RTA conditions were optimized for nucleation of SBT. The effect of a seed layer on the film properties became obvious. This process allowed top electrode materials other than Pt. High remanent polarization (Pr) values could be also obtained with Pd top electrodes.     

Ferroelectric properties of SrBi2Ta2O9 thin films on Si (100) with a LaZrO x buffer layer

To obtain a metal–ferroelectric–insulator–semiconductor (MFIS) structure, we fabricated ferroelectric SrBi₂Ta₂O₉ (SBT) film on a p-type Si (100) wafer with a LaZrO _x (LZO) buffer layer by means of a sol–gel technique. The sol–gel deposited LZO film according to the different annealing temperatures had a good surface morphology even though the crystalline phase was not an amorphous phase. In particular, the root-mean-squared (RMS) surface roughness of the 750-°C-annealed LZO film was about 0.365 nm and its leakage current density was about 8.2?×?10^?7 A/cm² at 10 V. A Au/SBT/LZO/Si structure with different SBT film was fabricated. The C–V characteristics of the Au/SBT/LZO/Si structure showed a clockwise hysteresis loop. The memory window width increased as the SBT film thickness increased. The 600-nm-thick SBT film was crystallized in a polycrystalline phase with a highly preferred (115) orientation. The memory window width of the 600-nm-thick SBT film was about 1.94 V at the bias sweep voltage ±9 V and the leakage current density was about 6.48?×?10^?8 A/cm² at 10 V.     

Dielectric and Piezoelectric Properties of Nonstoichiometric SrBi2Ta2O9 and SrBi2Nb2O9 Ceramics

Nonstoichiometric SrBi₂Ta₂O₉ (SBT) and SrBi₂Nb₂O₉ (SBN) ceramics were prepared by a solid state reaction method. X-ray diffraction analysis showed that single-phase of Bi-layered perovskite was obtained. With different Sr/Bi content ratios of SBT and SBN, Curie temperature (T_C), electromechanical factor (K_p) and mechanical quality factor (Q_m) were measured. T_C of SBN (SBT) rose from 414C (314C) to 494C (426C) when Sr/Bi content ratio was increased from 0.55/2.3 to 1.2/1.8. In the most Sr-deficient/Bi-excess ratio of 0.55/2.3, the maximum values of Q_m were obtained approximately 1013 and 3325 for SBT and SBN, respectively.     

Degradation mechanisms of SrBi2Ta2O9 ferroelectric thin film capacitors during forming gas annealing

Abstract

The effects of annealing in forming gas (5% hydrogen, 95% nitrogen; FGA) are studied on spin coated SrBi₂Ta₂O₉ (SBT) thin films. SBT films on platinum bottom electrode are characterized with and without platinum top electrode by Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), High Temperature X-Ray Diffraction (HT-XRD) and Secondary Ion Mass Spectrometry (SIMS).

High Temperature X-Ray Diffraction (HT-XRD) of blanket Ti/Pt/SBT films in forming gas revealed that the bismuth layered perovskite structure of the SBT is stable up to approx. 500°C. SIMS analysis of Pt/SBT/Pt samples annealed in deuterated forming gas (5% D₂, 95% N₂) showed that the hydrogen accumulates in the SBT layer and at the platinum interfaces next to the SBT. After FGA of blanket SBT films, tall platinum-bismuth whiskers are seen on the SBT surface.

Performing the FGA of the whole Pt/SBT/Pt/Ti stack, two different results are found. For the samples with a high temperature annealing (HTA) step in oxygen after top electrode patterning, top electrode peeling is observed after FGA. For the samples without a HTA step after top electrode patterning, no peeling is observed after FGA.     

Pb(Zr,Ti)O3 thin film growth on yttrium-treated Si(100)

Abstract

Pulsed laser ablation has been used to deposit ferroelectric Pb(Zr, Ti)O₃ (PZT) thin films on Si(100) and on yttrium-treated Si(100) substrates. The yttrium (Y) treatment of a Si surface followed by oxidation resulted in formation of a very thin, Y-enhanced SiO₂ antidiffusion barrier layer, thereby suppressing the undesirable PZT/Si interdiffusion. The best PZT film grown on Y-treated Si(100) had a breakdown voltage of 0.6 MV/cm, a coercive field of 71 KV/cm, and a remanent polarization of 18 μC/cm².     

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.     

Influence of Ti-content in the bottom electrodes on the ferroelectric properties of SrBi2Ta2O9 (SBT)

Abstract

Stress behavior, results of AES analysis and electrical properties of SBT in dependence of electrode structure and annealing conditions are discussed. Evidence for degradation of the electrical properties of SBT due to diffusion of Ti is presented.     

Piezoelectric properties of SrBi2M2− xVxO9 (M = Nb and Ta) ceramics

Vanadium-substituted strontium bismuth tantalate, Sr_0.8Bi_2.2Ta_{2− x}V_xO₉ (SBTVx), and strontium bismuth niobate, SrBi₂Nb_{2− x}V_xO₉ (SBNVx), ceramics were synthesized by a low-temperature processing, and their dielectric, ferroelectric and piezoelectric properties were characterized. With the partial substitution of tantalum or niobium by vanadium cations, the single phase of the ABi₂M₂O₉-type structure was preserved and the sintering temperature was significantly decreased. For the SBNV ceramics, the T _c of 437^∘C for x = 0.0, the vanadium content hardly changed. On the other hand, the T _c of the SBTV ceramics increased from 408^∘C for the non-substituted SBTV to 414^∘C for x = 0.05 and then with the increasing vanadium content, the T _c decreased to 379^∘C for x = 0.20. The remanent polarizations, P _r, of SBTV and SBNV at room temperature were 4.9 and 5.4 μC/cm², respectively. All the obtained independent electromechanical coupling factors of the SBTV0.05 ceramics were as follows: k _p = 0.119, k ₃₁ = 0.073, k ₃₃ = 0.165, k ₁₅ = 0.051 and k _t = 0.134, and the SBNV0.05 ceramics were as follows: k _p = 0.074, k ₃₁ = 0.045, k ₃₃ = 0.175, k ₁₅ = 0.106 and k _t = 0.140. These coupling factors were higher than those of the non-substituted materials. From these results, the vanadium-substituted SBT and SBN-based materials can be expected to be lead-free piezoelectric resonator materials that can be prepared at low sintering temperatures.     

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.     

Synthesis and Structural Characterization of (SrCa)Bi 2 Ta 2 O 9 Ceramics

(Sr 1 m x Ca x )Bi 2 Ta 2 O 9 ceramics with compositions x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0 have been synthesized by conventional solid state route. Structural analysis of pellets were investigated using x-ray diffraction and micro-Raman spectroscopy. Substitution of Ca ion at Sr site was confirmed by decrease in lattice parameter calculated from x-ray diffraction data. Lowest Raman modes at 28.7 and 58 cm m 1 were found to increase in frequency with increasing Ca concentration and this was attributed to the lower mass and lower ionic radii of Ca. The temperature variation Raman studies showed a softening of the lowest phonon mode with increasing temperature. The increase in transition temperature with concentration of Ca in SBT compounds may be due to the decrease in tolerance factor.     

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.