Ferroelectric properties and reliability of La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O heterostructures on si for non-volatile memory applications

Abstract

Highly oriented La-Sr-Co-O(LSCO)/Pb-La-Zr-Ti-O(PLZT)/La-Sr-Co-O heterostructures have been successfully grown on a highly oriented Pt film which was grown on a thermally oxidized Si (SiO₂/Si) substrate. The growth of oriented Pt film on the SiO₂/Si substrate was made possible through the use of a thin bismuth titanate template layer which is c-axis oriented on the SiO₂/Si substrate. The hybrid LSCO/Pt structure effectively reduced the sheet resistance of the electrodes by at least 3–5 times compared with a single LSCO electrode. These ferroelectric PLZT capacitors on Si exhibited symmetric hysteresis loops with very desirable ferroelectric properties. The test capacitors showed reliable performance at both room and high (100°C) temperatures with respect to fatigue, retention, aging, and imprint, suggesting that they can be used as reliable, nonvolatile memory elements.     

Growth and characterization of non-c-axis-oriented SrBi2Ta2O9 epitaxial thin films on Si(100) substrates with SrRuO3 bottom electrodes

Abstract

We have successfully grown non-c-axis-oriented epitaxial ferroelectric SrBi₂Ta₂O₉ (SBT) films with (116) and (103) orientations on Si(100) substrates using epitaxial (110)- and (111)-oriented SrRuO₃ (SRO) bottom electrodes, respectively. The SRO orientations have been induced by coating the Si(100) substrates with epitaxial YSZ(100) and MgO(111)/ YSZ(100) buffer layers, respectively. All films were sequentially grown by pulsed laser deposition. Specific in-plane orientations of the epitaxial SBT films were found, which are in turn determined by specific in-plane orientations of the epitaxial SRO bottom electrodes. These include a diagonal rectangle-on-cube epitaxy of SRO(110) on YSZ(100) and a triangle-on-triangle epitaxy of SRO(111) on MgO(111).     

Fabrication and testing of micron-size (Pb,La)(Zr,Ti)O3 thin film capacitors

Abstract

Micron-scale (down to 2 μm lateral dimension) La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O ferroelectric capacitors for high density (> 1 Mbit) non-volatile memories have been successfully fabricated by a full wafer process including ion milling. Reduced dimensional effects as well as fabrication process damage on the micron-size capacitors have been studied. The remnant polarization value was only weakly dependent on the lateral dimension of ferroelectric capacitors. The reliability characteristics such as fatigue, retention and aging of the micronscale ion milled capacitors were similar to those of the large capacitors, which is adequate for non-volatile memories.     

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.     

Growth and Dielectric Properties of Ferroelectric BaTiO3 Thin Films for Cantilever-Type Microsensors

ABSTRACT

Ferroelectric BaTiO₃ (BTO) thin films were deposited on Si, silicon-on-insulator (SOI) and MgO substrates by pulsed laser deposition. The orientations of the films, polycrystalline and epitaxial phase, were controlled by the lattice mismatch between the BTO film and substrates. The structural properties and surface morphologies were examined using X-ray diffractometer and atomic force microscope. The dielectric properties of BTO films were investigated using metal-ferroelectric-metal (MFM) and interdigital co-planar capacitors. Conductive oxide layers, SrRuO₃(SRO) and La_0.5Sr_0.5CoO₃ (LSCO), were grown on Si and SOI substrates as bottom electrodes. For MFM capacitors based on Au/BTO/SRO/Si and Au/BTO/LSCO/SOI layer structures, a little asymmetric capacitance-voltage curves were obtained with about 36% capacitance tunability. The remanent polarizations were about 21 μC/cm² and the coercive fields were about 71 kV/cm. For an interdigital capacitor based on Au/BTO/MgO layer structure, a little lossy capacitance-voltage curve was obtained with about 64% capacitance tunability.     

Pulsed laser deposition (PLD) of oriented bismuth titanate films for integrated electronic applications

Abstract

In this paper we describe recent successes of growth of epitaxial bismuth titanate (BTO) films by pulsed laser deposition (PLD) suitable for electro-optic and electrical switching device structures, and fabrication of an improved gate structure for a ferroelectric memory FET (FEMFET). TEM and x-ray results indicate that excellent crystalline quality BTO films were achieved on LaAlO₃. Polarization switching was demonstrated for BTO capacitors with epitaxial superconducting YBa₂Cu₃O₇ as the lower electrode. Using an SiO₂ buffer layer, a BTO/Si structure was fabricated and direct charge modulation in the Si by polarization reversal in the BTO was demonstrated.     

Improvement of Dielectric and Interface Properties of CeO2 Buffer Layer by Using the Metal Seed Layer and N2 Plasma Treatment

In this paper, we investigated the feasibility of cerium oxide (CeO₂) films as buffers layer of MFIS (metal ferroelectric insulator semiconductor) type capacitors. CeO₂ layer were prepared by a two-step process of a low temperature film growth and subsequent RTA (rapid thermal annealing) treatment. By applying a cerium (Ce) metal seed layer of 4 nm, unwanted SiO₂ layer generation was successfully suppressed at the interface between the buffer layer and the Si substrate. After N₂ plasma treatment, the leakage current was reduced by about 2-orders. By employing a N₂ plasma treatment, we were able to successfully obtain good properties at the interface between the buffer layer and the Si substrate.     

Novel diffusion control process using ultra thin buffer layer for MFIS memory

Abstract

MFIS structures having excellent clear interfaces and well-crystallized ferroelectric layer were successfully fabricated by a newly developed ultra thin metal buffer layer process on SiO₂/Si. We examined the effect of sputtered Zr or ZrO₂ ultra thin films as a buffer layer for Pb_xLa_1?xTiO₃ (PLT) growth. TEM observation revealed that the buffer layer formation process in which Zr oxidized after the metal deposition had advantages to produce MFIS structures. This method is also superior for the crystallization and the control of the orientation of PLT thin film on amorphous SiO₂. Especially, for buffer layer thicknesses below 10 nm, preferred c-axis oriented PLT thin films were grown. The I-V characteristics of MFIS-FET fabricated by the proposed method showed a clear memory window due to the remanent polarization of the ferroelectric thin film. This process is the most attractive candidate for realizing MFIS structure memory.     

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.     

Improvement of the electrical properties of PZT thin films using TiO2 buffer layer

Abstract

Thin TiO₂ layers were sputter-deposited on Pt/Ti/SiO₂/Si wafers, as buffer layers for PZT thin film capacitors. It was found that TiO2 buffers of less than 4-nm-thickness could assist in obtaining highly uniform PZT thin films with no second phase. The leakage current behaviors of the PZT based capacitor are improved, while retaining the ferroelectric properties of PZT thin films such as remanent polarization and coercive field. In addition, the uniform distribution of oxygen in PZT on TiO₂/Pt indicates that the TiO₂ buffer layer act as a barrier for lead-platinum reaction, as well as for oxygen diffusion.     

Asymmetrical single-mode silica waveguide deposited by PECVD

Silicon oxynitride (SiON) layer and SiO₂ buffer layer were deposited on silicon wafers by PECVD technique using SiH₄, N₂O and N₂. The refractive index of SiON films measured at a wavelength of 1552 nm using a prism coupler, could be continuously varied from 1.4480 to 1.4508. Optical planar waveguides with a thickness of 6 μm and a refractive index contrast (Δn) of 0.36% have been obtained. In addition, etching experiments were performed using ICP dry etching equipment on thick SiON films grown on Si substrates covered with a thick SiO₂ buffer layer. In order to measure optical properties, a polarization maintaining single-mode fiber was used for the input and a microscope objective for the output at 1.55 μ m. A low-loss and low propagation SiON-based waveguide was fabricated with easily adjustable refractive index of core layer.     

Application of fluorinated SiO2 interlayer dielectrics for ferroelectric memory

Abstract

Fluorine-doped silicon oxide (SiOF) as interlayer dielectric (ILD) was deposited over PZT capacitors by electron cyclotron resonance (ECR) chemical vapor deposition using SiF₄ and N₂O gases. In the conventional deposition of SiO₂ ILD layer using hydrogen-contained source gases, the properties of ferroelectric capacitors are known to be degraded during the formation of SiO₂ layer. In this study, we examined the degradation of electrical properties of SiOF-deposited PZT capacitors. The remnant polarization and leakage currents were not degraded after the deposition of SiOF. We observed that the fluorine atoms were not diffused into the metal electrode in both cases of the SiOF deposited PZT capacitors and post-deposition annealed capacitors. The SiOF films deposited in the high CF₄ flow rate exhibited rough columnar structure on the metal electrodes. We can successfully deposit SiOF in a smooth morphology by introducing TiO₂buffer layer or using the novel deposition method of changing the SiF₄ flow rate, namely two-layer-deposition method.     

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.     

Ferroelectric memory FET with Ir/IrO2 electrodes

Abstract

We proposed a MFMIS structure having a floating gate as a bottom electrode between a ferroelectric thin film and the gate SiO₂. Conventional gate SiO₂ can be used and ferroelectric thin films can be grown on bottom electrodes which have a good matching with the ferroelectric materials due to adopt the MFMIS structure. Ir and IrO₂ on poly-Si were used as floating gate. When a IrO₂ layer was formed between PZT and poly-Si, a high-quality PZT thin film was obtained and the PZT films show no fatigue up to 10¹² cycles of switching pulses. From the I_D-V_G characteristics measurement for 1·2 μm P-ch MFMIS FET, the shift in V_th or the memory window for a bias sweep of ±15V was about 3·3V. The difference of I_D-V_D curves which corresponded to I_D-V_G characteristics were found between before and after a programming pulse was applied.     

Iridium thin film as a bottom electrode for high dielectric (Ba,Sr)TiO3 capacitors

Abstract

We propose Ir thin films as new electrode materials for high dielectric BST capacitors. Ir was found to be superior to Pt in a number of aspects such as resistivity, adhesion and surface roughness. The Pt/BST/Ir/SiO₂/Si capacitors showed leakage currents as low as Pt/BST/Pt/SiO₂/Si ones, but higher capacitance resulted. For endurance properties with +5V unipolar pulse trains, the dielectric constant of BST films on Ir decreased by only 10% below its initial value after switching of 10⁹ cycles while that on Pt degraded by 30% after 10⁸ cycles. Ir bottom electrode effects on BST film properties were well explained by the formation of IrO₂ phases on the surface of Ir electrodes.     

Effects of bi2o3 buffer layer on ferroelectric properties of srbi2ta2o9 thin films by liquid-delivery mocvd

Abstract

Ferroelectric SrBi₂Ta₂O₉ thin films were deposited on the Bi₂O₃ buffered Pt/Ti/SiO₂/Si substrates using liquid-delivery metalorganic chemical vapor deposition. SBT films with 5nm thick-Bi₂O₃ buffer layer on Pt bottom electrode showed stronger (115) orientation than those without Bi₂O₃ buffer layer after annealing at 750°C. The value of the remanent polarization of SBT films with Bi₂O₃ buffer layer were improved significantly in comparison with those for the films without Bi₂O₃ buffer layer. The remanent polarization(2Pr) and coercive field(Ec) of SBT films without and with Bi₂O₃buffer layer annealed at 750°C were 11.9, 20.8 μ C/cm2 and 57, 37.8kV/cm at an applied voltage of 5 V, respectively.     

Effect of excess-PB and prenucleation layer on properties of Pb(ZryTi1-y)O3 thin films prepared by mod process

Abstract

A modified metal-organic decomposition process, MOD has been successfully utilized to improve the ferroelectric properties of Pb(Zr_0.52Ti_0.48)O₃, PZT, thin films. Multilayer PZT/Pt(Si) films, which contain 0.12 μm layer of spin coated PbO-excess (10 mol%) precursors on top of 0.12 μm layer of stoichiometric PZT precursors, exhibit superior ferroelectric properties (P_r=14.2 μC/cm²; E_c=62 kV/cm) to the single layer PZT/Pt(Si) films of the same thickness (0.24 μm), which are either stoichiometric or 10 mol% Pb-enriched. The ferroelectric properties are further improved when the PZT films were synthesized using a thin pulsed laser deposited (PLD) prenucleation layer (0.06 μm). The subsequently MOD-prepared PZT films posses high remanent polarization (P_r=23.2–26.6 μC/cm²) and low coercive field (E_c=62.9–69.0 kV/cm).     

Preparation of Textured Growth Pb(Zr,Ti)O3 Thin Films on Si Substrate Using SrTiO3 as Buffer Layers

PZT thin films are deposited on SiO₂/Si substrate by metallo-organic decomposition (MOD) process, using SrTiO₃ (STO) as buffer layer for textured growth. The STO layers deposited on SiO₂/Si substrate by pulsed laser deposition process show (100)/(200) preferred orientation, whereas the STO buffer layer deposited on silica substrate using spin-coating technique show random orientation behavior. The use of STO as buffer layers enhanced the crystallization and the preferred orientations of the PZT films. The PZT on STO buffered SiO₂/Si substrates thus obtained possess high refractive index, (n)_PZT/STO = 2.1159, and are of good enough quality for optical waveguide applications.     

Properties of PbZrxTi1−xO3/CeO2/SiO2/Si structure

Abstract

We report the crystalline quality and electrical properties of PbZr_xTi_1?xO₃ (PZT) films on n-type Si(100) substrates with CeO₂/SiO₂ dual buffer layers. PZT films and CeO₂ buffer layers were prepared by pulsed laser deposition technique, and SiO₂ buffer layers were formed by thermal dry oxidation. It was found that CeO₂/SiO₂ dual buffer layers effectively prevented Si and Pb interdiffusion between PZT and Si substrates. Furthermore, the capacitance-voltage (C-V) characteristics of the PZT/CeO₂/SiO₂/Si heterostructures demonstrated ferroelectric switching properties, showing a memory window as large as 2.7 V at 1 MHz.     

Thick electrodes for high frequency high Q tunable ferroelectric thin film varactors

Abstract

Thin film barium strontium titanate (BST) shows great promise for voltage tunable dielectric devices for use at RF and microwave frequencies. An MOCVD process has been developed for production of BST, resulting in films with very low losses (as low as 0.002–0.004) and tunabilities over 50% at low operation voltages. With these values of BST loss, overall device quality factors at RF (100 MHz+) frequencies are primarily limited by losses in the thin metal electrodes, such as Pt, normally used for ferroelectric thin films. The bottom electrode in parallel plate capacitor structures is particularly challenging, since it must provide a good growth surface for BST and be stable at high (>600 °C) growth temperatures in an oxidizing atmosphere yet have high conductivity and compatibility with Si or SiO₂/Si substrates. These challenges have previously prevented use of Pt thicknesses over 0.1–0.2 urn. Our solution to this problem, involves combinations of adhesion layers at the Pt/SiO₂ interface and embedded stabilization layers to make functioning Pt bottom electrodes as thick as 2 μm. Devices with dielectric Q factors over 150 at 100 MHz (tan δ ～ 0.006 as measured and modeled by S-parameters) and overall device Q factors over 50 at 30 MHz are described. We have also inserted these devices into tunable filters, achieving tunabilities of 50% and low insertion losses (0.3 dB) at RF frequencies.