Formation of ferroelectric thin films on ruthenium electrodes

Abstract

Sr_0.8Bi_2.4Ta₂O₉ (SBT) and Bi_3.25+xLa_0.75Ti₃O₁₂ (BLT) films were prepared on Ru electrodes by a sol-gel spin-coating method. It was found in the case of SBT/Ru that the oxidation of Ru was suppressed by annealing at temperatures lower than 650°C in O₂ atmosphere or by annealing lower than 700°C in N₂. However, the remanent polarization values of the films were as low as 2.3 μC/cm2 (2Pr) for the former case and 4.4 μC/cm2 for the latter case. On the other hand, the BLT/Ru samples crystallized at 650°C showed good crystallinity without oxidation of the Ru electrode. It was found that the ferroelectric properties depended on the amount of excess-Bi sensitively, and the film prepared under the optimum Bi composition showed an excellent P-V hysteresis loop with 2 Pr of 25 μC/cm2.     

Ferroelectric and dielectric properties of sol-gel and excimer-laser-deposited lead zirconate titanate and barium titanate films

Abstract

Switched remanent polarization was measured as a function of accumulated switching cycles for a variety of ferroelectric films using sinusoidally driven hysteresis loops. Switched remanent polarization and dielectric constant and loss were also obtained as a function of the cycling frequency. PZT films with niobium additives appeared to lose switched remanent polarization with accumulated cycles at a lesser rate than films without niobium. The switched remanent polarization was found to decrease with increasing frequency, which we attribute to the effect of grain size. Also, a decrease of dielectric constant with increasing frequency and an increase of dielectric constant with increased applied voltage are attributed to the effects of domain wall motion contributions to dielectric constant.     

Preparation of ferroelectric thin films for Si-based devices

Abstract

Lead titanate (PbTiO₃) thin films have been prepared on titanium dioxide coated silicon wafers by chemical vapor deposition (CVD). The pure PbTiO₃ thin films were deposited by controlling the experimental conditions. The gas phase reaction of TiO₂ occurred by exceeding the critical value of titanium input fraction at constant oxygen partial pressure. Strontium titanate (SrTiO₃) thin films have been prepared on p-type silicon wafers by radio frequency (RF) magnetron sputtering. The SrTiO₃ thin film was polycrystalline and the Sr/Ti ratio of this film was 0.91. The SrTiO₃ thin films contain three regions, an external surface layer, a main layer and an interfacial layer. The stoichiometric SrTiO₃ thin film was obtained by using the SrO excess target. The SrTiO₃ film annealed at 600[ddot]C has an ideal capacitance-voltage (C-V) curve and maximum effective dielectric constant.     

Enhanced ferroelectric properties of multilayer SBT-BTN thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉ – (Bi₄Ti₃)_1-xNb_xO₁₂ (SBT-BTN) multilayer thin films with various stacking periodicity have been synthesized on Ir/Ti/SiO₂/Si substrates by metal organic chemical vapor deposition technique (MOCVD). Tributylbismuth [Bi(C₄H₉)₃], strontium-bis[tantal(pentane-ethoxy)(2-methoxyethoxide)] [Sr[Ta(OEt)₅(OC₂H₄OMe)]₂], titanium bis(isopropoxy)bis(1-methoxy-2-methyl-2-propoxide) [Ti(OiPr)₂(mmp)₂] and niobium-ethoxide [Nb(OC₂H₅)₅] were selected as precursors. X-ray diffraction patterns show that the multilayer films annealed at 800°C consisted of a fully formed perovskite phase with polycrystalline structure. The remanent polarization (2·P_r) and coercive field strength (E_c) were 16.2 μC/cm² and 230 kV/cm, respectively, values which are much higher compared to pure SBT film (2·P_r = 6.4 μC/cm², E_c = 154 kV/cm).     

Short-time switching of polarization in thin ferroelectric films

Abstract

The peculiarities of repolarization in thin-film metal-PZT-metal structures with varioùs areas of electrodes have been investigated. The nonclassical mechanism of polarization switching was determined to take place at short durations of voltage pulses. The repolarization was shown to carry out according to the mechanism of formation and lateral widening of domains at long times.     

Excimer laser ablation processed ferroelectric and antiferroelectric thin films

Abstract

The dielectric and electrical properties of excimer laser ablated processed paraelectric (Ba_0.5, Sr_0.5)TiO₃, ferroelectric Bi-layered SrBi₂(Ta_0.5Nb_0.5)₂O₉, and antiferroelectric (PbZrO₃) thin films have been investigated. The effect of processing parameters on the microstructure of the films and the functional properties has been presented in detail. Some of the recent studies of stress induced effects, dielectric, hysteresis and ac and dc electrical properties have been highlighted in conjunction with microstructures of the films.     

Structure and properties of sol-gel processed (Pb,La)TiO3 ferroelectric thin films

Abstract

The influence of heat treatment and substrate materials on PLT thin films by sol-gel processing has been researched. Epitaxial growth PLT thin films with perovskite-type structure on sapphire, SrTiO₃ and MgO single crystal substrates have been prepared. The epitaxial relations are (100)PLT28/(100)SrTiO₃, (111)PLT28//(0001)sapphire and (100)PLT14//(100)MgO. The PLT polycrystal thin films with perovskite-type structure on Si single crystal and quartz glass substrates have been prepared. The remanent polarization Pr and the coercive field Ec of PLT15 ceramic thin films are 7.7 μc/cm² and 34 kv/cm at 4 KHz respectively. The optical transmittance of PLT28 ceramic thin films within the wavelength range of λ = 500–1000 nm is approximately 80%.     

Progress in economically viable phase shifters based on thin ferroelectric films

Abstract

A considerable amount of work has been done in the area of frequency and phase agile microwave circuits employing thin ferroelectric films. The best films to date have been Ba_xSr_1-xTiO₃ (BST) grown by pulsed laser ablation. But laser ablation does not seem readily scalable for volume manufacturing, partly because the process appears limited to 5 cm diameter wafers or smaller. Another impediment to commercialization is testing. Testing is cumbersome because the devices must be inserted into a fixture to interface with coaxial launchers. And, high voltage bias tees are not commercially available to safeguard the microwave instrumentation. We have investigated alternate growth methods including MOCLD, CCVD, and sputtering and developed an on-wafer testing approach for screening phase shifters. Some of the results are reported in a companion paper. Here we report results for sputtered PLZT films on LaA1O₃. Coupled microstrip phase shifters at K-band produced a figure of merit of ≈29°/dB. This is within a factor of two of the best laser ablated BST films. The devices also had an uncharacteristically flat frequency response between 12 and 20 GHz. Considering the large lattice mismatch between LaA1O₃ and PLZT, the film crystallinity is very good as determined by XRD. Surprisingly, the films also appeared to be cubic. We also report results for CCVD Ba_0.57Sr_0.43TiO₃ on sapphire. 20 GHz phase shifters yielded a figure-of-merit of 18°/dB. Finally we report the design and performance of a coplanar-to-microstrip transition that permits the phase shifters to be tested on wafer. Devices that pass have the virtual ground probe pads diced off so the phase shifter can be integrated into a phased array. Bias is fed directly through the coplanar probes and isolated from the network analyzer by custom high voltage bias tees.     

Electric field dependence of piezoelectric coefficient in ferroelectric thin films

A simple model is developed to explain the hysteretic electric field dependence of the piezoelectric coefficient in ferroelectric thin films. The nonlinear susceptibility and hysteretic electrical polarization behavior can explain the piezoelectric hysteresis characteristics. An empirical model introducing a weighting factor is utilized to represent the electric field dependence of the nonlinear susceptibility. Experimentally, the magnitude of the maximum of the piezoelectric coefficient measured in the backward direction of the piezoelectric hysteresis loop is usually larger than that of the maximum measured in the forward direction. The proposed model shows that the weighting factor in modeling the nonlinear susceptibility may account for this observed phenomenon. The nonlinear susceptibility may also explain the peaked shape observed in piezoelectric coeffieint-electric field hysteresis loops. The approach in this work does not require the “hard ferroelectric approximation” of the polarization characteristics, and provides a method of predicting the piezoresponse from measured capacitance and polarization properties of the ferroelectric thin film.     

GHZ polarization dynamics in ferroelectric thin films

Abstract

We present results from experiments which measure the local dielectric response of ferroelectric thin films driven by microwave-frequency electric fields. The repetition rate of a mode-locked Ti:Sapphire laser is used to generate a microwave drive signal that is phase-locked to an optical probe pulse and applied to the ferroelectric thin film. The induced polarization change in the ferroelectric film is measured stroboscopically via the electro-optic effect. Polarization images are acquired by scanning the laser beam across the sample in a confocal geometry. Time resolution is achieved by changing the delay between the electrical pump and the optical probe. Initial results show large local phase shifts in the ferroelectric response of closely separated regions of a Ba_0.5Sr_0.5TiO₃ thin film. This new experimental technique may help to understand the physical mechanisms of dielectric loss in these materials.     

Low temperature process and thin SBT films for ferroelectric memory devices

Abstract

At crystallization temperatures of about 800°C bismuth layered oxide SrBi₂Ta₂O₉ (SBT) deposited by MOD develops good ferroelectric properties for use in FeRAM devices. But scaling down the film thickness of SBT below 150 nm only shorts are measured at this crystallization temperture after top electrode deposition. Working Pt/SBT/Pt-capacitors are achieved by reducing the crystallization temperature. Also temperatures of 800°C are too high for integration of the SBT module in a stacked capacitor architecture for high density memory devices. Therefore, a process is needed to reduced the crystllization temperature of SBT, called ”Low Temperature Process“.

In this work the electric properties of spin-on processed SBT crystallized in a temperature window from 650°C up to 800°C are investigated. As shown by XRD, transtion of the nonferroelectric Fluorite phase to the Aurivillius phase takes place at approximately 625°C. Increasing the cystallization temperature gives better crystaallized SBT films with bigger SBT graains. However, film prosity is also increasing with temperature. Electrical results of stoichiometric variations of SBT are presented. SEM pictures show that cluster formation is correlated with less film porosity at lower temperatures.     

Thickness dependent ferroelectric properties of BSTO thin films deposited by RF magnetron sputtering

The thickness dependence of ferroelectric permittivity of (Ba, Sr)TiO₃ has been investigated. The BST films could be obtained to have a simple cubic perovskite structure, space group Pm3m, and practically c-axis epitaxial structure deposited at 800^∘C. Through post-annealing process, we have improved the dielectric properties; dielectric permittivity, dielectric loss, and tunability. The change in dielectric properties before and after annealing is attributed to the change in film strain and the contraction in film lattice. As the thickness of BST films increases from 55 nm to 350 nm, the dielectric constant of BST films increases from about 100 to above 670 due to the reduction of interfacial dead layers with low dielectric constant between films and top electrodes. The dielectric loss of BST thin films decreased as the thickness increases. The existence of interfacial dead layers in a thinner film had a larger effect on the effective dielectric constant than tensile strain between the BST films and MgO substrate.     

Electrodes for ferroelectric thin films

Abstract

Platinum and ruthenium oxide (RuO₂) deposited by ion beam sputter-deposition are evaluated for use as electrodes for PZT thin film capacitors. The effect of deposition temperature, film thickness, and the presence of oxygen on hillock formation in platinum is discussed. It is shown that the hillock density in Pt/Ti/SiO₂/Si films can be significantly reduced by properly controlling the processing conditions and film thickness. Stress measurements correlate with the experimental observation that depositing thinner platinum films (<800 Å) is an effective means of reducing hillock formation. The use of an intermediate deposition temperature 200–250°C also helps minimize hillock formation. Diffusion of the Ti adhesion layer into and/or through the platinum was significantly reduced by replacing the Ti with a TiO_x adhesion layer. RuO₂ electrodes are compared to Pt in terms of resistivity, surface morphology, microstructure and film orientation.     

乙二胺四乙酸含量对M型钡铁氧体薄膜磁性能和微波性能的影响

采用有机金属裂解法在Pt/TiO2/SiO2/Si基板上制备M型钡铁氧体(Ba M)薄膜,并着重研究了螯合剂乙二胺四乙酸(EDTA)含量对Ba M薄膜结构、磁性和微波性能的影响。研究发现,当EDTA∶(Ba2++Fe3+)=1(摩尔比)时,Ba M薄膜形成较多的六角形状晶粒,而且磁性能和微波性能较佳,沿c轴生长的取向度高达0.91,饱和磁化强度Ms为302k A/m(μ0Ms=0.38T),在50GHz时铁磁共振线宽ΔH为22k A/m(277Oe)。这是因为适量的EDTA不仅在溶液挥发时能够阻止金属离子的分离和间歇性的沉淀,并且能够促进成形成均匀的前驱液,从而在前驱液分解时能促进形成Ba M,在经过热处理后易形成沿c轴取向、具有六角形状晶粒的Ba M薄膜。     

High quality BaxSr1-xTiO3 films grown by mocld and novel ferroelectric/ferrite structures for dual-tuning microwave devices

Abstract

Excellent single crystal Ba_xSr_1-xTiO₃ (BST) films were grown on LaAlO₃ substrates using the metal-organic chemical liquid deposition (MOCLD) method. Very low losses (tanδ ∽0.002-0.008) were measured from these films at 400 KHz. Biaxially oriented BST films were successfully grown on polycrystalline YIG substrates using both MOCLD and pulsed laser deposition methods with biaxially oriented MgO and YSZ buffer layers. The dielectric losses of the films range from 0.005 to 0.015 while 25% of dielectric constant change was observed with 40V bias voltage up to 10 MHz. Both the dissipation and dielectric constant of the films remained nearly constants over a wide temperature range (77 K to 380 K). A dual-tuning microwave coplanar phase shifter using a BST film grown on a MgO buffered polycrystalline YIG substrate was fabricated. A significant phase shift was observed in GHz frequency range when an electric bias or a magnetic field was applied to the device.     

High temperature processing of ferroelectric thin films using interconnect wafer technology

Abstract

There is interest in ferroelectric thin films for uncooled IR detector applications. Currently the processing of these devices takes a fully integrated approach where the thin films are deposited directly onto underlying CMOS readout circuitry, thereby imposing severe limits on the thermal budget available for the crystallisation of the ferroelectric material. This is incommensurate with obtaining the best ferroelectric properties from materials such as lead scandium tantalate (PST) which requires elevated temperature processing to attain the highest merit figures for IR detection. In this paper thin film PST processed within the CMOS survivability envelope will be compared to that processed at temperatures up to 850°C. A novel interconnect wafer technology will be outlined which enables processing to be extended to such temperatures. It will be shown that elevated temperature processing of the PST film can result in dramatic improvement of the materials merit figure for IR detection     

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.     

Sol-gel PZT and Mn-doped PZT thin films for pyroelectric applications

Abstract

Thin films of ferroelectric lead zirconate titanate (PbZr_0.3Ti_0.7O₃ PZT30/70) and manganese doped lead zirconate titanate ((Pb(Zr_0.3Ti_0.7)_1?xMn_x)O_{3 ? x} = 0.01, PM01ZT30/70 and x = 0.03, PM03ZT30/70) have been prepared using sol-gei processing techniques. These materials can be used as the pyroelectric thin films in uncooled infrared (IR) detectors. Films deposited on Pt/Ti/SiO₂/Si substrates and annealed on a hot plate at 530°C for 5 min were seen to fully crystallize into the required perovskite phase and showed excellent ferroelectric behavior, demonstrated by reproducible hysteresis loops (P_r = 33 to 37 μC/cm², Ec(+) = 70 to 100 kV/cm, E_c(-) = -170 to -140 kV/cm). The pyroelectric coefficients (p) were measured using the Byer-Roundy method. At 20°C, p was 2.11×10^?4 Cm^?2K^?1 for PZT30/70, 3.00×10^?4 Cm^?2K^?1 for PM01ZT30/70 and 2.40×10^?4 Cm^?2K^?1 for PM03ZT30/70 thin films. The detectivity figures-of-merit (F_D) were 1.07×10^?5 Pa^?0.5 for PZT30/70, 3.07×10^?5 Pa^?0.5 for PM01ZT30/70 and 1.07×10^?5 Pa^?0.5 for PM03ZT30/70. These figures compare well with values reported previously.     

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.     

钛酸铋钙和稀土复合掺杂对BaTiO3陶瓷微结构和介电性能的影响

研究了稀土及CaBi4Ti4O15（CBT）的复合掺杂对BaTiO3（BT）陶瓷微结构及介电性能的影响。结果表明：单独添加CBT使晶粒细化,促进了陶瓷的烧结致密化,居里温度随着CBT含量的增加（≤0．5mol％）而逐渐移向高温端;当CBT含量由0．3mol％增加到0．5mol％时,BT陶瓷的电容量变化率逐渐减小;当CBT含量超过0．5mol％时,电容量变化率又增大。在BaTiO,CBT（BT—CBT）基础上单独添加1．0mol％La2O3,四方率减小,居里点移向低温端;保持La2O3掺杂量不变,随着CeO2含量的增加,BT—CBT陶瓷的晶胞体积呈现先减小后增大的变化趋势,四方率保持不变;1．0mol％La2O3和0．01mol％CeO2掺杂BT—CBT（0．5m01％）陶瓷在-55℃和125℃的电容变化率分别为-14．78％和-11．44％。完全符合EIAX7R标准,有望用于X7R型多层陶瓷电容器的制备。