铅过量PLZT铁电薄膜的制备及其电学性质研究

采用Sol Gel法 ,在Pt TiO2 Si基片上制备了具有不同铅过量 (0— 2 0mol% )的PLZT铁电薄膜。分析了薄膜的晶相结构 ,研究了铅过量对PLZT铁电薄膜的介电性能和铁电性能的影响。结果表明 ,各薄膜均具有钙钛矿型结构 ,且各薄膜均呈 (110 )择优取向。PLZT铁电薄膜的介电性能和铁电性能随铅过量的变化而改变。铅过量为 10mol%的薄膜具有最佳的的介电性能和铁电性能。     

热处理温度对铁电薄膜底电极Pt和Pt／Ti物相与形貌的影响

随着热处理温度上升，在ＳｉＯ２／Ｓｉ衬底上溅射的Ｐｔ、Ｐｔ／Ｔｉ电极中，构成Ｐｔ薄膜的晶粒由小变大，由分布均匀到晶粒局部聚集，最后分离成小岛。Ｔｉ层可提高Ｐｔ薄膜与基片间的粘附性和高温下的稳定性。快速热处理可提高Ｐｔ薄膜在高温下的连续性。并研究了Ｐｔ薄膜对ＰＬＴ铁电薄膜的成品率和分散性的影响。     

Thickness dependence of structural and ferroelectric properties of sol-gel Pb(Zr0.56Ti0.44)0.90(Mg1/3Nb2/3)0.10O3 films

Sol-gel Pb(Zr_0.56Ti_0.44)_0.90(Mg_1/3Nb_2/3)_0.10O₃ (PZT-PMN) films were prepared onto the Ti/Pt/Ti bottom electrode by multilayer spin coating. The film thickness ranged from 0.22 to 0.88 μm. The Pt top electrodes were deposited on the PZT-PMN films by DC sputtering. The structural and ferroelectric properties of PZT-PMN films were investigated as a function of film thickness by X-ray diffraction (XRD), scanning electron microscopy (SEM), cross-sectional transmission electron microscopy (XTEM), and by measuring the relative permittivity. The film retains the tetragonal perovskite structure with the [111] and [100] preferred orientations perpendicular to the film surface independent of film thickness. The [100] texture increases with increasing film thickness although the [111] texture is always predominant. The film consists of columnar grains. The average grain size is nearly independent of film thickness. The surface layer containing fine grains about 30 nm in diameter is induced on the top of the film. As the film thickness exceeds 0.44 μm, the number of the fine grains decreases remarkably. The crystalline interface layer about 10 nm thick is formed between the film and the bottom electrode. This interface layer is composed of Pt, Pb, Zr, Ti and O, while it is rich in Ti and deficient in Pb and O as compared with the inside of the film. The measured relative permittivity of the film increases with increasing film thickness, following the low permittivity interface model. On the basis of this model, the relative permittivity is estimated to be 3200 for the intrinsic PZT-PMN film, 750 for the surface layer and 50 for the interface layer.     

Preparation and characterization of highly (1 1 1)-oriented (Pb,La)(Zr,Ti)O3 thin films by sol-gel processing

Lanthanum modified lead zirconate titanate (Pb_0.91La_0.09)(Zr_0.65Ti_0.35)O₃ (PLZT) ferroelectric thin films were grown on Pt/Ti/SiO₂/Si(1 0 0) and fused quartz substrates using a sol-gel method with rapid thermal annealing processing. The results showed that the highly (1 1 1)-oriented pervoskite PLZT thin film growth on Pt/Ti/SiO₂/Si(1 0 0) substrates. The electrical measurements were conducted on PLZT films in metal-ferroelectric-metal capacitor configuration. The PLZT thin films annealed at 600 °C showed well-saturated hysteresis loops with remanent polarization and coercive electric field values were 10.3 μC/cm² and 36 kV/cm, respectively, at an applied field of 300 kV/cm. At 100 kHz, the dielectric constant and dielectric loss of the film are 682 and 0.021, respectively. The PLZT thin film on fused quartz substrate, annealed at 600 °C, exhibited good optical transmittance, the band gap of optical direct transitions is 3.89 eV.     

Pt／Ti电极的扩散行为及其对铁电薄膜的影响

采用直流磁控溅射方法制备Ｐｔ／Ｔｉ电极，用ＲＢＳ、ＸＲＤ、ＳＥＭ方法研究了Ｐｔ和Ｔｉ的扩散行为，发现在氧气氛中进行热处理造成Ｔｉ层的快速氧化，Ｔｉ厚度对Ｐｔ／Ｔｉ的扩散有很大影响。Ｐｔ／Ｔｉ的扩散造成其上的铁我差的显微结构和性能。     

Comparative analysis for the crystalline and ferroelectric properties of Pb(Zr,Ti)O3 thin films deposited on metallic LaNiO3 and Pt electrodes

The crystalline quality and ferroelectricity of the Pb(Zr,Ti)O₃ (PZT) films deposited on the metallic LaNiO₃ (LNO) and Pt electrodes were comparatively analyzed to investigate the possibility for their application to non-volatile memory devices. LNO thin films were successfully deposited on various substrates by using r.f. magnetron sputtering even at a low temperature ranging from 250 to 500 °C, and the ferroelectric PZT thin films were spin-coated onto the LNO and Pt bottom electrodes. Metallic LNO thin films exhibited [100] orientation irrespective of the substrate species and PZT films coated onto LNO films had highly a- and c-axis orientations, while those with Pt bottom electrode were polycrystalline. PZT films with LNO bottom electrode had smaller grain size and larger dielectric constant compared to those grown on the Pt electrode. The ferroelectric thin films fabricated on LNO bottom electrode displayed an asymmetric D–E hysteresis loop, which was explained by the defect effects formed at the interface. Especially, the LNO/PZT/LNO capacitor was found to significantly improve the polarization fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Effect of post-deposition annealing on phase formation and properties of RF magnetron sputtered PLZT thin films

In this work, we report the preparation of lanthanum-modified lead zirconate titanate (PLZT) thin films by RF magnetron sputtering on platinized silicon (Pt/Ti/SiO₂/Si) substrate. Sputtering was done in pure argon at 100 W RF power without external substrate heating. X-ray diffraction studies were performed on the films to study the effect of post-deposition furnace annealing temperature and time on the perovskite phase formation of PLZT. Annealing at 650 °C for 2 h was found to be optimum for the preparation of PLZT films in pure perovskite phase. The effect of different annealing conditions on surface morphology of the films was examined using AFM. The dielectric, ferroelectric and electrical properties of these films were also investigated in detail as a function of different annealing conditions. The pure perovskite film exhibits better properties than the other films which have some fraction of unwanted pyrochlore phase. The remanent polarization for pure perovskite film was found to be ∼29 μC/cm² which is almost double compared to the films having mixed phases. The dc resistivity of the pure perovskite film was found to be 7.7 × 10¹⁰ Ω cm at the electric field of ∼80 kV/cm.     

Structure evolution and ferroelectric properties of Bi3.4Yb0.6Ti3O12 thin films crystallized under a moderate temperature

Ytterbium-doped Bi₄Ti₃O₁₂ (Bi_3.4Yb_0.6Ti₃O₁₂, BYT) ferroelectric thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by chemical solution deposition (CSD). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to identify the crystal structure, the surface and cross-section morphology of the deposited ferroelectric films. Structure evolution and ferroelectric properties of the as-prepared thin films annealed under different temperatures (600 °C-750 °C) were studied in detail. Additionally, the mechanism concerning the dependence of electrical properties of the BYT ferroelectric thin films on the annealing temperature was discussed.     

Interfacial reaction and electrical properties of HfO2 film gate dielectric prepared by pulsed laser deposition in nitrogen: role of rapid thermal annealing and gate electrode

The high-k dielectric HfO(2) thin films were deposited by pulsed laser deposition in nitrogen atmosphere. Rapid thermal annealing effect on film surface roughness, structure and electrical properties of HfO(2) film was investigated. The mechanism of interfacial reaction and the annealing atmosphere effect on the interfacial layer thickness were discussed. The sample annealed in nitrogen shows an amorphous dominated structure and the lowest leakage current density. Capacitors with high-k HfO(2) film as gate dielectric were fabricated, using Pt, Au, and Ti as the top gate electrode whereas Pt constitutes the bottom side electrode. At the gate injection case, the Pt- and Au-gated metal oxide semiconductor devices present a lower leakage current than that of the Ti-gated device, as well as similar leakage current conduction mechanism and interfacial properties at the metal/HfO(2) interface, because of their close work function and chemical properties.     

The effects of substrate and annealing on structural and electrochemical properties in LiCoO2 thin films prepared by DC magnetron sputtering

LiCoO2 thin films were fabricated by direct current magnetron sputtering method on STS304 and Ti substrates. The effects of substrate and annealing on their structural and electrochemical properties of LiCoO2 thin film cathode were studied. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction and field emission scanning electron microscopy. The as-deposited films on both substrates have amorphous structure. The (104) oriented perfect crystallization was obtained by annealing over 600 degrees C in STS304 substrate. The LiCoO2 thin film deposited on Ti substrate shows the (003) texture after annealing at 700 degrees C. The electrochemical properties were investigated by the cyclic voltammetry and charge-discharge measurement. The 600 degrees C-annealed LiCoO2 film deposited on STS304 substrate exhibits the inithial discharge capacity of 22 uAh/cm2 and the 96% capacity retention rate at 50th cycles. The electrochemical measurement on annealed films over 600 degrees C was impossible due to the formed TiO2 insulator layer using Ti substrate. As a result, it was found that the STS304 substrate seems to be more suitable material than the Ti substrate in fabricating LiCoO2 thin film cathode.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.     

Structural and dielectric properties of Ba0.7Sr0.3TiO3 thin films grown on thin Bi layer-coated Pt(111)/Ti/SiO2/Si substrates

In this work, the growth and study of dielectric properties of Ba_0.7Sr_0.3TiO₃ (BST) thin films grown on thin Bi layer coated Pt(111)/Ti/SiO₂/Si substrates, depending on thin Bi layer thickness is reported. The BST thin film (thickness 180 nm) grown on 10-nm-thick Bi layer exhibited more improved structural and dielectric properties than that grown on bare Pt(111)/Ti/SiO₂/Si substrate. The 10-nm-thick Bi layer in optimum configuration was effective for the grain growth of BST phase and suppressed the formation of the oxygen-deficient layer at the interface between the BST thin film and bottom electrode, which resulted in an increase in dielectric constant and a decrease in leakage current density of the Pt/BST thin film/Pt capacitor.     

Ultrafast crystallization kinetics in (Pb,La)Zr₀.₃₀Ti₀.₇₀O₃ thin films by pulsed excimer laser annealing

The crystallization kinetics of laser-annealed Lamodified Pb(Zr,Ti)O? (PLZT) thin films on LaNiO?-coated silicon substrates were investigated for substrate temperatures below 400 °C. A KrF excimer laser having a ~20 ns pulse width and an energy density ~40 mJ/cm2 was used to crystallize the films. The perovskite phase developed with cumulative laser pulse exposures; it was found that ~380 to 400 nm thick films could be fully crystallized for a total exposure time of 0.1 to 1 ms. Laser-crystallized films exhibited comparable dielectric and ferroelectric properties to those prepared by rapid thermal annealing at 650 °C for 1 min. The evolution of the dielectric properties as a function of the number of laser strikes suggests that once nuclei are present, they rapidly grow through the depth of the film. This is consistent with the electron microscopy results, which did not show a well-defined planar growth front that proceeds from the top to the bottom of the film. The resulting films showed comparatively large lateral grain sizes (on the order of 250 to 300 nm), with high defect concentrations. The nucleation and growth mechanisms were modeled using Avrami kinetics under rate-dependent and nonisothermal conditions. These results indicate that PLZT crystallization via laser annealing is nucleation-limited.     

Low-temperature crystallization of sol-gel-derived lead zirconate titanate thin films using 2.45 GHz microwaves

Lead zirconate titanate (PZT) thin films of thickness 420 nm were deposited on Pt/Ti/SiO₂/Si substrate using a spin coating sol-gel precursor solution, and then annealed using 2.45 GHz microwaves at a temperature of 450 °C for 30 min. The film has a high perovskite content and high crystallinity with a full width at half maximum of 0.35°. The surface roughness of the PZT thin film was 1.63 nm. Well-saturated ferroelectric properties were obtained with a remanent polarization of 46.86 μC/cm² and coercive field of 86.25 kV/cm. The film also exhibited excellent dielectric properties with a dielectric constant of 1140 and a dissipation factor of 0.03. These properties are superior to those obtained by conventional annealing at a temperature of 700 °C for 30 min.     

The thickness effect of Bi3.25La0.75Ti3O12 buffer layer in PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 (PZT/BLT) multilayered ferroelectric thin films

A series of PbZr_0.58Ti_0.42O₃ (PZT) thin films with various Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer thicknesses were deposited on Pt/TiO₂/SiO₂/p-Si(100) substrates by RF magnetron sputtering. The X-ray diffraction measurements of PZT film and PZT/BLT multilayered films illustrate that the pure PZT film shows (111) preferential orientation, and the PZT/BLT films show (110) preferential orientation with increasing thickness of the BLT layer. There are no obvious diffraction peaks for the BLT buffer layer in the multilayered films, for interaction effect between the bottom BLT and top PZT films during annealing at the same time. From the surface images of field-emission scanning electron microscope, there are the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples. The growth direction and grain size have significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics of PZT and PZT/BLT films suggest that 30-nm-thick BLT is just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results with that of PZT/Pt/TiO₂/SiO₂/p-Si(100) basic structured film suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Structural evaluation of sol-gel derived lead strontium titanate diffusion barrier for integration in lead zirconate titanate transducer design

Sol-gel derived Pb₄₀Sr₆₀TiO₃ (PST) thin film has been investigated as a diffusion barrier for integrating in PbZr₃₀Ti₇₀O₃ (PZT) device structures on Si substrates. PST film was deposited on SiO₂/Si substrate and annealed at a relatively low temperature range of 550-600 °C producing a crack-free, smooth and textured surface. Following deposition on PST/SiO₂/Si template PZT thin film was crystallised exhibiting random grain orientations and an insertion of the bottom Pt/Ti electrode forming PZT/Pt/Ti/PST/SiO₂/Si stacks promoted the preferred PZT (111) perovskite phase. PZT (111) peak intensity gradually decreased along with slight increase of the PZT (110) peak with increasing annealing temperature of the buffer PST film. The dielectric and ferroelectric properties of the PZT with barrier PST deposited at 550 °C were assessed. The dielectric constant and loss factor were estimated as 390 and 0.034 at 100 kHz respectively and the remnant polarisation was 28 µC/cm² at 19 V. The performance of the PZT/PST device structures was compared to similar PZT transducer stacks having widely used barrier TiO₂ layer.     

结构设计对铁电薄膜系统电滞回线的影响

为制备符合Si集成铁电器件要求的高质量Si基铁电薄膜，采用溶胶—凝胶(sol—gel)工艺，制备了MFM及MFS结构的铁电薄膜系统，研究了不同结构及不同衬底对铁电薄膜系统铁电性能及电滞回线的影响，并对这些差异产生的主要影响因素进行了分析，在此基础上，提出并制备了Ag／Pb(Zr0.52Ti0.48)O3／Bi4Ti3O12／p—Si多层结构，该结构铁电薄膜系统的铁电性能及电滞回线的对称性有明显改善，有望应用于Si集成铁电器件。     

Aluminum-doped zinc oxide electrode for robust (Pb,La)(Zr,Ti)O3 capacitors: effect of oxide insulator encapsulation and oxide buffer layer

Conductive aluminum-doped zinc oxide (AZO) was deposited by pulsed laser deposition as top electrodes for chemical solution deposition derived lanthanum modified lead zirconate titanate (PLZT) capacitors. Compared with PLZT capacitors with Pt top electrodes (Pt/PLZT/Pt), PLZT capacitors with AZO as top electrodes (AZO/PLZT/Pt) showed improved fatigue endurance after cycles of 200 kV/cm (10 V) were applied with a 100 μs pulse width at 1 ms intervals. By using a combination of AZO as the top electrode and as a thin buffer layer (10 nm) under PLZT thin films (AZO/PLZT/AZO/Pt), fatigue behavior was also improved compared with the case without an AZO buffer layer. The addition of either an Al₂O₃ or HfO₂ encapsulation layer increased the remnant polarization ratio of PLZT capacitors (after annealing at 200 °C, 1 Torr, 3 % hydrogen atmosphere) to 0.80 and 0.57, respectively, comparing with 0.52 without an encapsulation layer.     

Crystallization behavior and domain structure in textured Pb(Zr0.52Ti0.48)O3 thin films by different annealing processes

Amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were prepared on the Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering at room temperature. After rapid thermal annealing (RTA) and conventional furnace annealing (CFA) at different temperatures, the films were transformed into polycrystalline PZT thin films with (111) and (100) orientation, respectively. The phase formation and ferroelectric domains correlated with different orientation were systematically investigated by X-ray diffraction and piezoresponse force microscopy. The results showed that the perovskite PZT crystal with [111] orientation hetero-nucleated preferentially on top of the PtPb intermetallic phase at the PZT/Pt interface during RTA process. It is of interest to find that the domain self-organized into a structure with rounded shape at the early stage of crystallization. While the nucleation of the films treated by CFA dominantly homo-nucleated, thus the (100) orientation grains with minimum surface energy were easy to grow. The texture effects on ferroelectric properties of PZT films were also discussed in relation to the domain structure.     

Damping properties of epoxy-based composite embedded with sol–gel-derived Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin film annealed at different temperatures

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrate by sol–gel method. The effect of annealing temperature on microstructure, ferroelectric and dielectric properties of PZT films was investigated. When the films were annealed at 550–850 °C, the single-phase PZT films were obtained. PZT films annealed at 650–750 °C had better dielectric and ferroelectric properties. The sandwich composites with epoxy resin/PZT film with substrate/epoxy resin were prepared. The annealing temperature of PZT films influenced their damping properties, and the epoxy-based composites embedded with PZT film annealed at 700 °C had the largest damping loss factor of 0.923.