不同晶化工艺对非晶PZT纳米薄膜形核取向生长机理的影响

射频磁控溅射法室温下在Pt/Ti/SiO2/Si上制备非晶Pb(Zr048Ti052)O3薄膜，非晶PZT薄膜分别经常规炉退火(CFA)处理和快速热退火(RTA)处理晶化为（100），（111）不同择优取向的多晶薄膜. 采用x射线衍射测定了薄膜相组分、择优取向度；用原子力显微镜和压电响应力显微镜观察了薄膜表面形貌，以及对应区域由自发极化形成的铁电畴像，观察了不同取向薄膜的电畴分布特征. 结果表明，RTA晶化过程钙钛矿结构PZT结晶主要以PZT/Pt界面处的PtPb化合物为成核点异质形核并类似外延的结晶生长，沿界面结晶速率远大于垂直膜面结晶速率，而CFA晶化样品成核发生在膜内杂质缺陷处，以同质成核为主. 不同的成核机理导致了不同晶面择优取向生长. 关键词： PZT薄膜 结晶 形核 力显微技术     

Investigation the effects of the excess Pb content and annealing conditions on the microstructure and ferroelectric properties of PZT (52-48) films prepared by sol-gel method

The effects of the PbO volatilization, excess Pb content of PbZr_0.52Ti_0.48 (PZT) precursor, PbTiO₃ (PT) seeding layers and annealing condition on the microstructures, surface morphologies, preferred orientation and ferroelectric properties of PbZr_0.52Ti_0.48 films were systematically investigated. PZT films with a variety of excess Pb (0-20%) were spin-deposited on Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by sol-gel technique. The films composition, Pb/Zr/Ti/O atom rate and Pb loss were semiquantitative analyzed by X-ray photoelectron spectrometer (XPS). When the excess Pb of PZT precursor was 10%, the Pb/Zr/Ti/O atomic rate of the fabricated films was very close to the designed rate of 1:0.52:0.48:3. The XRD and AFM investigations confirmed that PT seeding layer promoted the PZT films perovskite phase transformation and grains growth with (1 1 0) plane preferred orientation, accordingly lowered perovskite phase crystallization temperature and reduced Pb loss. The PZT films annealed in O₂ flow demonstrated better microstructure and ferroelectric properties comparing with films annealed in air by double remnant polarization increase and 8% coercive field increase. The underlying mechanism was also investigated.     

Pb(Zr0.53Ti0.47)O3 thin films with different thicknesses obtained at low temperature by microwave irradiation

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films with different thicknesses (99-420 nm) were prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by sol-gel method and films were annealed at 450 °C for 30 min using a single-mode cavity of 2.45 GHz microwaves. X-ray diffraction analysis indicated that the pyrochlore phase was transformed to the perovskite phase at above 166 nm films. The grain sizes were increased, surface roughnesses were decreased, and electrical properties were improved with film thickness. The leakage current density was 9 × 10⁻⁸ A/cm² at an applied electrical field of 100 kV/cm. The ohmic and field-enhanced Schottky emission mechanisms were used to explain leakage current behavior of the PZT thin films. These results suggest that microwave annealing is effective for obtaining low temperature crystallization of thin films with better properties.     

Comparison of the effect of PLT and PZT buffer layers on PZT thin films for ferroelectric materials applications

In order to study the effect of different buffer layers on the Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films, 10-nm thick (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) and Pb(Zr_0.52Ti_0.48)O₃ buffer layers have been deposited on the Pt(1 1 1)/Ti/SiO₂/Si substrates by pulsed laser deposition, respectively. The top buffer layers were also deposited on PZT thin films with the same thickness of the seed layers in order to enhance the fatigue characteristics of PZT thin films. We compared the results of dielectric constant, hysteresis loops and fatigue resistance characteristics. It was found that the dielectric properties of PZT thin films with PLT buffer layers were improved by comparing with PZT thin films with PZT buffer layers. The polarization characteristics of PZT thin films with PLT buffer layers were observed to be superior to those of PZT thin films using PZT buffer layers. The remanent polarization of PZT thin films showed 36.3 μC/cm² and 2.6 μC/cm² each in the case of use PLT and PZT buffer layers. For the switching polarization endurance analysis, PZT thin films with PLT buffer layers showed more excellent result than that of PZT thin films with PZT buffer layers.     

An XPS study and electrical properties of Pb1.1Zr0.53Ti0.47O3/PbO/Si (MFIS) structures according to the substrate temperature of the PbO buffer layer

PbO and PZT thin films were deposited on the p-type (1 0 0) Si substrate by the rf magnetron sputtering method with PbO and Pb_1.1Zr_0.53Ti_0.47O₃ targets for the application of the metal-ferroelectric-insulator-semiconductor (MFIS) structure. The MFIS structures with the PbO buffer layer show the good electric properties including a high memory window and a low leakage current density. The maximum value of the memory window is 2.0 V under the applied voltage of 9 V for the Pt/PZT (200 nm, 400 °C)/PbO (80 nm)/Si structures with the PbO buffer layer deposited at the substrate temperature of 300 °C. From the X-ray photoelectron spectroscopy (XPS) results, we could confirm that the substrate temperature of PbO affects the chemical states of the interface between the PbO buffer layer and Si substrate, which results in the inter-diffusion of Pb and the formation of the intermediate phases (PbSiO₃). And the existence of the undesired SiO₂ layer, which is the low dielectric layer, was confirmed at the surface region of the Si substrate by the XPS depth profile analysis.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.     

Enhanced ferroelectric property of (Pb0.95Ca0.05)(Nb0.02Zr0.80Ti0.20)O3 thin films prepared by RF magnetron sputtering

(Pb_0.95Ca_0.05)(Nb_0.02Zr_0.80Ti_0.20)O₃ [PCNZT] thin films were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering with and without a LaNiO₃ [LNO] buffer layer. Ca and Nb elements in PZT films enhance the ferroelectric property, LaNiO₃ buffer layer improves the crystal quality of the PCNZT thin films. PCNZT thin films possess better ferroelectric property than that of PZT films for Ca and Nb ion substitution, moreover, PCNZT thin films with a LNO buffer layer possess (1 0 0) orientation and good ferroelectric properties with high remnant polarization (P_r = 38.1 μC/cm²), and low coercive field (E_c = 65 kV/cm), which is also better than that of PCNZT thin films without a LNO buffer layer (P_r = 27.9 μC/cm², E_c = 74 kV/cm). The result shows that enhanced ferroelectric property of PZT films can be obtained by ion substitution and buffer layer.     

Enhanced fatigue property of PZT thin films using LaNiO3 thin layer as bottom electrode

A highly (100)-oriented metallic LaNiO₃ film was prepared directly on a Si substrate by a simple metalorganic decomposition (MOD) technique using lanthanum nitrate and nickel acetate as the starting sources. Subsequent Pb(Zr,Ti)O₃ (PZT) thin films deposited on the LaNiO₃-coated Si substrate were obtained by a modified sol–gel method. It was found that the PZT thin films began to form a single perovskite phase at a low annealing temperature of 530 °C, and exhibited highly (100) orientation. A ferroelectric capacitor of Pt/Pb(Zr,Ti)O₃/LaNiO₃/Si annealed at 600 °C displayed a good P-E hysteresis characteristic and was fatigue-free even after 10¹¹ switching cycles. Received: 25 May 2000 / Accepted: 9 August 2000 / Published online: 30 November 2000     

Influence of MgO and ZrO2 buffer layers on dielectric properties of Ba(Zr0.20Ti0.80)O3 thin films prepared by sol-gel processing

Ba(Zr_0.20Ti_0.80)O₃ (BZT) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel process. The BZT thin films directly grown on Pt(1 1 1)/Ti/SiO₂/Si substrates exhibit highly (1 1 1) preferred orientation, while the films deposited on Pt(1 1 1)/Ti/SiO₂/Si substrates with MgO and ZrO₂ buffer layers show highly (1 1 0) preferred orientation. At 100 kHz, dielectric constants are 417, 311 and 321 for the BZT thin films grown on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates, respectively. The difference in dielectric properties of three BZT films can be attributed to the series capacitance effect, interface conditions and their orientations.     

不同衬底上Pb(Zr0.52Ti0.48)O3择优取向铁电薄膜的制备和研究

通过MOD法在Si(100)和Pt(111)/Ti/SiO₂/Si基片上制备出LaNiO₃ ( LNO)薄膜.再通过修 正的Sol-gel法，在Pt(111)/Ti/SiO₂/Si,LNO/Si(100)和LNO/Pt/Ti/SiO_{2< /sub>/Si三种衬底上 制备出具有择优取向的Pb(Zr0.52Ti0.48)O3铁电薄膜. 经XRD分析表明，L NO薄膜具有(100)择优取向的类钙钛矿结构；PZT薄膜均具有钙钛矿结构，且在Pt(111)/Ti/S iO2/Si衬底上的薄膜以(110)择优取向，在LNO/Pt/Ti/SiO2/Si和LN O/Si(100)衬底上的 薄膜以(100)择优取向.经场发射SEM分析和介电、铁电性能测试表明，在LNO/Si和LNO/Pt/Ti /SiO2/Si衬底上的PZT薄膜的平均粒径、介电常数以及剩余极化强度均比以Pt/T i/SiO2/Si为衬底的薄膜大. 关键词： 3}薄膜')" href="#">LaNiO₃薄膜 PZT铁电薄膜 择优取向 剩余极化强度     

Preparation and crystallization of Pb(Zr0.95Ti0.05)O3 thin films deposited by radio-frequency magnetron sputtering with a stoichiometric ceramic target

0.95 Ti_0.05)O₃ (PZT 95/5) thin films of perovskite structure were prepared on various substrates by the radio-frequency magnetron sputtering with a stoichiometric ceramic target. The crystal structure of the films showed a strong dependency on the crystal structure of the substrates. After conventional-furnace annealing at 750 °C, crack-free and transparent epitaxial PZT 95/5 films were successfully obtained on SrTiO₃(100) substrates, and highly oriented films on LaAlO₃(012). The films on r-sapphire exhibit slightly preferred orientation along both the (040) and (122) axes of the orthorhombic PZT 95/5 phase. The films on YSZ(100) consist principally of the perovskite PZT 95/5 phase with random orientation with a small portion of unknown phase. However, the formation of the perovskite PZT 95/5 phase was not observed in the films on Si(110) or (111)Pt-coated Si substrates. The crystallization of the perovskite PZT 95/5 on these substrates could be improved by rapid thermal annealing (RTA). Single perovskite phase was obtained in the films on (111)Pt/Si which had RTA at 750 °C for 1 min. No tangible loss of Pb from the films occurred during either the sputtering or annealing. Received: 17 April 1997/Accepted: 18 November 1997     

Influence of the substrate on ferroelectric properties of 〈1 1 1〉 oriented rhombohedral Pb(Zr0.6Ti0.4)O3 thin films

〈1 1 1〉-oriented Pb(Zr_0.6Ti_0.4)O₃ thin films were elaborated in the same run by RF multitarget sputtering on Si/SiO₂/TiO₂/Pt(1 1 1) and LaAlO₃/Pt(1 1 1) substrates. PZT thin films were textured, exhibiting 〈1 1 1〉 fibre texture on silicon substrates whereas epitaxial relationships were found when grown on LaAlO₃/Pt(1 1 1). On the latter substrate, values of spontaneous polarization and of dielectric permittivity were measured close to that calculated previously along the 〈1 1 1〉 direction of PZT rhombohedral single crystal. On the contrary, spontaneous polarization and dielectric permittivity measured on PZT thin films deposited on platinized silicon were found deviating from calculated values. These different electrical results are attributed to different ferroelectric domain configurations.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

Influence of plasma pressure on the growth characteristics and ferroelectric properties of sputter-deposited PZT thin films

PZT thin films of thickness (320-1040) nm were synthesized on Si/SiO₂/Ti/Pt multilayered substrates by radio frequency magnetron sputtering. The influence of plasma pressure in the range of (0.24-4.9) Pa, during deposition, on the structural, electrical and ferroelectric properties of the PZT films was systematically studied. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and cross-sectional transmission electron microscopy (XTEM) were employed for structural study. Nano-probe Energy Dispersive (EDX) line scanning was employed to investigate the elemental distribution across the film-bottom electrode interface. I-V characteristics and polarization-electric field (P-E) hysteresis loop of the films were measured. The study reveals that the plasma pressure has a strong influence on the evolution and texture of the ferroelectric perovskite phase and microstructure of the films. At an optimum plasma pressure of 4.1 Pa, PZT films are grown with 93% perovskite phase with (1 1 1) preferred orientation and uniform granular microstructure. These films show a saturation polarization of 67 μC/cm², remnant polarization of 30 μC/cm² and coercive field of 28 kV/cm which, according to the literature, seem to be suitable for device applications.Transmission electron microscopy (TEM) study shows that at a plasma pressure of 4.1 Pa, the PZT/bottom Pt interface is sharp and no amorphous interlayer is formed at the interface. At a higher plasma pressure of 4.9 Pa, poor I-V and P-E hysteresis loop are observed which are interpreted as due to an amorphous interlayer at the film-bottom electrode interface which is possibly enriched in Pb, Zr, O and Pt.     

Improved dielectric properties of (Pb,Ca)TiO3 thin films prepared by metal-organic decomposition method

(Pb,Ca)TiO₃ (PCT) thin films have been deposited on Pt/Ti/SiO₂/Si substrate by metal-organic decomposition (MOD) technique. The film processing parameters such as drying and annealing temperatures have been optimized to obtain good-quality PCT films. Compositional analysis of the film has been studied by X-ray photoelectron spectroscopy (XPS). The effect of the annealing temperature on the crystalline structure, microstructure and electrical properties have been investigated by X-ray diffraction, atomic force microscopy (AFM) and impedance analyzer, respectively. Amorphous PCT films form at 350 °C and crystallize in the perovskite phase following the isothermal annealing at ?650 °C for 3 h in oxygen ambient. Typical tetragonal structure of the PCT film is evidenced from X-ray diffraction pattern. The grain size in the PCT films increases with an increase in annealing temperature. Significant improvement in the dielectric constant value is observed as compared to other reported work on PCT films. The observed dielectric constant and dissipation factor at 100 kHz for 650 °C annealed PCT films are 308 and 0.015, respectively. The correlation of the film microstructural features and electrical behaviors is described.     

Activation of Mg-doped P-GaN by using two-step annealing

One- and two-step rapid thermal annealing (RTA) for activating Mg-doped p-type GaN films had been performed to compare with conventional furnace annealing (CFA). The two-step annealing process consists of two annealing steps: the first step is performed at 750 °C for 1 min and the second step is performed at 600 °C for 5 min in pure O₂ or air ambient. It is found that the samples annealed in air ambient exhibit poor electrical properties as compared to those annealed in pure O₂. Compared to one-step RTA annealing and CFA annealing, the samples with two-step annealing exhibit higher hole concentration and lower resistivity. This means that the two-step annealing is a powerful method to enhance the electrical performance of Mg-doped p-type GaN films. Similar results were also evidenced by photoluminescence (PL) measurement. Possible mechanism was confirmed by secondary ion mass spectrometry analysis.     

Fatigue-free Pb(Zr0.52Ti0.48)O3 thin films on indium tin oxide coated substrates by a sol-gel process

Fatigue-free Pb(Zr_0.52Ti_0.48)O₃ (PZT) ferroelectric thin films were successfully prepared on indium tin oxide (ITO) coated glass substrates using the sol-gel method combined with a rapid thermal annealing process (RTA). The films post-annealed at a temperature of 700 °C for 2 min by RTA process formed (110)-oriented Pb(Zr_0.52Ti_0.48)O₃ thin films with pure perovskite structure, and had a good morphology as well. The good ferroelectricity of the prepared PZT films was confirmed by P–E hysteresis loop measurements. Fatigue characteristics showed stable behavior. Degradation in polarization was not found while the repeating cycles were up to 10¹¹, and a low leakage current density of 10⁻⁸ A/cm² was also obtained from the highly fatigue-resisted PZT thin films on ITO/glass substrates. Received: 19 October 1998 / Accepted: 29 March 1999 / Published online: 26 May 1999     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Thickness effect in Pb(Zr0.2Ti0.8)O3 ferroelectric thin films grown by pulsed laser deposition

Epitaxial Pb(Zr_,Ti)O₃ (PZT) thin films with thicknesses in the range of 50-200 nm and with 0.2 Zr/(Zr + Ti) ratio, were grown by pulsed laser deposition (PLD).The substrates used for PLD deposition are single crystalline 0.5% Nb-doped (1 0 0) SrTiO₃ (STON). SrRuO₃ (SRO) thin films were deposited as bottom and top electrodes in order to have minimum structural misfit, to insure on one side high quality growth, and on the other side to minimize the influence of the extended structural defects. Structural and electrical characterization was performed. The epitaxial PZT films are c-axis oriented and have an average roughness of 0.4 nm. The ferroelectric behavior was proved in all investigated films by the presence of the hysteresis loops and by the butterfly shape of the capacitance-voltage (C-V) characteristics. The ferroelectricity was present even in the samples with relative high leakage currents, down to a thickness of 50 nm. These results are essential when small thickness is needed for miniaturization of ferroelectric devices using PZT.     

Crystallization behaviour of PZT in multilayer heterostructures

Microstructural and electrical properties of PZT (lead zirconate titanate) thin films prepared by sol-gel techniques at annealing temperatures in the range from 550°C to 900°C are studied. Perovskite (Pe) grain nucleation in PZT film starts but not completes at 550°C. Along with formation of round Pe (111) grains on the Pt (111) interface, the film contains small Pe and pyrochlore (Py) grains. Films annealed at the temperatures higher than 600°C demonstrate column structure of Pe grains, the amount of Py inclusions reduces with the annealing temperature and practically disappears at 700°C. An increase of annealing temperature leads to enhancement of (100) Pe orientation as a result of Ti diffusion on the Pt surface. Polarization decreases with the annealing temperature (maximum at 600°C), whereas permittivity increases up to the annealing temperature of 750°C.