Influence of LaNiO3 bottom electrode on the structural and physical properties of ferroelectric capacitors

Techniques such as high energy electron diffraction (RHEED), atomic force microscope (AFM) are used to characterize LNO film prepared by rf sputtering. It is found that LNO films are epitaxially grown on the SrTiO₃ (STO) substrates. Root mean square roughness (RMS) of LNO film increases with increasing growth temperature, and then becomes somewhat saturated when deposition temperature is higher than 350 °C. Meanwhile, resistivity of LNO film decreases with increasing growth temperature, and becomes relatively stable when deposition temperature is higher than 200 °C. It is found that ferroelectric properties of LaNiO₃/Pb(Zr,Ti)O₃/LaNiO₃ (LNO/PZT/LNO) capacitors prepared on STO substrate strongly depend on the deposition temperature of LNO bottom electrode. The higher the deposition temperature of LNO bottom electrode, the larger is the switchable polarization of LNO/PZT/LNO capacitor.     

Ferroelectric properties of dysprosium-doped Bi4Ti3O12 thin films crystallized in various atmospheres

Dysprosium-doped Bi4Ti3O12 （Bi3.4Dy0.6Ti3O12, BDT） ferroelectric thin films were deposited on Pt（111）/Ti/SiO2/Si（111） substrates by chemical solution deposition （CSD） and crystallized in nitrogen, air and oxygen atmospheres, respectively. 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. The results show that the crystallization atmosphere has significant effect on determining the crystallization and ferroelectric properties of the BDT films. The film crystallized in nitrogen at a relatively low temperature of 650 ℃, exhibits excellent crystallinity and ferroelectricity with a remanent polarization of 2Pr = 24.9 ℃/cm^2 and a coercive field of 144.5 kV/cm. While the films annealed in air and oxygen at 650 ℃ do not show good crystallinity and ferroelectricity until they are annealed at 700 ℃. The structure evolution and ferroelectric properties of BDT thin films annealed under different temperatures （600-750 ℃） were also investigated. The crystallinity of the BDT films is improved and the average grain size increases when the annealing temperature increases from 600 ℃ to 750 ℃ at an interval of 50 ℃. However, the polarization of the films is not monotonous function of the annealing temperature.     

Phase composition of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 film deposited by radio frequency magnetron sputtering

The 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN–PT) films were prepared by radio frequency magnetron sputtering deposited on Pt/Ti/SiO₂/Si substrate. The paper aims to study the effect of sputtering gas and the effect of annealing temperature on perovskite phase formation. Phase compositions were analyzed by X-ray diffraction and the surface morphologies of the films were characterized by scanning electronic microscopy. The polarization behavior of PMN–PT films was measured using the Radiant Technologies RT6000 ferroelectric test system. The results indicate that the appropriate sputtering gas contribute to the formation of pure-perovskite phase at the appropriate post-annealing temperature.     

Interface between electrode and PZT memory device

PbZrTiO₃ (PZT) is one of the most promising ferroelectric materials for ferroelectric random access memory (FeRAM). But, there is a problem that the PZT ferroelectric properties are degraded with platinum (Pt) electrodes after annealing in a hydrogenous atmosphere during LSI fabrication. This degradation has been attributed to the catalytic nature of Pt, which dissociates H₂ into protons which then migrate into the PZT and reduce it at elevated temperature. In this theory, it is unclear how Pt and PZT physically interact at the interface. Also, the mechanism concerning the generation of an interfacial layer of oxygen vacancies has not been addressed, which creates some ambiguity in the model. We researched the interface using secondary ion mass spectroscopy (SIMS) and field-emission type transmission electron microscopy (FE-TEM) in order to more clearly understand its impact on the degradation mechanism. We have verified atomically that annealing a Pt/PZT/Pt capacitor results in Pb diffusion from the PZT into the Pt electrode and Pt diffusion from the electrode into the PZT. We next verified that the interdiffusion is not a usual thermal interdiffusion process, but appears rather to be generated by the reaction with hydrogen on both top and bottom Pt electrodes. Finally, we present a model of how the effects of hydrogen reduction combine with the Pt catalysis to form oxygen vacancies. Lead and Pt interdiffuse easily through these vacancies at both interfaces. The model presented here can predict the distribution of vacancies and demonstrates the limitations of the recovery anneal. It also supplements our understanding of the degradation process and provides additional credibility to the above theory.     

Structural, electrical and mechanical properties of magnetron sputtered NiTi/PZT/TiOx thin film heterostructures

Shape memory alloy (NiTi) thin films coupled to ferroelectric lead zirconate titanate (PZT) produce an intelligent material capable of performing both sensing and actuating functions. In the present study, we report on the in-situ growth of NiTi/PZT/TiO_x heterostructure on Pt/Ti/SiO₂/Si substrates using magnetron sputtering technique. Deposition processing, microstructure, surface morphology, electrical properties and mechanical properties of these heterostructures were systematically investigated. The top NiTi films exhibit austenitic B2 structure with preferred (110) orientation. The varying thickness of NiTi films had a significant influence on properties of NiTi/PZT/TiO_x heterostructure. The bottom TiO_x layer was observed to favor the growth of perovskite PZT films with (100) orientation. Nanoindentation tests of these heterostructures were performed at room temperature. The mechanical hardness of the top NiTi layer of lower thickness was found to be highly influenced by underneath PZT layer. The heterostructure exhibited an interesting martensite to austenite phase transformation and polarization-electric field hysteresis behavior with remanent polarization (P_r) and the coercive field (E_r) of 17.1 μC/cm² and 69.6 kV/cm, respectively. These heterostructures having a layer of SMA material coupled to a ferroelectric material with underneath TiO_x layer are of immense technological importance for MEMS devices.     

Surface morphology of sputtered NiTi-based shape memory alloy thin films

The effect of substrate condition and annealing treatment on the surface morphology of sputter-deposited NiTi-based thin films was studied by means of atomic force microscope. It is found that the surface of the film deposited at 450 °C on a (100) Si wafer is composed of large island groups, consisting of islands of 150–300 nm in diameter. Annealing treatment at 400 °C results in a more homogeneous distribution of the island size. However, for the film deposited at 450 °C on a (111) Si wafer, its surface consists of more homogeneous islands, being about 200–250 nm in diameter. For the film deposited at 450 °C on a SiO₂ buffer layer on top of the Si-substrate, the surface islands have ideal spherical shape. After annealed at 650 °C, the islands have grown to about 300 nm in width and 550 nm in length. The surface roughness of the deposited film is related not only to the island sizes but also to the island distributions.     

Synthesis of titanium aluminide coatings on aluminum and titanium surfaces by mechanical alloying and subsequent annealing

Intermetallic Ti-Al-based coatings were synthesized by mechanical alloying in a vibratory ball mill and subsequent annealing. A titanium layer was deposited on aluminum specimens and an aluminum layer and aluminum-titanium mixture were deposited on titanium specimens. Under the effect of milling balls, powder particles deposit at the substrates, forming layers that have a very good cohesion with the substrate. During subsequent heating, diffusion layers on the basis of titanium-aluminum phases are synthesized as a result of the chemical interaction between titanium and aluminum. In the case of titanium layer deposited on aluminum, the temperature interval of transformations is 600–650°C; first, a Ti₃Al₅-based phase is formed; then, as diffusion saturation with Al increases, an Al₂Ti-based layer appears; and finally, the Al₃Ti compound is formed. The reaction rates depend on the temperature and the duration of annealing. On titanium with a (Ti + Al) layer deposited on its surface, the Al₃Ti, Al₂Ti, TiAl, and Ti₃Al compounds are formed in a temperature interval of 600–900°C. In the case of deposition a homogeneous aluminum layer on titanium, only Al₃Ti and Ti₃Al phases were observed after annealing.     

Preparation of a BiFeO3/LaNiO3 multiferroic oxide superlattice structure by RF magnetron sputtering

Artificial superlattices consisting of multiferroic BiFeO₃ (BFO) and conductive LaNiO₃ (LNO) were grown epitaxially on a Nb-doped SrTiO₃ (STO) (001) single-crystal substrate at temperatures in a range 560–810 °C with a RF magnetron sputtering system. The superlattice contained 30 periods of symmetric BFO/LNO bilayers with a thickness of 2 nm of each individual layer. Ferroelectric and conductive superlattice materials of this type can serve for an investigation of the strain dependence of ferroelectric properties of BFO layers in superlattice structures.Measurements of X-ray reflectivity and X-ray diffraction at high resolution were employed to characterize the microstructure of these films. The formation of a superlattice structure was confirmed by the appearance of Bragg peaks separated by Kiessig fringes in the X-ray reflectivity curve and a diffraction pattern. The clearly discernible main feature and satellite features on both sides of the substrate feature about the (002) STO Bragg peak indicate the high quality of the BFO/LNO artificial superlattice structure formed on a STO substrate at all deposition temperatures.X-ray measurements show that these superlattice films become subject to greater compressive strain in the in-plane direction, and possess increased crystalline quality when increasing the deposition temperature to 660 °C. The measurement of hysteresis loops shows that the largest remanent polarization (P_r) occurs at 660 °C.     

Structural, ferroelectric and dielectric properties of In2O3:Sn (ITO) on PbZr0.53Ti0.47O3 (PZT)/Pt and annealing effect

Ferroelectric indium tin oxide (ITO) on PbZr_0.53Ti_0.47O₃ (PZT)/Pt structure, prepared by RF sputtering onto SiO₂/Si substrates, is studied in order to investigate the effect of ITO as a top electrode in these systems. X-ray diffraction, scanning electron microscopy (SEM) and atomic force microscopy (AFM) experiments were performed to study the structure and the surface morphology of the samples. From X-ray diffraction, we observe that the ITO thin film grows with the (1 1 1) texture and the peaks attributed to PZT are all from the perovskite phase. The average roughness (RMS) of the PZT surface is found to be 1.650 nm from AFM experiment. The ferroelectric and dielectric properties were inferred from polarization hysteresis loops, capacitance and dielectric constant measurements. These properties have been compared to those of the widely studied Pt/PZT/Pt system prepared under the same conditions. The effect of ITO/PZT/Pt annealing has been studied. Annealing at 400 °C leads to 13% increase in the dielectric constant ?_r.     

Epitaxial SrRuO3 thin films deposited on SrO buffered-Si(001) substrates for ferroelectric Pb(Zr0.2Ti0.8)O3 thin films

SrRuO₃ thin film electrodes are epitaxially grown on SrO buffered-Si(001) substrates by pulsed laser deposition. The optimum conditions of the SrO buffer layers for epitaxial SrRuO₃ films are a deposition temperature of 700 °C, deposition pressure of 1 × 10^?6 Torr, and thickness of 6 nm. The 100 nm thick-SrRuO₃ bottom electrodes deposited above 650 °C on SrO buffered-Si (001) substrates have a rms (root mean square) roughness of approximately 5.0 Å and a resistivity of 1700 µω-cm, exhibiting an epitaxial relationship. The 100 nm thick-Pb(Zr_0.2Ti_0.8)O₃ thin films deposited at 575 °C have a (00l) preferred orientation and exhibit 2P_r of 40 µC/cm², E_c of 100 kV/cm, and leakage current of about 1 × 10^?7 A/cm² at 1 V. The silicon oxide phase which presents within PZT and SrRuO₃ films, influences the crystallinity of the PZT films and the resistivity of the SrRuO₃ electrodes.     

Substrate heterostructure effects on interface composition,microstructure development and functional properties of PZT thin films

Platinum- and (La_0.8,Sr_0.2)MnO₃ (LSMO)-terminated silicon substrates were used for the liquid-phase deposition of Pb(Zr_0.52,Ti_0.48)O₃ (PZT) thin films. Different layer thicknesses ranging from 100 to 600 nm were processed by sequential coating. Characterization of the films involved X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy (XPS) combined with depth profiling to probe the interface composition. The films deposited on Pt exhibit an intermetallic layer, Pt_xPb, after annealing at 500 °C in air. This film has been used to establish the XPS signature of the intermetallic phase which consists of a negative shift of the peak position of Pt(4f) due the electron transfer from Pb to Pt. In all cases pure phase perovskite thin films were obtained after short annealing at 700 °C. XPS depth profiling shows unambiguously the existence of an intermetallic layer, Pt_xPb, of approximately 10 nm at the interface between Pt and PZT, while an interdiffusion layer of ～30 nm was observed between LSMO and PZT. The impacts of interfacial layers on microstructure development and functional properties translate in the formation of specific textures, i.e. a pronounced (1 1 1)-texture on Pt due to lattice matching between (1 1 1)-PZT and (1 1 1)-Pt_xPb, and a random film orientation on LSMO, and a substantial thickness dependence of the dielectric and ferroelectric properties, though specific behaviors were observed for the two different substrate heterostructures.     

Cyclic oxidation and interdiffusion behavior of a NiAlDy/RuNiAl coating on a Ni-based single crystal superalloy

A novel NiAlDy/RuNiAl coating was deposited onto a Ni-based single crystal superalloy DD3. The cyclic oxidation and interdiffusion of the NiAlDy/RuNiAl coating and a NiAlDy coating at 1100 °C were investigated. For the NiAlDy coating, secondary reaction zone (SRZ) consisting of γ′, γ and σ-topologically-closed-packed phase (σ-TCP) needles was formed in the superalloy after 100 h annealing. The NiAlDy/RuNiAl coating effectively suppressed the formation of SRZ as the RuNiAl layer worked as a buffer layer. Premature scale spallation was observed on the NiAlDy coating after about 80 h cyclic oxidation, whereas the NiAlDy/RuNiAl coating exhibited improved oxidation-resistance property.     

Steam oxidation resistance and thermal stability of chromium aluminide/chromium hybrid coating on alloy steels formed at low temperatures

This study investigated the feasibility of forming a hybrid coating with a structure consisting of a top Cr-aluminide layer and an inner Cr layer on alloy steels by using a two step process: electro-Cr plating and then pack aluminising at low temperatures. The oxidation resistance of the coating so formed was tested in ultrasupercritical steam of 650 °C and 30 MPa. The factors affecting the oxidation kinetics of the coating were studied by comparing its oxidation behaviour with that of the pack Fe-aluminide coating tested in the same ultrasupercritical steam. The thermal stability of the coating at 650 °C was investigated by a series of isothermal annealing experiments in argon atmosphere. It was demonstrated that the outer Cr-aluminide layer of the coating can improve the steam oxidation resistance of the steel substrate. The inner Cr layer can function as an effective barrier preventing the outward diffusion of Fe from the steel substrate; it can also act as a buffer zone, substantially reducing the rate of the inward Al diffusion process.     

Preparation and characterization of sol–gel derived (1 0 0)-textured Pb(Zr,Ti)O3 thin films: PbO seeding role in the formation of preferential orientation

Lead zirconate titanate (PZT) thin films with a composition near the morphotropic phase boundary region were deposited onto Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates using a sol–gel method. A seeding layer was introduced between the most underlying surface of the PZT film and the platinum electrode surface to control the texture of the PZT thin film. The lead oxide seeding layer resulted in the formation of a single-phase perovskite and absolutely (1 0 0)-textured PZT film. SEM, XRD, XPS, and AES were used to characterize the evolution of the lead oxide layer and the PZT thin films. The growth kinetic mechanism of the (1 0 0)-textured PZT thin films was proposed phenomenologically. The ferroelectric and piezoelectric properties of the PZT films were also evaluated and discussed in association with different preferential orientations.     

Effects of substrate temperature and annealing on the anisotropic magnetoresistive property of NiFe films

Ni83Fei7 films with a thickness of about 100 ran were deposited on thermal oxidized silicon substrates at ambient temperature, 240, 350, and 410℃ by DC magnetron sputtering. The deposition rate was about 0.11 nm/s. The as-deposited films were annealed at 450, 550, and 650℃, respectively, in a vacuum lower than 3 x 10-3 Pa for 1 h. The Ni83Fei7 films mainly grow with a crystalline orientation of [111] in the direction of the film growth. With the annealing temperature increasing, the [111] orientation enhances. For films deposited at all four different temperatures, the significant improvement on anisotropic magnetoresistance occurs at the annealing temperature higher than 550℃. But for films deposited at ambient temperatures and 240 ℃, the anisotropic magnetoresistance can only rise to about 1% after 650 ℃ annealing. For films deposited at 350℃ and 410℃, the anisotropic magnetoresistance rises to about 3.8% after 650℃ annealing. The atomic force microscopy (AFM) observation shows a significant i     

Preparation and Performance of the Sm0.2Ce0.8O1.9-x Single Buffer Layer Fabricated with Dip-Coating

在双轴织构的Ni-5％W合金基带上,采用高分子辅助化学溶液沉积法通过提拉涂敷法,制备了厚度达250 nm的Sm0.2Ce0.8O1.9(SCO)外延织构单层缓冲层.通过严格控制前驱溶液的浓度、提拉速度、成相温度和热处理时间,所获的SCO单层缓冲层涂层平整、无微裂纹、且具有较强的(200)c轴外延织构.在其他条件假设不变的情况下,主要研究不同提拉速度对SCO缓冲层薄膜性能的影响.在此基础上,采用化学溶液法在SCO/NiW缓冲层上制备了YBCO超导层,其具有高度的双轴织构和均匀的表面形貌.结果表明:用提拉法获得的SCO单层缓冲层在具有适度的厚度下,仍然具有很好的织构传递特性,为低层本制造YBCO涂层导体长带提供了一条可靠的路线.     

Growth and characterization of Al2O3 thin films for the buffer insulator in Pt/SrBi2Nb2O9/Al2O3/Si ferroelectric gate oxide structure

Pt/SrBi₂Nb₂O₉ (SBN)/Al₂O₃/Si (MFIS) ferroelectric gate oxide structures were prepared with the rf (radio frequency) magnetron sputtering method for the application of non-destructive read-out ferroelectric RAM (NDRO-FRAM) devices. An Al₂O₃ intermediate layer between the perovskite SrBi₂Nb₂O₉ film and Si substrate prevents the serious inter-diffusion of the SrBi₂Nb₂O₉ (SBN) into the Si substrate. The coercive field that decisively affects the memory window was increased by inserting the Al₂O₃ insulator between the SBN and Si, and thus the memory window also increased with the increase in the electric field to the SBN. The memory windows of the metal-ferroelectric-insulator-semiconductors (MFIS) structures were in the range of 0.7–3.4 V when the gate voltage varied from 3 to 9 V. The memory windows of the MFIS structures were found to be dependent on the thickness and stoichiometry of the buffer layer. We obtained the maximum memory window in an MFIS with an insulator of 11.4 nm in thickness deposited in the deposition condition of a 15∶5 flow ratio (Ar:O₂) during sputtering.     

Deposition of PZT thin film onto copper-coated polymer films by mean of pulsed-DC and RF-reactive sputtering

In this work, Pb(Zr,Ti)O₃ (PZT) thin films were deposited onto flexible Cu-coated Kapton® substrates by means of reactive magnetron sputtering for the first time. Different power supplies were selected for each of the 200 mm targets to adjust film composition and substrate ion bombardment. High-power pulse sputtering has been employed for the Zr-target to enhance for formation of nanocrystals, pulsed DC sputtering for the Ti-target to provide a high enough sputter yield, and RF-sputtering for the Pb-target to prevent droplet formation. The deposited films had a lead-enriched layer at the surface and their film composition was in rhombohedral range near the morphotropic phase boundary of the PZT phase diagram. XRD revealed a nanocrystallite mixture of lead, zirconium and titanium oxides in the as-deposited films which can be transferred into perovskite Pb(Zr,Ti)O₃ by rapid temperature annealing. Observed piezoelectric properties demonstrate that rapid-temperature-annealed films are promising for application in flexible piezoelectric sensors, actuators and power generators.     

Magnetoelectric CoFe2O4/Pb(Zr0.53Ti0.47)O3 composite thin films of 2-2 type structure derived by a sol-gel process

CoFe₂O₄/Pb(Zr_0.53Ti_0.47)O₃ (CFO/PZT) magnetoelectric composite thin films of 2-2 type structure have been prepared onto Pt/Ti/SiO₂/Si substrate by a sol-gel process and spin coating technique. The optimal annealing process of composite thin films was determined by using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It is found that the amount of the citric acid and concentration of CFO starting precursor solution have great impact on morphologies of composite thin films. Subsequent scanning electron microscopy (SEM) investigations show that the prepared thin films exhibit good morphologies and compact structure, and cross-sectional micrographs clearly display a multilayered nanostructure of multilayered thin films. The purpose of this work is to determine the optimal annealing processes of composite thin films and to prepare magnetoelectric composite thin films with good microstructure. It is shown that the films exhibit both good magnetic and ferroelectric properties, as well as a magnetoelectric effect.     

Effect of buffer layer annealing temperature on the crystalline quality of In0.82Ga0.18As layers grown by two-step growth method

In_0.82Ga_0.18As epilayers were grown by LP-MOCVD on InP substrates with the insertion of In_0.82Ga_0.18As buffer layers, which were annealed at various temperatures between 490 °C and 630 °C for 5 min in AsH₃ ambient. The effect of buffer layer annealing temperatures on the crystalline quality of In_0.82Ga_0.18As epilayers was investigated by atomic force microscopy, scanning electron microscopy, double-crystal X-ray diffraction, and room-temperature Hall measurement. The characterization results showed that high quality In_0.82Ga_0.18As epilayers were obtained by optimizing the annealing temperatures of buffer layers. In particular, the In_0.82Ga_0.18As epilayer with buffer layer annealed at 530 °C showed the best crystalline quality. The changes of crystalline quality of In_0.82Ga_0.18As epilayers at high and low annealing temperature can be attributed to the recrystallization and reevaporation of the In_0.82Ga_0.18As buffer layers.