Fabrication and Optical Properties of Pb(Mg/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/Thin Films on Si Substrates Using the PLD Method

Epitaxial 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) thin films with electro-optic effects were fabricated on (La_0.5Sr_0.5)CoO₃(LSCO)/CeO₂/YSZ-buffered Si(001) substrates using double-pulse excitation pulsed laser deposition (PLD) method with a mask placed between the target and the substrate. Epitaxial growth of PMN-PT thin films was undertaken using the two-step growth method of PMN-PT film. The PMN-PT seed layer was deposited at 500degC on the LSCO/CeO₂/YSZ/Si, which temperature was the same as that used for LSCO deposition. The PMN-PT thin films were deposited on the PMN-PT seed layer at 600degC, which enables growth of high-crystallinity PMN-PT films with smooth surfaces. We obtained optimum fabrication conditions of PMN-PT film with micrometer-order thickness. Resultant films showed high crystallinity with full width at half maximum (FWHM)=0.73 deg and 1.6 mum thickness. Electro-optic properties and the refractive index value were measured at 633 nm wavelength using the prism coupling method. The obtained refractive index was 2.59. The electro-optic coefficients r₁₃ and r₃₃ were determined by applying the electrical field between a semitransparent, thin top electrode of Pt and a bottom LSCO electrode. The electro-optic coefficient was r₁₃=17 pm/V at transverse electric field (TE) mode and r₃₃=55 pm/V at transverse magnetic field (TM) mode.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.     

Large electrocaloric effect of highly (100)-oriented 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 thin films with a Pb(Zr0.3Ti0.7)O3/PbOx buffer layer

0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) thin films with a lead zirconate titanate Pb(Zr_0.3Ti_0.7)O₃ (PZT)/PbO_x buffer layer were deposited on Pt/TiO₂/SiO₂/Si substrates by radio frequency magnetron sputtering technique, and pure perovskite crystalline phase with highly (100)-preferred orientation was formed in the ferroelectric films. We found that the highly (100)-oriented thin films possess not only excellent dielectric and ferroelectric properties but also a large electrocaloric effect (13.4 K at 15 V, i.e., 0.89 K/V) which is attributed to the large electric field-induced polarization and entropy change during the ferroelectric-paraelectric phase transition. The experimental results indicate that the use of PZT/PbO_x buffer layer can induce the crystal orientation and phase purity of the PMN-PT thin films, and consequently enhance their electrical properties.     

Effects of ferroelectric/metal interface on the electric properties of PMN-PT thin films epitaxially grown on Si substrates

Lead magnesium niobate-lead titanate 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (PMN-PT) ferroelectric thin films were deposited on SrRuO₃ (SRO), SrTiO₃, and TiN-buffered Si substrates by pulsed laser deposition. X-ray diffraction θ–2θ and Phi scans reveal that PMN-PT films were epitaxially grown on Si substrates. Pt, Al, and Gd metals were employed as top electrodes to investigate the ferroelectric and dielectric properties of these metal/PMN-PT/SRO capacitors. It was found that the coercive field (E _C) of the Gd(or Al)/PMN-PT/SRO capacitor is 4.5 times larger than that of the Pt/PMN-PT/SRO capacitor while the permittivity for the former is only ~27 % of that for the latter, which is analyzed using the model for metal-ferroelectric-metal heterostructures with Schottky contacts. Compared with the Pt/PMN-PT/SRO capacitor, the higher E _C and lower permittivity of the Gd(or Al)/PMN-PT/SRO capacitor are attributed to the stronger space charge field at the Gd(or Al)/PMN-PT interface. The capacitance–voltage characteristics of the metal/PMN-PT/SRO capacitors were also discussed.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Quadratic electro-optic properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 transparent ceramics under both DC and AC bias

The basic quadratic electro-optic properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) transparent ceramics have been studied under both DC and AC electric field bias. The contribution of piezoelectric resonance to electro-optic effect for this quadratic electro-optic ceramics material has been experimentally demonstrated and theoretically analyzed. It is found that, at the piezoelectric resonance frequencies, the piezoelectric induced electro-optic effect dominates and leads to a dramatically high sensitivity for weak electric signal detection. About 20 dB signal-to-noise ratio is attained when detecting AC electric field strength of 1 V/m with optimized DC bias. Besides, the effects of AC frequency and amplitude on halfwave voltage V(π) of PMN-PT are investigated.     

Low-temperature epitaxial growth of conductive LaNiO3 thin films by RF magnetron sputtering

Epitaxial growth of LaNiO₃ (LNO) thin films was successful on CeO₂/YSZ/Si(100), MgO(100) and SrTiO₃ (STO)(100) substrates by RF magnetron sputtering at 300 °C, although pulsed laser deposition requires 600 °C to prepare epitaxial LNO films according to the literature. Epitaxial LNO films deposited on CeO₂/YSZ/Si(100) and STO(100) had single orientation of LNO[100]//CeO₂[110]//YSZ[110]//Si[110]) and LNO[100]//STO[100], respectively. On the other hand, epitaxial LNO films deposited on MgO(100) had mixed orientations of LNO[100]//MgO[100] and LNO[100]//MgO[110]. The lattice parameter, composition and resistivity of the LNO thin films were strongly dependent on the substrate temperature. The minimum resistivity of LNO films was approximately 5×10⁻⁶ Ω m, which value almost agrees with the resistivity in the literature. It was found that the temperature to achieve minimum resistivity was 200 °C, irrespective of the type of substrate. The surface of the LNO films was smooth and flat.     

Optical waveguiding in epitaxial PbTiO(3) thin films

Epitaxial lead titanate (PbTiO(3)) thin films on SrTiO(3) (100) substrate were grown in situ by radio-frequency sputtering for optical waveguiding applications. The crystalline quality of the PbTiO(3) films deposited at 550 degrees C has been investigated through x-ray diffraction analysis. It indicates that thin films are completely c-axis oriented (rocking curve FWHM of 0.2 degrees for the 001 reflection). The transmission spectrum method has been used to measure the dispersion of the refractive index. At 632.8 nm, the PbTiO(3) film with an (001) orientation exhibits a refractive index of 2.61, which represents 98% of the bulk material. The prism-coupling technique has been also employed to determine the optical attenuation in the planar waveguide. In this study, we report a low propagation loss of 2.2 ? 0.2 dB/cm obtained in a PbTiO(3) optical waveguide.     

Piezoelectric properties of (K,Na)NbO3 thin films deposited on (001)SrRuO3/Pt/MgO substrates

(K(x),Na(1-x))NbO(3) (KNN) thin films were deposited on (001)SrRuO(3)/(001)Pt/(001)MgO substrates by RF-magnetron sputtering, and their piezoelectric properties were investigated. The x-ray diffraction measurements indicated that the KNN thin films were epitaxially grown with the c-axis orientation in the perovskite tetragonal system. The lattice constant of the c-axis increased with increasing concentrations of potassium. The KNN thin films showed typical ferroelectric behavior; the relative dielectric constant epsilon(r) was 270 to approximately 320. The piezoelectric properties were measured from the tip displacement of the KNN/MgO unimorph cantilevers; the transverse piezoelectric coefficient epsilon*(31) (= d(31)/s(E)(11)) of KNN (x = 0) thin films was calculated to be -0.9 C/m(2). On the other hand, doping of potassium caused an increase in the piezoelectric properties, and the KNN (x = 0.16) films showed a relatively large transverse piezoelectricity of epsilon*(31) = -2.4 C/m(2).     

Deflection of wafers and cantilevers with Pt/LNO/PZT/LNO/Pt/Ti/SiO2 multilayered structure

The present paper describes a Pt/LNO/PZT/LNO/Pt/Ti/SiO₂ multilayers deposited on 4-inch Si wafers. We have evaluated the variation of the deflection of the Si wafers with deposition of each of the thin films. The deposition of the multilayers has resulted in downward deflection (center is higher than edge) of the Si wafers. The multilayers have been also deposited onto SOI wafers and fabricated into piezoelectric micro cantilevers through MEMS bulk micromachining. The micro cantilevers have shown the upward deflection. We have characterized the ferroelectric and piezoelectric properties of the PZT thin films through electrical tests of the micro cantilevers. The dielectric constant, saturation polarization, remanent polarization and coercive field were measured to be 1050, 31.3 μC/cm², 9.1 μC/cm² and 21 kV/cm, respectively. The transverse piezoelectric constant, d₃₁, was measured to be − 110 pm/V from the DC response of the micro cantilevers.     

Temperature dependence of oriented growth of Pb[Yb(1/2)Nb(1/2)]O(3)-PbTiO(3) thin films deposited on LNO/Si substrates

(1-x)Pb[Yb(1/2)Nb(1/2)]O(3)-xPbTiO(3) (PYbN-PT, x=0.5)(001) oriented thin films were deposited onto LaNiO3 (LNO)/Si(001) substrates by sol-gel processing. The crystallographic texture of the films was controlled by the annealing temperature and heating rate. Highly (001) oriented LNO thin films were prepared by a simple metal organic decomposition technique, and the samples were annealed at 700 °C and 750 °C using a rapid thermal annealing process and furnace, respectively. X-ray diffraction analysis revealed that the films of PYbN-PT were highly (001) oriented along LNO/Si substrates. The degree of PYbN-PT orientation is dependent on the heating rate and annealing temperature. Annealing heating rate of 10 °C/s and high annealing temperature near 750 °C produce the greatest degree of (001) orientation, which gives rise to improved dielectric properties.     

Preparation of (001)-oriented Pb(Zr,Ti)O3 thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O(3) (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001) oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d(31), of -100 pm/V, and an extremely low relative dielectric constant, epsilon(r), of 240. The PZT thin films on Si substrate had a very high d(31) of -150 pm/V and an epsilon(r) = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Properties of epitaxial, (001)- and (110)-oriented (PbMg1/3Nb2/3O3)2/3-(PbTiO3)1/3 films on silicon described by polarization rotation

Epitaxial (PbMg_1/3Nb_2/3O₃)_2/3-(PbTiO₃)_1/3 (PMN-PT) films with different out-of-plane orientations were prepared using a CeO₂/yttria stabilized ZrO₂ bilayer buffer and symmetric SrRuO₃ electrodes on silicon substrates by pulsed laser deposition. The orientation of the SrRuO₃ bottom electrode, either (110) or (001), was controlled by the deposition conditions and the subsequent PMN-PT layer followed the orientation of the bottom electrode. The ferroelectric, dielectric and piezoelectric properties of the (SrRuO₃/PMN-PT/SrRuO₃) ferroelectric capacitors exhibit orientation dependence. The properties of the films are explained in terms of a model based on polarization rotation. At low applied fields domain switching dominates the polarization change. The model indicates that polarization rotation is easier in the (110) film, which is ascribed to a smaller effect of the clamping on the shearing of the pseudo-cubic unit cell compared to the (001) case.     

Preparation of (001)-oriented Pb(Zr,Ti)O/sub 3/ thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O₃ (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001)-oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d₃₁, of -100 pm/V, and an extremely low relative dielectric constant, epsiv_r, of 240. The PZT thin films on Si substrate had a very high d₃₁ of -150 pm/V and an epsiv_r = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Epitaxial growth of SrTiO3 films with different orientations on TiN buffered Si(001) by pulsed laser deposition

Epitaxial SrTiO₃ (STO) films have been grown on TiN buffered Si(001) by pulsed laser deposition. The TiN layer was in situ deposited at 540, 640 or 720°C whereas the STO film was grown at a fixed temperature of 640°C. We have studied the effect of the growth temperature of TiN on the epitaxial relationship of STO/TiN heterostructures. It is found that for TiN grown at 540 or 640°C the epitaxial relationship is 001STO 001TiN, and for TiN grown at 720°C it changes to (101)STO (001)TiN and [ 01]STO [1 0]TiN (or [ 01]STO [110]TiN). This change of relationship is accompanied by a sharp reduction in the out-of-plane lattice constant of the TiN layer. Fourier transform infrared spectra show that the longitudinal optic modes are active for all the STO films, but the absorption peak associated with the transverse optic mode is observed only in the (101) oriented STO films.     

Pb(Zr0.52Ti0.48)O3/TiNi multilayered heterostructures on Si substrates for smart systems

Ferroelectric/shape memory alloy thin film multilayered heterostructures possess both sensing and actuating functions and are considered to be smart. In this article, Pb(Zr_0.52Ti_0.48)O₃ (PZT) ferroelectric thin films and Ti-riched TiNi shape memory alloy thin films have been deposited on Si and SiO₂/Si substrates in the 400-600 °C temperature range by pulsed laser deposition technique. Deposition processing, microstructure and surface morphology of these films are described. The TiNi films deposited at 500 °C had an austenitic B2 structure with preferred (110) orientation. The surfaces of the films were very smooth with the root-mean-square roughness on a unit cell level. The structure of the TiNi films had a significant influence on that of the subsequently deposited PZT films. The single B2 austenite phase of the TiNi favored the growth of perovskite PZT films. The PZT/TiNi heterostructures with the PZT and TiNi films respectively deposited at 600 and 500 °C exhibited a polarization-electric field hysteresis behavior with a leakage current of about 2 × 10^− 6 A/cm².     

Growth and characterization of (Pb,La)(Zr,Ti)O3 thin film epilayers on SrTiO3-buffered Si(001)

Ferroelectric Pb_0.92La_0.08Zr_0.4Ti_0.6O₃ (PLZT) thin films were deposited on SrTiO₃-buffered Si(001) substrate by on-axis radio frequency magnetron sputtering. X-ray diffraction analysis revealed epitaxial growth of monocrystalline PLZT films, with an (001) rocking curve full width at half maximum of ∼ 0.3°. φ-scans showed 45° in-plane orientation of the perovskite unit cell relative to that of silicon. The elemental composition of the thin film heterostructure was examined by Auger sputter depth profiling measurements. The recorded profiles suggest that the SrTiO₃ buffer layer serves not only as a template for epitaxial growth, but also as a barrier suppressing Pb-Si interdiffusion between the PLZT layer and the Si substrate. The surface roughness of the PLZT layer was measured at ∼ 4 nm for films with ∼ 500 nm thickness. Wavelength dispersions for the refractive index (n) and the extinction coefficient (k) were obtained from spectroscopic ellipsometry measurements, with n ∼ 2.48 at the main communication wavelength λ = 1550 nm and k < 0.001 for λ > 650 nm. Recorded polarization vs. electric field loops for the PLZT epilayer, with a SrRuO₃ electrode layer interposed between PLZT and SrTiO₃, showed a remnant polarization P_r ≈ 40 µC/cm² and coercive field E_c ≈ 100 kV/cm. These findings suggest that the sputter-deposited PLZT thin films retain the functional properties critical to ferroelectric and electro-optic device applications, also when integrated on a semiconductor substrate.     

电子能谱研究生长高质量CeO_2/Si异质结

用低能双离子束淀积技术，在清洁的Si衬底上外延生长出了CeO2／Si异质结构。利用俄歇电子能谱、X射线光电子能谱的深度剖析技术对此类样品进行了测量分析。结果表明，样品界面清晰、陡峭，无氧化硅生成，这反映了外延层与Si衬底间过渡区很窄；外延层内组成元素Ce，O分布均匀，为正化学比CeO2相。原生样品经高温退火后，界面出现了氧化硅层，且过渡层增厚。最后讨论了有关影响CeO2／Si外延生长质量的因素，可认为高质量CeO2／Si结构生长的关键主要依赖于生长初期Si衬底表面不受氧化污染。为此，在IBD生长时，采取了一系列技术措施，得到了满意的结果。     

氧等离子体辅助脉冲激光沉积法制备PMN-PT薄膜的微观结构和电学性能

采用氧等离子体辅助脉冲激光沉积方法(PLD)在硅衬底上, 制备出高度(001)取向的钙钛矿相结构钛铌镁酸铅(PMN-PT)薄膜. 研究了氧等离子体辅助对PMN-PT薄膜相结构、微观形貌和电学性能的影响. 结果表明, 通过在薄膜沉积过程中引入高活性的氧等离子, 可以有效地提高PMN-PT薄膜的结晶质量和微观结构. 未采用氧等离子体辅助PLD方法制备PMN-PT薄膜的介电常数(10 kHz)和剩余极化(2P_r)分别为1484和18 μC/cm², 通过采用氧等离子体辅助, 其介电常数和剩余极化分别提高至3012和38 μC/cm².     

Waveguiding properties of pulsed-laser deposition Ca4GdO(BO3)3 thin films

Waveguiding properties of stoichiometric Ca₄GdO(BO₃)₃ (GdCOB) thin films deposited on quartz substrates by the pulsed-laser deposition (PLD) technique are reported. The optical properties and the anisotropy of the obtained thin films are investigated using the prism-coupling technique. Refractive indices (n_x=1.666, n_y=1.673 and n_z=1.680 at 632.8 nm) were, respectively, determined from the transverse electric (TE) and the transverse magnetic (TM) mode excitations. These values are found to be 3% lower than those of the bulk material, which is likely due to the structural and morphological features of the deposited GdCOB films.