Characteristics of post-annealed SrTiO3 thin films prepared by mirror-confinement-type ECR plasma sputtering

SrTiO₃ films were synthesized on Pt/Ti/SiO₂/Si multilayer substrates by mirror-confinement-type ECR plasma sputtering without substrate heating. All films were found to be well crystallized at a substrate temperature below 450 K. A low temperature post-annealing of the films by electromagnetic-wave radiation drastically improved the crystallographic and electric properties of Pt/SrTiO₃/Pt/Ti/SiO₂/Si capacitors. The crystallinity of the films indicated little variation by post-annealing, but irradiation of electromagnetic wave was confirmed to be effective for decreasing the post-annealing time and temperature. The electric properties of films annealed without Pt upper electrodes were better than those with them, and the film dielectric constant reached a value of 260, which is nearly equal to the bulk one, at an annealing temperature of 573 K.     

Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Effects of process parameters on the LaNiO3 thin films deposited by radio-frequency magnetron sputtering

LaNiO₃ thin films were deposited by radio-frequency magnetron sputtering on both (100) Si and platinized Si substrates. The effects of relative oxygen ratio, substrate and annealing temperatures on the microstructure and the electrical properties of the films were investigated. The La/Ni ratio was found to be influenced by the relative oxygen ratio. On the other hand, the orientation of LaNiO₃ was significantly influenced by the substrate temperature. Highly (100)-oriented LaNiO₃ thin films were obtained on SiO₂/Si(100) and Pt/Ti/SiO₂/Si substrates when the substrates temperature was 300 °C with the relative oxygen ratio below 33%. In addition, the (100)-oriented LaNiO₃ showed the lower resistivity than that of random-oriented LaNiO₃.     

Characteristics of SrTiO3 thin films deposited under various oxygen partial pressures

SrTiO₃ thin films were deposited by rf-magnetron sputtering under various sputtering conditions followed by conventional furnace annealing at 600 and 700 °C. The amorphous SrTiO₃ thin films crystallized into polycrystals at 600 °C. The leakage current of the SrTiO₃ thin films decreased with increasing oxygen partial pressure in the sputtering gas. On the contrary, the dielectric constant increased with increasing the oxygen content in the sputtering gas. The leakage current and dielectric constant increased with increasing substrate temperature and post-annealing temperature. The ratio of SrTi approached 11 with increasing oxygen content in the sputtering gas and substrate temperature during deposition. The oxygen content in the film decreased with increasing the substrate temperature. The capacitance-voltage (C-V) curves showed that the capacitance was nearly independent of the applied voltage. Scanning electron microscopy (SEM) micrographs showed that interdiffusion between the bottom electrode (Pt) and the buffer layer (Ti) occurred during post-annealing, but that the interface between SrTiO₃ and Pt was stable.     

Dielectric properties of (Ba,Ca)(Zr,Ti)O3/CaRuO3 heterostructure thin films prepared by pulsed laser deposition

(Ba_0.90Ca_0.10)(Zr_0.25Ti_0.75)O₃ (BCZT) thin films were grown on Pt/Ti/SiO₂/Si substrates without and with a CaRuO₃ (CRO) buffer layer using pulsed laser deposition (PLD). The structure and surface morphology of the films have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). At room temperature and 1 MHz, the dependence of dielectric constant and tunability of the films with electric field were investigated; the dielectric constant and tunability are 725 and 47.0%, 877 and 50.4%, respectively, for the BCZT film on Pt/Ti/SiO₂/Si substrates without and with the CRO buffer layer at 400 kV/cm. The tunability of the BCZT/CRO heterostructure thin films on Pt/Ti/SiO₂/Si substrates was higher than that of the BCZT thin films on Pt/Ti/SiO₂/Si substrates. The high constant likely results from the oxide electrode (CRO).     

Studies of BaTiO3 thin films on different bottom electrode

BaTiO₃ (BT) thin films were prepared on Pt/Ti/SiO₂/Si and Ru/Ti/SiO₂/Si substrates by a modified sol-gel technique. The microstructure of the films was characterized by atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy. The results showed that BT thin films crystallized with perovskite structure. Compared to BT film on Pt/Ti/SiO₂/Si substrate, BT thin film deposited on Ru electrode has similar dielectric constant, while it has higher dielectric loss. C–E curve for BT film on Pt/Ti/SiO₂/Si was more symmetrical around zero-bias field than C–E curve for BT film on Ru/Ti/SiO₂/Si substrate. The tunability was 52.02% for BT film on Pt electrode, which was 33.42% on Ru electrode, at 275 kV/cm and room temperature. The leakage current density of BT on Pt electrode was about an order of magnitude lower than BT film on Ru electrode at the applied electrical field below 150 kV/cm. The leakage conduction mechanism was investigated.     

High dielectric constant of SrTiO3 thin films prepared by chemical process

SrTiO₃ thin films were prepared by the polymeric precursor method and deposited by spin-coating onto Pt/Ti/SiO₂/Si(100) substrates. The spin-coated films heat treated at 700°C were crack-free, dense, and homogeneous. Microstructural and morphological evaluations were followed by grazing incident X-ray, scanning electron microscopy and atomic force microscopy. Dielectric studies indicated a dielectric constant of about 475, which is higher than that of ceramic SrTiO₃, and a factor dissipation of about 0.050 at 100 kHz. SrTiO₃ thin films were found to have paraelectric properties with C-V characteristics.     

Ferroelectricity of ultrathin ferroelectric Langmuir-Blodgett polymer films on conductive LaNiO3 electrodes

LaNiO₃ (LNO) films with a surface roughness rms of 0.384 nm and a sheet resistance of about 200 Ω were prepared on SrTiO₃ and Si/SiO₂ substrates respectively by rf magnetron sputtering technique. The surface of LNO on Si/SiO₂ substrate is smoother than that on SrTiO₃ substrate. A nominal 2-monolayer (ML) poly(vinylidenefluoride-trifluoroethylene) film with a thickness of about 3 nm was deposited on LNO coated Si/SiO₂ substrate by Langmuir-Blodgett (LB) technology. Piezoresponse force microscopy (PFM) measurements show that the LB films demonstrate an obvious feature of polarization switching and good voltage durability. The results suggest that the ultrathin polymer films may be utilized to explore ferroelectric tunnel junctions.     

Enhanced electrical properties of PZT thick films prepared by sol–gel technique through step-by-step crystallization process

[Pb(Zr_xTi_1-x)O₃: PZT] films at morphotropic phase boundary composition (x = 0.52) were deposited on bare Si, ZrO₂/Si and Pt/Ti/SiO₂/Si substrates by sol–gel spin on technique. Films deposited on the bare Si and ZrO₂/Si substrates had low degree of crystallization and micro cracks. Well crystallized films with smooth microstructure were obtained on Pt/Ti/SiO₂/Si substrates. Further, the thickness of the films on Pt/Ti/SiO₂/Si substrate was increased up to ~1 μm by step-by-step crystallization process. The single perovskite phase of the above films was confirmed with X-ray diffraction analysis. Films had enhanced dielectric properties at room temperature and the dielectric constant values were comparable to those of bulk values at Curie temperature (T_c) from the temperature dependent dielectric measurements. Films exhibit higher remnant polarization (P_r) and lower coercive field (E_c) values. Further, capacitance–voltage (C–V), current–voltage (I–V) measurements and rough estimation of piezoelectric coefficient of the films were carried out.     

Dielectric enhancement of BaTiO3/BaSrTiO3/SrTiO3 multilayer thin films deposited on Pt/Ti/SiO2/Si substrates by sol–gel method

Polycrystalline BaTiO₃/Ba_0.6Sr_0.4TiO₃/SrTiO₃ (BT/BST/ST) multilayer thin films with different periodicities have been deposited on Pt/Ti/SiO₂/Si substrates by using a sol–gel method. The multilayer thin films were crack free, compact and crystallized in a perovskite structure. The dielectric constant of the multilayer thin films was significantly increased and the dielectric loss was almost the same as those of uniform BT, ST and BST thin films. The dielectric constant increased with increasing stacking periodicity as the thickness of each individual layer decreased. The multilayer thin films showed excellent dielectric properties and can be promisingly used for the dielectric layer of silicon-based embedded capacitors in package substrate.     

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.     

Impedance spectroscopy and relaxation phenomena of (Na,K) excess Na0.5K0.5NbO3 thin films grown by chemical solution deposition

Na_0.5K_0.5NbO₃ (NKN) and 10 mol% (Na,K) excess Na_0.5K_0.5NbO₃ (NKN10) thin films on Pt/Ti/SiO₂/Si substrate were prepared by chemical solution deposition. Crystallization of NKN10 thin films was confirmed by X-ray diffraction. The (Na,K) excess Na_0.5K_0.5NbO₃ thin film shows a ferroelectric P-E hysteresis loop. Dielectric properties and impedance spectroscopy of thin films were investigated in the frequency range from 0.1 Hz to 100 kHz and the temperature range of 25 ~ 500 °C. By analyzing the complex impedance relaxation with Cole-Cole plots, we found impedance relaxations for the thin film. The contribution of electrical conduction is discussed in relation to grain, grain boundary, and interface effects.     

The effects of oxygen partial pressure on BST thin films deposited on multilayered bottom electrodes

Ba_0.5Sr_0.5TiO₃ (BST) thin films have been deposited by r.f. magnetron sputtering on silicon and platinum-coated silicon substrates with different buffer and barrier layers. BST films deposited on Si/SiO₂/SiN/Pt and Si/SiO₂/Ti/TiN/Pt multilayer bottom electrode have been used for the fabrication of capacitors. XRD and SEM studies were carried out for the films. It was found that the crystallinity of the BST thin film was dependent upon oxygen partial pressure in the sputtering gas. The role of multilayered bottom electrode on the electrical properties of Ba_0.5Sr_0.5TiO₃ films has been also investigated. The dielectric properties of BST films were measured. The results show that the films exhibit pure perovskite phase and their grain sizes are about 80–90 nm. The dielectric properties of the BST thin film on Si/SiO₂/Ti/TiN/Pt electrode was superior to that of the film grown on Si/SiO₂/SiN/Pt electrode.     

Thickness scaling and electric properties of highly (111) oriented Nb-doped Pb(Zr,Ti)O<Subscript>3</Subscript> thin film prepared at low temperature by a sol–gel route

A series of highly (111) oriented Pb(Nb_0.01Zr_0.2Ti_0.8)O₃ (PNZT) thin films of variant thickness were successfully achieved on Pt/Ti/SiO₂/Si substrate by a sol–gel route. By introducing Pb_0.8Ca_0.1La_0.1Ti_0.975O₃ (PLCT) layer between the PNZT film and Pt electrode, the PNZT film could be crystallized at as low as 500 °C. When a maximum applied voltage is 3 V, it was found that the PNZT film with PLCT seed layer possessed higher remnant polarization (22 μC/cm²) as film thickness was scaled down to 50 nm. It was also found that enhanced pyroelectric properties could be observed in 50-nm thickness PNZT thin film due to its relatively low dielectric constant. The results demonstrated that the film thickness could be scaled down for low voltage operations using lattice matched interface between PNZT film and PLCT seed layer on Pt/Ti/SiO₂/Si substrate, and this interface optimization is the key technology for synthesizing thin PNZT films at low temperature with good insulating and electric properties.     

Preparation,microstructure and dielectric properties of Ba0.5Sr0.5TiO3 thin films grown on Pt/Ti/SiO2/Si substrates by pulsed laser deposition

Barium strontium titanate Ba_0.5Sr_0.5TiO₃ (BST) thin films have been deposited on Pt/Ti/SiO₂/Si substrates by a pulsed laser deposition method. The low-frequency dielectric responses of the BST films, grown at different substrate temperatures (T_s), were measured as functions of frequency in the frequency range from 1 kHz to 1 MHz. With increase of T_s, the grain size of BST thin films became larger and the crystallinity was greatly improved, and then the dielectric permittivity increased, while the dielectric dispersion rose drastically. The origin of the large dielectric relaxation is believed to result from the aggravation of oxygen diffusion at the BST/Pt interface for the BST thin films grown at comparatively higher temperatures. This concept could be further explained by considering the influence of post-annealing in oxygen ambient on the dielectric properties of BST thin films. Our results reveal that the dielectric properties are strongly dependent on the processing conditions and the microstructure of thin films.     

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.     

Phase formation and characteristics of r.f.-sputtered barium-strontium titanate thin films on various bottom layers

(Ba_0.7Sr_0.3)TiO₃ thin films were deposited by r.f.-magnetron sputtering on Pt/Ti/Si, Pt/TiSi₂/Si and Pt/Ti/SiO₂/Si substrates, respectively, and annealed at 650 C for 30s by Rapid Thermal Annealing (RTA). XRD (X-ray diffraction) patterns revealed that the BST films had perovskite structure without preferred orientation. Auger depth profiles of barium-strontium titanate (BST) films on various substrates were performed. In the Pt/Ti/Si and Pt/TiSi₂/Si structures, Si diffused into the BST film, but in the Pt/Ti/SiO₂/Si structure, the diffusion of Si into the BST film was prevented and the interface between the BST film and the electrode was stable. The dielectric constants were about 310–260 (100 kHz–1 MHz).     

Solid-state dewetting of Pt on (100) SrTiO3

Continuous thin films of Pt on (100) SrTiO₃ substrates were dewetted to form Pt particles at 1,150 °C, using an oxygen partial pressure of 10^?20 atm. After retraction of thick (50 or 100 nm) Pt films, SrTiO₃ anisotropic rods, slightly depleted in Ti, were found on the surface of the substrate. Rods did not form after dewetting of thinner (10 nm) Pt films. After dewetting, a ~10 nm thick interfacial phase was found between the Pt and the SrTiO₃. The interfacial phase, based on Sr and containing ~25 at% oxygen, is believed to be a transient state, formed due to Ti depletion from the substrate, resulting in a Pt(Ti) solution in the particles. The interfacial phase forms due to the low oxygen partial pressure used to equilibrate the system, and is expected to influence the electrical properties of devices based on Pt–SrTiO₃.     

Influences of post-annealing on structural and electrical properties of Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were prepared on Pt/TiO₂/SiO₂/Si(100) substrates at 650 °C under an oxygen pressure of 10 Pa by using pulsed laser deposition process. The crystallinity, microstructure and electrical properties of BZN thin films were investigated to verify the influences of post-annealing thermal process on them. The X-ray diffractometer (XRD) results indicate that all Bi_1.5Zn_1.0Nb_1.5O₇ thin films without post-annealing process or with post-annealing in situ vacuum chamber and in oxygen ambient exhibit a cubic pyrochlore structure. The improved crystallinity of BZN thin films through post-annealing was confirmed by XRD and scanning electron microscope (SEM) analysis. Dielectric constant and loss tangent of the as-deposited BZN thin films are 160 and 0.002 at 10 kHz, respectively. After annealing, dielectric properties of thin films are significantly improved. Dielectric constant and loss tangent of the in situ annealed films are 181 and 0.0005 at 10 kHz, respectively. But the films post-annealed in O₂ oven show the largest dielectric constant of 202 and the lowest loss tangent of 0.0002, which may attribute to the increase in grain size and the elimination of oxygen vacancies. Compared with the as-deposited BZN thin films, the post-annealed films also show the larger dielectric tunability and the lower leakage current density.     

Laser molecular beam epitaxy growth and properties of SrTiO3 thin films for microelectronic applications

Dielectric SrTiO₃ thin films were deposited on LaAlO₃ and Si substrates using laser molecular beam epitaxy. The correlations between the deposition parameters of SrTiO₃ thin films, their structural characteristics, and dielectric properties were studied. The conditions for achieving epitaxial SrTiO₃ thin films were found to be limited to deposition conditions such as deposition temperature. We show that the SrTiO₃ films with single (110) orientation can be grown directly on Si substrates. The nature of epitaxial growth and interfacial structures of the grown films were examined by various techniques, such as Laue diffraction and X-ray photoelectron spectroscopy. The SrTiO₃/Si interface was found to be epitaxially crystallized without any SiO₂ layer. Furthermore, we have measured dielectric properties of the grown SrTiO₃ multilayer suitable for tunable microwave device. A large tunability of 74.7%, comparable to that of SrTiO₃ single-crystal, was observed at cryogenic temperatures. Such STO thin films will be very promising for the development of microelectronic device applications.