Low-temperature synthesis in vacuum of c-axis oriented ferroelectric YMnO3 thin films using alkoxy-derived precursors

Abstract

Hexagonal YMnO₃ thin films were prepared on Pt(111)/TiO_x/SiO₂/Si and Pt(111)/Al₂O₃(0001) substrates using alkoxy-derived precursor solutions. The films were prepared by spin coating the YMnO₃ precursor solutions and then, the films were calcined and crystallized via rapid thermal annealing in oxygen or vacuum ambient. The annealing conditions and substrates were critical for crystallization of ferroelectric YMnO₃ films. When annealed in vacuum, the films both on Pt(111)/TiO_x/SiO₂/Si and Pt(111)/Al₂O₃(0001) substrates crystallized to hexagonal YMnO₃ and the orientation depended on the substrates. The film on Pt(111)/Al₂O₃(0001) had c-axis orientation and the film on Pt(111)/TiO_x/SiO₂/Si had no preferred orientation. In addition, it was found that crystallization behavior, orientation and morphology of YMnO₃ films on Pt(111)/TiO_x/SiO₂/Si substrates depended on the annealing condition. The heat-treatment in vacuum at initial stage for crystallization affected the restraint of perovskite phase and formation of hexagonal phase. The following heat-treatment in oxygen promoted the c-axis orientation and grain growth. The optimum annealing procedure for crystallization of the c-axis oriented YMnO₃ films on Pt(111)/TiO_x/SiO₂/Si was addressed.     

Low-Temperature Process of Ferroelectric (Y0.95,Bi0.05)MnO3 Thin Films and Their Structural and Electrical Properties

[(Y_0.95,Bi_0.05)MnO₃] (YBM) films have been grown on Y₂O₃ buffered Si (001) by pulsed-laser deposition (PLD). We have compared the structural and dielectric properties of YBM films with those of typical YMnO₃ films from the viewpoint of lowering the process temperature. The highly c-axis oriented YBM film have been obtained on Y₂O₃/Si (001) at 700°C, which is a significantly reduced growth temperature from that of typical YMnO₃ films (850°C). The Bi modification was effective for the low temperature processing of YBM films. These highly c-axis oriented YBM films was obtained only at high ambient oxygen pressures, for example above 100 mTorr, contrary to YMnO₃ films which requires low ambient oxygen pressure for the growth of c-axis preferred orientation. The dielectric constant and dissipation factor was 29 and 0.017 at 1 MHz, respectively. The memory window due to ferroelectric polarization switching was found in a capacitance-voltage (C-V) characteristic. The YBM/Y₂O₃/Si structure with above characteristics of YBM films exhibited the C-V memory window of 1.2 V at a sweep voltage of 5 V. The flat-band voltage shifted symmetrically with increasing the sweep voltage up to 8 V due to little charge injection from Si. As a result, the memory window increased progressively with increasing the sweep voltage and amounted to 2 V at a sweep voltage of 8 V. The leakage current density was below 5 × 10^?7 A/cm² at a bias voltage of 8 V.     

The Effect of La-Doped Bi4Ti3O12 Buffer Layer on Crystallinity and Ferroelectric Properties of PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 Multilayered Thin Films

PbZr_0.58Ti_0.42O₃ (PZT) ferroelectric thin films with Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer of various thickness were fabricated on Pt/TiO₂/SiO₂/p-Si(100) substrates by rf-magnetron sputtering method. The pure PZT film showed (111) preferential orientation in the XRD patterns, and the PZT/BLT films showed (110) preferential orientation with increasing thickness of the BLT layer. There were no obvious diffraction peaks for the BLT buffer layer, for its thin thickness in PZT/BLT multilayered films. There were the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples from the surface images of FESEM. The growth direction and grain size had significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics suggested that 30-nm-thick BLT was just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Characterization of the CeO2 thin films for insulation layer and Pt/SrBi2Ta2O9/CeO2/Si MFISFET structure

Abstract

CeO₂ and SrBi₂Ta₂O₉ (SBT) thin films for MFISFET (metal-fcrroelectrics-insulator-semiconductor field effect transistor) were deposited by rf sputtering and pulsed laser deposition method, respectively. The effects of oxygen partial pressure during deposition for CeO₂ films were investigated. The oxygen partial pressure significantly affected the preferred orientation, grain size and electrical properties of CeO₂ films. The CeO₂ thin films with a (200) preferred orientation were deposited on Si(100) substrates at 600°C. The films deposited under the oxygen partial pressure of 50 % showed the best C-V characteristics among those under various conditions. The leakage current density of films showed order of the 10^?7～10^?8 A/cm² at 100 kV/cm. The SBT thin films on CeO₂/Si substrate showed dense microstructure of polycrystalline phase. From the C-V characteristics of MFIS structure composed of the SBT film annealed at 800°C, the memory window width was 0.9 V at ±5 V. The leakage current density of Pt/SBT/CeO₂/Si structure annealed at 800°C was 4×10^?7 A/cm² at 5 V.     

Growth and electrical properties of (211) BaTiO3 thin films on Pt-coated Si(100) substrates

Abstract

Barium titanate (BaTiO₃) thin films with high (211) orientation have been prepared on Pt(111)/Si(100) substrates by R. F. magnetron sputtering at a substrate temperature between 550°C and 580°C in an Ar/O₂ atmosphere. The I-V curve of a thin film capacitor (Ag-BaTiO_3-Pt) has been measured and the C-V curves are obtained for frequencies between 100Hz and 1MHz. Neither the I-V curve nor the C-V curves are symmetrical and a very large change in the slope of all curves is found to occur at ～+0.5v.     

Ferroelectric-Gate Field Effect Transistors Using (Y,Yb)MnO3/Y2O3/Si(111) Structures for 1T-Type FeRAMs

Fabrication and characterization of metal-ferroelectric-insulator-semiconductor field-effect-transistors (MFIS FETs) using (Y,Yb)MnO₃/Y₂O₃/Si structures were introduced for the first time. P-channel MFIS FETs were fabricated on n-type Si(111) substrates, in which an Y_0.5Yb_0.5MnO₃(200 nm)/Y₂O₃(25 nm) structure was used as gate insulator. The Y_0.5Yb_0.5MnO₃ and Y₂O₃ films were prepared by chemical solution deposition. A fabricated MFIS FETs showed the hysteresis loop due to spontaneous polarization in the I_D-V_GS characteristic, in which the memory window was about 0.9V when the applied gate voltage was swept between 8 V and ?8 V. Especially, the alternative drain current was retained after applying a single voltage pulse with a magnitude of +9 V or ?9 V.     

Preparation of SrBi2Ta2O9 ferroelectric thin film by rf magnetron sputtering

Abstract

SrBi₂Ta₂O₉ (SBT) thin films were deposited on 6-inch Pt/Ti/SiO₂/Si substrates by rf magnetron sputtering using a 12-inch ceramic SBT single target. It is found that several sputtering parameters such as argon (Ar) pressure and rf power were very effective to control the Bi content of SBT thin films which is essential for obtaining good ferroelectric properties.     

Improvement on ferroelectric properties of metal-organic decomposited PZT thin film prepared by using prenucleation layer

Abstract

Perovskite SrRuO₃ (SRO) layer was, for the first time, been successfully synthesized by using metal-organic decomposition (MOD) process. The presence of SRO buffer layer on Pt(Si) substrates has significantly enhanced the crystallization and densification behavior of the subsequently deposited Pb(Zr_0.52Ti_0.48)O₃ films. The pyrochlore free perovskite phase can be obtained by post-annealing the PZT/SRO/Pt(Si) films at 500°C, which is 50°C lower than that needed in PZT/Pt(Si) films. The fine grain (～0.3 μm) microstructure can be attained by post-annealing at 650°C for PZT/SRO/Pt(Si) films and 700°C for PZT/Pt(Si) films. The ferroelectric hysteresis properties of the two PZT films are comparable to each other. The leakage current properties of PZT/SRO/Pt(Si) films increased pronouncedly with post-annealing temperature, resulting in inferriar leakage behavior to PZT/Pt(Si) films.     

Preparation of BaPbO3 Electrode Thin Films by RF Magnetron Sputtering

For electrode materials of Pb(Zr,Ti)O₃ (PZT) thin films in ferroelectric random access memory (FeRAM), various materials have been studied. As new electrode material with which the polarization and fatigue properties are improved, we take notice of barium metaplumbate BaPbO₃ (BPO). Because the BPO contained lead (Pb) and oxygen is conductor that adopted same perovskite structure as PZT. BPO thin films were prepared by rf magnetron sputtering on various substrates. (SiO₂/Si, MgO, Al₂O₃ and Pt-coated substrates), and influence of growth conditions (sputtering gas, rf power, the substrate-heating temperature and post anneals) on crystallization and conductivity were investigated. In case of post anneal after sputtering at room temperature, perovskite single phase was obtained above 400°C. In case of substrate heating while sputtering, without post anneal, perovskite single phase was obtained at 350–500°C on SiO₂/Si substrates (110) preferred orientation BPO films obtained at low temperature, and resistivity of the films decreased at decreasing sputtering temperature. Resistivity of the film at substrate temperature 350°C was 3 × 10^?3 Ω cm. In the case of single crystal substrate, the BPO films were epitaxially grown. Orientation of the films was varied with the sputtering condition. The epitaxial PZT thin films were also grown on the BPO, revealing that PZT(111)[011] //BPO(111)[011] //Pt(100)[011] //MgO(100)[011] and PZT(111)[011] //BPO(111)[011] //Pt(111)[011] //Al₂O₃(001)[100] structures were obtained, and their ferroelectric properties were also evaluated.     

Laser ablation preparation and property of bismuth-layer-structured SrBi2Ta2Ta2O9 and Bi4Ti3O12 ferroelectric thin films

Abstract

Bismuth-layer-structured ferroelectric thin films, SrBi₂Ta₂O₉ and Bi₄Ti₃O₁₂, have been prepared by laser ablation method on both Pt sheets and Si wafers at low temperatures of 400 ～ 500°C. These thin films have been characterized by XRD, XPS, AFM, C-V, D-E hysteresis and J-V measurement. SrBi₂Ta₂O₉ thin films have a good (105) preferential orientation, and Bi₄Ti₃O₁₂ thin films have (117) and c-axis orientation on these substrates. Ferroelectric film-SiO₂-Si structures show good C-V hysteresis curve owing to Si surface potential controlled by the D-E hysteresis. D-E hysteresis is obtained in Bi₄Ti₃O₁₂ thin film prepared on Pt sheet, and the remnant polarization and the coercive force are 7.5 μC/cm² and 72 kV/cm, respectively.     

Hysteresis caused by defects in buffer layer of metal-ferroelectric-insulator-semiconductor (MFIS) devices

Abstract

We have investigated the roles of buffer layer in the Pt/SBT-Y₂O₃/p-Si (MFIS) capacitors. We found that the insertion of Y₂O₃ buffer layer prevents the charge injection from the Si substrate to ferroelectric layer. However, negative charges with the effective density of 3.21×10¹²/cm² were generated due to the additional process step for Y₂O₃ deposition. We suggested that the asymmetrical increase of a memory window is due to the domain pinning caused by negative charges in buffer layer. In addition, we reported that the mobile positive charges in ferroelectric layer can induce the shift of the hysteresis loops depending on the gate-bias polarity and a ramp rate during the capacitance-voltage (C-V) measurement. Since Y₂O₃ buffer layer minimize the charge injection, the shift of the hysteresis loops was asymmetrical.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Growth of MgTiO3 thin films by pulsed laser deposition and their electrical properties

Abstract

MgTiO₃ thin films have been grown on various substrates by pulsed laser deposition (PLD) to investigate the application for microwave dielectrics and optical devices. Highly oriented MgTiO₃ thin films were obtained on sapphire (c-plane Al₂O₃). MgTiO₃ thin films deposited on SiO₂/Si and platinized silicon (Pt/Ti/SiO₂/Si) substrates were polycrystalline nature. MgTiO₃thin films grown on sapphire were transparent in the visible and had a sharp absorption edge at 280 nm. These MgTiO₃ thin films had extremely fine feature of surface morphology, i.e., rms roughness of 0.87 nm. Dielectric constant and loss of MgTiO₃ thin films deposited by PLD were about 24 and 1.5% at 1MHz, respectively. These MgTiO₃ thin films also exhibited little dielectric dispersion.     

Characterization of MOCVD Pt electrode for ferroelectric thin films

Abstract

Platinum thin films were deposited by low pressure chemical vapor deposition (LPMOCVD) on SiO₂/Si and (Ba, Sr)TiO₃/Pt/SiO₂/Si substrates using Pt-hexafluoroacetylacetonate at various deposition temperatures. The shiny mirror-like Pt thin films of a high electrical conductivity were obtained, when the deposition temperature is between 325°C and 350°C, whereas above 375°C Pt thin films showed rough surface as well as poor adhesion property to oxide substrate. Pt thin films had a good step coverage of 90%. The results indicate that LPMOCVD Pt thin films can be applied for the top electrode of high dielectric thin film, which is thought to be one of the best candidate materials for a capacitor of ULSI DRAM.     

Barrier mechanism of Pt/Ta and Pt/Ti layers for SrTiO3 thin film capacitors on Si

Abstract

The barrier effect of Pt/Ta and Pt/Ti has been investigated, when used as bottom electrodes for SrTiO₃ thin film capacitors on Si. The Pt/Ta/Si stacks were more stable than the Pt/Ti/Si, both in vacuum and in oxygen annealing. Though the Pt/Ta bilayer was suitable for the SrTiO₃ deposition at 400[ddot]C, its resistivity became slightly higher after the deposition at 600[ddot]C, due to Ta layer oxidation during the SrTiO₃ deposition. This would result in a contact resistance problem for high density dynamic random access memory application.     

Effects of bi2o3 buffer layer on ferroelectric properties of srbi2ta2o9 thin films by liquid-delivery mocvd

Abstract

Ferroelectric SrBi₂Ta₂O₉ thin films were deposited on the Bi₂O₃ buffered Pt/Ti/SiO₂/Si substrates using liquid-delivery metalorganic chemical vapor deposition. SBT films with 5nm thick-Bi₂O₃ buffer layer on Pt bottom electrode showed stronger (115) orientation than those without Bi₂O₃ buffer layer after annealing at 750°C. The value of the remanent polarization of SBT films with Bi₂O₃ buffer layer were improved significantly in comparison with those for the films without Bi₂O₃ buffer layer. The remanent polarization(2Pr) and coercive field(Ec) of SBT films without and with Bi₂O₃buffer layer annealed at 750°C were 11.9, 20.8 μ C/cm2 and 57, 37.8kV/cm at an applied voltage of 5 V, respectively.     

Electrical characteristics of high dielectric constant BCTZ thin films

Abstract

High dielectric constant Ba_0.96Ca_0.04Ti_0.84Zr_0.16O₃ (BCTZ) thin films were deposited on Pt/Ti/SiO₂/Si substrates by spin on metal-organic decomposition (MOD) technique. Undoped and 0.4% Mg-doped BCTZ thin films were annealed in the temperature range from 600 to 900 °C for 1 hour in oxygen environment. The crystal structure of BCTZ thin films was analyzed by X-ray diffraction. The electrical properties of BCTZ thin films were investigated by capacitance—voltage (C—V) characteristics. Also, the electrical properties of these films were compared in conjunction with 0.4% Mg doping effect of BCTZ thin films for possible high dielectric constant material applications.     

Effect of Poling on Photovoltaic Properties in Highly Oriented BiFeO3 Thin Films

We report enhancement of photovoltaic properties of highly oriented BiFeO₃ (BFO) thin films. The single phase rhombohedral R3c space group structure was confirmed by XRD and Raman spectra in the films grown on SrTiO₃ (111) substrates using RF magnetron sputtering. The films of BFO were characterized in planar geometry with top Pt electrodes having 200μm diameter, ～40nm thickness and at a regular spacing of ～150μm deposited by DC sputtering process. For photovoltaic studies the current voltage characteristic of as grown and poled samples were studied under the white light illumination having energy density of ～1kW/m². The as grown films showed open circuit voltage (Voc) of ～3.9V which increased up to ～17.8V on poling with 200V. This enhancement in Voc by poling was attributed to increase in net polarization due to alignment of domains in the direction of applied electric field and hence potential barriers between the domains.     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

Fabrication and Characterization of Ba(Ti,Zr)O3 Thin Films Through the Chemical Solution Deposition Process

Lead- and bismuth-free Ba(Ti_{1 ? x} Zr _x )O₃ (BTZ) thin films were fabricated on Pt(111)/Ti/SiO₂/Si(100) substrates by the chemical solution deposition (CSD) process. The single phase BTZ thin films were obtained at 650°C by conventional process and the control of lattice parameter a was possible by Zr substitution. As the D-E hysteresis loops and J-V characteristics depended on the precipitates on film surface, the fabrication process was reexamined by 2-step sintering process. Consequently the decreasing of first sintering time was able to prevent the precipitates, and the larger grain of about 40–50 nm were obtained by additional sintering for 2 hour.