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.     

MOCVD of Pb(Zr x Ti1-x )O3 thin films on MgTiO3/Si substrates and their electrical properties

Abstract

Pb(Zh _x , Ti_1-x )O₃(PZT) thin films were deposited on Si substrates using MgTiO₃ as the buffer layer and the electrical properties of those MFIS structures were investigated. PZT and MgTiO₃ films were made by MOCVD using ultrasonic spraying technique. Perovskite PZT films have been succesfully made at the substrate temperature of 550 to 600°C only when using MgTiO₃ buffer layer. AES depth profile analysis and RBS analysis revealed that there is no remarkable interdiffusion and no formation of reaction layer between PZT and MgTiO₃ and/or between MgTiO₃ and Si substrate. The capacitance-voltage (C-V) curves of the MFIS structure which were made with PZT and MgTiO₃buffer layer have shown the hysteresis resulted from the ferroelectric switching of the PZT films.     

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.     

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.     

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.     

PREPARATION AND PROPERTIES OF LITHIUM-DOPED K0.5Na0.5NbO3 THIN FILMS BY CHEMICAL SOLUTION DEPOSITION

ABSTRACT

Lithium-doped K_0.5Na_0.5NbO₃ (KLNN) films were fabricated by chemical solution deposition on Pt/TiO₂/SiO₂/Si substrates. Homogeneous and stable precursor solutions were prepared by controlling the reaction of starting metal alkoxides. Perovskite KLNN single-phase thin films were successfully synthesized on Pt/TiO _x /SiO₂/Si substrates. The 0.75-μ m-thick KLNN film annealed at 650°C exhibited ferroelectric polarization hysteresis loops at ?250°C. The loop at room temperature was round, indicating the film contained leakage components. The dielectric constant under zero bias was 490 at room temperature. A typical upside-down butterfly DC bias-capacitance curve was obtained in the KLNN film capacitors at room temperature, indicating that polarization reversal occurred in the obtained KLNN 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.     

Inverse Capacitance-Voltage Characteristics of Bi3.25La0.75Ti3O12 Thin Film Pulsed Laser Deposited on Thermally Oxidized n-Type Si Substrates

Comparative studies on the electrical properties of a metal-ferroelectric-insulator-semiconductor field effect transistor were conducted using pulsed laser ablated ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films deposited on SiO₂/Si substrates with different SiO₂ thicknesses. The SiO₂ layer was prepared on n-type Si substrates by dry oxidation at a temperature of 800°C. Small angle x-ray reflectivity studies were used to measure the SiO₂ thickness. The capacitance-voltage (C-V) measurements revealed that the films showed good interfacial properties. Shifts in flatband voltages were observable, but were effectively reduced by deposition of the ferroelectric films. Au/BLT/SiO₂/Si diodes with 8 nm SiO₂ layer showed to be stable with relatively large memory window values of about 0.3 V, 2.5 V, 5.0 V, and 7.0 V, at increasing bias voltages of ±5 V, ±7 V, ±10 V, and ±12 V, respectively.     

Distributed phase shifters using (Ba,Sr)TiO3 thin films on sapphire and glass substrates

Abstract

Sol-gel solutions were synthesized by using various alkoxides of polyhydric alcohol, carboxylate and stabilizer. Stability of modified sol-gel solution was good enough to keep its properties after at least three months although that of ordinary sol-gel solution is not good.

SBT films were fabricated on Pt(200nm)/Ti(20nm)SiO₂(500nm)/Si substrate at under 700°C by using modified sol-gel solution. Range of drying temperature was 200 to 400°C and that of RTA was 550 to 700°C. At high drying temperature, decrease of crystallinity for SBT films was observed accompanied by nucleation of Sr carbonate. On the other hand, SBT film dried at under 250°C and crystallized at 700°C shows high crystallinity of layer perovskite.

SBT film derived from conventional sol-gel solution used to show strong crystal orientation of c-axis. In case of modified sol-gel solution, RTA temperature and amount of added stabilizer influenced crystal orientation of film. So it was possible that to control crystal orientation of SBT films by adjust RTA condition and amount of stabilizer. Stability of sol-gel solution and property of SBT films were influenced by component of solvent, electric properties of SBT films especially I-V property were improved.

Using low temperature deposition process at 650°C, SBT films derived from modified sol-gel solution show superior ferroelectric properties to SBT thin films derived from conventional MOD solution.     

Preparation of Bi4Ti3O12 thin films by electron cyclotron resonance sputtering

Abstract

Ferroelectric Bi₄Ti₃O₁₂ thin films were deposited on Pt-coated oxidized Si substrate by electron cyclotron resonance (ECR) sputtering using ceramic targets. Crystal structure and dielectric properties of the films were investigated as functions of sputtering conditions such as substrate temperature and sputtering gas. Using a target with excess Bi content compared to stoichiometric composition was required to compensate Bi re-evaporation from the substrate and to obtain a perovskite single phase at 600°C. (117)-oriented films exhibited ferroelectric hysteresis loops. The remanent polarization and coercive field of the films were 9.8 μC/cm² and 180 kV/cm, respectively.     

Chemical solution processing of sr2(nb,ta)2o7 thin films

Abstract

Sr₂(Nb,Ta)₂O₇ thin films have been synthesized by chemical solution deposition. Homogeneous and stable Sr₂(Nb,Ta)₂O₇ precursor solutions with various Nb/Ta ratios were prepared by controlling the reaction of metal alkoxides in ethanol with a key additive of 2-ethoxyethanol. The crystallization temperature of the perovskite-type Sr₂(Nb,Ta)₂O₇ slabs structure decreased with increasing Nb substitution in amount. The crystallization temperature of Sr₂(Nb_0.2Ta_0.8)₂O₇ films on Pt/Ti/SiO₂/Si and Pt/Ir/Ti/SiO₂/Si substrates was above 800°C. On the other hand, by using Pt(100)/MgO(100) as a substrate, Sr₂(Nb,Ta)₂O₇ thin films crystallized into the Sr₂(Nb,Ta)₂O₇ phase at 700°C.     

Electrodes for ferroelectric thin films

Abstract

Platinum and ruthenium oxide (RuO₂) deposited by ion beam sputter-deposition are evaluated for use as electrodes for PZT thin film capacitors. The effect of deposition temperature, film thickness, and the presence of oxygen on hillock formation in platinum is discussed. It is shown that the hillock density in Pt/Ti/SiO₂/Si films can be significantly reduced by properly controlling the processing conditions and film thickness. Stress measurements correlate with the experimental observation that depositing thinner platinum films (<800 Å) is an effective means of reducing hillock formation. The use of an intermediate deposition temperature 200–250°C also helps minimize hillock formation. Diffusion of the Ti adhesion layer into and/or through the platinum was significantly reduced by replacing the Ti with a TiO_x adhesion layer. RuO₂ electrodes are compared to Pt in terms of resistivity, surface morphology, microstructure and film orientation.     

Effects of Substrate and Annealing Temperatures on the Characteristics of SrBi4Ti4O15 Thin Films

In this study, radio frequency (RF) sputtering was used as the method and the layer-structured bismuth compound of SrBi₄Ti₄O₁₅ + 4 wt% Bi₂O₃ ferroelectric ceramic was used as the target to deposit the SrBi₄Ti₄O₁₅ (SBT) thin films. The addition of excess Bi₂O₃ content in the target ceramic was used to compensate the vaporization of Bi₂O₃ during the sintering and deposition processes. SBT ferroelectric thin films were deposited on Pt/Ti/SiO₂/Si under optimal RF magnetron sputtering parameters with different substrate temperatures for 2 h. After that the SBT thin films were post-heated using rapid temperature annealing (RTA) method. The dielectric and electrical characteristics of the SBT thin films were measured using metal-ferroelectric-metal (MFM) structure. From the physical and electrical measurements of X-ray diffraction pattern, scanning electronic microscope (SEM), I-V curve, and C-V curve, we had found that the substrate temperature and RTA-treated temperature had large influences on the morphology, the crystalline structure, the leakage current density, and the dielectric constant of the SBT thin films.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

The Characteristics of Magnesium Titanate Thin Film as Buffer Layer by Electron Beam Evaporation

We have studied the application of magnesium titanate thin films as buffer layer for the improvement of adhesion of Pt films to Si substrate. Magnesium titanate films were successfully prepared on Si(100) substrate by electron beam evaporation. The crystal phase of MgTi₂O₅ and MgTiO₃ films on Si substrate were observed. These films had a very smooth and densely packed surface morphology and showed a good characteristic as the adhesion layer for Pt. Also, AES analysis showed the excellent properties as the reaction barrier layer between Pt and Si.     

Influence of deposition parameters on physico-chemical and optical properties of sputtered PbTiO3 thin films

Abstract

Stoichiometric thin films of lead titanate (PbTiO₃) have been grown “in situ” without postannealing on (0001) sapphire substrates by rf magnetron sputtering technique. X-ray diffraction scans have revealed that as-grown films consist of the perovskite phase and are polycrystalline with a high (111) orientation. The structure, the microstructure and the optical properties have been studied as a function of the process parameters i.e., substrate temperature, gas pressure and the target composition, in particular the lead content. We report the dependence of the deposition conditions on the optical constants. The optimum experimental conditions (100m Torr and 600°C) to produce thin films with high transparency and refractive indices (n = 2.61 at 633 nm), similar to values for bulk materials, are given in this paper.     

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.     

Pulsed Laser Deposited Ba(Mg1/3Ta2/3)O3 Microwave Dielectric Thin Films

Ba(Mg_1/3Ta_2/3)O₃ (BMT) microwave dielectric thin films were successfully synthesized by a modified pulsed laser deposition (PLD) process, which includes low temperature (200°C) deposition and high temperature (>500°C) annealing. Crystalline structured BMT thin films were obtained when the PLD-deposited films were post-annealed at a temperature higher than 500°C in oxygen atmosphere. The characteristics of BMT thin film, including crystallinity, grain size, film roughness, and dielectric properties were improved with annealing temperature, achieving dielectric constant K = 23.5 and dissipation factor tan δ = 0.015 (at 1 MHz) for the 800°C-annealed films.     

Glycolate tantalum based solutions for the sol-gel spin-coating deposition of SrBi2Ta2O9 thin films

Abstract

The reaction of tantalum ethoxide with a glycol solvent produces the interchange of the ethoxide groups with the glycol. As a result, a polymeric derivative is formed with a high resistance towards hydrolysis. Compounds of Sr(II) and Bi(II) can be added to this Ta-glycol sol, leading to strontium bismuth tantalate (SBT) precursor solutions stable in air. These solutions were spin-coated onto two substrates: Pt/TiO₂/SiO₂/(100)Si and Ti/Pt/Ti/SiO₂/(100)Si. Crystallisation of the SBT phase was carried out by a first formation of a fluorite phase that evolves to the layered perovskite at temperatures over 600°C. During crystallisation, a larger tendency to the formation of a substrate/film interface was observed in the films deposited onto Ti/Pt/Ti/SiO₂/(100)Si than onto Pt/TiO₂/SiO₂/(100)Si. A remanent polarisation of P_r5 μC/cm² and a coercive field of E_c <100 kV/cm were measured in the films on Pt/TiO₂/SiO₂/(100)Si. These films retain its remanent polarisation, P_r, up to 10⁵seconds and are fatigue-free up to 10⁹ cycles.     

Phase Formations and Electrical Properties of Various (Bi, La)4Ti3O12 Thin Films by Chemical Solution Deposition

The phase formation and electrical properties of (Bi, La)₄Ti₃O₁₂ (BLT) thin film and V-, Sm-doped BLT thin films prepared by the chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrates have been investigated. It was observed that the microstructure and electrical properties of BLT thin films dramatically varied with V- and Sm-doping. The crystallinity and grain size of BLT thin films were definitely increased by V- and Sm-doping into BLT films, which resulted in the enhancement of remanent polarization in doped BLT films. The remanent polarization (Pr) of Sm-doped BLT films annealed for 3 min by an RTA system was about 9 C/cm². The V- and Sm-doped BLT films also exhibited good fatigue characteristics under bipolar stressing to 10¹⁰ cycles.