Structure and dielectric properties of BaTi4O9 thin films for RF-MIM capacitor applications

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using RF magnetron sputtering. A homogeneous BaTi₄O₉ crystalline phase developed in the films deposited at 550^∘C and annealed above 850^∘C. When the thickness of the film was reduced, the capacitance density and leakage current density increased. Furthermore, the dielectric constant was observed to decrease with decreasing film thickness. The BaTi₄O₉ film with a thickness of 62 nm exhibited excellent dielectric and electrical properties, with a capacitance density of 4.612 fF/μm² and a dissipation factor of 0.26% at 100 kHz. Similar results were also obtained in the RF frequency range (1–6 GHz). A low leakage current density of 1.0 × 10⁻⁹ A/cm² was achieved at ± 2 V, as well as small voltage and temperature coefficients of capacitance of 40.05 ppm/V² and –92.157 ppm/^∘C, respectively, at 100 kHz.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

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.     

Low frequency and microwave performances of Ba0.6Sr0.4TiO3 films on atomic layer deposited TiO2/high resistivity Si substrates

We report on high tunablity of Ba_0.6Sr_0.4TiO₃ (BST) thin films realized through the use of atomic layer deposited TiO₂ films as a microwave buffer layer between BST and a high resistivity (HR) Si substrate. Coplanar waveguide (CPW) meander-line phase shifters using BST/TiO₂/HR-Si and BST/MgO structures exhibited a differential phase shift of 95^∘ and 24.4^∘, respectively, at 15 GHz under an electric field of 10 kV/cm. The figure of merit of the phase shifters at 15 GHz was 30.6^∘/dB for BST film grown on a TiO₂/HR-Si substrate and 12.2^∘/dB for BST film grown on a MgO single crystal substrate. These results constitute significant progress in integrating BST films with conventional silicon technology.     

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.     

Control of 0.2CaTiO3-0.8Li0.5Nd0.5TiO3 microwave dielectric ceramics by additions of Bi2Ti2O7

Ceramics of 0.2CaTiO₃-0.8Li_0.5Nd_0.5TiO₃) have been prepared by the mixed oxide route using additions of Bi₂O₃-2TiO₂ (up to 15 wt%). Powders were calcined 1100^∘C; cylindrical specimens were fired at temperatures in the range 1250–1325^∘C. Sintered products were typically 95% dense. The microstructures were dominated by angular grains 1–2 μm in size. With increasing levels of Bi₂O₃-2TiO₂ additions, needle and lath shaped second phases developed. For Bi₂Ti₂O₇ additions up to 5 wt%, the relative permittivity increased from 95 to 131, the product of dielectric Q value and measurement frequency increased from 2150 to 2450 GHz and the temperature coefficient of resonant frequency (τ _f ) increased from −28pp/^∘C to +22pp/^∘C. A product with temperature stable τ _f could be obtained at ∼2 wt% Bi₂Ti₂O₇ additions. For high levels of additives, there is minimal change in relative permittivity, the Qxf values degrade and τ _f becomes increasingly negative.     

Scaling Effect on the Dielectric Constant in Ba(Ti x Zr1−x )O3 Thin Films

Recent work on PZT and BST thin films reveal a thickness dependence of the dielectric constant for a film thickness below 100 nm. This effect is commonly attributed to an interfacial layer between the electrode and the dielectric film (dead layer). In this contribution we report on the influence of the film thickness on the dielectric constant of Ba(Ti_xZr_{1 – x})O₃ thin films with different Zr-contents (x = 0–30 at.%). The films were prepared by chemical solution deposition (CSD) with thickness between 30 and 350 nm.The electrical characterization was performed in a temperature range between 25 and 200C. Results were interpreted with respect to the formation of a serial dead layer capacitance.     

Ferroelectric Properties of (Bi, Sm)4Ti3O12 (BST) Thin Films Fabricated by a Metalorganic Solution Deposition Method

Ferroelectric properties of samarium substituted Bi₄Ti₃O₁₂ films, Bi_3.15Sm_0.85Ti₃O₁₂ (BST), were evaluated for use as lead-free thin film ferroelectrics for FeRAM applications. The BST films were fabricated on the Pt/Ti/SiO₂/Si(100) substrates by a metalorganic solution deposition method. The measured XRD patterns revealed that the BST films showed only a Bi₄Ti₃O₁₂-type phase with a random orientation. The BST film capacitors showed excellent ferroelectric properties. For the film capacitor annealed at 700C, 2P_r of 64.2 C/cm² and 2E_c of 101.7 kV/cm at applied electric field of 150 kV/cm were observed. The capacitor did not show any significant fatigue up to 1.5 × 10⁸ read/write switching cycles at a frequency of 1 MHz, which suggests that the samarium should be considered for a promising lanthanide elements to make a good thin ferroelectric film for memory applications.     

Ferroelectric Properties of Bi3.25Nd0.75Ti3O12 Thin Films Prepared by MOD Process

Ferroelectric Bi_{4 – x}Nd_xTi₃O₁₂(BNdT) thin films with the composition (x = 0.75) were prepared on Pt/Ti/SiO₂/Si(100) substrate by metal-organic deposition. The films were annealed by various temperatures from 550 to 650C and then the electrical and structural characteristics were investigated for the application of FRAM. Electrical properties such as dielectric constant, 2Pr and capacitance were quite dependent on the thermal heat treatment. The measured 2Pr value on the BNdT capacitor annealed at 650C was 56 C/cm² at an applied voltage of 5 V. No fatigue was observed up to 8 × 10¹⁰ read/write switching cycles at a frequency of 1 MHz regardless of annealing temperatures.     

Optical Properties of LiTaO3 Thin films crystallized by RTA processes

High-performance pyroelectric infrared detectors have been fabricated using Lithium tantalite (LiTaO₃) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel method and rapid thermal annealing (RTA) technique. The dielectric and pyroelectric properties of IR detectors of LiTaO₃ thin films crystallized by conventional and RTA processes are investigated. Experimental results reveal that the heating rate will influence strongly on dielectricity and pyroelectricity of LiTaO₃ thin films. The voltage responsivities (Rv) measured at 80 Hz increase from 5496 to 8455 V/W and the specific detecivities (D^∗) measured at 300 Hz increase from 1.94 × 10⁸ to 2.38 × 10⁸ cmHz^1/2/W with an increase of heating rate from 600 to 1800^∘C/min. However, the voltage responsivity and the specific detecivity decrease with heating rate in excess of 1800^∘C/min. The results show that the LiTaO₃ thin film detector with a heating rate of 1800^∘C/min exists both the maximums of voltage responsivity and specific detecivity.     

The resistance degradation of (Ba0.5Sr0.5)TiO3 thin films

Abstract

The leakage current and dielectric properties of (Ba_0.5Sr_0.5)TiO₃(BST) thin films prepared by pulsed laser deposition (PLD) were investigated. It was found that leakage currents for positive bias voltage were higher than that for negative bias voltage, which was attributed to the lattice mismatch between bottom Pt electrode and BST thin film. The time-dependent breakdown process under positive voltage was observed, which was interpreted as the increase of the internal electric field in the film near the bottom electrode. However, the internal electric field can be decreased and eventually recovered by applying negative bias voltage. It was found that internal electric field near the interface can influence the capacitance of the BST thin film capacitor. An explanation for the thickness effect of BST thin films was given.     

Thermoelectric properties of p-type Bi0.5Sb1.5Te3 compounds fabricated by spark plasma sintering

P-type thermoelectric Bi_0.5Sb_1.5Te₃ compounds were prepared by the spark plasma sintering method with temperature ranges of 300–420^∘C and powder sizes of ∼75 μm, 76–150 μm, 151–250 μm. As the sintering temperature increased, the electrical resistivity and thermal conductivity of the compound were greatly changed due to an increase in the relative density. The Seebeck coefficient and electrical resistivity were varied largely with decreasing the powder size. Subsequently, the compound sintered at 380^∘C with the powders of ∼75 μm showed the maximum figure-of-merit of 2.65 × 10⁻³K⁻¹ and the bending strength of 73 MPa.     

ZnGa2O4 thin films fabricated by Sol-gel spinning coating process

ZnGa₂O₄ thin film phosphors have been synthesized on ITO coated glass and soda-lime glass at a firing temperature of 500^∘C and an annealing temperature of 500^∘C and 600^∘C via a chemical solution method using Zinc acetate dihydrate, Gallium nitrate hydrate and 2-methoxiethanol as a solution. XRD patterns of the film phosphors synthesized showed the peaks of ZnGa₂O₄ crystalline phases. AFM surface morphologies of the ZnGa₂O₄ thin film phosphors revealed marked differences according to an annealing temperature of 500^∘C and 600^∘C under an annealing atmosphere (3% H₂/Ar). On the other hand, the sheet resistance of ZnGa₂O₄ thin film phosphors, which were measured by four-point probe instrument, was approximately 5.76 Ω /square and 7.86 Ω /square with annealing temperature, respectively. The ZnGa₂O₄ thin film phosphors exhibited blue emission spectra with peak wavelength of 434 nm and 436 nm by ultra-violet excitation around 230 nm.     

STRESS CONTROLLED FERROELECTRIC (BA0.5Sr0.5)TiO3 THIN FILMS PREPARED ON GD2O3/SRTiO3(001) BY A PULSED LASER DEPOSITION

ABSTRACT

Stress controlled epitaxial ferroelectric Ba_0.5Sr_0.5TiO₃ (BST) films have been deposited on Gd₂O₃/SrTiO₃ by pulsed laser deposition with oxygen background pressure of 200 mTorr at the deposition temperature of 750°C. In order to control the stress in BST films, oxygen pressures for Gd₂O₃ buffer layers have been varied from 0.1 to 100 mTorr, while that of BST films have been fixed at 200 mTorr. It has been found that the lattice parameters of the BST films deposited on Gd₂O₃ were changed. Furthermore, microwave properties of co-planar waveguide (CPW) fabricated on BST films were investigated by a HP 8510C vector network analyzer from 1–20 GHz. Large dielectric tunabilities were observed from the CPW's fabricated on BST films deposited on Gd₂O₃ layers deposited at low and high oxygen pressures, 0.1 and 100 mTorr, respectively.     

Iridium thin film as a bottom electrode for high dielectric (Ba,Sr)TiO3 capacitors

Abstract

We propose Ir thin films as new electrode materials for high dielectric BST capacitors. Ir was found to be superior to Pt in a number of aspects such as resistivity, adhesion and surface roughness. The Pt/BST/Ir/SiO₂/Si capacitors showed leakage currents as low as Pt/BST/Pt/SiO₂/Si ones, but higher capacitance resulted. For endurance properties with +5V unipolar pulse trains, the dielectric constant of BST films on Ir decreased by only 10% below its initial value after switching of 10⁹ cycles while that on Pt degraded by 30% after 10⁸ cycles. Ir bottom electrode effects on BST film properties were well explained by the formation of IrO₂ phases on the surface of Ir electrodes.     

An Equivalent Circuit Model for Ba0.5Sr0.5TiO3-Based Capacitors

In order to integrate a ferroelectric-based device into a larger circuit, one must create an equivalent circuit model for the device. Ferroelectric materials contain a number of complicated parameters that make this task far from trivial. In a Ba_0.5Sr_0.5TiO₃-based capacitor, for example, the capacitance and leakage current vary with applied voltage, temperature and frequency. In addition, at high frequencies the equivalent series inductance and resistance (ESL and ESR) become non-negligible. All of these factors must be understood and quantified in order to create a working circuit. Such an analysis is reported for capacitors fabricated from Pt/BST/Pt films.     

Microwave Tunable Properties of Ni-Doped (Ba0.5Sr0.5)TiO3 Thin Films Grown by Pulsed Laser Deposition

(Ba_0.5Sr_0.5)TiO₃ (BST) thin films were deposited by pulsed laser deposition (PLD) and investigated as a function of Ni dopant concentration in low and high frequency regions. In low frequency region (<10 MHz), the Ni-dopant concentration in BST films has a strong influence on the material properties including dielectric and tunable properties. Ni-doped (≤3 mol%) BST films showed denser, smoother morphologies and smaller grain sizes than those with 6 and 12 mol% Ni. Dielectric constant and loss of 3 mol% Ni-doped BST films were about 980 and 0.3%, respectively. In addition, tunability and figure of merit of 3 mol% doped BST films showed maximum values of approximately 39% and 108, respectively. In high frequency region (>1 GHz), the frequency tunability range at center frequency of undoped BST and 3 mol% Ni-doped BST coplanar waveguide (CPW) resonators showed 102 and 152 MHz, respectively at 30 V dc bias. The Ni-doped BST thin films are possible in applications of microwave tunable capacitors.     

Crystallinity and photocatalytic activity of liquid phase deposited TiO2 films

Anatase TiO₂ films were deposited on glass substrates at 50 and 200^∘C to investigate the effect of growth temperature on the photocatalytic acitivity of the films. It was observed that the films grown at 200^∘C were composed of columnar crystallites and were more porous than the films grown at 50^∘C which had more compact structures. Also, the film crystallinity increased from 75 to 90% if the higher growth temperature was used. Despite the higher crystallinity, it was observed that for crystallinities between 60 and 90%, the photocatalytic behavior of the films was more significantly affected by changes in the surface area.     

The Effect of Stress on the Microwave Dielectric Properties of Ba0.5Sr0.5TiO3 Thin Films

Single phase, (1 0 0) epitaxial Ba_0.5Sr_0.5TiO₃ (BST) films have been deposited onto (1 0 0) LaAlO₃ and MgO substrates by pulsed laser deposition (PLD). The capacitance and dielectric losses of as-deposited and annealed films have been measured from 1–20 GHz as a function of electric field (0–80 kV/cm) at room temperature. The dielectric properties are strongly affected by the substrate type, post-deposition annealing time (6 h) and temperature (1200°C). For epitaxial BST films deposited onto MgO, it is observed that, after a post-deposition anneal the dielectric constant and the dielectric loss decreases. For epitaxial BST films deposited onto LAO, a post-deposition anneal (1000°C) results in an increase in the dielectric constant and an increase in the dielectric loss. The dc electric field induced change in the dielectric constant tends to increase with the dielectric constant and is largest for as-deposited films on MgO and post-deposited annealed films on LAO. In general, for epitaxial BST films, a large electric field effect is observed in films that have a large dielectric loss and a small electric field effect in films that have a low dielectric loss. High resolution X-ray diffraction measurements indicate that deposited film exhibit a significant tetragonal distortion which is strongly affected by a by a post deposition anneal. The observed differences in dielectric properties of the epitaxial BST films on MgO and LAO are attributed to the differences in film stress which arise as a consequence of the lattice mismatch between the film and the substrate and the differences in the thermal coefficient of expansion between the film and the substrate. A thin amorphous buffer layer of BST has been used to relieve stress induced by the lattice mismatch between the film and the substrate. Unlike epitaxial films, stress relieved films do not show an inverse relationship between dielectric tuning and Q (1/tan) and may be superior materials for tunable microwave devices.