Preparation of BST thin films on Pt electrode on Si wafer with down-flow LSMCVD reactor

Abstract

A novel type of down-flow LSMCVD (Liquid Source Mist CVD) reactor was developed to prepare a high dielectric BST thin film on Pt electrode on Si wafer. Barium acetate [Ba (OOCCH₃)₂], strontium acetate [Sr (OOCCH₃)₂], and titanium isoproxide [Ti (OC₃H₇ ⁱ )₄] were used as metal sources. Metal sources were dissolved in acetic acid, 1-butanol, or 2-methoxyethanol. BST [Ba/(Ba + Sr) = 0.7] film annealed on Pt/Ti/SiO₂/Si above 650°C was polycrystalline. BST film has a (110) preferred orientation with increasing temperature. Surface roughness of BST film and grain size increased with increasing temperature. The metal-oxygen bond was formed at 650°C as shown in the spectra of FTIR. The depth profiles of elements of BST thin films indicated a uniform composition throughout the film. BST films annealed at 750°C showed a dielectric constant and a tanδ of 390 (thickness: 150 nm) and 0.06 at a frequency of 100 kHz, respectively. The behavior of capacitance of the BST film with bias voltage showed paraelectric property. BST film annealed at 750°C had the leakage current density of 3.2 (μA/cm²) at a bias voltage of 2V.     

Structure and dielectric properties of Ca-doped (Ba0.7Sr0.3) TiO3 thin films fabricated by sol–gel method

A wide range of Ca-doped (Ba_0.7Sr_0.3)TiO₃ (BST) thin films (from 0 to 20 mol%) have been prepared on Pt/Ti/SiO₂/Si (100) substrates by sol–gel technique. The structural and dielectric properties of BST thin films were investigated as a function of Ca dopant concentration. The results showed that the microstructure and dielectric properties of the BST films were strongly dependent on the Ca contents. With the Ca dopant concentration increasing, the grain size, dielectric constant and dielectric loss of the BST thin films decreased. As the content of Ca dopant reaches 10 mol%, the dielectric constant, dielectric loss, tunability, the value of FOM and the leakage current density are 281, 0.0136, 16.7%, 12.3 and 5.5?×?10^?6 A/cm², respectively.     

PREPARATION OF BaTiO3 FILMS FOR MLCCS BY DIRECT VAPOR DEPOSITION

ABSTRACT

BaTiO₃ films were deposited by the direct vapor deposition (DVD) technique to prepare thin dielectric layers for multilayer ceramic chip capacitors (MLCCs). The BaTiO₃ films were successfully prepared by co-evaporation of the BaTiO₃ ceramic and Ti metal source. The films deposited at room temperature and 600°C were amorphous and crystalline phases, respectively. The intensity of (110) and (111) peaks increased as Ba/Ti ratios were close to stoichiometric composition. BaTiO₃ films deposited with e-beam power of 700 W showed the deposition rate of 33 nm/min. The dielectric constant and dissipation factor of BaTiO₃ films measured at 1 kHz were 150～ 180 and 2～ 5%, respectively. The capacitance decreased with increasing the temperature and varied only between 787pF and 752pF in the temperature range 15～ 125°C.     

Influence of Y and Mn alternately doped order on the microstructures and dielectric properties of Ba0.6Sr0.4TiO3 films

ABSTRACT

The influences of Y and Mn alternately doped order on the microstructures and dielectric properties of the Ba_0.6Sr_0.4TiO₃ (BST) films were reported in this paper. The Y and Mn alternately doped BST films were designed as YBST/MnBST/… and MnBST/YBST…multilayer films orderly expressed as (Y/Mn)_M and (Mn/Y)_M for short, and prepared on Pt/Ti/SiO₂/Si wafers by an improved sol-gel method, where Y and Mn represent yttrium doped BST layer and manganese doped BST layer, and M is cycle unit, respectively. The microstructures of the alternately doped BST films were observed by SEM and the capacitance-voltage curves at 100 kHz or 1 MHz were measured by a HP4284A LCR meter and the dielectric properties in the range of 1GHz were measured by an E4991A impedance analyzer. Compared to Y or Mn doped multilayer BST film, (Y/Mn)_M and (Mn/Y)_M show higher dielectric tunability and lower dielectric loss with higher dielectric constant. Moreover, (Y/Mn)_M show better dielectric properties than (Mn/Y)_M because (Y/Mn)_M show granular microstructures independent of M, while the (Mn/Y)_M show granular microstructures when M is 2 and add to a surface layer of columnar microstructures on the granular microstructures when M is 4. The related mechanisms were obtained in terms of the XRD phase structures, the cross-sectional SEM microstructures and the AFM morphologies.     

Dielectric characteristics investigation of (Ba0.7Sr0.3)(Ti0.9Zr0.1)O3 ferroelectric thin films

By the radio frequency (RF) magnetron sputtering methods, (Ba_0.7Sr_0.3)(Ti_0.9Zr_0.1)O₃ (BSTZ) ferroelectric thin films were deposited on the Pt/Ti/SiO₂/Si(100) substrates. The crystal structural and microstructure of these thin films were analyzed by means of the XRD, SEM, and AFM. Moreover, the dielectric characteristics were also investigated by the C-V and J-E analyses. The optimal deposition parameters for these BSTZ thin films were: RF power is 160 W, oxygen concentration is 25%, substrate temperature is 580°C, and chamber pressure is 0.075 mPa. Under these optimal deposition conditions, the (111) and (110) oriented polycrystalline of the BSTZ thin films grow easily. And under a bias voltage of 0.5 MV/cm, the dielectric constant and leakage current density of the BSTZ thin films are 191 and 3×10^?8 A/cm², respectively. In addition, under various measured temperatures (0 ～ 80°C) and frequencies (100 kHz ～ 1 MHz), all the dielectric constants remain almost unchanged. Compared to BSTZ thin films reported previously, in this study, the deposited thin films have the advantage of lower leakage current and hence are suitable for the applications of dynamic random access memory.     

Microstructure and dielectric properties of ferroelectric barium strontium titanate ceramics prepared by hydrothermal method

Ba _x Sr_1-x TiO₃, nanoparticles with different Ba compositions were synthesized by a hydrothermal method. The mechanism of hydrothermal reactions was discussed based on DTA/TG, XRD and TEM characterizations. The result showed that perovskite structure was developed through the mutual diffusion between the intermediate phases and TiO₂ phase. The grain size of the Ba_0.77Sr_0.23TiO₃ (BST77) powders was about 20–40 nm. BST ceramics were made from the hydrothermal-derived BST powders and the dielectric properties of the BST ceramics were measured. Due to the small grain size and active surface energy of the BST powders prepared by hydrothermal method, the BST ceramics showed low sintering temperature. It was found that the BST77 ceramics sintered at 1280 °C showed dielectric constant peak dispersion which was believed to be caused by dimension domino effect.     

The electrical properties of Ba1-x SrxTiO3 thin films grown by sputter deposition

Abstract

Ba_1-x Sr_xTiO₃ (BST) thin films were deposited by reactive rf-magnetron sputtering onto Si substrates. The influence of the deposition parameters such as temperature and oxygen ambient on the dielectric constant of the films is presented. BST films deposited at 450°C and optimum conditions exhibited a dielectric constant of approximately 200 at frequencies as high as 1GHz. In addition, the films were found to have leakage current densities of <0.1μAmp/cm² at fields of 5×10⁵V/cm. An extrapolated lifetime greater than 10 years was obtained from stress tests at elevated temperatures and fields. These films compared favorably with published data.     

A comparison of mocld with PLD BaxSr1−xTiO3 thin films on LaAIO3 for tunable microwave applications

Abstract

Historically, tunable dielectric devices using thin crystalline Ba_xSr_1-x TiO₃ (BST) films deposited on lattice-matched substrates, such as LaAlO₃, have generally been grown using pulsed laser deposition (PLD). Highly oriented BST films can be grown by PLD but large projects are hampered by constraints of deposition area, deposition time and expense. The Metal-Organic Chemical Liquid Deposition (MOCLD) process allows for larger areas, faster turnover and lower cost. Several BST films deposited on LaAlO₃ by MOCLD have been tested in 16 GHz coupled microstrip phase shifters. They can be compared with many PLD BST films tested in the same circuit design. The MOCLD phase shifter performance of 293° phase shift with 53 V/μm dc bias and a figure of merit of 47°/dB is comparable to the most highly oriented PLD BST films. The PLD BST films used here have measured XRD full-width-at-half-maxima (FWHM) as low as 0.047°. The best FWHM of these MOCLD BST films has been measured to be 0.058°.     

Sol-gel processed ferroelectric and multiferroic thin films for integrated devices

Abstract

Ferroelectric barium titanate and multiferroelectric bismuth ferrite thin films have been fabricated by using sol-gel processing technique. The starting materials for fabrication of were barium 2-ethyl hexanoate and titanium (IV) isoproposxide. Bismuth nitrate and ferric nitrate were the precursors for the fabrication of thin films. The as-deposited films were annealed at higher temperature for crystallization. The X-ray diffraction study on the films showed that the as-grown films were found to be amorphous that crystalized to proper phases by annealing at 550?°C in air for one hour. All the samples showed high optical transparencies in the visible frequency range. The room temperature dielectric constant and loss tangent of barium titanate thin films at 1?kHz frequency were found to be 400 and 0.01 respectively. Both the dielectric constant and loss tangent showed small dispersion in the frequency range of 0.10–1000?kHz range. The ferroelectricity in barium titanate thin films was confirmed by the presence of bell shaped capacitance-voltage (C-V) butterfly loop and saturated polarization-field (P-E) hysteresis loop. The as-grown bismuth ferrite thin films were also found to be amorphous that crystallizes after annealing at 500?°C. These films also showed high optical transparencies in the visible region. The bismuth ferrite thin film samples showed saturated hysteresis loop and magnetic polarization-magnetic field hysteresis loop as well, confirming the multiferroic nature of the samples.     

Fabrication and electrical properties of barium strontium titanate thick films by modified sol–gel method

A modified sol–gel method has been developed to prepare for the barium strontium titanate (Ba_0.6Sr_0.4TiO₃, BST) thick films. The films were deposited on either Pd–Ag electroded alumina substrates (Pd–Ag/Al₂O₃) or silver electroded alumina (Ag/Al₂O₃) substrates by spin coating technique or screen printing technique. The thickness of the film was in the range of 2–10 μm. The key point of the process is to disperse fine-grained BST ceramic powders prepared by high energy ball mill into BST sol solution to form a slurry for spin coating and screen printing. In order to enhance the stability of the slurry and to avoid crack formation of the thick film, organic macromolecular poly-vinylpyrrolidone (PVP) was added to the sol solution. The structure and surface morphology of the films were studied by X-ray diffraction and Scanning Electron Microscope (SEM) techniques. It is revealed that the thick films exhibit pure perovskite phase and are crack-free, dense and homogeneous. The dielectric constant and loss tangent of the thick films are about 1200 and 0.01, at 10 °C and 1 KHz, respectively.     

Frequency and Voltage Dependent Dielectric Properties of Ni-doped Ba0.6Sr0.4TiO3 Thin Films

Highly (100) preferred undoped and 1–5% Ni-doped Ba_1–xSr_xTiO₃ (BST) thin films were deposited onto MgO (100) single crystal substrate at 750°C using pulsed laser deposition. BST thin film-based interdigital capacitors (IDC) were prepared by standard photolithography process. The microwave properties of BST films were measured at 10 GHz. Ni-doped BST films showed better dielectric properties by exhibiting improved dielectric Q while retaining an appropriate capacitance tuning compared to undoped BST films. 1% Ni-doped BST film showed the maximum figure of merit of 2896.1. It is suggested that 1 mol% Ni doped BST film is an effective candidate for high performance tunable device applications.     

Microstructures and dielectric properties of Zn2SnO4 thin films by sputtering from a ZnO doped ceramic target

The dielectric properties of Zn₂SnO₄ thin films with various degrees of ZnO dopant concentration were investigated. Zn₂SnO₄ thin films were prepared using the radio frequency magnetron sputtering. The X-ray diffraction patterns of the 0 and 75 mole % ZnO doped Zn₂SnO₄ thin films revealed that Zn₂SnO₄ is the main crystalline phase, which is accompanied by a little SnO₂ as the second phase. The second phase SnO₂ in specimens vanished when the extent of ZnO additive was increased to 100 mole%. A dielectric constant of 15–40 and a loss factor of 0.10–0.14 of Zn₂SnO₄ thin films were measured at 1 MHz with ZnO dopant concentration in the range of 0–100 mole%.     

Optical properties of RF-sputtered Ba0.65Sr0.35TiO3 thin films

Ba_0.65Sr_0.35TiO₃ (BST) thin films have been prepared by radio frequency magnetron sputtering on fused quartz at different substrate temperatures. Optical constants (refractive index n, extinction coefficient k) were determined from the optical transmittance spectra using the envelope method. The dispersion relationship of the refractive index vs. substrate temperature was also investigated. The refractive index of BST thin films increased from 1.778 to 1.961 (at λ?=?650 nm) as deposited temperature increases from 560°C to 650°C. The extinction coefficient of as-deposited BST thin films increased with the increase of the oxygen-to-argon ratio, which was due to the change of the film stoichiometry, structure, and texture of BST thin films. The oxygen-to-argon ratio also affected the fluorescence spectra. The fluorescence peaks intensity was greatly increased, apparent frequency shift was detected, and the linewidth became narrow as the ratio of oxygen to argon increased from 1:4 to 1:1. The fluorescence spectra also indicated the band transition of BST thin films was an indirect gap transition.     

CHARACTERIZATIONS OF W-DOPED (Ba0.5Sr0.5)TiO3 THIN FILMS USING LaNiO3 ELECTRODE

ABSTRACT

The (Ba_0.5Sr_0.5)TiO₃ thin films were deposited onto LaNiO₃ by RF-magnetron sputtering at 550°C. The influence of W content on microstructure and electrical properties of BST films were investigated. The surface and grain size become smoother and smaller as the W content increased. Besides, the dielectric constant, tunability, dissipation factor, and leakage current decreased when the W content increased. The 1% W is the optimal doping concentration. The resultant BST film, with proper dielectric constant and leakage current, has a tunability of 32%, a dissipation factor of 0.006, a FOM value of 53.3 under applied field of 450 kV/cm.     

Dielectric properties of zinc titanate thin films prepared by Rf magnetron sputtering

Zinc titanate thin films of ~500 nm in thickness were synthesized by an RF magnetron sputtering using a sintered ceramic target. After annealing in temperature ranges of 300–800 °C, their phase transition and dielectric properties were investigated as a function of annealing temperature. Crystalline ZnTiO₃ phase was first detected at the annealing temperature of 500 °C within XRD detection limit though the sputtered film was mainly amorphous. ZnTiO₃ still remained as a main phase although the slight decomposition of ZnTiO₃ into Zn₂TiO₄ and TiO₂ occurred in association with the increase of annealing temperature. Dielectric properties were apparently improved with increase of annealing temperature and showed maximum value at 650 °C. Further higher temperature annealing caused inferior dielectric property. These results were explained in terms of the presence of TiO₂ (rutile) phase, resulting from the decomposition of ZnTiO₃ phase, and the morphology of the thin film.     

Fabrication and dielectric properties of Na0.5Bi0.5Cu3Ti4O12 from co-precipitation method

High dielectric Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were firstly prepared by co-precipitation method at low temperature. X-ray diffraction results revealed that pure phase of NBCTO was achieved by calcination at 950 °C for 2 h. Thermo-gravimetric analysis on a dried NBCTO precursor was carried out to study the thermal decomposition process. The microstructure and dielectric properties of NBCTO ceramics sintered at different temperatures were investigated. The results indicate that the sintering temperature has a sensitive influence on the microstructure and dielectric properties. Higher sintering temperature gave rise to increased dielectric constant and dielectric loss of NBCTO samples, and the sample sintered at 975 °C for 8 h exhibits high dielectric constant of 8.3?×?10³ and low dielectric loss of 0.069 at 10 kHz. The dielectric properties were further discussed by the impedance spectroscopy.     

Design and implementation of combline bandpass tunable filter using barium-strontium-titanate thin-film capacitors

The design, fabrication and microwave properties of tunable fifth-order combline bandpass filter using etched barium-strontium-titanate (BST) thin films on sapphire (0001) substrates were investigated. At 1 MHz and 1000 kV/cm electric field, the dielectric tunability, the remanent polarization (2P_r) and the coercive electric field (2E_C) of BST films were 45.96%, 2.26 µC/cm² and 81.83 kV/cm, respectively. The loss tangent was 1.36% at zero electric field. After the BST parallel plate capacitors characterization, BST capacitors were loaded at the end of parallel coupled resonators in the design of the tunable filter. With the application of 20 V DC voltage, the center frequency of the filter varied from 1.17 GHz to 1.34 GHz which corresponds to a relative shift of 13.5%.     

High quality BaxSr1-xTiO3 films grown by mocld and novel ferroelectric/ferrite structures for dual-tuning microwave devices

Abstract

Excellent single crystal Ba_xSr_1-xTiO₃ (BST) films were grown on LaAlO₃ substrates using the metal-organic chemical liquid deposition (MOCLD) method. Very low losses (tanδ ∽0.002-0.008) were measured from these films at 400 KHz. Biaxially oriented BST films were successfully grown on polycrystalline YIG substrates using both MOCLD and pulsed laser deposition methods with biaxially oriented MgO and YSZ buffer layers. The dielectric losses of the films range from 0.005 to 0.015 while 25% of dielectric constant change was observed with 40V bias voltage up to 10 MHz. Both the dissipation and dielectric constant of the films remained nearly constants over a wide temperature range (77 K to 380 K). A dual-tuning microwave coplanar phase shifter using a BST film grown on a MgO buffered polycrystalline YIG substrate was fabricated. A significant phase shift was observed in GHz frequency range when an electric bias or a magnetic field was applied to the device.     

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.     

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.