Variations of interface potential barrier height and leakage current of (Ba,Sr)TiO3 thin films deposited by sputtering process

Abstract

Variations of the leakage current behaviors and interface potential barrier height (Φ_B) of rf-sputter deposited (Ba, Sr)TiO₃ (BST) thin films with thicknesses ranging from 20 nm to 150 nm are investigated as a function of the thickness and bias voltages. The top and bottom electrodes are dc-sputter-deposited Pt films. Φ_B critically depends on the BST film deposition temperature, postannealing atmosphere and time after the annealing. The postannealing under N₂ atmosphere results in a high interface potential barrier height and low leakage current. Maintaining the BST capacitor in air for a long time reduces the Φ_B from about 2.4 eV to 1.6 eV due to the oxidation. Φ_B is not so dependent on the film thickness in this experimental range. The leakage conduction mechanism is very dependent on the BST film thickness; the 20 nm thick film shows tunneling current, 30 and 40 nm thick films show Schottky emission current.     

Interface potential barrier height and leakage current behavior of Pt/(Ba,Sr)TiO3/Pt capacitors fabricated by sputtering process

Abstract

Variations of the leakage current behaviors and interface potential barrier height (φ _B ) of rf-sputter deposited (Ba, Sr)TiO₃ (BST) thin films, with thickness ranging from 20nm to 150 nm are investigated as a function of the thickness and bias voltages. The top and bottom electrodes are dc-sputter-deposited Pt films. φ _B critically depends on the BST film deposition temperature, postannealing atmosphere and time after the annealing. The postannealing under N₂ atmosphere results in a high interface potential barrier height and low leakage current. Maintaining the BST capacitor in air for a long time reduces the φ _B from about 2.4 eV to 1.6eV due to the oxidation. φ _B is not so dependent on the film thickness in this experimental range. The leakage conduction mechanism is very dependent on the BST film thickness; the 20nm thick film shows tunneling current, 30 and 40 nm thick films show Schottky emission current and the thicker films show a mixed characteristics and bulk and interface limited currents although the mechanism is not clearly understood at this moment.     

Pulsed Laser Deposition of Ba0.6Sr0.4TiO3 Thin Films and Their Optical Properties

ABSTRACT

Barium strontium titanate [Ba_0.6Sr_0.4TiO₃ or BST (60/40)] thin films were deposited on MgO (100) substrates using pulsed laser deposition. X-ray diffraction (XRD) measurements revealed that the BST thin films had epitaxially grown on the MgO (100) substrates. The surface morphology of the thin films was observed using an atomic force microscope and the grain size was found to be about 100–150 nm. The surface roughness was around 4.9 nm for a 250 nm thick film. The optical transmittance of the BST thin film was measured using a transmission mode ellipsometer. The BST/MgO configuration was highly transparent in the visible region. The optical band gap energy of the BST film, calculated by applying the Tauc relation, was 3.56 eV. Optical waveguide characteristics of the BST (60/40) thin film were determined using a prism coupler. The electro-optic (E-O) properties were measured at 632.8 nm wavelength using a phase modulation detection method. The BST film exhibited a predominately quadratic E-O behavior and the quadratic E-O coefficient was found to be 0.58 × 10^{? 17} m²/V².     

The effects of the LaNiO3 interlayer in the preferential orientation and the dielectrical properties of Ba x Sr1− x TiO3 thin films

Ba _x Sr_1?x TiO₃ (BST) thin films were grown on different substrates with or without LaNiO₃ (LNO) layer by a modified sol–gel process. The BST thin films obtained have full perovskite phase with dense and crack-free surface. BST thin films on different substrates with LNO layer show (100) preferential orientation, the texture coefficient (TC) value is calculated to be about 42.7%, whereas those without LNO layer show a fairly reduced preferential orientation, the TC value is just about 24.8%. It is considered that the preferential orientation is induced by the interface stress between LNO and BST. Electrical property measurements showed that BST thin film with a LNO interlayer has lower capacitance and larger dielectric loss, which is due to smaller grains of the thin film.     

Epitaxial Ba0.5Sr0.5TiO3 thin films for microwave phase shifters

Abstract

A tunable phase shifter was fabricated with epitaxial Ba_0.5Sr_0.5TiO₃ (BST) thin film and gold coplanar waveguide. BST thin film of the thickness ～0.5 μm was deposited by laser ablation on the MgO(OOl) single crystalline substrate. Gold electrode of the thickness ～2 μm was prepared by the sequence of thermal evaporation, electroplating, and wet etching. Epitaxial quality of the BST thin film was confirmed by X-ray diffraction. The microwave performance of phase shifter was measured at room temperature in the frequency range of 8–12 GHz, and with applied bias voltage of up to 30 V. Effect of Mn dopant in the epitaxial films was also considered.     

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.     

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.     

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.     

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.     

Growth characteristics and film properties of gallium doped zinc oxide prepared by atomic layer deposition

We carried out comprehensive studies on structural, optical, and electrical properties of gallium-doped zinc oxide (Ga:ZnO) films deposited by atomic layer deposition (ALD). The gallium(III) isopropoxide (GTIP) was used as a Ga precursor, which showed pure Ga₂O₃ thin film with high growth rate. Using this precursor, conductive Ga doped ZnO thin film can be successfully deposited. The electrical, structural and optical properties were systematically investigated as functions of the Ga doping contents and deposition temperature. The best carrier concentration and transmittance (7.2?×?10²⁰ cm^?3 and 83.5 %) with low resistivity (≈3.5?×?10^?3?Ωcm) were observed at 5 at.% Ga doping concentration deposited at 250 °C. Also, low correlation of deposition temperature with the carrier concentration and film structure was observed. This can be explained by the almost same atomic radius of Ga and Zn atom.     

Lateral Epitaxial Growth of Ba0.6Sr0.4TiO3 Thin Films

We report a novel growth technique for epitaxial thin films by combination of selective heteroepitaxial growth and lateral homoepitaxial growth. Ba_0.6Sr_0.4TiO₃ (BST) thin films were deposited on the substrates having patterned SiO_x layers at 450°C using pulsed laser deposition. Post annealing was carried out thereafter for lateral epitaxial growth. The difference in the crystallization temperature of BST thin film on the amorphous masking layers and lattice-matched single crystalline substrate enables selective nucleation and heteroepitaxial growth from the regions of single crystalline substrates during the film deposition. Lateral homoepitaxial growth is expected from the crystallized BST thin film toward the amorphous BST on SiO_x during the post annealing process. In this paper, a study on the difference in nucleation and growth behavior of BST thin films on the amorphous masking layers and lattice-matched single crystal substrates is presented.     

Leakage Current Measurements of STO and BST Thin Films Interpreted by the "Dead" Layer Model

Electrical properties of Strontium-Titanate (STO) and Barium-Strontium-Titanate (BST) thin films capacitors were investigated. The STO films were fabricated by chemical solution deposition (CSD) with thickness between 50 and 150 nm, while the BST films were deposited by metal organic chemical vapor deposition (MOCVD) with thickness between 20 and 110 nm. All films were grown on platinized and oxidized silicon wafers. As top electrodes platinum (Pt) was deposited on top of the ceramic film by sputtering. The electrode size varied between 8*10 m 3 to 1 mm 2 . The leakage current measurements were performed at different temperatures ranging from 15 to 200C and the applied voltage varied between 0 and - 4 V. Capacitance was measured at RT up to - 3 V bias at 1 kHz and 50 mV oscillation voltage. The main results are: The effective barrier heights extracted from the temperature dependence of leakage current are about 1.35 eV for STO and 0.94 eV for BST for the temperature region >100C. The field dependencies of the leakage current show almost perfect linear behavior in a "Schottky" plot for BST while STO reveals 2 separated Schottky regions. The permittivity extracted from the field dependence using the simple thermionic emission model with Schottky lowering results in rather improbable values of the effective Richardson constant A * and unphysical values of the relative optical permittivity, l r, opt <1. The use of a modified model with low permittivity interface layers ("dead layers"), as suggested by the thickness dependence of the inverse capacitance, solved these difficulties. The parameters extracted from fits of this model are discussed.     

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.     

DESIGN,FABRICATION AND MATERIAL PROPERTIES OF TEMPERATURE STABLE PERFORMANCE CONSISTENT TUNABLE DEVICES

ABSTRACT

The premier candidate active material for tunable microwave phase shifter devices is single composition, paraelectric BaSrTiO₃ (BST). However, there is concern that in practical applications the device performance will be compromised due to the temperature dependence of the BST based device capacitance. We report a device design which controls the magnitude and the sign of the temperature coefficient of capacitance (TCC) via a multilayer paraelectric BST/buffer layer/ferroelectric BST coplanar device structure. To realize this multilayer device structure we have designed, fabricated, and optimized a 10 mol% Al doped Ta₂O₅ barrier layer with low loss (tan δ = 0.004), moderate permittivity (?_r = 42.8), low TCC (?20 ppm/°C), and a low bias stability of capacitance (0.4%). The thin film integration of the barrier layer with the BST layers was optimized for structure, microstructure, interfacial/surface morphology, and dielectric properties as a function of Al doping concentration, annealing temperature, material growth and integration process parameters.     

Ferroelectric properties of Ba1−x Sr x TiO3 thin films synthesized by using novel sol–gel technique through carbonates

Ba_1?x Sr _x TiO₃ (BST) thin films were prepared on the substrate of Pt/Ti/SiO₂/Si by using novel sol–gel process through carbonates. The surface morphology and domain contrast of the films were investigated by atomic force microscopy (AFM), and the domain structures of the BST film were observed when AFM were operated in piezoelectric force microscopic (PFM) analysis and in the friction mode (FFM). The ferroelectric properties of the films were also investigated. It is shown that BST films obtained by the new sol–gel process through carbonates exhibit good properties.     

Spectroscopic ellipsometric determination of optical properties of V-Al co-doped ZnO films by rf magnetron sputtering

Zn_0.9?xV_0.1Al_xO aerogel nanopowders were prepared in thin film form on glass substrates using a rf magnetron sputtering system. The films were characterized by Scanning electron microscopy (SEM) and X-ray diffraction technique (XRD). The XRD results indicate that all the films have c-axis preferred orientation due to self-texturing mechanism. The ellipsometric spectra of the films were recorded in the photon energy range of 1 eV–5 eV. The SE spectra were analyzed with an appropriate model to accurately determine the thickness and optical constants of the ZnO:(V,Al) thin films. The profiles of refractive index and extinction coefficient with photon energy were extracted. The refractive index of the ZnO:(V,Al) film is decreased from 2.14 to 2.07 with increasing Al concentration and then is increased to 2.19 for x?=?0.04. A maximum band gap energy of ~3.57 eV was obtained for x?=?0.02. The optical band gaps of the films were found to vary from 3.57 eV to 3.41 eV, with Al content. It is evaluated that the optical constants of the ZnO:(V,Al) films can be controlled by Al content.     

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.     

Magnetron sputter-deposited multilayer (BaxSr1x)Ti1+yO3+z thin films for passive and active devices

Abstract

High permittivity (Ba_xSr_1?x)Ti_1+yO_3+z(BST) thin films are being investigated for integration into charge storage dielectrics and electric-field tunable elements for high frequency devices. For the latter application, it is desirable to have BST capacitors with high tunability and low losses. Therefore, we investigated the use of multilayer BST thin films consisting of very low dielectric loss BST/electrode interfacial layers ((Ba+Sr)/Ti = 0.73) sandwiching a high tunability, high permittivity primary BST layer ((Ba+Sr)/Ti = 0.9). BST capacitors with multiple layers of controlled composition can be effectively produced insitu by magnetron sputter deposition, using a single stoichiometric target and controlling the layer composition by changing the total process gas (Ar+O<₂) pressure. The layered BST film capacitors exhibit simultaneous low loss (tan Δ = 0.005), high tunability (76%), high charge storage energy density (34 J/cm³), low leakage, and high dielectric breakdown (>2.8 MV/cm).     

Liquid source chemical vapor deposition of high-dielectric-constant (Ba,Sr)TiO3 films

High-dielectric-constant (Ba, Sr)TiO₃ [BST] films were deposited by the liquid source chemical vapor deposition (CVD) method. The system consisted of a single-wafer, low-pressure thermal CVD reactor, a vaporizer for liquid source materials, and a shower-type gas nozzle head, giving stable BST film deposition on a 6-in. diam. substrate with uniform thickness and uniform chemical composition ratio. The source materials employed were Ba(DPM)₂, Sr(DPM)₂, and TiO(DPM)₂ dissolved in tetrahydrofuran (THF), resulting in conformal step coverage of BST films at lowered substrate temperatures, where DPM denotes dipivaloylmethanate. Moreover, the two-step deposition technique was developed to restart protrusions formed on BST film surfaces at low temperatures, where the BST films consisted of a buffer layer and a main layer; the buffer layer was a layer about 60 Å thick of CVD-BST film annealed in N₂. Thus, the two-step CVD deposition of BST films on Pt and Ru electrodes achieved an equivalent SiO₂ thickness of t_eq ∼ 0.5 nm, a leakage current of J_L ∼ 1.0 × 10⁻⁸ A/cm² (at +1.1 V), and a dielectric loss of tan δ ∼ 0.01 at a total film thickness of 250 Å, along with conformal coverage of 80% for a trench with an aspect ratio of 0.65. Then, for BST films deposited on patterned electrodes 0.24 μm wide, 0.60 μm deep, and 0.15 μm high (each spaced by 0.14 μm), the capacitance was demonstrated to be increased without significant deterioration of the leakage current: the capacitance was increased in comparison with that for films on flat electrodes, by a factor corresponding to the increase in surface area due to sidewalls of storage-node-like pattern features. This capacitance increase reflects the most characteristic advantage of CVD, an excellent step coverage on microscopic pattern features. These electrical properties satisfy the specifications for capacitors for Gb-scale dynamic random access memories (DRAMs), giving a storage capacitance of more than 25 fF/cell for a stacked capacitor having a storage node 0.2 to 0.3 μm high. © 1998 Scripta Technica, Electr Eng Jpn, 125(1): 47–54, 1998     

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.