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.     

Microwave Characterization of BST Thin Films on LAO Interdigital Capacitor

The dielectric properties of (Ba_0.5Sr_0.5)TiO₃ (BST) thin films on LaAlO₃ (LAO) single crystals were studied over a wide frequency range. The samples with interdigital electrodes were prepared by microelectronic processing. The dielectric characterizations were carried out in the following steps: 1) the standard calibration of the instrument, 2) the removal of parasitic capacitance and the extraction of the capacitance of the interdigital capacitor (IDC) and 3) the extraction of the dielectric permittivity (?) of BST. It was found that ? of BST has a constant value (about 400) from 50 MHz to 2 GHz; at higher frequencies, ? gradually decreases. The BST interdigital capacitors exhibited good dielectric tunability.     

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.     

Microwave Dielectric Properties of (111) Oriented Ferroelectric (Ba1 − xSrx)TiO3 Thin Films

Epitaxial (111) oriented ferroelectric (Ba_{1 ? x}Sr_x)TiO₃ (BST) films were deposited on MgO (111) single crystals using pulsed laser deposition. Structural properties of BST films were investigated using X-ray diffractometer. The dielectric properties of BST films were investigated under the dc bias field of 0–40 V using interdigital capacitors (IDT) fabricated by photolithography and etching process. The small signal dielectric properties of BST films were calculated by modified conformal mapping both the measured data using an impedance gain/phase analyzer and the reflection coefficient data measured using a HP 8510C vector network analyzer in 0.05–10 GHz at room temperature. The IDT capacitor based on (111) oriented BST film exhibits about 40% of capacitance change with an dc bias of 40 V which value is somewhat smaller than that of the IDT device based on (001) oriented BST film. But the dielectric quality factor value is about twice that of the device based on (001) oriented BST film.     

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.     

Thickness dependent ferroelectric properties of BSTO thin films deposited by RF magnetron sputtering

The thickness dependence of ferroelectric permittivity of (Ba, Sr)TiO₃ has been investigated. The BST films could be obtained to have a simple cubic perovskite structure, space group Pm3m, and practically c-axis epitaxial structure deposited at 800^∘C. Through post-annealing process, we have improved the dielectric properties; dielectric permittivity, dielectric loss, and tunability. The change in dielectric properties before and after annealing is attributed to the change in film strain and the contraction in film lattice. As the thickness of BST films increases from 55 nm to 350 nm, the dielectric constant of BST films increases from about 100 to above 670 due to the reduction of interfacial dead layers with low dielectric constant between films and top electrodes. The dielectric loss of BST thin films decreased as the thickness increases. The existence of interfacial dead layers in a thinner film had a larger effect on the effective dielectric constant than tensile strain between the BST films and MgO substrate.     

Science and Technology of High Dielectric Constant Thin Films and Materials Integration for Application to High Frequency Devices

Thin films of Ba_1?x Sr _x Ti_1+y O_3+z (BST), were fabricated using both by RF-magnetron sputtering and MOCVD to demonstrate application to high frequency devices. Precise control of composition and microstructure is critical for the production of (Ba _x Sr_1?x )Ti_1+y O_3+z (BST) dielectric thin films with the large dependence of permittivity on electric field, low losses, and high electrical breakdown fields that are required for successful integration of BST into tunable high frequency devices. Here we review results on composition-microstructure-electrical property relationships of polycrystalline BST films produced by magnetron sputter deposition that are appropriate for microwave devices such as phase shifters. BST films with a multilayer structure were also developed with different Ti-elemental ratio in each layer to minimize losses and leakage current. Interfacial contamination from C and H species was studied and implications on electrical properties are highlighted. Finally, York's group at the University of California-Santa Barbara successfully integrated our BST films onto phase shifter arrays. The results show potential of BST films in such applications. Results from initial work on the integration of Cu-electrodes with BST films are also presented.     

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.     

Synthesis and characterization of (BaxSr1−x)Ti1+yO3+z thin films and integration into microwave varactors and phase shifters

Abstract

Precise control of composition and microstructure is critical for the production of (Ba_xSr_1?x)Ti_1+yO_3+z (BST) dielectric thin films with the large dependence of permittivity on electric field, low losses, and high electrical breakdown fields that are required for successful integration of BST into tunable high frequency devices. Here we review recent results on composition-microstructure-electrical property relationships of polycrystalline BST films produced by magnetron sputter deposition, that are appropriate for microwave devices such as phase shifters. Films with controlled compositions were grown from a stoichiometric Ba_0.5Sr_0.5TiO₃ target by control of the background processing gas pressure. It was determined that the (Ba+Sr)/Ti ratios of these BST films could be adjusted from 0.73 to 0.98 by changing the total (Ar+O₂) process pressure, while the O₂/Ar ratio did not strongly affect the metal ion composition. Film crystalline structure and dielectric properties as a function of the (Ba+Sr)/Ti ratio are discussed. Optimized BST layers yielded capacitors with low dielectric losses (0.0047), among the best reported for sputtered BST, while still maintaining tunabili-ties suitable for device applications. These BST films were used to produce distributed-cir-cuit phase-shifters, using a discrete periodic loading of a coplanar waveguide with integrated BST varactors on high-resistivity silicon. Phase shifters yielding 30 degrees of phase shift per dB of insertion loss were demonstrated at 20GHz.     

Deposition and characterization of low-loss epitaxial non-linear dielectric thin films for microwave devices

Abstract

Oxide ferroelectric thin films for frequency-tunable microwave devices, in which the dielectric constant of the non-linear dielectric is varied by application of electric fields, have been deposited using PLD. We have fabricated single phase epitaxial Ba_0.6Sr_0.4TiO₃ and KTaO₃ thin film capacitors for applications at 300K and 77K, respectively. Single phase KTaO₃ films were obtained only with excess potassium source in the target along with KTaO₃ perovskite phase. The films have been characterized for structure and morphology by X-ray diffraction and AFM. The dielectric properties were measured in the low frequency range from 100 kHz to 10 MHz, using interdigitated capacitors. Low loss tangents (0.002 at 300K) were observed for highly oriented Ba_0.6Sr_0.4TiO₃ films. The importance of low losses for various devices is discussed and the dielectric constants, loss tangents and tunability of these films are reported in this paper.     

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).     

Growth and Studies of Calcium Doped Laser Ablated Barium Titanate Thin Films

Ba_{1 ? x}Ca_xTiO₃ targets were prepared by conventional solid state reaction with varied amounts of the calcium content (5 at.%, 10 at.%) and the thin films were deposited on Pt(111) coated Si substrate using pulsed laser ablation technique. The thin films were deposited at different pressures and temperatures, so as to determine the optimized growth parameter for the good quality BCT thin films. The pressure variation on the growth parameters made a dramatic impact in tailoring the dielectric constant and phase transition. The phase evolution of the BCT thin films evolves from 450°C and at higher substrate temperatures (～700°C) for different partial pressures of oxygen, the preferred orientation of the thin films were observed. The SIMS analysis reveals a sharp interface exist at the bottom electrode (Pt)–BCT thin films indicating no interdiffusion taking place which might lead to the degradation of devices. The BCT thin films deposited at higher pressures (>60 mtorr) exhibited higher Ba content indicating the possibility of the Ca occupying the Ti site and is reflected in the decrease of the dielectric phase transition temperature. The ferroelectric hysteresis and Capacitance voltage measurement shows the signature of ferroelectricity.     

Deposition of large-area graded (Pb1−xLax)TiO3 thin films by pulsed laser depesition

Abstract

Thin films of the composition (Pb_1?xLa_x)TiO₃, PLT, with x=0.05, 0.10 and 0.15 were sequentially pulsed laser deposited on Pt(Si) substrates at 200°C, followed by post-annealing at 550–600°C in furnace to result in a film with graded composition. The ferroelectric properties of the graded materials are markedly different from those of the uniform thin PLT films. For down graded materials, which contain PLT5 composition (x=0.05) at the top and PLT 15 composition (x=0.15) at the bottom of the films, the hysteresis loops are slim and the width of the P-E curves increases with voltage cycling, attaining an equilibrium polarization states similar to the P-E properties of PLT 15 thin films. By contrast, the ferroelectric hysteresis properties reaches the same value as those of PLT5 thin films when the composition is up-graded.     

Growth of BaTiO3/SrTiO3 superlattices by injection MOCVD

Abstract

BaTiO₃ (BTO) and SrTiO₃ (STO) and Ba_xSr_1-xTiO₃ (x=0–1) (BST) thin films have been epitaxially grown on LaAlO₃ and SrTiO₃:Nb at a substrate temperature of 800°C using a new liquid source delivery technique called injection MOCVD. A X-ray study evidenced FWHMs of 0.16° and 0.45° for SrTiO₃ and BaTiO₃ respectively.

In a next step the feasibility of BaTiO₃/SrTiO₃ superlattices was studied. The multilayers obtained were epitaxially grown on LaAlO₃ as well as on SrTiO₃:Nb. The structural properties were studied using X-ray diffraction as well as XPS, proving the low interface roughness of 1nm. The XPS study also confirmed the absence of carbon contamination in the film.     

Epitaxial growth of multilayered (Bi,La)4Ti3O12/Pb(Zr,Ti)O3 ferroelectric thin films with different orientations

Epitaxial (Bi,La)₄Ti₃O₁₂ (BLT) thin films, epitaxial Pb(Zr,Ti)O₃ (PZT) thin films, and epitaxial multilayered BLT/PZT ferroelectric thin films with different orientations were prepared on SrTiO₃ (STO) single crystal substrates by pulsed laser deposition. From X-ray pole-figures and electron diffraction patterns, the epitaxial orientation relationships between BLT layers, PZT layers, and STO substrates were identified to be (1) BLT(001)//PZT(001)//STO(001), and BLT[110]//PZT[100]//STO[100] for the multilayered thin films on (001)-oriented STO substrates, and (2) BLT(118)//PZT(011)//STO(011), and $ {\text{BLT}}{\left[ {\overline{1} \overline{1} 0} \right]}//{\text{PZT}}{\left[ {100} \right]}//{\text{SrTiO}}_{3} {\left[ {100} \right]} $ for the multilayered films on (011)-oriented STO substrates. Tri-layered films of the same compositions showed well-defined hysteresis loops as well as a high fatigue resistance up to 1?×?10¹⁰ switching cycles.     

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.     

Preparation of Barium Strontium Titanate Thin Film by Spray Deposition

Barium strontium titanate ((Ba,Sr)TiO 3 ; BST) thin films were prepared on platinum-coated silicon substrates using spray deposition. The spray condition (substrate temperature and chamber pressure) dependence on surface roughness for the fired BST thin films was investigated. We obtained BST films thinner than 100 nm on the following properties. Average roughness (Ra) and peak-to-valley value (Rmax) were 3.9 and 130 nm. Dielectric constant and dissipation factor at 1 kHz were 250 and 1.6%. These excellent properties were obtained with even thickness. This method is considered to be advantageous for use with electronic devices that have thin dielectric layers, which make for thin films.     

The tunability and dielectric properties of the compositionally graded Ba(Zr x Ti1−x )O3 thin films

The compositionally graded Ba(Zr _x Ti_1?x )O₃ films with a compositional gradient from BaTiO₃ to BaZr_0.35Ti_0.65O₃ were fabricated on LNO-buffered Pt/Ti/SiO₂/Si substrates by a sol-gel deposition method. In order to confirm the compositional gradient, a combination of X-ray Photoelectron Spectroscopy (XPS) and Ar ion etching was employed to produce the composition depth profile. Dielectric constant peaks, common to a ferroelectric transition, were not observed in the temperature range from ?50 to 100 °C, within which the dielectric constant showed negligible temperature dependence. The compositionally graded Ba(Zr _x Ti_1?x )O₃ thin films with weak temperature dependence of tunability could be attractive materials for situations in which precise control of temperature would be either impossible or too expensive.     

Electrical and optical properties of microwave dielectric thin films prepared by pulsed laser deposition

Abstract

Bi₂(Zn_1/3Nb_2/3)₂O₇, BiZN, materials possess high dielectric constant and low loss factor in microwave frequency region. They have good potential for device application, especially in the form of thin films. However, the microwave dielectric properties of a thin film are very difficult to be accurately measured. Evaluation on the dielectric behavior of the films through the performance of the microstrip line devices made of these films involves metallic conduction and stray field losses. A novel measuring technique, which can directly evaluate the microwave dielectric properties of a thin film is thus urgently needed.

In this paper, BiZN thin films were grown on [100] MgO single crystal substrates using pulsed laser deposition process. The high-frequency dielectric properties of thus obtained thin films were determined using optical transmission spectroscopy (OTS). The [100] preferentially oriented films with pyrochlore structure can be obtained for the thin films deposited at 400–600°C substrate temperature under 0.1 mbar oxygen pressure. OTS measurements reveal that the index of refraction (n=1.95–2.35) and absorption coefficient (k=0.28x10^?4-2.25 × 10^?4 nm^?1) of the films vary insignificantly with the crystallinity of the BiZN films.     

Preparation and properties of Pb(Zr, Ti)O3 ferroelectric thin films and compositionally graded thin films on LaNiO3/Si substrates

LaNiO₃ (LNO) thin films were prepared on Si (100) wafer by MOD method. Pb(Zr, Ti)O₃ ferroelectric thin films and their compositionally graded thin films were prepared on LNO/Si (100) substrates by a modified sol–gel method. The composition depth profile of a graded film was determined by using a combination of Auger electron spectroscopy and Ar ion etching. The results confirmed that the processing method produces graded composition change. XRD analysis showed that the graded thin film possessed a composite structure of tetragonal and rhombohedral. The dielectric constant of the graded thin films was higher than that of each thin film unit, but the loss tangent was near to each other at 10 kHz. The temperature characteristics of the dielectric constant of the graded thin films at different frequencies showed three peaks and ferroelectric relaxor feature to some extent. Hysteresis loops showed that graded thin film had higher remanent polarization, smaller coercive field than each thin film unit. The pyroelectric coefficient of the graded thin films increased gradually with temperature, and was higher than that of each thin film unit.