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.     

Enhanced piezoelectricity around the tetragonal/orthorhombic morphotropic phase boundary in (Na,K)NbO3–ATiO3 solid solutions

The high density perovskite titanates-modified potassium–sodium niobate solid solutions (1?x)(Na_0.5K_0.5)NbO₃?xBaTiO₃ and (1?x)(Na_0.5K_0.5)NbO₃?xSrTiO₃ have been prepared by the solid state reaction method. The phase diagram summarized from the dielectric property measurement reveals that there exists a tetragonal/orthorhombic morphotropic phase boundary for both the solid solutions. The piezoelectric properties show enhanced behavior at around the tetragonal/orthorhombic morphotropic phase boundary. It is believed that the origin for the high piezoelectric performance (Na,K)NbO₃-based lead-free piezoelectric ceramics is the same as that for the lead zinc niobate-lead titanate solid solution.     

Effect of BaTiO3 size on dielectric property of BaTiO3/PVDF composites

The BaTiO₃/polyvinylidene fluoride (BaTiO₃/PVDF) polymer-based composites with different size and concentration of BaTiO₃ particles were fabricated via a simple physical mixing and subsequently hot-press processing. Effect of the filler size and frequency on the dielectric properties of the BaTiO₃/PVDF binary composites was discussed. The result shows that the BaTiO₃ size has an effect on the morphology of the BaTiO₃/PVDF composites. The composites with 0.2 and 0.3 μm BaTiO₃ exhibit high dielectric permittivity than those with 0.4 and 0.5 μm BaTiO₃. The composite with 0.4 μm BaTiO₃ has a minimum dielectric permittivity except one with 0.1 μm BaTiO₃. Dielectric loss of the BaTiO₃/PVDF binary composites changes slightly with the BaTiO₃ sizes. The ternary BaTiO₃/PVDF composites with 0.1 and 0.7 μm BaTiO₃ in coexistence exhibit good dielectric properties. As a result, the BaTiO₃/PVDF ternary composites in this study may have a promising application as dielectric material in embedded capacitor.     

EFFECT OF ANNEALING ON THE ELECTRICAL PROPERTIES OF SrTiO3 THIN FILMS PRODUCED BY ION BEAM SPUTTERING

ABSTRACT

Thin film capacitors with SrTiO₃ (STO) as dielectric and Pt as electrode material have been prepared by ion beam sputtering. The as-deposited film is amorphous and exhibits a crystallization temperature around 321°C as proved by X-ray diffraction. The effect of post annealing on the crystalline quality of the films was systematically studied by x-ray diffraction and Atomic Force microscopy (AFM). The temperature and frequency dependent dielectric properties were measured from 30°C to 200°C and 0.01 Hz to 10⁵ Hz, respectively. The influence of the microstructure of SrTiO₃ thin films on their electrical properties was investigated through an extensive characterization. The electrical properties of SrTiO₃ films appear to be strongly depending on the annealing temperatures. The capacitance voltage (C-V) characteristics reveal an improvement of capacitance density with increasing the annealing temperature.     

Properties of interfaces between SrTiO3 thin films and electrodes

Abstract

SrTiO₃ films with thickness ranging from 25nn to 2.5μm were grown on LaAlO₃ substrates with SrRuO₃ electrode layers. Measurements of the dielectric properties were performed over a range of temperatures The dielectric loss depends strongly on the thickness, but differently above and below T ～ 80 K. Our result suggests that, in the high temperature regime, the interfacial dead layer effect dommates while, in the low temperature regime, the losses related to the structural phase transition and quantum fluctuations are important. The contribution to the interfacial potential from Schottky barriers was investigated for different electrode materials. Preliminary results of this study suggest that the continued dielectric nonlinearity of the thin films at high temperatures (above T ～ 80 K) complicates the analysis of the Schottky barrier height measurements.     

Growth and Dielectric Properties of Ferroelectric BaTiO3 Thin Films for Cantilever-Type Microsensors

ABSTRACT

Ferroelectric BaTiO₃ (BTO) thin films were deposited on Si, silicon-on-insulator (SOI) and MgO substrates by pulsed laser deposition. The orientations of the films, polycrystalline and epitaxial phase, were controlled by the lattice mismatch between the BTO film and substrates. The structural properties and surface morphologies were examined using X-ray diffractometer and atomic force microscope. The dielectric properties of BTO films were investigated using metal-ferroelectric-metal (MFM) and interdigital co-planar capacitors. Conductive oxide layers, SrRuO₃(SRO) and La_0.5Sr_0.5CoO₃ (LSCO), were grown on Si and SOI substrates as bottom electrodes. For MFM capacitors based on Au/BTO/SRO/Si and Au/BTO/LSCO/SOI layer structures, a little asymmetric capacitance-voltage curves were obtained with about 36% capacitance tunability. The remanent polarizations were about 21 μC/cm² and the coercive fields were about 71 kV/cm. For an interdigital capacitor based on Au/BTO/MgO layer structure, a little lossy capacitance-voltage curve was obtained with about 64% capacitance tunability.     

Low-temperature sintering of BaTiO3 with Mn-Si-O glass

In order to reduce sintering temperature and prevent adverse dielectric effects, pure BaTiO₃ powder with the addition of Mn-Si-O glass was sintered in the temperature range of 1175–1300°C. Microstructural observation showed that BaTiO₃ grains of the sintered samples only grew from the initial 400 nm to an average of 430 nm between 1175–1275°C for 1 h, or sintered at 1250°C as long as 27 h. Abnormal BaTiO₃ grains are not found in the sintered samples. The microstructure and phase analysis showed that the dielectric properties, tetragonality, and grain growth of BaTiO₃ are closely controlled by the formation of the liquid phase, newly formed Ba₂TiSi₂O₈ grains, and Mn solid solution in BaTiO₃ grains.     

Preparation,microstructure, and ferroelectric properties of laser-deposited thin BaTiO3 and lead zirconate-titanate films

Abstract

Ferroelectric thin films of BaTiO₃ and lead zirconate titanate, PbZr_0.53Ti_0.47O₃ (PZT), have been prepared by pulsed excimer laser deposition. The microstructure and crystallography of these films have been studied by scanning electron microscopy (SEM), energy dispersive x-ray spectrometry (EDX), transmission electron microscopy (TEM), x-ray diffraction (XRD), and differential scanning calorimetry (DSC). Electrical properties, including remanent polarization, dielectric loss, and dielectric constant, have been measured. Also, switched remanent polarization has been measured under conditions of continuous cycling.     

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.     

Effects of oxidants on the deposition and dielectric properties of the SrTiO3 thin films prepared by liquid source metal-organic chemical vapor deposition (MOCVD)

Abstract

SrTiO₃ thin films are deposited by a liquid source metal-organic chemical vapor deposition (MOCVD). The effects of oxidants on the deposition characteristics and dielectric properties of the films are mainly tested. O₂, N₂O and O₂ + N₂O gases are used as the oxidants and the films with Ti-rich and Sr-rich compositions are obtained when O₂ and N₂O is used, respectively. Deposition of thin initial layer under O₂ atmosphere is very effective to obtain large dielectric constant of the SrTiO₃ thin film when the main layer is deposited under O₂ + N₂O atmosphere. The dielectric constants of 40 nm thick SrTiO₃ films with thin O₂, N₂O initial layers and without the initial layers are 235, 145 and 210, respectively.     

Dielectric and lattice dynamical properties of SrTiO3 thin films

Abstract

Pulsed-laser-deposited SrTiO₃ thin films are used as all example to illustrate the effects of strain. oxygen vacancies, and interfacial dead layer on the dielectric and lattice dynamical properties in ferroelectric thin films. We found that strain, both lattice mismatch-induced and due to local defects such as oxygen vacancies, dramatically influences the properties of the thin films. The cubic-to-tetragonal structural phase transition is greatly modified by the strain in the films. Raman scattering shows the symmetry-forbidden optical phonons, indicating the reduction of symmetry. The line shape of the polar phonon shows a Fano asymmetry, which we suggest to be due to the micro polar regions or other local polar structures around the oxygen vacancies. The temperature dependence of the low-frequency complex dielectric constant shows markedly distinct quantum fluctuation behaviors from those of the single crystals. The soft mode is considerably hardened in the thin films compared to the single crystals.     

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.     

High piezoelectric activity in lead-free BaTiO3-BaZrO3-CaTiO3 ceramics with near polymorphic phase boundary

Abstract

Lead-free 0.88BaTiO₃–(0.12-x)BaZrO₃–xCaTiO₃ (BT-BZ-xCT) ceramics were fabricated via solid state reaction. The effect of CaTiO₃ content on crystal structure, phase transition, and electrical properties was investigated systematically. The crystal structure and phase transition of ceramics were characterized by X-ray diffraction (XRD), Raman spectra and dielectric measurement. Results show that ceramic in the composition, x?=?0.02, exhibits a rhombohedral structure. Ceramics with increasing CT content transformed from a rhombohedral to orthorhombic structure in the composition, x?=?0.04, and eventually became a tetragonal structure at the composition, x?≥?0.08. The polymorphic phase boundary (PPB) was observed at the composition, x?=?0.06, with coexistence of orthorhombic and tetragonal phases showing at almost room temperature. This PPB composition exhibited a high piezoelectric response (d₃₃*) of 1,150?pm/V at 10?kV/cm as an electric field was applied. These results indicate that the materials studied have potential as candidates for lead-free piezoelectric ceramics.     

Effect of doped Ni2+ on the dielectric properties of NiO-BaTiO3 composites

NiO-BaTiO₃ composites were prepared by sintering BaTiO₃ together with NiO in air at 1300°C. Microstructure and morphology of the composites were detected by XRD and SEM, and the dielectric properties were measured by LCZ meter. The results indicate that the perovskite phase is formed in fact in status of solid solution doped with Ni²⁺, although only a small amount of Ni ions can dissolve into the perovskite phase. Ni doping decreases the formation temperature of the composite without inhibiting the grain growth of the crystalline phase. The dielectric constant decreases sharply and the dielectric loss decreases smoothly with increasing Ni²⁺ below NiO addition of 0.5 wt.%. When NiO addition increases above 0.5 wt.%, the dielectric constant and loss correlate with mixing rule of the two phases. Meanwhile, the replacement of Ni²⁺ for Ti⁴⁺ decreases the Curie temperature of perovskite phase by 30°C.     

Processing and properties of nanocrystalline Pb(Sc0.5Ta0.5)O3, Pb(Sc0.5nb0.5)O3 and Pb(Mg1/3Nb2/3)O3 films produced by RF-sputtering from ceramic targets

Abstract

Nanocrystalline thin films of different relaxor materials, namely Pb(Sc_0.5Ta_0.5)O₃ (PST), Pb(Sc_0.5Nb_0.5)O₃(PSN), Pb(Mg_1/3Nb_2/3)O₃(PMN) have been produced by RF-sputtering to investigate whether it will affect their dielectric properties if their grain size is reduced to the dimensions known from their nanodomains. The XRD shows that the amorphous film crystallizes in pyrochlore structure at lower temperatures and short times. Annealing at higher temperatures and far longer time intervals leads to an increasing amount of perovskite phase with a grain size in the nanometer range. These results including dielectric measurements will be presented and discussed.     

Strain tensor effects on SrTiO3 incipient ferroelectric phase transition

Structural distortion of ferroelectric thin films caused by film strain has a strong impact on the microwave dielectric properties. SrTiO₃ thin films epitaxially grown on (110) DyScO₃ substrates using molecular beam epitaxy (MBE) are extremely strained (i.e., ～1% in-plane tensional strain) from 3.905 Å of bulk SrTiO₃. The room temperature dielectric constant and its tuning of the films are observed to be 6000 and 75% with an electric field of 1 V/μm, respectively. The control of strain in SrTiO₃ provides a basis for room temperature tunable microwave applications by elevating its phase transition peak to room temperature. Also, a significant in-plane anisotropy in dielectric constant and tuning was observed in these SrTiO₃ films. The observed in-plane anisotropic dielectric properties have been interpreted based on the phenomenological thermodynamics of film strain.     

SrTiO3 thin films by mocvd for 1 gbit DRAM application

Abstract

Three important aspects of the preparation of SrTiO₃ thin films by MOCVD are discussed in detail in view of the application of these films as the capacitor dielectric of Gbit-scale DRAMs: CVD reactions in the Sr(DPM)₂-Ti(i-OC₃H₇)₄-O₂ system, step coverage and relations between microstructure and electrical properties. The effect of the substrate temperature on the Sr and Ti deposition rates was first investigated for thermal and ECR CVD SrTiO₃ films. SrO and TiO₂ deposition by thermal CVD above 550°C were found to be controlled by the surface reaction and gas transport, respectively, whereas both SrO and TiO₂ deposition are controlled by gas transport for ECR CVD at 450 to 600°C. The influence of the Sr and Ti deposition regimes on the step coverage of SrO, TiO₂ and SrTiO₃ were then assessed. SrO films prepared by thermal CVD at 600°C exhibited the best step coverage, indicating that a relation exists between reaction controlled deposition and good step coverage. The effect of the film composition and film thickness on the microstructure of SrTiO₃ thin films were finally investigated and correlations were made to other analyzed physical and electrical properties. Polycrystalline perovskite phase SrTiO₃ films were obtained for a composition 0.7 ≤ Sr/Ti ≤ 1.2. The best crystallinity, maximum permittivity and maximum refractive index were obtained for Sr/Ti = 0.95. Titanium rich films are thought to be composed of a mixture of a titanium rich amorphous phase and crystalline SrTiO₃, and strontium rich films are believed top correspond to a (SrTiO₃)_m (SrO)_n structure. The dielectric constant slowly decreased as the film thickness was reduced. The sharp decrease observed near 400–500 Å could be due to the existence of some perturbed layer at the interface with one or both of the electrodes     

Dielectric relaxation phenomenon of rare earth Nd3+ modified bismuth layer ferroelectric ceramics fabricated by plasma active sintering method

Abstract

The crystalline structure, dielectric relaxation and ferroelectric properties of the solid solution, Nd _x Bi_4-x Ti₃O₁₂ (NBIT) compound were measured. The Curie temperature of the NBIT ceramics was determined to be 490°C from dielectric measurements. The dielectric constant of the NBIT ceramics shows a small anisotropic property. Polarization switching was observed using a Sawyer-Tower circuit at 50 Hz. Remnant polarizations and coercive fields could not be confirmed since the hysteresis loops were not saturated. The large dielectric relaxation is observed in the frequency range between 100 kHz and 1 MHz.     

Lead-free (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)<Subscript>0.95</Subscript>(LiSb)<Subscript>0.05</Subscript>Nb<Subscript>0.95</Subscript>O<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> piezoceramics

Lead-free (1-x)(K_0.5Na_0.5)_0.95(LiSb)_0.05Nb_0.95O₃-xBaTiO₃ (abbreviated as (1-x)KNNLS-xBT) piezoceramics were synthesized by conventional solid state sintering and the effect of BaTiO₃ on the microstructure, dielectric and piezoelectric properties was investigated. It was found that both orthorhombic-tetragonal (T _O-T) and tetragonal-cubic (T _C) phase transition temperatures decreased obviously with increasing BaTiO₃ content. Although proper amount of BaTiO₃ facilitated the sintering of (1-x)KNNLS-xBT ceramics, the addition of BaTiO₃ affected the relaxor behavior slightly and it was not beneficial to improve piezoelectric strain coefficient d ₃₃, remnant polarization P _r and piezoelectric coupling constant k _p.     

Preparation of ferroelectric thin films for Si-based devices

Abstract

Lead titanate (PbTiO₃) thin films have been prepared on titanium dioxide coated silicon wafers by chemical vapor deposition (CVD). The pure PbTiO₃ thin films were deposited by controlling the experimental conditions. The gas phase reaction of TiO₂ occurred by exceeding the critical value of titanium input fraction at constant oxygen partial pressure. Strontium titanate (SrTiO₃) thin films have been prepared on p-type silicon wafers by radio frequency (RF) magnetron sputtering. The SrTiO₃ thin film was polycrystalline and the Sr/Ti ratio of this film was 0.91. The SrTiO₃ thin films contain three regions, an external surface layer, a main layer and an interfacial layer. The stoichiometric SrTiO₃ thin film was obtained by using the SrO excess target. The SrTiO₃ film annealed at 600[ddot]C has an ideal capacitance-voltage (C-V) curve and maximum effective dielectric constant.