Properties of strontium titanate in the SrTiO3/CeO2/Al2O3 multilayered structure

Studies of the crystal structure, elemental composition, and dielectric properties of strontium titanate films in SrTiO₃/CeO₂/Al₂O₃ multilayered structures are reported. Data on the crystal lattice and impurity contents have been obtained, and temperature and electric field dependences of the dielectric properties of SrTiO₃ films in the microwave range have been measured. An analysis of the results is made to establish the reason for the nonmonotonic dependence of the small-signal dielectric permittivity of SrTiO₃ films on temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1024–1029 (June 1997)     

RF-plasma assisted pulsed laser deposition of nitrogen-doped SrTiO3 thin films

Perovskite-type nitrogen substituted SrTiO₃ thin films were deposited with a one-step process by RF-plasma assisted pulsed laser deposition from a SrTiO₃ target using a N₂ plasma, while deposition with a NH₃ plasma yields films with almost no incorporated nitrogen. The deposited films exhibit a cubic perovskite-type crystal structure and reveal oriented growth on MgO(100) substrates. The unit cell parameters of the studied N-doped SrTiO₃ films range within 3.905<a<3.918 Å, which is slightly larger than for SrTiO₃ (a=3.905 Å). The nitrogen content in the deposited films varies from 0.2 to 0.7 atom%. The amount of incorporated nitrogen in the films decreases with increasing RF-power, while the N₂ flow rate does not have any pronounced influence on the N content. Nitrogen incorporation results in an increased optical absorption at 400–600 nm, which is associated with N(2p) energy states that have a higher energy level than the valence band in strontium titanate. The optical band gap energies in the studied N-doped SrTiO₃ films are at 3.2–3.3 eV, which is very similar to that of pure strontium titanate (～3.2 eV). Films deposited with NH₃ for the RF-plasma exhibit a lower degree of crystallinity and reveal almost no nitrogen incorporation into the crystal lattice.     

Response of the capacitance and dielectric loss of the SrRuO<Subscript>3</Subscript>/SrTiO<Subscript>3</Subscript>/SrRuO<Subscript>3</Subscript> film heterostructures to variations in temperature and electric field

Three-layer epitaxial heterostructures with a 750-nm-thick intermediate strontium titanate layer between two strontium ruthenate conductive thin-film electrodes have been grown by laser deposition. Photolithography and ion etching have been used to form film parallel-plate capacitors based on the grown heterostructures. The capacitance (C) and dielectric loss tangent (tanδ) of the parallel-plate capacitors have been measured in the temperature range T = 4.2–300 K at an applied bias voltage of up to ±2.5 V and without it. At T > 100 K, the temperature dependence of the dielectric permittivity (ε) of the SrTiO₃ intermediate layer is well approximated by the Curie–Weiss law taking into account the capacitance induced by the penetration of an electric field into the oxide electrodes. At T ≈ 20 K, the dielectric permittivity ε of the SrTiO₃ intermediate layer decreases by approximately 20% in an electric field of 25 kV/cm. The dielectric loss tangent of the film capacitor heterostructures decreases monotonically with a decrease in the temperature in the range from 300 to 80 K and almost does not depend on the electric field strength. However, in the range from 80 to 4.2 K, the dielectric loss tangent increases nonmonotonically (abruptly) with a decrease in the temperature and decreases significantly in an applied electric field.     

Controlling precursor stability and evaporation through molecular design. Pseudo single source precursor approach to MOCVD SrTiO3 thin films

Strontium titanate SrTiO₃ thin films have attracted interest as a possible gate dielectric material. Preparation of its high quality coatings is hindered by difference in volatility of the homometallic precursors - strontium beta-diketonates and titanium alkoxides. The only earlier known single-source precursor, a sec-alkoxide derivative Sr₂Ti₂(thd)₄(OiPr)₈, has limited volatility. Bimetallic primary alkyl chain complexes, Sr₄Ti₂O(thd)₄(OR)₁₀(ROH)₂, R = Et, ⁿPr, are stable and volatile, but possess a wrong composition. Highly volatile precursor Sr₂Ti₂(thd)₄(OⁱBu)₈ has been prepared using an iso-alkoxide, combining proper ligand size with the sterical requirements, and characterized by multivariate evaporation analysis. Its evaporation is associated with complete decomposition into homometallic species, which, however, are evaporated in a single step. This permits to successfully use this novel precursor for SrTiO₃ thin film deposition by DLI-MOCVD technique in a sufficiently broad established temperature range. Using optimized experimental conditions, 100 nm thick strontium titanate films with high permittivity have been successfully obtained on (1 0 0) Si.     

Microstructural and electrical properties of Y0.07Sr0.93-x TiO3-δ perovskite ceramics

In order to find a relationship between electrical and microstructural properties, yttrium-doped strontium titanate (7 mol%) with various values of strontium nonstoichiometry was investigated and shown in this work. It has been observed that yttrium doping can affect the electrical properties of SrTiO₃ to a great extent. Moreover, the microstructural and electrical properties can be influenced by strontium nonstoichiometry. The defect chemistry explaining obtained results was also suggested and discussed.     

Effect of SrTiO3 on dielectric and piezoelectric properties of NBT

Composites of (1 ? x)Na_0.5Bi_0.5TiO₃-(x)SrTiO₃, where x = 0.05, 0.10, 0.15, 0.2, 0.3 and 0.9 are studied. Individual compounds are synthesized by sol gel, and composites are prepared by solid-state sintering process. Through the analysis of X-ray diffraction, lattice parameters are obtained and, from scanning electron microscope (SEM), micro-structure of the samples is observed. The depolarization temperature (T_d) and the Curie temperature (T_c) are determined from dielectric studies. Relaxor behavior of the samples is interpreted using modified Curie Weiss law. Control of polarization in sodium bismuth titanate (NBT) is achieved using strontium titanate (SrTiO₃-ST) and studied through polarization vs. electric field (PE) loops and piezoelectric measurements. The intra-granual and inter-granual effects on the electrical properties of the ceramics are studied from impedance analysis.     

EPR study of charge compensation of chromium centers in the strontium titanate crystal

Chromium centers and their charge compensation in two single strontium titanate crystals, i.e., SrTiO₃: Cr (0.05 at %) and Sr_0.9995TiO₃: Cr_0.0005 grown with strontium deficiency, have been studied by the electron paramagnetic resonance method. The crystals have been investigated both immediately after growth and after oxidation and reduction procedures. Oxidation and reduction are performed by crystal annealing in a corresponding gas atmosphere at high temperature. Chromium centers associated with oxygen vacancy (Cr³⁺-V _O) are detected in the reduced crystals. It is shown that strontium vacancies are formed in the crystal grown with strontium deficiency, which leads to a lowering of the tetragonal symmetry of (Cr³⁺-V _O) and Cr⁵⁺ centers to the orthorhombic symmetry. Possible compensation mechanisms for charges of various chromium centers are considered.     

Study on Mn-doped SrTiO3 with first principle calculation

The defect formation energies and electronic structures of Mn doped strontium titanate have been studied using CRYSTAL-09 code. The defect formation energies for Mn_Sr and Mn_Ti, under different chemical potential conditions, have been obtained to determine the way Mn prefers to occupy in the Mn doped SrTiO₃ crystal. From the electronic structures of Mn doped SrTiO₃, it is shown that Mn_Sr cannot change the band gap of SrTiO₃. However, Mn_Ti can effectively reduce the band gap of SrTiO₃ and improve the photocatalysis.     

Impact of anisotropic strains on low-frequency dielectric properties and room-temperature polar phases of SrTiO3 epitaxial thin films

Impact of anisotropic strains on low-frequency dielectric properties and room-temperature polar phases of SrTiO₃ epitaxial thin films is investigated. The dielectric properties show a remarkable change as a function of anisotropic strains. The number of room-temperature polar phases is as twice as that of isotropically strained SrTiO₃ thin films.     

Lead titanate ferroelectric films on single-crystal silicon

This paper reports on the results of investigations into the phase transformations observed in Pb/Ti/Si and Ti/Pb/Si thin-film heterostructures upon layer-by-layer magnetron sputtering of lead and titanium onto a single-crystal silicon substrate and subsequent annealing in an oxygen atmosphere. It is shown that the dielectric properties of lead titanate films depend on the order of sputtering of lead and titanium metal layers onto the surface of single-crystal silicon. The ferroelectric properties are revealed in 3000-nm-thick lead titanate films prepared by two-stage annealing of the Pb/Ti/Si thin-film heterostructure (with the upper lead layer) at T ₁=473 K and T ₂=973 K for 10 min. These films are characterized by the coercive field E _c=4.8 kV/cm and the spontaneous polarization P _s=16.8 μC/cm². The lead titanate films produced by annealing of the Ti/Pb/Si thin-film heterostructure (with the upper titanium layer) do not possess ferroelectric properties but exhibit properties of a conventional dielectric. __________ Translated from Fizika Tverdogo Tela, Vol. 44, No. 4, 2002, pp. 745–749. Original Russian Text Copyright ? 2002 by Sidorkin, Sigov, Khoviv, Yatsenko, Logacheva.     

Pulsed laser deposition and characterization of nitrogen-substituted SrTiO3 thin films

Nitrogen-substituted cubic perovskite-type SrTiO₃ thin films were deposited in a one-step process using pulsed reactive crossed beam laser ablation (PRCLA) and RF-plasma assisted pulsed laser deposition (RF-PLD). Both techniques yield preferentially oriented films on SrTiO₃(0 0 1), LaAlO₃(0 0 1) and MgO(0 0 1) substrates with the unit cell parameters within 0.390(5) < a < 0.394(9) nm. The nitrogen content is higher in films deposited by PRCLA (0.84-2.40 at.%) as compared to films deposited by RF-PLD with nitrogen plasma (0.10-0.66 at.%). PRCLA with an ammonia gas pulse leads to a higher nitrogen content compared to the films grown with a nitrogen gas pulse, while films deposited by RF-PLD with ammonia plasma reveal only minor nitrogen contents (<0.10 at.%). The amount of the incorporated nitrogen can be tuned by adjusting the deposition parameters. Films deposited by PRCLA have a lower roughness of 1-3 nm compared to 12-18 nm for the films grown by RF-PLD. PRCLA yields partially reduced films, which exhibit electronic conductivity, while films deposited by RF-PLD are insulating. There is also a pronounced influence of the substrate material on the resistivity of the films deposited by PRCLA: films grown on SrTiO₃ substrates exhibit a metallic-like behaviour, while the corresponding films grown on MgO and LaAlO₃ substrates reveal a metal-to-semiconductor/insulator transition. Nitrogen incorporation into the SrTiO₃ films results in an increased optical absorption at 370-500 nm which is associated with N(2p) localized states with the energy about 0.7 eV higher than the valence band energy in strontium titanate. The optical band gap energies in the studied N-substituted SrTiO₃ films are 3.35-3.40 eV.     

Dielectric response of a (1000 nm)SrTiO<Subscript>3</Subscript> layer epitaxially grown on (001)La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> to temperature variation and electric field

The structure and dielectric characteristics of the (1000 nm)SrTiO₃ spacer in a (001)SrRuO₃ ‖ (001)SrTiO₃ ‖ (001)La_0.67Ca_0.33MnO₃ trilayer heterostructure grown on a (001)(LaAlO₃)_0.3+(Sr₂AlTaO₆)_0.7 substrate have been studied. Both oxide electrodes, as well as the strontium titanate layer, were cube-on-cube epitaxially grown. The unit cell parameter in the SrTiO₃ layer measured in the substrate plane (3.908±0.003 Å) practically coincided with that determined along the normal to the substrate surface (3.909±0.003 Å). The temperature dependence of the real part of the permittivity ?′ of the SrTiO₃ layer in the range 70–180 K fits the relation (?′)^?1 ～ ? ₀ ^?1 C ₀ ^?1 (T-T _C ) well, where C₀ and T_C are the Curie constant and the Curie-Weiss temperature, respectively, for bulk strontium titanate crystals and ?₀ is the free-space permittivity. The data obtained on the temperature dependence of the permittivity of SrTiO₃ films enabled us to evaluate the effective depth of electric field penetration into the manganite electrode (L _e ≈ 0.5 nm) and the corresponding capacitance (C _e ≈1×10^?6 F/cm²) of the interface separating the (001)SrTiO₃ layer from the (001)La_0.67Ca_0.33MnO₃ bottom electrode.     

Growth of SrTiO3 on Si(001) by hybrid molecular beam epitaxy

We report the heteroepitaxial growth of SrTiO₃ thin films on Si(001) by hybrid molecular beam epitaxy (hMBE). Here, elemental strontium and the metal‐organic precursor titanium tetraisopropoxide (TTIP) were co‐supplied in the absence of additional oxygen. The carbonization of pristine Si surfaces during native oxide removal was avoided by freshly evaporating Sr into the hMBE reactor prior to loading samples. Nucleation, growth and crystallization behavior as well a structural properties and film surfaces were characterized for a series of 46‐nm‐thick SrTiO₃ films grown with varying Sr to TTIP fluxes to study the effect of non‐stoichiometric growth conditions on film lattice parameter and surface morphology. High quality SrTiO₃ thin films with epitaxial relationship (001)SrTiO₃ || (001)Si and [110]SrTiO₃ || [100]Si were demonstrated with an amorphous layer of around 4 nm thickness formed at the SrTiO₃/Si interface. The successful growth of high quality SrTiO₃ thin films with atomically smooth surfaces using a thin film technique with scalable growth rates provides a promising route towards heterogeneous integration of functional oxides on Si. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Morphology dependence of the dielectric properties of epitaxial BaTiO3 films and epitaxial BaTiO3/SrTiO3 multilayers

Epitaxial BaTiO₃ films and epitaxial BaTiO₃/SrTiO₃ multilayers were grown by pulsed laser deposition on vicinal surfaces of (001)-oriented Nb-doped SrTiO₃ (SrTiO₃:Nb) single-crystal substrates. Atomic force microscopy was used to investigate the surface topography of the deposited films. The morphology of the films, of the BaTiO₃/SrTiO₃ interfaces, and of the column boundaries was investigated by cross-sectional high-resolution transmission electron microscopy. Measurements of the dielectric properties were performed by comparing BaTiO₃ films and BaTiO₃/SrTiO₃ multilayers of different numbers of individual layers, but equal overall thickness. The dielectric loss saturates for a thickness above 300 nm and linearly decreases with decreasing film thickness below a thickness of 75 nm. At the same thickness of 75 nm, the thickness dependence of the dielectric constant also exhibits a change in the linear slope both for BaTiO₃ films and BaTiO₃/SrTiO₃ multilayers. This behaviour is explained by the change observed in the grain morphology at a thickness of 75 nm. For the thickness dependence of the dielectric constant, two phenomenological models are considered, viz. a series-capacitor model and a dead-layer model. PACS 77.22.-d; 77.22.Ch; 77.55.+f; 77.22.Gm; 77.84.Dy; 81.15.-z ; 81.16.Mk; 81.65.-b; 68.55.-a; 68.37.-d     

Effect of light-induced drop in electrical resistance of bulk SrTiO3 crystals

This paper reports on the results of the experimental investigation of the light-induced drop in electrical resistance of undoped SrTiO₃ crystals exposed to illumination for a time of 10³–10⁴ s. The revealed effect reaches five orders of magnitude and has been observed even in samples irradiated with a weakly absorbed light that is not capable of inducing interband transitions in strontium titanate. The nature of the revealed phenomenon has been explained within the framework of modern concepts, according to which in SrTiO₃ crystals there is a three-dimensional network of metallized nanowires formed by extended defects, for example, edge and screw dislocations.     

Dielectric and insulating properties of SrTiO3/Si heterostructure controlled by cation concentration

SrTiO3 films with different cation concentration were deposited on Si(001)substrates by oxide molecular beam epitaxy.An amorphous layer was observed at the interface whose thickness depends on the oxygen pressure and the substrate temperature during growth.Although lowering the oxygen vacancy concentration in SrTiO3led to better insulating performance as indicated by the lowered leakage current density of the heterostructure,the dielectric performance was deteriorated because of the thickened interfacial layer that dominated the capacitance of SrTiO3/Si heterostructure.Instead of adjusting the oxygen vacancy concentration,we propose that controlling the film cation concentration is an effective way to tune the dielectric and insulating properties of SrTiO3/Si at the same time.     

Preparation of monodispersed Pd nanoparticles by laser ablation at air–suspension interface

Strontium titanate (SrTiO₃) has attracted a lot of attention because of its possible applications in new microelectronic devices. It is a material with a high dielectric constant, low leakage current, and some of its properties can be changed by adding or modifying the concentration of a dopant, which can be used for a wide range of functional purposes, from simple capacitors to complicated microwave devices. Therefore, in this work, we report the development of a new route to synthesize SrTiO₃ nanoparticles based on the solvothermal method by employing two precursor solutions: strontium chloride and titanium(IV) butoxide. Our route allows the production of cubic SrTiO₃ nanoparticles with a narrow size distribution. The particle sizes range between 8 and 24 nm, forming agglomerates of SrTiO₃ in the range of 128–229 nm. It was demonstrated that the Ti/Sr molar ratio employed into the precursor solution has an important effect onto the chemical composition of the resulting SrTiO₃ nanoparticles: when using Ti/Sr < 1, the formation and incorporation of the SrCO₃ compound into the nanoparticles was observed while with Ti/Sr ≥ 1 nanoparticles are free of contaminants. The as-prepared nanoparticles were characterized by energy-dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy, high-resolution TEM, selected area electron diffraction, scanning electron microscopy, and dynamic light scattering.     

Low temperature ferroelectrics: Dielectric nonlinearity,losses, and parametric interactions at ultrahigh frequencies

Conclusions The material presented above, concerning the properties and possible radiophysical applications of low-temperature ferroelectrics, strontium titanate and potassium tantalate crystals, can be summarized as follows.The problem of the dielectric nonlinearity of these crystals can be assumed to be mainly solved. The mechanism for the nonlinearity is known; successful approaches to the problem exist: thermodynamic, microscopic, and model approaches; experimental results agree with theory.Much less success has been attained up to now in understanding the mechanism of dielectric losses, in particular, in the uhf range, and especially with deep cooling of the non-linear crystals. Information concerning losses in strontium titanate is relatively complete, although in this case a number of fundamental problems remain. These include problems related to the effect of a structural phase transition at 110°K, volume charge, and nearelectrode phenomena on the losses. Losses in potassium tantalate have not been studied adequately. It is necessary to study experimentally the frequency and temperature dependences of losses in KTaO₃ at least in the range 1–40 GHz with cooling to 4.2°K and lower. Comparison of the properties of KTaO₃ and SrTiO₃ crystals can greatly improve our understanding of the mechanisms for low-temperature dielectric losses in ferroelectrics.The problem of parametric interactions in nonlinear systems based on low-temperature ferroelectrics is solved simultaneously with the problem of losses because, as noted in Section 3, excess losses in these crystals are the main obstacle to creating efficient parametric uhf systems operating in the continuous regime.Deceased.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 6–27, August, 1981.     

Effect of Bi substitution on the magnetic and dielectric properties of epitaxially grown BaFe0.3Zr0.7O3−δ thin films on SrTiO3 substrates

The structural, dielectric and magnetic properties of single crystalline Ba_1−xBi_xFe_0.3Zr_0.7O_3−δ (x=0.0-0.29) thin films have been studied. The pseudotetragonal epitaxial thin films were obtained by pulsed laser-beam deposition (PLD) on (0 0 1) SrTiO₃ (STO) single-crystal substrates. The Bi substitution for the Ba ions up to an extent of x=0.18 caused a slight improvement in the leakage current properties, as well as an enhancement of the apparent dielectric constant. The saturation magnetization of the films was significantly decreased following Bi substitution. These changes were thought to be related to the increase in oxygen deficiencies in the films. The effect of the Bi substitution on the dielectric and magnetic properties was analyzed in conjunction with the change in valence value of the Fe ions.     

High-quality epitaxial LaNiO3 thin films on SrTiO3(100) and LaAlO3(100)

LaNiO₃ thin films have been deposited by pulsed laser deposition on SrTiO₃(100) and LaAlO₃(100) substrates. The processing conditions have been investigated in order to optimize electrical resistivity, crystal quality, and surface morphology. Excellent properties are achieved at moderate substrate temperature and relatively low oxygen pressure, without the need for annealing. Thickness exerts an important influence on electrical transport, as the electrical resistivity increases quickly in films thicker than a few tens of nanometer. The surface of the films on LaAlO₃ is very flat in all the studied thickness range, but the films on SrTiO₃ develop a pattern of boundaries and even cracks as the thickness is higher. Below the critical thickness, high-quality epitaxial films with very smooth surface and low electrical resistivity are obtained under the optimum conditions of substrate temperature and oxygen pressure. The optimum processing conditions are different depending on the substrate, and control is especially critical in films deposited on SrTiO₃.