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Microstructure and dielectric properties of La2O3 doped Ti-rich barium strontium titanate ceramics for capacitor applications

Zhang C., Chen F., Ling Z., Jian G., Li Y.

Materials Science Poland

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2017

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Vol. 35, No. 4

806--815

EN

Microstructure and dielectric properties of La2O3 doped Ti-rich barium strontium titanate ceramics, prepared by solid state method, were investigated with non-stoichiometric level and various La2O3 content, using XRD, SEM and LCR measuring system. With an increase of non-stoichiometric level, the unit cell volumes of perovskite lattices for the single phase Ti-rich barium strontium titanate ceramics increased due to the decreasing A site vacancy concentration V″A. The unit cell volume increased and then decreased slightly with the increasing La2O3 content. Relatively high non-stoichiometric level and high La2O3 content in Ti-rich barium strontium titanate ceramics contributed to the decreased average grain size as well as fine grain size distribution, which correspondingly improved the temperature stability of the relative dielectric constant. The relative dielectric constant єrRT, dielectric loss tanδRT and the maximum relative dielectric constant єrmax decreased and then increased with the increasing non-stoichiometric level. With the increase of La2O3 doping content, the relative dielectric constant єrRT increased initially and then decreased. The maximum relative dielectric constant єrmax can be increased by applying low doping content of La2O3 in Ti-rich barium strontium titanate ceramics due to the increased spontaneous polarization.

2

Synthesis and characterization of nanocrystalline barium strontium titanate powder by a modified sol-gel processing

Araghi A. M. E., Shaban N., Bahar M.

Materials Science Poland

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2016

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Vol. 34, No. 1

63--68

EN

In this research work, nanocrystalline BST (Ba0.6Sr0.4 TiO3) powders were synthesized through a modified sol-gel process, using barium acetate, strontium acetate and titanium isopropoxide as the precursors. In this process, stoichiometric proportions of barium acetate and strontium acetate were dissolved in acetic acid and titanium (IV) isopropoxide was added to form BST gel. The as-formed gel was dried at 200 °C and then calcined in the temperature range of 600 to 850 °C for crystallization. The samples were characterized by infrared spectroscopy method (FT-IR), X-ray diffraction technique (XRD) and field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectroscopy. EDS analysis of these samples confirmed the formation of the final phase with the special stoichiometry. The formation of a cubic perovskite crystalline phase with nanoscale dimension was detected using the mentioned techniques. The results showed that the obtained crystallite sizes were 33 and 37 nm for BST powder calcined at 750 and 850 °C, respectively.

3

Tunable ceramic-polymer composites for electronic applications

Pietrzak E., Pawlikowska E., Godziszewski K., Yashchyshyn Y., Szafran M.

Composites Theory and Practice

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2015

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R. 15, nr 1

54--57

EN

The ceramic-polymer composites presented in the paper have unusual properties. These materials can operate in a wide range of electromagnetic spectrum and consequently they can be potentially used in imaging techniques, chemical characterization, security systems, quality control and very high data rate communication systems. Microwave applications are widely understood as antennas and radiocommunication devices. Materials used to produce equipment operating at high frequencies, even subterahertz, must be subjected to restrictive verification. The most commonly used materials in radio technology are ferroelectrics. They are characterized by a high value of dielectric permeability. A typical example of ferroelectric material used and widely known is barium strontium titanate (abbr. BST), which is applied in microwave technology. Barium strontium titanate was prepared using solid-state synthesis process. The materials used in the fabrication were ceramic powders: BaCO3, SrCO3 and TiO2. Thanks to the combination of an elastic polymer and ceramic powder with ferroelectric properties, it is possible to use such a material in devices operating at a very high frequency. The commercial materials used in the research allow one to produce composites by the tape casting method and obtain antennas. Ferroelectric ceramic-polymer tapes based on doped and undoped ceramic powder with different BST stoichiometrics have been prepared. The tunability of samples prepared of pure and doped Ba0.65Sr0.35TiO3, Ba0.58Sr0.42TiO3 and Ba0.51Sr0.49TiO3 was measured. The relationship between the stoichiometry, or doped and undoped powder has been also found. It was observed that a higher ratio of Ba to Sr caused an increase in tunability values. Moreover, the addition of Ni2O3 to ceramic powder positively effected the tunability parameter.

PL

Kompozyty ceramiczno-polimerowe przedstawione w niniejszej pracy charakteryzują się niezwykłymi właściwościami. Materiały te posiadają zdolność pracy w szerokim spektrum elektromagnetycznym, dzięki czemu mogą być wykorzystywane w obrazowaniu materiałów, analizie chemicznej, systemach ochrony, kontroli jakości oraz w telekomunikacji intersatelitarnej. Zastosowania mikrofalowe są szeroko rozumianymi antenami oraz urządzeniami radiokomunikacyjnymi. Materiały wykorzystywane do otrzymywania urządzeń pracujących w wysokich częstotliwościach sub-THz są poddawane restrykcyjnej weryfikacji. Najbardziej powszechnymi materiałami używanymi w technologii radiowej są ferroelektryki. Charakteryzują się one bardzo wysoką wartością przenikalności dielektrycznej. Typowym przykładem materiału ferroelektrycznego jest powszechnie znany tytanian barowo-strontowy (BST). Proszek stosowany do badań syntezowany był w fazie stałej z następujących substratów: BaCO3, SrCO3 i TiO2. Charakterystyczne właściwości BST powodują, że stał się on kluczowym komponentem ceramicznej masy lejnej, która umożliwia, za pomocą metody tape casting, otrzymanie cienkich i elastycznych folii kompozytowych. Ferroelektryczne ceramiczno-polimerowe folie bazowały na czystych oraz domieszkowanych proszkach BST o różnym stosunku baru do strontu. Pomiary przestrajalności przeprowadzono dla proszków Ba0.65Sr0.35TiO3 i Ba0.58Sr0.42TiO3 z dodatkiem Ni2O3 oraz bez dodatku. Zaobserwowano zależność stechiometrii proszków oraz domieszki tlenku niklu na przestrajalność kształtek. Im większa zawartość Ba do Sr, tym wyższe wartości przestrajalności. Z badań wynika również, że pozytywny wpływ na przestrajanie ma dodatek 5% mol Ni2O3.

4

Ceramic-polymer composites for microwave applications

Szafran M., Bogdańska B., Bobryk E., Jaszczyszyn E., Derzakowski K.

Composites Theory and Practice

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2012

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R. 12, nr 1

9-13

EN

Ceramic-polymer composites with ferroelectric properties provide significant opportunities in the design and manufacture of modern electronic materials whose functional characteristics are constantly being improved. Barium titanate (BT) and barium strontium titanate (BST) are known and widely used materials in electronics. The paper presents the results of research on a receiving ceramic-polymer composite with an as low as possible permittivity and loss tangent. As a ceramic fraction barium-strontium titanate (BST) with various dopants (Fe2O3, Ni2O3, La2O3, SnO2 and Y2O3) were tested and as an organic one - water dispersions of styrene-acrylic polymers. The influence of BST doped with metal oxides on the sintering process was observed. X-ray diffraction patterns were made for sintered powders while the Vickers hardness, relative density and volume shrinkage of sintered pellets were studied. The zeta potential as a function of pH for pure BST and doped with Ni2O3 were measured. BST doped with Ni2O3 had the best relative density and this powder was used for further research. For the aqueous tape casting method four water dispersions of polymers with different concentrations and structures as binders were tested. For these polymers heat flow as a function of temperature by differential scanning calorimetry (DSC) and the glass transition temperature were measured. Additionally, the concentration of water dispersion of the polymers was tested by the gravimetric method. For the obtained ceramic - polymer composites, the relative permittivity and loss tangent were measured at a 9 GHz frequency.

PL

Kompozyty ceramiczno-polimerowe o właściwościach ferroelektrycznych dają znaczne możliwości przy projektowaniu i wytwarzaniu nowoczesnych materiałów elektronicznych o nowych i wciąż udoskonalanych cechach użytkowych. Znanym od lat i powszechnie stosowanym materiałem w elektronice jest tytanian baru (BT) oraz tytanian barowo-strontowy (BST). Domieszkowanie BST tlenkami metali powoduje zmianę parametrów elektrycznych (np. przenikalności dielektrycznej, tangensa kąta strat) oraz fizycznych (twardości, zagęszczenia). W niniejszej pracy badano wpływ domieszek (Fe2O3, Ni2O3, La2O3, SnO2 i Y2O3) na proces spiekania BST w zakresie 1200÷1400°C. Przeprowadzono analizę rentgenograficzną otrzymanych proszków, a także zbadano mikrotwardość Vickersa, względne zagęszczenie spieków oraz ich skurczliwość objętościową. Wykonano pomiary potencjału zeta w funkcji pH dla czystego BST oraz domieszkowanego 2 i 8% mol Ni2O3. Na podstawie otrzymanych wyników wybrano proszek o najlepszym zagęszczeniu (BST + 5% mol Ni2O3) i dobrano spoiwo polimerowe oraz upłynniacz, aby otrzymać gęstwę odpowiednią do odlania folii metodą aqueous tape casting. Istotne było dobranie polimerów obniżających lub niewpływających znacząco na wartość względnej przenikalności dielektrycznej, ponieważ po procesie formowania folia nie była już spiekana. Badano wodne dyspersje polimerów styrenowo-akrylowych o różnych stężeniach, które wyznaczono metodą wagową. Wykonano pomiary zmiany strumienia ciepła w funkcji temperatury metodą skaningowej kalorymetrii różnicowej (DSC) i na podstawie tej zależności wyznaczono temperaturę zeszklenia analizowanych polimerów. Uzyskane kompozyty ceramiczno-polimerowe o różnych zawartościach proszku ceramicznego (60 i 55%) oraz różnych ilościach domieszek (2, 5 i 8% mol) poddano badaniom względnej przenikalności dielektrycznej oraz tangensa kąta strat przy częstotliwości 9 GHz.

5

Influence of antimony oxide on the dielectric properties of barium strontium titanate based ceramics

Zhang C., Qu Y.

Materials Science Poland

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2009

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Vol. 27, No. 2

443--452

EN

The dielectric properties of Sb2O3 doped (Ba0.992-xSrxDy0.008)TiO3.004ceramics fabricated by a solid state route with various Sb2O3 contents and Sr/Ba ratios were investigated. The XRD patterns confirm the samples to be multiphase compounds composed of perovskite major phase and Ba4Ti13O30, Ba6Ti17O40, Ti7O13 secondary phases. The average lattice constant indicates that Sb3+ ions initially occupy the A-sites and then enter the B-sites serving as acceptor dopants. The Curie temperature decreases as the Sb2O3 content increases and as the Sr/Ba ratio increases also. The thermal stability of the electric permittivity increases as the Sb2O3 concentration increases but decreases as the Sr/Ba ratio increases. The resistivity and ac standing voltage decrease as the Sr/Ba ratio decreases. The Sb2O3 doped (Ba0.992-xSrxDy0.008)TiO3.004 ceramics with high permittivity, low dielectric loss, high ac standing voltage and low temperature coefficient of capacitor are obtained for applications in environment friendly capacitors.

6

Diffused phase transition of polycrystalline (Ba0.80Sr0.20)TiO3

Kajtoch C., Bąk W., Gabryś M., Handke B., Starzyk F.

Archives of Materials Science and Engineering

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2009

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Vol. 39, nr 2

88-91

EN

Purpose: The purpose of this work was to determinate the influence of the 20% Sr substitutions (in sublattice A) on changes of the character of phase transition (PT) in comparison with pure barium titanate BaTiO3 (BT). Design/methodology/approach: Polycrystalline samples of (Ba0.80Sr0.20)TiO3 (BS20T) were prepared by calcinations method at temperature 1620 K. X-ray measurements were executed from 10 deg to 120 deg with the 0.008 deg step. Images of the morphology of the samples were taken by means of electron microscope Philips SEM 525M at room temperature. Dielectric measurements were performed with application of Quatro Cryosystem 4.0 Agilent Precision LRC meter HP4824A equipped with WinDETA 5.62 software Novocontrol. Measurements were taken under cooling with 2 K/min speed. Measuring electric field frequency was from the range 20 Hz - 1 MHz. Findings: The difference between the value of temperature of structural transition (cubic-tetragonal) equal 310K and the temperature Tm (the temperature of maximum of real part electric permittivity) equal 340 K was affirmed. It was affirmed, that 20% substitution of Sr ions changed the type of phase transition. The transition was strongly diffused (DPT). The polar character of this solid solution was also observed in a broad temperature range (in the paraelectric phase too). It is connected with the occurrence of polar regions (clusters). Research limitations/implications: The results can be used to describe changes of PT in the DPT solid solutions with ferroactive substitutions in sublattice A. Originality/value: Value of this work relies on the experimental examination of the dielectric properties of (Ba0.80Sr0.20)TiO3 (BS20T) solid solution. The temperature of the DPT was calculated. The low value of phase angle is connected with the existence of the polar regions.

7

The effect of spin coating rate on the microstructure, grain size, surface roughness and thickness of Ba0.6Sr0.4TiO3 thin film prepared by the sol-gel process

Dewi R., Baa'yah N. I., Talib I. A.

Materials Science Poland

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2007

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Vol. 25, No. 3

657--662

EN

The paper reports on the effect of spin coating rate during the sol-gel process on the microstructure, grain size, surface roughness and thickness of barium strontium titanate (Ba0.6Sr0.4TiO3) thin films. Variable coating rates do not influence the microstructure of the films. All films are polycrystalline and single phase, as was found from X-ray diffraction analysis. Changing the spin rates also does not influence the grain sizes of the films. All films have nanometer particle size ranging from 37.2 nm to 30.7 nm. However, roughness and thickness of the film depend on the spin coating rates. The highest spin rates produce the thinnest film with the roughest surface, while the lowest spin rate produced the thickest films with the smoothest surface.