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<p>BaTi<sub>1−<i>x</i></sub>Ca<sub><i>x</i></sub>O<sub>3</sub> (BTC100<i>x</i>, <i>x</i> = 0.01, 0.02, 0.03, 0.04) nano-powders were synthesized via the oxalate chemical coprecipitation method, and sintered into ceramics by solid-state sintering in a reducing atmosphere. The effects of Ca ion doping on the phase structure, dielectric properties, and insulating characteristics of BTC100<i>x</i> ceramics produced in a reducing atmosphere were systematically investigated. The typical tetragonal phase structure is observed in ceramics when <i>x</i> ≤ 0.01, however, the tetragonal phase of the ceramics gradually disappears when <i>x</i> ≥ 0.02, and the (200) diffraction peak shifts to lower angles. As a comparison, Ba<sub>0.96</sub>Ca<sub>0.04</sub>TiO<sub>3</sub> (BC4T) ceramic was prepared under identical conditions and contrasted with BTC4 ceramic by XRD, Raman spectroscopy, and dielectric temperature characteristics, effectively proving that Ca<sup>2+</sup> ions entered the B-site of BaTiO<sub>3</sub>(BT) ceramics to replace Ti<sup>4+</sup> ions. The dielectric temperature spectrum shows that the dielectric temperature stability of BTC100<i>x</i> ceramics is effectively improved by Ca doping. Notably, when <i>x</i> = 0.04, the temperature stability satisfied the criteria for EIA X5S specifications (−55&#xa0;°C ~ + 85&#xa0;°C, ΔC/C<sub>25&#xa0;°C</sub> ≤ ± 22%) and a high insulation resistivity of 1.27 × 10<sup>11</sup>Ω&#xa0;cm was observed at same time. The anti-reduction mechanism of BTC100<i>x</i> ceramics was explored by XPS and TSDC techniques, indicating that the exceptional antigenic properties were attributed to the formation of defect dipoles [<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10854_2025_14690_Article_IEq1.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="79" /> </InlineMediaObject> <EquationSource Format="TEX">\({Ca}_{Ti}^{{\prime}{\prime}}-{V}_{O}^{..}\)</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msubsup> <mrow> <mi mathvariant="italic">Ca</mi> </mrow> <mrow> <mi mathvariant="italic">Ti</mi> </mrow> <mrow> <mo>′</mo> <mo>′</mo> </mrow> </msubsup> <mo>-</mo> <msubsup> <mi>V</mi> <mrow> <mi>O</mi> </mrow> <mrow> <mo>.</mo> <mo>.</mo> </mrow> </msubsup> </mrow> </math></EquationSource> </InlineEquation>], which inhibited the reduction of Ti<sup>4+</sup> to Ti<sup>3+</sup>. Outstanding dielectric temperature stability and anti-reduction properties make BTC100<i>x</i> ceramic materials have potential applications in BME-MLCC devices.</p>

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The structure, dielectric characteristics and anti-reduction mechanism of B-site Ca-doped nano-BaTiO3 ceramics for BME-MLCC application

  • 期刊论文

  • 发表日期：

    2025年4月11日

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  • Jianjian Wu,
  • Qinghu Guo,
  • Haizhou Liu,
  • Zhonghua Yao,
  • Hanxing Liu,
  • Hua Hao

摘要

BaTi1−xCaxO3 (BTC100x, x = 0.01, 0.02, 0.03, 0.04) nano-powders were synthesized via the oxalate chemical coprecipitation method, and sintered into ceramics by solid-state sintering in a reducing atmosphere. The effects of Ca ion doping on the phase structure, dielectric properties, and insulating characteristics of BTC100x ceramics produced in a reducing atmosphere were systematically investigated. The typical tetragonal phase structure is observed in ceramics when x ≤ 0.01, however, the tetragonal phase of the ceramics gradually disappears when x ≥ 0.02, and the (200) diffraction peak shifts to lower angles. As a comparison, Ba0.96Ca0.04TiO3 (BC4T) ceramic was prepared under identical conditions and contrasted with BTC4 ceramic by XRD, Raman spectroscopy, and dielectric temperature characteristics, effectively proving that Ca2+ ions entered the B-site of BaTiO3(BT) ceramics to replace Ti4+ ions. The dielectric temperature spectrum shows that the dielectric temperature stability of BTC100x ceramics is effectively improved by Ca doping. Notably, when x = 0.04, the temperature stability satisfied the criteria for EIA X5S specifications (−55 °C ~ + 85 °C, ΔC/C25 °C ≤ ± 22%) and a high insulation resistivity of 1.27 × 1011Ω cm was observed at same time. The anti-reduction mechanism of BTC100x ceramics was explored by XPS and TSDC techniques, indicating that the exceptional antigenic properties were attributed to the formation of defect dipoles [ \({Ca}_{Ti}^{{\prime}{\prime}}-{V}_{O}^{..}\) Ca Ti ′ ′ - V O . . ], which inhibited the reduction of Ti4+ to Ti3+. Outstanding dielectric temperature stability and anti-reduction properties make BTC100x ceramic materials have potential applications in BME-MLCC devices.