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<p>In this study, we present a novel and chemically symmetric form of nanoscale rectification arising at the interfacial contact between yttria stabilized zirconia (YSZ) nanoparticles of identical composition but deliberately differentiated crystallite sizes. Using 8 mol% Y<sub>2</sub>O<sub>3</sub>-doped YSZ synthesized via co-precipitation and thermally annealed at 400–800°C, we obtained crystallite sizes from ~ 7.5 to ~ 16 nm while retaining the cubic fluorite phase, compositional homogeneity, and controlled microstructural evolution, confirmed by TEM, XRD, and Raman spectroscopy. Electrical properties of these heterojunctions were probed via current–voltage measurements under relative humidity (RH) of 65%, 75%, and 85% in H<sub>2</sub>O- and D<sub>2</sub>O-enriched atmospheres. Junctions with size disparity exhibited pronounced rectification, increasing with humidity. Replacement of H<sub>2</sub>O with D<sub>2</sub>O consistently reduced current, indicating hydrated proton dominance in interfacial ionic transport. A symmetric 400 °C–400 °C junction served as a control, confirming that rectification arose from crystallite size differences rather than compositional variation. Dynamic electrical measurements, including I–V hysteresis cycling and chronoamperometry, revealed humidity-dependent memory effects and relaxation dynamics. The findings establish microstructural heterogeneity and interfacial hydration as powerful, intrinsic drivers of rectification in compositionally homogeneous oxides. Our findings in this study open new directions for the design of solid state nanoionic rectifiers, proton conducting interfaces, and memory enabled oxide electronics, where ionic transport can be precisely modulated by environmental conditions and nanoscale structural control.</p>

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Investigation into the H–D kinetic isotope effect (KIE) on the humidity sensing characteristics of YSZ

  • 期刊论文

  • 发表日期：

    2026年3月2日

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  • Mahmoud Ibrahim,
  • Heba A. Esawii,
  • Zh. V. Mezentseva,
  • Oleksandr Sergiyovich Doroshkevich,
  • Roman Laptev

摘要

In this study, we present a novel and chemically symmetric form of nanoscale rectification arising at the interfacial contact between yttria stabilized zirconia (YSZ) nanoparticles of identical composition but deliberately differentiated crystallite sizes. Using 8 mol% Y2O3-doped YSZ synthesized via co-precipitation and thermally annealed at 400–800°C, we obtained crystallite sizes from ~ 7.5 to ~ 16 nm while retaining the cubic fluorite phase, compositional homogeneity, and controlled microstructural evolution, confirmed by TEM, XRD, and Raman spectroscopy. Electrical properties of these heterojunctions were probed via current–voltage measurements under relative humidity (RH) of 65%, 75%, and 85% in H2O- and D2O-enriched atmospheres. Junctions with size disparity exhibited pronounced rectification, increasing with humidity. Replacement of H2O with D2O consistently reduced current, indicating hydrated proton dominance in interfacial ionic transport. A symmetric 400 °C–400 °C junction served as a control, confirming that rectification arose from crystallite size differences rather than compositional variation. Dynamic electrical measurements, including I–V hysteresis cycling and chronoamperometry, revealed humidity-dependent memory effects and relaxation dynamics. The findings establish microstructural heterogeneity and interfacial hydration as powerful, intrinsic drivers of rectification in compositionally homogeneous oxides. Our findings in this study open new directions for the design of solid state nanoionic rectifiers, proton conducting interfaces, and memory enabled oxide electronics, where ionic transport can be precisely modulated by environmental conditions and nanoscale structural control.