论文标题
中性离子界面的极性CT晶体中有趣的休闲铁电性
Intriguing relaxor ferroelectricity in a polar CT crystal at the neutral-ionic interface
论文作者
论文摘要
我们研究了混合堆栈电荷转移晶体,N,N'-二甲基苯嗪-TCNQ(M $ _2 $ p-TCNQ),该晶体在室温下是极性的,并且在中性到离子界面(Ionicities $ρ\ρ\约0.5 $)。我们检测出宽松的铁电和不对称阳性阴性行为的典型介电特征。尽管通常将松弛剂铁电性归因于晶体中的疾病,但我们没有发现所研究晶体中结构性疾病的证据。为了阐明M $ _2 $ p-TCNQ的介电性能的起源,我们执行并行结构和光谱测量,与理论建模和量子力学计算有关。我们的合并工作指向高度极化的电子系统,该系统与晶格振动密切相结合。偏振反转的发现的指示表明,M $ _2 $ p分子的弯曲构象与几十个EV的相关能屏障的弯曲构象,与介电弛豫时间的Arrhenius拟合很大程度上一致。虽然极化主要是电子起源,但其可能的逆转意味着较慢的集体运动受到固态分子间相互作用的影响。
We investigated the mixed-stack charge-transfer crystal, N,N'-dimethylphenazine-TCNQ (M$_2$P-TCNQ), which is polar at room temperature and just at the neutral-to-ionic interface (ionicity $ρ\approx 0.5$). We detect the typical dielectric signature of a relaxor ferroelectric and an asymmetric positive-up-negative-down behavior. While relaxor ferroelectricity is usually ascribed to disorder in the crystal, we find no evidence for structural disorder in the investigated crystals. To elucidate the origin of M$_2$P-TCNQ's dielectric properties we perform parallel structural and spectroscopic measurements, associated with theoretical modeling and quantum-mechanical calculations. Our combined effort points to a highly polarizable electronic system that is strongly coupled to lattice vibrations. The found indications for polarization reversal imply flipping of the bent conformation of the M$_2$P molecule with an associated energy barrier of a few tens of an eV, broadly consistent with an Arrhenius fit of the dielectric relaxation times. While the polarization is mostly of electronic origin, its possible reversal implies slow collective motions that are affected by solid-state intermolecular interactions.