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随着可穿戴电子产品要求提升，无毒的有机钙钛矿铁电体成为潜在候选材料.本工作应用第一性原理计算系统研究了无铅有机钙钛矿A-NH4-(PF6)3(A=MDABCO, CNDABCO, ODABCO, NODABCO, SHDABCO)的电子态密度、自发极化、弹性特性和压电效应.通过分子动力学和结合能计算发现，有机钙钛矿在室温下具有稳定性且预测其在实验上易于合成.对电子态密度研究发现，A-NH4-(PF6)3的价带主要来自F元素的贡献，价带顶和导带底分别来自取代基团中的元素和N元素的贡献，因此有利于电子空穴对的分离.依据Born稳定性判据，有机钙钛矿具有稳定的机械性质.除此之外，A位有机阳离子的取代基团可以改变材料中氢键的数量，对总铁电极化的贡献有着明显影响.最后通过压电性能计算，揭示了有机钙钛矿具有良好的压电效果，该效应源于材料引入的有机阳离子增加的材料的柔性.计算结果为后续实验提供了理论基础.Organic ferroelectrics are desirable for the application in the field of wearable electronics due to their eco-friendly process-ability, mechanical flexibility, low processing temperatures, and lightweight. In this work, we used five organic groups as substitution for organic cation and studied the effects of organic cations on the structural stability, electronic structure, mechanical properties and spontaneous polarization of metal-free perovskite A-NH4-(PF6)3(A=MDABCO, CNDABCO, ODABCO, NODABCO, SHDABCO) through first-principles calculations. Firstly, the stability of the five materials was calculated by molecular dynamics simulations, and the energy of all systems is negative and stable after 500 fs, which demonstrated the stability of the five materials in 300 K. The electronic structure calculation shows that the organic perovskite materials have wide band gap with the value of about 7.05 eV. The VBM(Valence Band Maximum) and CBM (Conduction Band Minimum) are occupied by different elements, which is conductive to the separation of electrons and holes. We found that organic cations have an important contribution to the spontaneous polarization of materials, with the contributing over 50%. The presence of hydrogen atoms in the substituting groups (MDABCO, ODABCO) enhances the hydrogen bond interaction between the organic cations and PF6-and increases the displacement of the organic cation, resulting in an increase in the contribution of the polarization of the organic cation to the total polarization. In addition, we observed large piezoelectric strain components, the calculated d33 is 36.5 pC/N for CNDABCO-NH4-(PF6)3, 32.3pC/N for SHNDABCO-NH4-(PF6)3, which is larger than the known d33 of MDABCO-NH4-I3(14pC/N). The calculated d14 is 57.5 pC/N for ODABCO-NH4-(PF6)3, 27.5 pC/N for NODABCO-NH4-(PF6)3. These components are at a high level among known organic perovskite materials and comparable to many known inorganic crystals. The large value of d14 is found to be closely related with the large value of elastic compliance tensor s44. The analysis of Young’s modulus and bulk’s modulus found that these organic perovskite materials have good ductility. These results show that these organic materials are excellent candidates for future environmentally friendly piezoelectric materials.
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Keywords:
- Metal-free perovskites /
- first-principles calculations /
- piezoelectricity /
- spontaneous polarization
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