m-DABDT金属有机骨架电子性质和应变调控效应的第一性原理研究  

First-principles study on electronic properties and strain regulation effects of m-DABDT metal-organic frameworks

作　　者：刘金宝 结文·乃比 崔恩豪 姚晓龙 LIU Jin-Bao;NABI Jawhar;CUI En-Hao;YAO Xiao-Long(School of Physical Science and Technology,Xinjiang Key Laboratory of Solid-State Physics and Devices,Xinjiang University,Urumqi 830017,China)

机构地区：[1]新疆大学物理科学与技术学院新疆固态物理与器件自治区重点实验室,乌鲁木齐830017

出　　处：《原子与分子物理学报》2025年第2期124-134,共11页Journal of Atomic and Molecular Physics

基　　金：新疆维吾尔自治区自然科学基金(2022D01C689);新疆大学博士启动基金(620320033)。

摘　　要：金属有机骨架材料具有低密度,高孔隙率和充分暴露的活性位点等结构特点,在光电探测、分子识别和分离以及催化等等领域具有良好的应用前景.合理地选择金属中心是新型金属有机骨架材料设计及性能调控的有效策略.本文利用基于密度泛函理论的第一性原理计算方法,研究了五种不同金属中心的一维链状金属有机骨架m-2,5-二氨基-1,4-苯二硫醇(DABDT)(m=Fe,Co,Ni,Cu,Zn)的电子性质.计算结果表明:考虑自旋极化条件下的HSE06杂化泛函计算的带隙值与实验值最为符合;随着金属中心d轨道占据数增加,能带结构呈现直接-间接-直接带隙的转变过程;当金属中心为Ni和Zn时,应变可诱导m-DABDT发生直接-间接带隙转变且带隙呈单调变化,同时其电子迁移率均大于空穴迁移率;当金属中心为Fe时,外加应变下m-DABDT保持直接带隙且带隙呈非单调变化,同时其空穴迁移率大于电子迁移率.这些研究结果揭示了m-DABDT金属有机骨架电子性质的调控机制,为光电器件的设计提供理论指导.Metal-organic Frameworks(MOFs)have the structural characteristics of low density,high porosity and fully exposed active sites,and thus possessing broad application prospects in the fields of photoelectric detection,molecular recognition/separation and catalysis.Reasonable selection of metal center is an effective strategy for the design and property modulation of novel MOF materials.The electronic properties of one-dimensional(1D)chain-type MOFs m-2,5-diamino-1,4-benzenedithiol(DABDT)(m=Fe,Co,Ni,Cu,Zn)with five different metal centers have been investigated using a first-principles calculation method based on density functional theory(DFT).The results show that the band gaps calculated by HSE06 hybrid functional considering spin polarization are in good agreement with the experimental values.As the occupation number of metal center’s d orbital increasing,the band structure presents a direct-indirect-direct band gap transition process.When the metal centers are Ni and Zn,the direct-indirect band gap transition is induced by strain,and the band gap changes monotonically.Meanwhile,the electron’s mobilities of m-DABDT are larger than their hole’s mobilities.When the metal center is Fe,m-DABDT maintains a direct band gap and the band gap changes non-monotonically under the applied strain.Besides,the hole’s mobility is greater than the electron’s mobility.These results reveal the regulation mechanism of the electronic properties of m-DABDT MOFs and provide theoretical guidance for the design of optoelectronic devices.

关 键 词：金属有机骨架 电子性质 应变调控 金属中心 第一性原理 

分 类 号：O472[理学—半导体物理]