石墨烯制备及其缺陷研究
摘要
石墨烯的出现在科学界激起了巨大波澜,这在于它严格的二维结构具有许多极佳的物理性质,蕴涵着许多潜在的应用。石墨烯是一种零带隙的二维材料,其中的碳原子通过SP2轨道杂化构成了二维蜂窝状结构。石墨烯具有良好的导热性、高强度和超大比表面积,这些良好的物理性质使得其在能量储存、电子器件、复合材料及传感器等方面有着广阔的应用前景。
本文首先利用氧化还原法制备石墨烯,研究其制备工艺及成核机理,在此基础上通过密度泛函理论的第一性原理方法,首先研究了三种缺陷(单空位缺陷、双空位缺陷和Stone-Wales缺陷)对石墨烯电子结构的影响；其次探索了Fe掺杂对石墨烯电学、磁学属性的影响。论文的主要工作及获得的主要结论如下：
(1)利用氧化还原法成功制备出石墨烯,在氧化还原法制备石墨烯的过程中,由于氧化石墨被还原后其结构不可能被完全恢复到单层石墨原来的结构状态,因此,所制备的石墨烯结构与理想的单层石墨结构还有一定的差别,石墨烯中会有一定的缺陷存在,包括单、双空位缺陷和Stone-Wales缺陷。
(2)单、双空位缺陷和Stone-Wales缺陷都可以改变石墨烯的电子结构,它们的引入使石墨烯的禁带得到扩展不再为零带隙,而且不同的缺陷对石墨烯的禁带影响不同,单空位缺陷、双空位缺陷和Stone-Wales缺陷石墨烯的禁带宽度分别为1.591ev、1.207ev和0.637eV。
(3)本征石墨烯为零带隙,是非磁性材料,但是对石墨烯进行Fe掺杂后既可以改变其禁带宽度,又能实现对石墨烯磁性的改造。Fe掺杂后石墨烯禁带宽度为1.51ev,且有磁性产生。
Due to the magnificent physical properties and potential applications, Graphene stir up a great wave in the community. Graphene is a two-dimension material with zero gaps, whose carbon atoms make up two-dimension cellular structure by SP2 orbitalhybridization. Graphene possesses good thermal conductivity, high strength and extra large specific surface area, which lead the wide application prospects in energy storage, electron device, composite materials and sensors.
In this work, graphene were prepared by oxidoreduction process, and the mechanism of nucleation was investigated. Beside, the effect of monovacancy defect, bivacancy defect and Stone-Wales defect on the electronic structure of graphene, and the effect of Fe-doping on the electricity and magnetic properties of graphene were calculated by first-principles methods based DFT (Density Functional Theory). The main work and conclusions are following:
(1) Graphene were successfully fabricated by oxidoreduction process. Owing to the limitation of prepare process, as-prepared graphene have some defects, including monovacancy defect, bivacancy defect and Stone-Wales defect.
(2) Monovacancy defect, bivacancy defect and Stone-Wales defect can affect the electronic structure of graphene, and have different influence on the gap of graphene. The gaps of graphene with monovacancy defect, bivacancy defect and Stone-Wales defect are 1.591 eV,1.207eV and 0.637eV, respectively.
(3) Intrinsic graphene is a material with zero gap and nonmagnetic. Fe-doping can change both the gap and the magnetic properties of graphene. Fe-doped graphene owns the gap of 1.51 eV and existence of magnetism.
本文首先利用氧化还原法制备石墨烯,研究其制备工艺及成核机理,在此基础上通过密度泛函理论的第一性原理方法,首先研究了三种缺陷(单空位缺陷、双空位缺陷和Stone-Wales缺陷)对石墨烯电子结构的影响；其次探索了Fe掺杂对石墨烯电学、磁学属性的影响。论文的主要工作及获得的主要结论如下：
(1)利用氧化还原法成功制备出石墨烯,在氧化还原法制备石墨烯的过程中,由于氧化石墨被还原后其结构不可能被完全恢复到单层石墨原来的结构状态,因此,所制备的石墨烯结构与理想的单层石墨结构还有一定的差别,石墨烯中会有一定的缺陷存在,包括单、双空位缺陷和Stone-Wales缺陷。
(2)单、双空位缺陷和Stone-Wales缺陷都可以改变石墨烯的电子结构,它们的引入使石墨烯的禁带得到扩展不再为零带隙,而且不同的缺陷对石墨烯的禁带影响不同,单空位缺陷、双空位缺陷和Stone-Wales缺陷石墨烯的禁带宽度分别为1.591ev、1.207ev和0.637eV。
(3)本征石墨烯为零带隙,是非磁性材料,但是对石墨烯进行Fe掺杂后既可以改变其禁带宽度,又能实现对石墨烯磁性的改造。Fe掺杂后石墨烯禁带宽度为1.51ev,且有磁性产生。
Due to the magnificent physical properties and potential applications, Graphene stir up a great wave in the community. Graphene is a two-dimension material with zero gaps, whose carbon atoms make up two-dimension cellular structure by SP2 orbitalhybridization. Graphene possesses good thermal conductivity, high strength and extra large specific surface area, which lead the wide application prospects in energy storage, electron device, composite materials and sensors.
In this work, graphene were prepared by oxidoreduction process, and the mechanism of nucleation was investigated. Beside, the effect of monovacancy defect, bivacancy defect and Stone-Wales defect on the electronic structure of graphene, and the effect of Fe-doping on the electricity and magnetic properties of graphene were calculated by first-principles methods based DFT (Density Functional Theory). The main work and conclusions are following:
(1) Graphene were successfully fabricated by oxidoreduction process. Owing to the limitation of prepare process, as-prepared graphene have some defects, including monovacancy defect, bivacancy defect and Stone-Wales defect.
(2) Monovacancy defect, bivacancy defect and Stone-Wales defect can affect the electronic structure of graphene, and have different influence on the gap of graphene. The gaps of graphene with monovacancy defect, bivacancy defect and Stone-Wales defect are 1.591 eV,1.207eV and 0.637eV, respectively.
(3) Intrinsic graphene is a material with zero gap and nonmagnetic. Fe-doping can change both the gap and the magnetic properties of graphene. Fe-doped graphene owns the gap of 1.51 eV and existence of magnetism.
引文
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