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双层石墨烯（BLG）的层自由度为调控其性质提供了新的维度，对其层间进行掺杂修饰，是调控其层间耦合作用及电子结构的有效手段。本文基于密度泛函理论的第一性原理计算方法，系统探究了官能团-OH、-CO、-CHO及-COOH插入BLG层间后，对BLG结构稳定性与电子特性的调控规律及作用机制。计算分析表明，-OH和-CHO在层间插入BLG更稳定，界面结合能更低，-CO和-COOH插入后则使BLG的稳定性变差。BLG的费米能级因官能团插入发生不同程度偏移，当-OH或-COOH插入后，费米能级向低能级移动，电子占据的最高能级降低；当-CO或-CHO插入后，费米能级向高能级移动，更多电子被激发至较高能级，使电子填充到更高能级。官能团使BLG的能带结构显著变化，原有的抛物线型能带形态受干扰，能带分布更趋复杂，线条的走向与交叉特征改变。分态密度（PDOS）和电荷密度差分计算结果显示，官能团与BLG之间存在轨道杂化及电荷转移，四种官能团均与BLG的碳原子形成共价键，表现为化学吸附特征，且不同官能团的电荷转移程度和对电荷密度的扰动存在显著差异。研究成果将为BLG基电子器件的设计与开发提供一定的理论支撑。Among the graphene family, bilayer graphene (BLG) exhibits more diverse electronic structures and higher tunability than monolayer graphene due to its unique interlayer coupling effect, emerging as a crucial branch in functionalization research. By utilizing its interlayer as an embedding channel, BLG avoids impairing graphene's intrinsic conductivity-a common issue with surface modification. Furthermore, the interlayer coupling allows for synergistic engineering of its electronic structure, yielding performance superior to that of monolayer graphene. Therefore, the interface of BLG represents a potential functionalization site. Based on the aforementioned research status and issues, all calculations in this study are performed using density functional theory (DFT) via the Vienna Ab-initio Simulation Package (VASP). To accurately describe the van der Waals (vdW) interactions (π-π stacking) between the layers of AB-stacked BLG, the DFT-D3 method is employed for vdW correction to investigate the influence of functional groups on BLG electrical properties. This study focuses on four functional groups (-OH, -CO, -CHO, and -COOH), whose contained O and H atoms can readily form chemical bonds with the carbon atoms in BLG. Through interlayer modification, the interactions between these functional groups and the carbon atoms are analyzed to realize the regulation of interlayer coupling and electronic structure characteristics of BLG. The insertion of -OH and -CHO into the interlayer of BLG results in higher stability and lower interfacial binding energy, whereas the insertion of -CO and -COOH leads to reduced stability. The Fermi level of BLG shifts to varying degrees upon the insertion of functional groups. Specifically, the insertion of -OH or -COOH causes the Fermi level to shift toward lower energy levels, reducing the highest occupied energy level. In contrast, the insertion of -CO or -CHO shifts the Fermi level toward higher energy levels, exciting more electrons to higher energy states and resulting in electron filling at elevated energy levels. The band structure of BLG undergoes significant modifications due to the insertion of functional groups. The original parabolic band dispersion is disrupted, and the band distribution becomes more complex, with altered line trajectories and crossing characteristics. Partial density of states (PDOS) and charge density difference calculations reveal orbital hybridization and charge transfer between the functional groups and BLG. All four functional groups form covalent bonds with the carbon atoms of BLG, exhibiting characteristics of chemical adsorption. Moreover, the extent of charge transfer and the perturbation of charge density vary significantly among the different functional groups. This study aims to elucidate the regulatory mechanisms and underlying principles of functional groups, providing a theoretical basis for designing BLG-based electronic materials with specific functionalities, while also enriching the research framework of interlayer functionalization in two-dimensional layered materials.
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Keywords:
- First-principles calculation /
- Bilayer graphene (BLG) /
- Functional group /
- Electronic structure /
- Charge transfer
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