β石墨炔衍生物结构稳定性及电子结构的密度泛函理论研究

石墨炔衍生物比石墨烯具有更多样化的原子结构,因而具有潜在的更丰富的电子结构.通过第一性原理密度泛函理论研究方法系统研究了β石墨炔衍生物的结构稳定性、原子构型和电子结构.本文计算的β石墨炔衍生物系列体系由六边形碳环(各边原子数N=1—10)通过顶点相连而成.对结构与能量的计算分析表明:当N为偶数时,β石墨炔拥有单、三键交替的C—C键结构,其能量比N为奇数时,拥有连续C=C双键的石墨炔衍生物更稳定.计算的能带结构和态密度显示:根据碳环各边原子个数N的奇偶性不同,β石墨炔可呈现金属性(N为奇数时)或半导体特性(N为偶数时).该奇偶依赖的原子构型和电学性质是由Jahn-Teller畸变效应导致,与碳环各边原子碳链的实际长度无关.计算发现部分半导体β石墨炔(N=2,6,10)呈现狄拉克锥能带特征,其带隙约10 meV,且具有0.255×10~6—0.414×10~6m/s的高电子速度,约为石墨烯电子速度的30%—50%.本密度泛函理论研究表明,将sp杂化碳原子引入石墨烯六边形碳环的边上,可通过控制六边形各边原子个数的奇偶性调制其金属和半导体电子特性或狄拉克锥的形成,为免掺杂和缺陷调控纳米碳材料的电学性质和设计碳基纳米电子器件提供了理论依据.

Density functional theory study of structure stability and electronic structures of β graphyne derivatives

Due to the diversified atomic structures and electronic properties, two-dimensional monolayer nanocarbon materials (graphyne or graphdiyne) composed of sp and sp² hybridization C atoms have received the widespread attention in recent years. The fundamental questions include how the sp orbital hybridization affects the electronic structure of graphyne. In order to investigate the structure dependent electronic structures of graphyne, the energetic stabilities and electronic structures of β-graphyne and its derivatives (β-N) with N carbon atoms on each edge of the hexagons are investigated by density functional theory (DFT) calculations in this work. In our DFT calculations we adopt generalized gradient approximation of Perdew, Burke, and Ernzerhof (GGA-PBE) using the CASTEP module implemented in Materials Studio. The studied β-Ns consist of hexagon carbon rings connected by vertexes whose edges have various numbers of carbon atoms N= 1-10. The structure and energy analyses show that β-Ns with even-numbered carbon chains have alternating single and triple C-C bonds, energetically more stable than those with odd-numbered carbon chains possessing continuous C-C double bonds. The calculated electronic structures indicate that β-Ns can be either metallic (odd N) or semiconductive (even N), depending on the parity of number of hexagon edge atoms regardless of the edge length due to Jahn-Teller distortion effect. Some semiconducting β-graphyne derivatives (β-N, N= 2, 6, 10) are found to possess Dirac cones (DC) with small direct band gaps 10 meV and large electron velocities 0.255×10⁶-0.414×10⁶ m/s, ～30%-50% of that of graphene. We find that Dirac cones also appear in β-3 and β-4 when we shorten the double bonds and elongate the triple bonds in β-3 and β-4 respectively. These results show that the bond length change will affect the characteristics of band structure and suggests that the band structure characteristics may be influenced by Peierls distortion in a two-dimensional system. Our DFT studies indicate that introducing sp carbon atoms into the hexagon edges of graphene opens the way to switching between metallic and semiconductor/DC electronic structures via tuning the parity of the number of hexagon edge atoms without doping and defects in nanocarbon materials and nanoelectronic devices.