Cultrara Nicholas D, Arguilla Maxx Q, Jiang Shishi, Sun Chuanchuan, Scudder Michael R, Ross R Dominic, Goldberger Joshua E
Department of Chemistry and Biochemistry, Ohio State University, Columbus, Ohio, 43210-1340, United States of America.
Beilstein J Nanotechnol. 2017 Aug 9;8:1642-1648. doi: 10.3762/bjnano.8.164. eCollection 2017.
Germanane, a hydrogen-terminated graphane analogue of germanium has generated interest as a potential 2D electronic material. However, the incorporation and retention of extrinsic dopant atoms in the lattice, to tune the electronic properties, remains a significant challenge. Here, we show that the group-13 element Ga and the group-15 element As, can be successfully doped into a precursor CaGe phase, and remain intact in the lattice after the topotactic deintercalation, using HCl, to form GeH. After deintercalation, a maximum of 1.1% As and 2.3% Ga can be substituted into the germanium lattice. Electronic transport properties of single flakes show that incorporation of dopants leads to a reduction of resistance of more than three orders of magnitude in HO-containing atmosphere after As doping. After doping with Ga, the reduction is more than six orders of magnitude, but with significant hysteretic behavior, indicative of water-activation of dopants on the surface. Only Ga-doped germanane remains activated under vacuum, and also exhibits minimal hysteretic behavior while the sheet resistance is reduced by more than four orders of magnitude. These Ga- and As-doped germanane materials start to oxidize after one to four days in ambient atmosphere. Overall, this work demonstrates that extrinsic doping with Ga is a viable pathway towards accessing stable electronic behavior in graphane analogues of germanium.
锗烷是一种氢终止的锗的石墨烷类似物,作为一种潜在的二维电子材料引起了人们的关注。然而,在晶格中引入并保留外来掺杂原子以调节电子性质,仍然是一项重大挑战。在此,我们表明,第13族元素Ga和第15族元素As可以成功地掺杂到前驱体CaGe相中,并在使用HCl进行拓扑脱嵌以形成GeH后,完整地保留在晶格中。脱嵌后,最多1.1%的As和2.3%的Ga可以取代锗晶格。单薄片的电子输运性质表明,掺杂剂的引入导致As掺杂后在含HO气氛中电阻降低超过三个数量级。用Ga掺杂后,降低幅度超过六个数量级,但具有明显的滞后行为,表明表面掺杂剂的水活化。只有Ga掺杂的锗烷在真空中仍保持活化状态,并且在薄层电阻降低超过四个数量级时也表现出最小的滞后行为。这些Ga和As掺杂的锗烷材料在环境气氛中一到四天后开始氧化。总体而言,这项工作表明,用Ga进行外部掺杂是在锗的石墨烷类似物中实现稳定电子行为的可行途径。