Group-13 and group-15 doping of germanane

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 CaGe2 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 H2O-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.