Interstitial sodium and lithium doping effects on the electronic and mechanical properties of silicon nanowires: a DFT study.

In this work, we present a theoretical study of the electronic band structure and the Young's modulus of hydrogen-passivated silicon nanowires (H-SiNWs), grown along the [110] crystallographic direction, as a function of the concentration of interstitial sodium (Na) and lithium (Li) atoms. The study is performed using the supercell scheme and the density functional theory (DFT), within the local density approximation (LDA). The results show that the presence of Na or Li atoms closes the former semiconducting band gap of the H-SiNWs and shifts the Fermi energy into the conduction band. The transition from semiconductor to metal occurs as soon as a single Na or Li atom is added to the nanowire and the number of occupied states near the Fermi level is larger for the H-SiNWs with Li atoms in comparison with those nanowires with the same concentration of Na atoms. The calculated formation energies reveal that the system becomes less stable when the concentration of Na and Li atoms augments. Moreover, the obtained binding energies indicate that Si-Li and Si-Na bonds are formed. It is worth mentioning that the binding energies of H-SiNWs with interstitial Li atoms are larger than those corresponding to the H-SiNWs with interstitial Na atoms. On the other hand, the Young's moduli of H-SiNWs with Na atoms are lower than those of pure H-SiNWs and their values diminish when the concentration of Na atoms increases. In contrast, Young's moduli of H-SiNWs present a non-monotonic behavior as a function of the concentration of interstitial Li atoms and for the largest studied concentration the nanowire fractures. These results give insight into the changes that electronic and mechanical properties of H-SiNWs suffer during the charge-discharge process, which should be taken into account in the design of electrodes of Na or Li-ion batteries.

Lithium effects on the mechanical and electronic properties of germanium nanowires.

Semiconductor nanowire arrays promise rapid development of a new generation of lithium (Li) batteries because they can store more Li atoms than conventional crystals due to their large surface areas. During the charge-discharge process, the electrodes experience internal stresses that fatigue the material and limit the useful life of the battery. The theoretical study of electronic and mechanical properties of lithiated nanowire arrays allows the designing of electrode materials that could improve battery performance. In this work, we present a density functional theory study of the electronic band structure, formation energy, binding energy, and Young's modulus (Y) of hydrogen passivated germanium nanowires (H-GeNWs) grown along the [111] and [001] crystallographic directions with surface and interstitial Li atoms. The results show that the germanium nanowires (GeNWs) with surface Li atoms maintain their semiconducting behavior but their energy gap size decreases when the Li concentration grows. In contrast, the GeNWs can have semiconductor or metallic behavior depending on the concentration of the interstitial Li atoms. On the other hand, Y is an indicator of the structural changes that GeNWs suffer due to the concentration of Li atoms. For surface Li atoms, Y stays almost constant, whereas for interstitial Li atoms, the Y values indicate important structural changes in the GeNWs.