A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI3 (MA+ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new stable 3D lead halide materials very relevant. A strategy is the use of intermediate size cations instead of MA, which are not suitable to form the 3D ABX3 perovskites or 2D perovskites. Here, we report on a novel 3D metal halide hybrid material based on the intermediate size cation hydroxypropylammonium (HPA+), (HPA)6(MA)Pb5I17. We will see that extending the carbon chain length from two CH2 units (in the hydroxylethylammonium cation, HEA+) to three (HPA+) precludes the formation of a perovskite network as found in the lead and iodide deficient perovskite (HEA,MA)1+xPbxI3−x. In (HPA)6(MA)Pb5I17 the 3D lead halide network results from a 2D perovskite subnetworks linked by a PbI6 octahedra sharing its faces. DFT calculations confirm the direct band gap and reveal the peculiar band structure of this 3D network. On one hand the valence band has a 1D nature involving the p orbitals of the halide. On the other, the conduction band possesses a clear 2D character involving hybridization between the p orbitals of the metal and the halide.

Roles of Oxygen Vacancies in NiMoO4: A First-Principles Study

Oxygen vacancy has been suggested to play a role in the electrochemical ability of NiMoO4. The band structure and density of state of NiMoO4 bulks with different concentrations of oxygen vacancy were investigated by the first-principles calculation. Original NiMoO4 shows semiconductive properties with a direct band gap of 0.136 eV. When one to three oxygen vacancies were introduced in the NiMoO4 supercell, the band structure of NiMoO4 transforms to metallic properties, and oxygen vacancies formation energy increases with the increased number of oxygen vacancies. The oxygen vacancies in NiMoO4 lead to the increased electron localization of Ni 3d and Mo 3d state nearby the Fermi level, resulting in higher concentration of carriers in NiMoO4 and thus increase in its electrical conductivity. The results demonstrate that introducing oxygen vacancies can improve the conductive property of NiMoO4.

Green Synthesis of Ge1-xSnx Alloy Nanoparticles for Optoelectronic Applications

Compositionally controlled, light-emitting, group IV semiconductor nanomaterials have potential to enable on-chip data communications and infrared (IR) imaging devices compatible with the complementary metal−oxide−semiconductor (CMOS) technology. The recent demonstration of a direct band gap laser in Ge-Sn alloys opens avenues to the expansion of Si-photonics. Ge-Sn alloys showed improved effective carrier mobility as well as direct band gap behavior at Sn composition above 6–11%. In this work, Ge1−xSnx alloy nanoparticles with varying Sn compositions from x = 0.124 to 0.178 were prepared via colloidal synthesis using sodium borohydride (NaBH4), a mild and non-hazardous reducing reagent. Successful removal of the synthesized long-alkyl-chain ligands present on nanoparticles’ surfaces, along with the passivation of the Ge-Sn nanoparticle surface, was achieved using aqueous (NH4)2S. The highly reactive surface of the nanoparticles prior to ligand exchange often leads to the formation of germanium oxide (GeO2). This work demonstrates that the (NH4)2S further acts as an etching reagent to remove the oxide layer from the particles’ surfaces. The compositional control and long-term stability will enable the future use of these easily prepared Ge1−xSnx nanoalloys in optoelectronic devices.