RESUMO
Non-native structures (NNS) differ in discrete translational symmetry from the bulk ground state native structure (NS). To explore the extent of deconvolution of various factors relevant to the stabilization of the wurtzite/NNS of MnSe via a heat-up method, we performed experiments using various ligands (oleic acid, oleylamine, octadecylamine, stearic acid, and octadecene), solvents (tetraethylene glycol and octadecene), and precursor salts (manganese chloride and manganese acetate). Experiments suggest that oleic acid in the presence of tetraethylene glycol and oleylamine in the presence of octadecene stabilize wurtzite/NNS. Further, density functional theory (DFT) computations explore the interaction between the functional groups in ligands and the most exposed surfaces of wurtzite/NNS and rocksalt/NS polymorphs. Computations suggest that the interactions between relevant surface facets with carboxylic acid and the double bond functional groups suppress the phase transformation from NNS to NS. In addition, the ionizability of the precursor salt also determines the rate of formation of the metal-ligand complex and the rate of nucleation. Consequently, the formation rate of the Mn-ligand complex is expected to be greater in the case of chloride salt than acetate salt because the chloride salt has higher ionizability in ethylene glycol. From the above, we conclude that the kinetics of the wurtzite/NNS to rocksalt/NS phase transformation depends mainly on two factors: (1) nucleation/growth kinetics which is controlled by the ionizability of the precursor salt, solvent, and stability of the metal-ligand complex, and (2) the activation energy barrier of the NNS to NS conversion which is controlled by surface energy minimization with the ligand.
RESUMO
Gas-induced growth of organic-inorganic hybrid perovskites, especially methylammonium lead iodide (MAPbI3), has shown interesting properties and applications in the area of optoelectronics. In this report, we introduce a method of gas-induced band gap engineering of thin films of MAPbI3 due to systematic dimensional confinement-deconfinement along the crystallographic c axis of growing MAPbI3. Interestingly, such a restricted growth phenomenon was observed when the hexylammonium lead iodide (two-dimensional hybrid perovskite) film was exposed to methylamine gas instead of the conventional PbI2 film-methylamine gas precursor pair. Hexylamine, formed due to the cation exchange reaction, interacts selectively with the Pb centers of growing MAPbI3 crystals, and this induces an enormous restriction in the growth of MAPbI3 along the crystallographic c direction, leading to a unique sheet-type MAPbI3 film having a much higher band gap (2.18 eV) compared to conventional bulk MAPbI3. However, careful control of exposure timing gradually evaporates the hexylamine, leading to systematic dimensional deconfinement, enabling modulation of the band gap from 2.18 to 1.69 eV. An interplay of adsorption and desorption of hexylamine is also utilized for generating patterns of two different fluorescent hybrid perovskite materials in a single pixel. This new mechanistic investigation highlighting gas-induced interplay of dimensional confinement-deconfinement associated with band gap tuning provides smooth thin films, which can be used to develop optoelectronic devices.
