Rapid nucleation and optimal surface-ligand interaction stabilize wurtzite MnSe.

Area of Science:

• Materials Science
• Nanotechnology
• Solid-State Chemistry

Background:

• Non-native structures (NNS) exhibit distinct symmetries compared to native structures (NS).
• Understanding factors stabilizing NNS is crucial for materials synthesis and property control.

Purpose of the Study:

• To investigate the stabilization of wurtzite/NNS of manganese selenide (MnSe) using a heat-up method.
• To explore the influence of ligands, solvents, and precursor salts on MnSe phase transformation.
• To elucidate the mechanisms governing the kinetics of NNS to NS phase transformation.

Main Methods:

• Experimental synthesis of MnSe using various ligands, solvents, and precursor salts.
• Density Functional Theory (DFT) computations to analyze ligand-surface interactions.
• Kinetic analysis of phase transformation based on experimental and computational data.

Main Results:

• Oleic acid/tetraethylene glycol and oleylamine/octadecene systems stabilize wurtzite/NNS.
• DFT calculations reveal that carboxylic acid and double bond functional groups suppress NNS to NS transformation.
• Precursor salt ionizability influences nucleation and growth rates; chloride salts promote faster complex formation than acetate salts.

Conclusions:

• Phase transformation kinetics of wurtzite/NNS to rocksalt/NS MnSe are governed by nucleation/growth kinetics and activation energy barriers.
• Nucleation/growth is controlled by precursor ionizability, solvent, and metal-ligand complex stability.
• Surface energy minimization via ligand interaction dictates the activation energy barrier for NNS to NS conversion.