Spontaneous structural reconstructions and properties of ultrathin triangular ZnSe nanoplatelets

TL;DR

This study discovers a new, energetically favorable hexagonal 2D ZnSe nanoplatelet structure formed by spontaneous reconstruction, with detailed analysis of its properties and surface interactions, advancing understanding of 2D semiconductor nanostructures.

Contribution

First-principles prediction of a new stable hexagonal ZnSe nanoplatelet structure resulting from spontaneous reconstruction, with comprehensive analysis of its vibrational, electronic, and optical properties.

Findings

New hexagonal ZnSe structure has lower energy than known forms.

Phonon spectra match experimental observations.

Surface molecule adsorption induces structural transformations and enhances optical activity.

Abstract

Two-dimensional (2D) materials have revolutionized all areas of development of high-performance electronic devices. In particular, the unique electronic and optical properties of II--VI semiconductor nanoplatelets have been found to be very promising for optoelectronics. However, not all properties of this intriguing class of materials are yet known. A new, previously unknown hexagonal 2D structure of ZnSe nanoplatelets whose energy is lower than the energies of all previously studied systems is found from first-principles calculations. This structure appears as a result of spontaneous reconstruction of the wurtzite structure and differs from it by the stacking order of the bulk and near-surface Zn atomic layers. The phonon spectrum, electronic structure, and band gap of the obtained nanoplatelets are calculated. The phonon spectra of the nanoplatelets are in complete agreement with the spectra observed in experiment and differ strongly from the vibrational spectra of ZnSe nanoclusters. The adsorption of ZnCl$_2$ and $L$-cysteine molecules on the surface of the nanoplatelets is studied and is shown to be accompanied by yet another spontaneous reconstruction of the hexagonal structure into a tetragonal one and a new rearrangement of Zn atoms in the near-surface layers. Calculations of the natural optical activity of nanoplatelets covered with $L$-cysteine reveal an increase in the specific (calculated per chiral molecule) optical activity, which is especially strong for the Janus structures, as compared to the free $L$-cysteine molecule.