Substitutional oxygen as the origin of the 3.5 eV luminescence in hexagonal boron nitride

TL;DR

This study identifies substitutional oxygen as the cause of 3.5 eV luminescence in hexagonal boron nitride, revealing the defect's structure, charge states, and emission properties through computational analysis.

Contribution

It provides a detailed microscopic understanding of oxygen-related luminescence in hBN, linking defect structure to optical emission.

Findings

The 3.5 eV emission originates from hole capture by neutral oxygen substituting for nitrogen.

The defect exhibits different geometries and symmetries in neutral and positive charge states.

Calculated emission energy (3.63 eV) matches experimental observations.

Abstract

Although point defects in hexagonal boron nitride exhibiting single-photon emission attract considerable interest, a broader understanding of defect physics and chemistry in hBN remains limited, potentially hindering further development. Oxygen is among the most common impurities in hBN, and numerous studies have reported a pronounced photoluminescence band centered near 3.5 eV following oxygen incorporation, yet its microscopic origin has remained unresolved. Here, we demonstrate that this emission originates from hole capture by neutral oxygen substituting for nitrogen (ON). The transition mechanism is non-trivial, involving not only a change in charge state but also a substantial structural reconfiguration: the positive and neutral states exhibit markedly different geometries and symmetries. In the neutral state the defect adopts a low-symmetry configuration with out-of-plane displacements of the oxygen and neighboring atoms. The calculated emission energy (3.63 eV) and lineshape are in excellent agreement with experiment.