Dimensionality-suppressed chemical doping in 2D semiconductors: the cases of phosphorene, MoS2, and ReS2 from first-principles

TL;DR

This paper investigates the challenges of chemical doping in 2D semiconductors like phosphorene, MoS2, and ReS2, revealing how reduced dimensionality causes high defect ionization energies and proposing strategies to mitigate this for better electronic applications.

Contribution

It introduces a conceptual framework decomposing defect ionization energies into components affected by dimensionality and demonstrates practical methods to reduce these energies in 2D materials.

Findings

Defect ionization energies increase with reduced screening in 2D materials.

Embedding BP monolayer in dielectric or h-BN layers reduces defect IEs.

Strategies to enhance doping efficiency in 2D semiconductors are proposed.

Abstract

In spite of great appeal of two-dimensional (2D) semiconductors for electronics and optoelectronics, to achieve required charge carrier concentrations by means of chemical doping remains a challenge, due to large defect ionization energies (IEs). Here by decomposing the defect IEs into the neutral single-electron defect level, the structural relaxation energy gain, and the electronic relaxation energy cost, we propose a conceptual picture that the large defect IEs are caused by two effects of reduced dimensionality. While the quantum confinement effect (QCE) makes the neutral single-electron point defect levels deep, the reduced screening effect (RE) leads to high energy cost for the electronic relaxation. The first-principles calculations for monolayer, few-layer, and bulk black phosphorus (BP), MoS2, and ReS2 with strong, medium, and weak interlayer interactions, respectively, as examples, do demonstrate the general trend. Based on the gained insight into defect behaviors, strategies can be envisaged for reducing defect IEs and improving charge carrier doping. Using BP monolayer either embedded into dielectric continuum or encapsulated between two h-BN layers, as practical examples, we demonstrate the feasibility of increasing the screening to reduce the defect IEs and boost carrier concentration. Our analysis is expected to help achieving effective carrier doping and thus to open ways towards more extensive applications of 2D semiconductors.