Single-Crystalline Metallic Films Induced by van der Waals Epitaxy on Black Phosphorus

TL;DR

This study reveals that certain metals can form single-crystalline, van der Waals epitaxial films on black phosphorus, providing insights into the atomic-scale structure of metal-2D semiconductor interfaces.

Contribution

It demonstrates the formation of atomically sharp, single-crystalline metal films on black phosphorus via guided van der Waals epitaxy, advancing understanding of metal-2D material interfaces.

Findings

Au, Ag, and Bi form single-crystalline films on BP

Atomically sharp van der Waals interfaces are confirmed

Interfacial structures vary with different metals

Abstract

The properties of metal-semiconductor junctions are often unpredictable because of non-ideal interfacial structures, such as interfacial defects or chemical reactions introduced at junctions. Black phosphorus (BP), an elemental two-dimensional (2D) semiconducting crystal, possesses the puckered atomic structure with high chemical reactivity, and the establishment of a realistic atomic-scale picture of BP's interface toward metallic contact has remained elusive. Here we examine the interfacial structures and properties of physically-deposited metals of various kinds on BP. We find that Au, Ag, and Bi form single-crystalline films with (110) orientation through guided van der Waals epitaxy. Transmission electron microscopy and X-ray photoelectron spectroscopy confirm that atomically sharp van der Waals metal-BP interfaces forms with exceptional rotational alignment. Under a weak metal-BP interaction regime, the BP's puckered structure play an essential role in the adatom assembly process and can lead to the formation of a single crystal, which is supported by our theoretical analysis and calculations. The experimental survey also demonstrates that the BP-metal junctions can exhibit various types of interfacial structures depending on metals, such as the formation of polycrystalline microstructure or metal phosphides. This study provides a guideline for obtaining a realistic view on metal-2D semiconductor interfacial structures, especially for atomically puckered 2D crystals.