Abstract

We present two-dimensional Mg(OH)2 sheets and their vertical heterojunctions with CVD-MoS2 for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)2 sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)2 have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)2 is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)2 sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)2 sheets together with CVD-MoS2 in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS2 sheets to Mg(OH)2, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)2, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.

Highlights

  • Layered crystals at the quantum confinement (2D) limit are emerging as an important class of materials for information and energy conversion technologies[1,2]

  • Raman spectroscopy measurements on Mg(OH)[2] show that the lattice vibration characteristics and their dimensionality dependence are in stark contrast to other 2D materials known to date

  • Polarization at the alkaline metal hydroxides (AMHs) surface, vertical stacking of Mg(OH)2/MoS2 enables tuning the MoS2 properties as evidenced by much enhanced photoluminescence (PL) emission and shifted PL peak position

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Summary

Methods

The ceramic boat was placed to the center of the heating zone of the furnace. Another alumina crucible containing sulphur (≥ 99.88% Sigma Aldrich) was placed in to the tube in a gas flow direction. The heterostructure was fabricated by transferring CVD-grown MoS2 monolayers (described above) onto exfoliated Mg(OH)[2] flakes on SiO2/Si substrate. The core-valence interaction was described by the frozen-core projector augmented wave (PAW) method[32]. Both the generalized gradient approximation of Perdew-Burke-Ernzerhof (GGA-PBE)[33] and the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional[34] were adopted for exchange-correlation functional. While DFPT calculations performed using the primitive unitcell of metal hydroxides, in SD calculations for the convergence of dynamical matrix we use 5 × 5 × 1 supercell

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