Following isolation of a single sheet of graphene, many other 2D systems such as hexagonal BN, transition metal dichalcogenides (TMDs) and silica bilayers were manufactured. All these systems contain defects and impurities, which may govern the electronic and optical properties of these materials, calling upon the studies on defect properties. In my talk, I will present the results [1-6] of our first-principles theoretical studies of defects (native and irradiation-induced) in inorganic 2D systems obtained in collaboration with several experimental groups. I will further dwell on the signatures of defects in Raman spectra and discuss defect- and impurity-mediated engineering of the electronic structure of inorganic 2D materials. I will also present the results [7] of our theoretical studies of electron-beam induced phase transformations in 2D TMDs when electric charge, mechanical strain and vacancies are present. Based on the results of our calculations, we propose an explanation for this phenomenon which is likely promoted by charge redistribution in the TMD monolayer combined with vacancy formation due to electron beam and associated mechanical strain in the sample.

References

1. E. Sutter et al., Nano Letters 16, 21 (2016).

2. T. Björkman et al., ACS Nano 10, 10929 (2016).

3. M. Ghorbani-Asl et al., 2D Materials 4 (2017) 025078.

4. H.-P. Komsa and A.V. Krasheninnikov, Adv. El. Mat. (2017) 1600468.

5. L. Nguyen, et al., ACS Nano 11 (2017) 2894.

6. C. Herbig, et al. Nano Letters (2017) DOI: 10.1021/acs.nanolett.7b00550.

7. S. Kretschmer et al., submitted.

Manipulation of low dimensional nanomaterials provides intriguing opportunities to design new functional materials as well as to develop next-generation device applications. To manipulate properties of low dimensional nanomaterials, extensive study has been conducted so far for interaction of energetic particles with low dimensional nanomaterials. However, most of the research has been focused on utilizing electron or light/heavy ion beams to study irradiation effects on alternation of structural, mechanical and electrical properties of nanomaterials. In this study, we investigated the effect of Argon molecular cluster beam irradiation on both defect formation and removal of organic contaminants on graphene. An Argon cluster beam was generated using the Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) combined with Atomic Force Microscopy (AFM). The ToF-SIMS allows for conducting in-situ monitoring of defect formation as well as organic contaminants removal. This leads to accomplishments of a high degree of controls over modification of graphene. A systematic study has been conducted to provide in-depth understanding about defect formation of graphene by synergistic theoretical and experimental approaches. Raman spectra clearly indicate that suspended graphene is more susceptible to Ar cluster beam irradiation than supported graphene on a SiO₂/Si substrate under the same irradiation conditions. The underlying mechanisms for the experimentally observed phenomena are demonstrated by theoretical analysis using the first-principles molecular dynamics calculations.

This work was supported by the Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility.

Graphene already shows promises for the next generation of electronics and optoelectronics devices and other applications where a band gap or magnetic response is necessary [1]. The availability of versatile processing techniques is thus crucial to the development of these graphene-based technologies. An ideal and efficient nitrogen doping would precisely tune the N-doping and keep a minimal defect density. In this work, we explore the potential of the late afterglow of a microwave N₂ plasma at reduced pressure (6 Torr) for post-growth tuning of CVD-grown graphene films on copper foils.

A single graphene sample received five subsequent 30-second plasma treatments between which X-Ray photoelectron spectroscopy (XPS) and Raman spectroscopy (RS) were carried out. XPS measurements confirmed a strong N-incorporation increasing with the plasma treatment time (up to N/C = 29%) while RS assessed an uncommonly low damage generation (D/G ratio below 0.4) for such incorporation.

XPS, RS and ultraviolet photoelectron spectroscopy (UPS) were also performed on the sample after transfer to an Si/SiO₂ substrate via the PMMA method [2]. The results show a strong decrease of the N content (N/C = 6%) which is attributed to the desorption of out-of-plane adsorbed N due to the transfer. RS and UPS techniques both support an n-doping which is associated to the different aromatic N-incorporations deconvoluted from the high resolution XPS spectra.

The low ion density (< 10⁷ cm^-3) and the high density of reactive neutral (> 10¹⁴ cm^-3) and metastable species (> 10¹⁰ cm^-3) of the nitrogen late-afterglow in our conditions [3] are believed to be the key of such efficient and low-defect N-incorporation in graphene.

[1] Vashist SK, Luong JH (2015) Carbon 84 519-550.

[2] Suk JW, Kitt A, Magnuson CW et al. (2011) ACS Nano 5(9):6916-6924.

Two-dimensional (2D) materials are intrinsically heterogeneous, therefore controlling defects, understanding the impact of boundaries and interfaces, and developing means to exploit these heterogeneities is a transformative opportunity that could underpin future technologies and energy applications. This talk will discuss the fundamental understanding of the roles of heterogeneity, atomic interface, and disorder in 2D materials and their heterostructures. Through isoelectronic doping in monolayer of MoSe₂, the Se vacancies are effectively suppressed and photoluminescence is significantly enhanced due to the decrease of defect-mediated non-radiative recombination. In addition, we demonstrate the non-equilibrium, bottom-up synthesis of single crystalline monolayers of 2D MoSe_2−x with controllable levels of Se vacancies far beyond intrinsic levels. Both substitutional dopants and vacancies were shown to significantly alter the carrier properties and transport characteristics within a single monolayer (e.g., n- to p-type conduction in W-doped MoSe₂ and in Se-deficient MoSe_2-x). The vertical and lateral 2D heterostructures by controlled assembly and doping will be discussed. In addition, the lattice misfit heterostructures of monolayer GaSe/MoSe₂ were synthesized by a two-step chemical vapor deposition (CVD) method. We find the vertically stacked GaSe/MoSe₂ heterostructures maintain vdW epitaxy with well-aligned lattice orientation between the two layers, forming an incommensurate moiré superlattice. The bottom up synthesis of 2D materials discussed here provides excellent control over the heterogeneity in 2D materials, which can tunably modulate the optical and electrical properties in 2D materials and their heterostructure.

Acknowledgment: Synthesis science was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division and characterizations were performed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility

In monolayer van der Waals-materials, grain boundaries become one-dimensional (1D) line defects. Here we show using angle resolved photoemission spectroscopy (ARPES) that twin-grain boundaries in the 2D semiconductor MoSe₂ exhibit parabolic metallic bands. The 1D nature is evident from a charge density wave transition, whose periodicity is given by k_F/p, where the Fermi momentum k_F is determined by ARPES. Most importantly, we provide evidence for spin- and charge-separation, the hallmark of 1D quantum liquids. ARPES shows that the spectral line splits into distinctive spinon and holon excitations whose dispersions exactly follow the energy-momentum dependence calculated by 1D Hubbard model, with suitable finite-range interactions. Our results also imply that quantum wires and junctions can be isolated in line defects in 2D materials, which may enable quantum transport measurements and devices.