Graphene, a single two-dimensional sheet of carbon atoms with an arrangement mimicking the honeycomb hexagonal architecture, has captured immense interest of the scientific community since its isolation in 2004. Besides its extraordinarily high electrical conductivity and surface area, graphene shows a long spin lifetime and limited hyperfine interactions, which favors its potential exploitation in spintronic and biomedical applications, provided it can be made magnetic. However, pristine graphene is diamagnetic in nature due to solely sp2 hybridization. Thus, various attempts have been proposed to imprint magnetic features into graphene. The present review focuses on a systematic classification and physicochemical description of approaches leading to equip graphene with magnetic properties. These include introduction of point and line defects into graphene lattices, spatial confinement and edge engineering, doping of graphene lattice with foreign atoms, and sp3 functionalization. Each magnetism-imprinting strategy is discussed in detail including identification of roles of various internal and external parameters in the induced magnetic regimes, with assessment of their robustness. Moreover, emergence of magnetism in graphene analogues and related 2D materials such as transition metal dichalcogenides, metal halides, metal dinitrides, MXenes, hexagonal boron nitride, and other organic compounds is also reviewed. Since the magnetic features of graphene can be readily masked by the presence of magnetic residues from synthesis itself or sample handling, the issue of magnetic impurities and correct data interpretations is also addressed. Finally, current problems and challenges in magnetism of graphene and related 2D materials and future potential applications are also highlighted.

Emerging chemical strategies for imprinting magnetism in graphene and related 2D materials for spintronic and biomedical applications

Two-dimensional materials have become the focus of research for their photoelectric properties, and are employed as saturable absorption materials. Currently, the challenge is how to further improve the modulation depth of saturable absorbers (SAs) based on two-dimensional materials. In this paper, three kinds of WSe2 films with different thicknesses are prepared using the chemical vapor deposition method. The nonlinear optical responses of the WSe2 films including the nonlinear saturable absorption and nonlinear refractive index are characterized by the double-balanced detection method and Z-scan experiments. Different modulation depths are successfully obtained by controlling the thickness of the WSe2 films. We further incorporate them into an all-fiber laser to generate mode-locked pulses. The mode-locked fiber lasers with a pulse duration of 185 fs, 205.7 fs and 230.3 fs are demonstrated when the thickness of the WSe2 films is measured to be 1.5 nm, 5.7 nm and 11 nm, respectively. This work provides new prospects for WSe2 in ultrafast photonic device applications.

Tungsten diselenide for all-fiber lasers with the chemical vapor deposition method.

The outstanding optoelectronic and valleytronic properties of transition metal dichalcogenides (TMDs) have triggered intense research efforts by the scientific community. An alternative to induce long-range ferromagnetism (FM) in TMDs is by introducing magnetic dopants to form a dilute magnetic semiconductor. Enhancing ferromagnetism in these semiconductors not only represents a key step toward modern TMD-based spintronics, but also enables exploration of new and exciting dimensionality-driven magnetic phenomena. To this end, tunable ferromagnetism at room temperature and a thermally induced spin flip (TISF) in monolayers of V-doped WSe2 are shown. As vanadium concentration increases, the saturation magnetization increases, which is optimal at ≈4 at% vanadium; the highest doping level ever achieved for V-doped WSe2 monolayers. The TISF occurs at ≈175 K and becomes more pronounced upon increasing the temperature toward room temperature. The TISF can be manipulated by changing the vanadium concentration. The TISF is attributed to the magnetic-field- and temperature-dependent flipping of the nearest W-site magnetic moments that are antiferromagnetically coupled to the V magnetic moments in the ground state. This is fully supported by a recent spin-polarized density functional theory study. The findings pave the way for the development of novel spintronic and valleytronic nanodevices and stimulate further research.

Tunable Ferromagnetism and Thermally Induced Spin Flip in Vanadium-Doped Tungsten Diselenide Monolayers at Room Temperature.

Sulfated TiO2/WO3 nanocomposite: An efficient photocatalyst for degradation of Congo red and methyl red dyes under visible light irradiation

Introducing ferromagnetism in transition metal dichalcogenides has attracted lots of attention due to the possible applications in spintronics devices. Generally, single magnetic element doping is used to introduce magnetism. However, mostly, weak ferromagnetism is observed. In this work, codoping of two kinds of transition metals (Nb and Co) into WSe2 is used to study its magnetic properties. In detail, single crystal WSe2 is codoped with 4 at% Co and various concentrations of Nb by employing the physical ion implantation method. Raman, X-ray diffraction and X-ray photoelectron spectroscopy results reveal the effective substitutional doping of implanted elements (Co and Nb). Magnetic measurements illustrate that both un-doped and 4 at% Co doped WSe2 show weak ferromagnetism whereas magnetization is strongly enhanced when Co and Nb are codoped into WSe2 . The magnetization is comparable with a ferromagnet, which may be attributed to Co, Nb doping and defects. In addition, a large coercivity of ≈1.2 kOe is observed in the 1 at% Nb-4 at% Co codoped WSe2 sample, which may be ascribed to the combined effect of doping-induced stress, defect-dictated pinning and anisotropy of NbSe bond owing to the charge transfer between Nb and Se ions.

High Coercivity and Magnetization in WSe2 by Codoping Co and Nb.

Bulk TMDCs are diamagnetic materials; however, two-dimensional TMDCs exhibit spin polarized edge states, which results in a coupling between the unsaturated transition metal and chalcogenide atoms at the edges. The magnetism in two-dimensional TMDCs broadens their applications in spintronic and multi-functional devices. Herein, by combining macro/micro-magnetic experimental measurements and density functional theory (DFT) calculations, we demonstrate that among five possible edge-terminated WSe2 nanosheets only two types have a magnetic ground state, corresponding to the 100% Se edge terminated and 50% Se edge terminated nanosheets, respectively. The calculation results on WSe2 clusters and WSe2 zig-zag nanoribbons with different terminations and Se coverage rate confirmed that the unpaired electrons of the edge atoms play a crucial role in the appearance of ferromagnetism in WSe2 nanosheets. Furthermore, due to the possible quantum confinement effect and surface effect, there exist thickness-dependent magnetic properties, and the magnitude of magnetism at the edge increases as the number of layers decreases.

Jianxin Yu

Papers

Experimental and theoretical evidence for the ferromagnetic edge in WSe2 nanosheets

Tunable Photoluminescence in WS2 /WO3 Monolayer/Nanoparticles Hybrid Structure