Laser-assisted phosphorus doping is demonstrated on ultrathin transition-metal dichalcogenides (TMDCs) including n-type MoS2 and p-type WSe2 . Temporal and spatial control of the doping is achieved by varying the laser irradiation power and time, demonstrating wide tunability and high site selectivity with high stability. The laser-assisted doping method may enable a new avenue for functionalizing TMDCs for customized nanodevice applications.
Recent studies have shown that vapor phase synthesis of structurally isotropic two-dimensional (2D) MoS2 and WS2 produces well-defined domains with clean grain boundaries (GBs). This is anticipated to be vastly different for 2D anisotropic materials like ReS2 mainly due to large anisotropy in interfacial energy imposed by its distorted 1T crystal structure and formation of signature Re-chains along [010] b-axis direction. Here, we provide first insight on domain architecture on chemical vapor deposited (CVD) ReS2 domains using high-resolution scanning transmission electron microscopy, angle-resolved nano-Raman spectroscopy, reflectivity, and atomic force microscopy measurements. Results provide ways to achieve crystalline anisotropy in CVD ReS2, establish domain architecture of high symmetry ReS2 flakes, and determine Re-chain orientation within subdomains. Results also provide a first atomic resolution look at ReS2 GBs, and surprisingly we find that cluster and vacancy defects, formed by collusion of Re-chains at the GBs, dramatically impact the crystal structure by changing the Re-chain direction and rotating Re-chains 180° along their b-axis. Overall results not only shed first light on domain architecture and structure of anisotropic 2D systems but also allow one to attain much desired crystalline anisotropy in CVD grown ReS2 for the first time for tangible applications in photonics and optoelectronics where direction-dependent dichroic and linearly polarized material properties are required.
a Zirconium trisulphide (ZrS 3 ), a member of the layered transition metal trichalcogenides (TMTCs) family, has been studied by angle-resolved photoluminescence spectroscopy (ARPLS). The synthesized ZrS 3 layers possess a pseudo one-dimensional nature where each layer consists of ZrS 3 chains extending along the b-lattice direction. Our results show that the optical properties of few-layered ZrS 3 are highly anisotropic as evidenced by large PL intensity variation with the polarization direction. Light is efficiently absorbed when the E-field is polarized along the chain (b-axis), but the field is greatly attenuated and absorption is reduced when it is polarized vertical to the 1D-like chains as the wavelength of the exciting light is much longer than the width of each 1D chain. The observed PL variation with polarization is similar to that of conventional 1D materials, i.e., nanowires, and nanotubes, except for the fact that here the 1D chains interact with each other giving rise to a unique linear dichroism response that falls between the 2D ( planar) and 1D (chain) limit. These results not only mark the very first demonstration of PL polarization anisotropy in 2D systems, but also provide novel insight into how the interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of pseudo-1D materials. Results are anticipated to have an impact on optical technologies such as polarized detectors, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS3) whiskers are made out of weakly interacting TiS3 layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS3 both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS3 have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the AgS–S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS3 with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.
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