ABSTRACT
Optical measurements under externally applied stresses allow us to study the materials' electronic structure by comparing the pressure evolution of optical peaks obtained from experiments and theoretical calculations. We examine the stress-induced changes in electronic structure for the thermodynamically stable 1T polytype of selected MX2 compounds (M=Hf, Zr, Sn; X=S, Se), using the density functional theory. We demonstrate that considered 1T-MX2 materials are semiconducting with indirect character of the band gap, irrespective to the employed pressure as predicted using modified Becke-Johnson potential. We determine energies of direct interband transitions between bands extrema and in band-nesting regions close to Fermi level. Generally, the studied transitions are optically active, exhibiting in-plane polarization of light. Finally, we quantify their energy trends under external hydrostatic, uniaxial, and biaxial stresses by determining the linear pressure coefficients. Generally, negative pressure coefficients are obtained implying the narrowing of the band gap. The semiconducting-to-metal transition are predicted under hydrostatic pressure. We discuss these trends in terms of orbital composition of involved electronic bands. In addition, we demonstrate that the measured pressure coefficients of HfS2 and HfSe2 absorption edges are in perfect agreement with our predictions. Comprehensive and easy-to-interpret tables containing the optical features are provided to form the basis for assignation of optical peaks in future measurements.
ABSTRACT
The optical properties of two-dimensional materials can be effectively tuned by strain induced from a deformable substrate. In the present work we combine first-principles calculations based on density functional theory and the effective Bethe-Salpeter equation with high-pressure optical measurements to thoroughly describe the effect of strain and dielectric environment onto the electronic band structure and optical properties of a few-layered transition-metal dichalcogenide. Our results show that WS2 remains fully adhered to the substrate at least up to a -0.6% in-plane compressive strain for a wide range of substrate materials. We provide a useful model to describe effect of strain on the optical gap energy. The corresponding experimentally determined out-of-plane and in-plane stress gauge factors for WS2 monolayers are -8 and 24 meV/GPa, respectively. The exceptionally large in-plane gauge factor confirms transition metal dichalcogenides as very promising candidates for flexible functionalities. Finally, we discuss the pressure evolution of an optical transition closely lying to the A exciton for bulk WS2 as well as the direct-to-indirect transition of the monolayer upon compression.
ABSTRACT
We present studies focused on the evolution of the electronic band structure of the Mo1-x W x Se2 alloy with the tungsten content, which was conducted by combining experimental and theoretical methods. Employed spectroscopic techniques, namely, photoreflectance, photoacoustic spectroscopy, and photoluminescence, allowed observing indirect and direct transitions at high and beyond high-symmetry points of the Brillouin zone (BZ). Two excitons (A and B) associated with the K point of the BZ were observed together with other optical transitions (C and D) related to band nesting. Moreover, we have also identified the indirect transition for the studied crystals. Obtained energies for all transitions were tracked with a tungsten content and compared with results of calculations performed within density functional theory. Furthermore, based on the mentioned comparison, optical transitions were assigned to specific regions of the BZ. Finally, we have obtained bowing parameters for experimentally observed features, for, i.e., thin-film samples: b(A) = 0.13 ± 0.03 eV, b(B) = 0.14 ± 0.03 eV, b(C) = 0.044 ± 0.008 eV, and b(D) = 0.010 ± 0.003 eV.
