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Breaking space-time symmetries in two-dimensional crystals (2D) can dramatically influence their macroscopic electronic properties. Monolayer transition-metal dichalcogenides (TMDs) are prime examples where the intrinsically broken crystal inversion symmetry permits the generation of valley-selective electron populations, even though the two valleys are energetically degenerate, locked by time-reversal symmetry. Lifting the valley degeneracy in these materials is of great interest because it would allow for valley-specific band engineering and offer additional control in valleytronic applications. While applying a magnetic field should in principle accomplish this task, experiments to date have observed no valley-selective energy level shifts in fields accessible in the laboratory. Here we show the first direct evidence of lifted valley degeneracy in the monolayer TMD WS2. By applying intense circularly polarized light, which breaks time-reversal symmetry, we demonstrate that the exciton level in each valley can be selectively tuned by as much as 18 meV via the optical Stark effect. These results offer a novel way to control valley degree of freedom, and may provide a means to realize new valley-selective Floquet topological phases in 2D TMDs.
We report on the nonequilibrium quasiparticle dynamics in BaFe$_2$As$_2$ on both the hole doped (Ba$_{1-x}$K$_x$Fe$_2$As$_2$) and electron doped (BaFe$_{2-y}$Co$_y$As$_2$) sides of the phase diagram using ultrafast pump-probe spectroscopy. Below $T_c $, measurements conducted at low photoinjected quasiparticle densities in the optimally and overdoped Ba$_{1-x}$K$_x$Fe$_2$As$_2$ samples reveal two distinct relaxation processes: a fast component whose decay rate increases linearly with excitation density and a slow component with an excitation density independent decay rate. We argue that these two processes reflect the recombination of quasiparticles in the two hole bands through intraband and interband processes. We also find that the thermal recombination rate of quasiparticles increases quadratically with temperature in these samples. The temperature and excitation density dependence of the decays indicates fully gapped hole bands and nodal or very anisotropic electron bands. At higher excitation densities and lower hole dopings, the dependence of the dynamics on quasiparticle density disappears as the data are more readily understood in terms of a model which accounts for the quasiequilibrium temperature attained by the sample. In the BaFe$_{2-y}$Co$_y$As$_2$ samples, dependence of the recombination rate on quasiparticle density at low dopings (i.e., $y=0.12$) is suppressed upon submergence of the inner hole band and quasiparticle relaxation occurs in a slow, density independent manner.
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