The semiconducting single-layer transition metal dichalcogenides have been identified as ideal materials for accessing and manipulating spin- and valley-quantum numbers due to a set of favorable optical selection rules in these materials. Here, we apply time- and angle-resolved photoemission spectroscopy to directly probe optically excited free carriers in the electronic band structure of a high quality single layer of WS$_2$. We observe that the optically generated free hole density in a single valley can be increased by a factor of 2 using a circularly polarized optical excitation. Moreover, we find that by varying the photon energy of the excitation we can tune the free carrier density in a given spin-split state around the valence band maximum of the material. The control of the photon energy and polarization of the excitation thus permits us to selectively excite free electron-hole pairs with a given spin and within a single valley.
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