We prepare and analyze Rydberg states with orbital quantum numbers using three-optical-photon electromagnetically-induced transparency (EIT) and radio-frequency (RF) dressing, and employ the high- states in electric-field sensing. Rubidium-85 atoms in a room-temperature vapor cell are first promoted into the state via Rydberg-EIT with three infrared laser beams. Two RF dressing fields then (near-)resonantly couple Rydberg states with high . The dependence of the RF-dressed Rydberg-state level structure on RF powers, RF and laser frequencies is characterized using EIT. Furthermore, we discuss the principles of DC-electric-field sensing using high- Rydberg states, and experimentally demonstrate the method using test electric fields of ~50~V/m induced via photo-illumination of the vapor-cell wall. We measure the highly nonlinear dependence of the DC-electric-field strength on the power of the photo-illumination laser. Numerical calculations, which reproduce our experimental observations well, elucidate the underlying physics. Our study is relevant to high-precision spectroscopy of high- Rydberg states, Rydberg-atom-based electric-field sensing, and plasma electric-field diagnostics.

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