An Impulse-Radio Ultra-Wideband (IR-UWB) cavitybacked slot antenna covering the [5.9803; 6.9989] GHz frequency band of the IEEE 802.15.4a-2011 standard is designed and implemented in airfilled substrate-integrated-waveguide (AFSIW) technology for localization applications with an accuracy of at least 3 cm. By relying on both frequency-and time-domain optimization, the antenna achieves excellent IR-UWB characteristics. In free-space conditions, an impedance bandwidth of 1.92 GHz (or 29.4%), a total efficiency higher than 89%, a front-to-back-ratio of at least 12.1 dB and a gain higher than 6.3 dBi are measured in the frequency domain. Furthermore, a system fidelity factor larger than 98% and a relative group delay smaller than 100 ps are measured in the time domain within the 3dB-beamwidth of the antenna. As a result, the measured time-of-arrival of a transmitted Gaussian pulse, for different angles of arrival, exhibits variations smaller than 100 ps, corresponding to a maximum distance estimation error of 3 cm. Additionally, the antenna is validated in a real-life worst-case deployment scenario, showing that its characteristics remain stable in a large variety of deployment scenarios. Finally, the difference in frequency-domain and time-domain performance is studied between the antenna implemented in AFSIW and in dielectric-filled SIW (DFSIW) technology. We conclude that DFSIW technology is less suitable for the envisaged precision IR-UWB localization application. Index Terms-Cavity-backed slot antenna, air-filled substrateintegrated-waveguide, impulse-radio ultra-wideband, high efficiency, indoor localization.