We report a systematic experimental study of terahertz (THz) streaking structures for ultrafast characterization of relativistic, high-brightness electron beams. Horn-coupled waveguide geometries are investigated, enabling a comparative characterization of streaking strength, dispersion, transmission, and temporal fidelity. Analytical models and electromagnetic simulations are used to describe the dependence of streaking power on the waveguide dimensions and the drive frequency. Experimentally, the structures are characterized using compressed electron beam from an RF photoinjector over a range of THz field strengths, beam energies, and bunch durations. These results establish general design principles and performance limits for THz streaking structures applicable to ultrafast electron beam diagnostics.

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