This paper presents the results of ionization scheme development for application at the ISOLDE Resonance Ionization Laser Ion Source (RILIS). Two new ionization schemes for mercury are presented: a three-step three-resonance ionization scheme, ionizing via an excitation to a Rydberg level and a three-step two-resonance ionization scheme, with a non-resonant final step to the ionization continuum that corresponded to a factor of four higher ionization efficiency. The efficiency of the optimal mercury ionization scheme was measured, together with the efficiency of a new three-step three resonance ionization scheme for tellurium. The efficiencies of the mercury and tellurium ionization schemes were determined to be 6 % and >18 % respectively.