The carrier of the dust-associated photoluminescence process causing the extended red emission (ERE) in many dusty interstellar environments remains unidentified. Several competing models are more or less able to match the observed broad, unstructured ERE band. We now constrain the character of the ERE carrier further by determining the wavelengths of the radiation that initiates the ERE. Using the imaging capabilities of the Hubble Space Telescope, we have resolved the width of narrow ERE filaments appearing on the surfaces of externally illuminated molecular clouds in the bright reflection nebula NGC 7023 and compared them with the depth of penetration of radiation of known wavelengths into the same cloud surfaces. We identify photons with wavelengths shortward of 118 nm as the source of ERE initiation, not to be confused with ERE excitation, however. There are strong indications from the well-studied ERE in the Red Rectangle nebula and in the high-|b| Galactic cirrus that the photon flux with wavelengths shortward of 118 nm is too small to actually excite the observed ERE, even with 100% quantum efficiency. We conclude, therefore, that ERE excitation results from a two-step process. While none of the previously proposed ERE models can match these new constraints, we note that under interstellar conditions most polycyclic aromatic hydrocarbon (PAH) molecules are ionized to the di-cation stage by photons with E > 10.5 eV and that the electronic energy level structure of PAH di-cations is consistent with fluorescence in the wavelength band of the ERE. Therefore, PAH di-cations deserve further study as potential carriers of the ERE. (abridged)