To become “hot” and enter the conduction band of SiO2, an electron must gain a kinetic energy of ~3.2 eV. For holes, the valence band offset in this case dictates they must have a kinetic energy of 4.6 eV. The term "hot electron" comes from the effective temperature term used when modelling carrier density (i.e., with a Fermi-Dirac function) and does not refer to the bulk temperature of the semiconductor (which can be physically cold, although the warmer it is, the higher the population of hot electrons it will contain all else being equal).