For diamond film the one-hit model that is used to interpret low-energy X-ray thermoluminescence (TL) will require some modifications. After the films were irradiated with a superficial X-ray machine with different peak voltages, a two-compartment model with three parameters, the target size, the microscopic saturation factor and the high-LET saturation factor, was used to more precisely describe the TL response to X-ray with energies down to 10 kV. The microdosimetric distribution was calculated using single-event Monte Carlo code developed by authors together with EEDL cross-section data library. Some mechanistic insight into the physical aspect of radiation interaction with solid detectors can be obtained. The sensitive size in diamond was found to be about 15 nm. The saturation of one group of sublevels combined with the activation of another group of sublevels caused the relative efficiency to have a local minimum near 20 keV. The relative efficiency becomes higher below 10 keV, which is similar to the increasing relative biological effectiveness when the linear energy transfer passing through a biological system increases. The similarity made this material to be a molecular-scale dosimeter in the future.