In a simple picture of an electron-nucleus two-spin system, the solid effect occurs when a transition involving an electron-nucleus mutual flip (called zero quantum or double quantum) is excited by a microwave irradiation, in the presence of relaxation. This kind of transition is in general weakly allowed, meaning that the transition moment for the above microwave excitation results from a second-order effect of the electron-nuclear interactions and thus requires stronger microwave power to be significant, and its intensity is decreased by an increase of the external magnetic field B. As a result, the DNP enhancement from the solid effect scales as B when all the relaxation parameters are kept constant. Once this transition is excited and the relaxation is acting, the magnetization is spread over the "bulk" nuclei (the major part of the detected nuclei in an NMR experiment) via the nuclear dipole network.
This polarizing mechanism is optimal when the exciting microwave frequency shifts up or down by the nuclear Larmor frequency from the electron Larmor frequency in the discussed two-spin system. The direction of frequency shifts corresponds to the sign of DNP enhancements.
Solid effect exist in most cases but is more easily observed if the linewidth of the EPR spectrum of involved unpaired electrons is smaller than the nuclear Larmor frequency of the corresponding nuclei.