Curie–Weiss behavior of the low-temperature paramagnetic susceptibility of semiconductors doped and compensated with hydrogen-like impurities

For the first time, a quantitative model of the Curie–Weiss behavior of a low-temperature paramagnetic susceptibility of electrically neutral donors in n-type diamagnetic covalent semiconductors is proposed. The exchange interaction between nearest two neutral donors was calculated with the use of the Heitler–London model. In this model, we take into account the change in the thermal ionization energy of donors due to the shift of the bottom of the conduction band to the bandgap with doping and compensation. The energy of the exchange spin–spin interaction between electrons localized on donors is calculated as a function of the donor concentration and the degree of their compensation by acceptors. The broadening of the donor band due to the Coulomb interaction of the nearest impurity ions was taken into account. We considered crystals of n-type germanium doped with arsenic up to the concentration close to the insulator–metal phase transition (Mott transition) and compensated with gallium. The compensation ratio K is the ratio of the concentration of compensating acceptors KN to the concentration of doping donors N. The model predicts a change in the sign of the Curie–Weiss temperature from minus to plus (a transition from the antiferromagnetic to ferromagnetic local ordering of electron spins on donors) for K ≈ 0.15–0.3, reaching its maximum positive values of ≈1.3 K for K ≈ 0.5 with the following decrease (a transition to paramagnetism) for K > 0.85. The calculated behavior of the paramagnetic susceptibility of donors is consistent with the experimental data for compensated n-Ge:As,Ga samples close to the Mott transition.