Keywords: boron-doped diamond, insulating side of the Mott transition, transition from valence-band to acceptor-band migration of holes, Nernst-Einstein-Smoluchowski relation, thermal activation energy of hopping conductivity Abstract Ionization equilibrium and dc electrical conductivity of crystalline diamond are considered, for the temperature T j in the vicinity of which valence band (v-band) conductivity is approximately equal to hopping conductivity via acceptors. For the first time, we find explicitly (in the form of definite integrals) the fundamental ratio of diffusion coefficient to drift mobility for both v-band holes and holes hopping via hydrogen-like acceptors for the temperature T j . The known ratios follow from the obtained ones as particular cases. The densities of the spatial distributions of acceptors and hydrogenlike donors as well as of holes are considered to be Poissonian and the fluctuations of electrostatic potential energy are considered to be Gaussian. The dependence of exchange energy of v-band holes on temperature is taken into account. The thermal activation energy of hopping conduction as a function of the concentration of boron atoms (as acceptors) is calculated for temperature T T 2 j 3 » . Without the use of any adjustable parameters, the results of calculations quantitatively agree with data obtained from the measurements of hopping conductivity of diamond with boron concentration from 3 10 17 to 3 10 20 cm −3 , i.e. on the insulating side of the Mott phase transition.
Raman spectra of irradiated with fast neutrons or MeV ion-implanted radiation-damaged natural and CVD diamonds and chemically purified detonation nanodiamonds are investigated. The influence of radiation damage level and effects of high-temperature annealing on the intensity and spectral shape of the 1640 cm−1 band is studied. It is shown that in radiation-damaged diamonds this band consists of at least six Gaussian peaks, the intensity of which varies one to one both with the level of radiation disordering and the temperature of the subsequent annealing. The “1640” band in radiation-damaged diamonds is completely annealed at temperatures above 1000 °C, while in detonation nanodiamonds annealing up to 1200 °C does not significantly affect its shape and intensity.
In the work the dependence of the thermal ionization energy of hydrogen-like donors and acceptors on their concentration in n- and p-type semiconductors is analyzed analytically and numerically. The impurity concentrations and temperatures at which the semiconductors are on the insulator side of the concentration insulator – metal phase transition (Mott transition) are considered. It is assumed that impurities in the crystal are distributed randomly (according to Poisson), and their energy levels are distributed normally (according to Gauss). In the quasi-classical approximation, it is shown, for the first time, that the decrease in the ionization energy of impurities mainly occurs due to the joint manifestation of two reasons. Firstly, from the excited states of electrically neutral impurities, a quasicontinuous band of allowed energy values is formed for c-band electrons in an n-type crystal (or for v-band holes in a p-type crystal). This reduces the energy required for the thermally activated transition of electron from the donor to the c-band (for the transition of the hole from the acceptor to the v-band). Secondly, from the ground (unexcited) states of impurities a classical impurity band is formed, the width of which at low temperatures is determined only by the concentration of impurity ions. In moderately compensated semiconductors (when the ratio of the concentration of minority impurities to the concentration of majority impurities is less than 50 %) the Fermi level is located closer to the edge of the band of allowed energy values than the middle of the impurity band, that issue reduces thermal ionization energy of impurities from states in the vicinity of the Fermi level (transition of electron from a donor to the c-band, or hole from an acceptor to the v-band). Previously, these two causes of decrease in the thermal ionization energy due to increase in the concentration of impurities were considered separately. The results of calculations according to the proposed formulas are quantitatively agree with the known experimental data for a number of semiconductor materials (germanium, silicon, diamond, gallium arsenide and phosphide, silicon carbide, zinc selenide) with a moderate compensation ratio.
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.
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