Magnetization steps in Zn_(1-x)Mn_xO: Four largest exchange constants and single-ion anisotropy

Magnetization steps (MST's) from Mn pairs in several single crystals of Zn_(1-x)Mn_xO (0.0056<=x<=0.030, and in one powder (x=0.029), were observed. The largest two exchange constants, J1/kB=-18.2+/-0.5K and J1'/kB=-24.3+/-0.6K, were obtained from large peaks in the differential susceptibility, dM/dH, measured in pulsed magnetic fields, H, up to 500 kOe. These two largest J's are associated with the two inequivalent classes of nearest neighbors (NN's) in the wurtzite structure. The 29% difference between J1 and J1' is substantially larger than 13% in CdS:Mn, and 15% in CdSe:Mn. The pulsed-field data also indicate that, despite the direct contact between the samples and a superfluid-helium bath, substantial departures from thermal equilibrium occurred during the 7.4 ms pulse. The third- and fourth-largest J's were determined from the magnetization M at 20 mK, measured in dc magnetic fields H up to 90 kOe. Both field orientations H||c and H||[10-10] were studied. (The [10-10] direction is perpendicular to the c-axis, [0001].) By definition, neighbors which are not NN's are distant neighbors (DN's). The largest DN exchange constant (third-largest overall), has the value J/kB=-0.543+/-0.005K, and is associated with the DN at r=c. Because this is not the closest DN, this result implies that the J's do not decrease monotonically with the distance r. The second-largest DN exchange constant (fourth-largest overall), has the value J/kB=-0.080 K. It is associated with one of the two classes of neighbors that have a coordination number z=12, but the evidence is insufficient for a definite unique choice. The dependence of M on the direction of H gives D/kB=-0.039+/-0.008K, in fair agreement with -0.031 K from earlier EPR work.Comment: 12 pages, 10 figures. Submitted to PR

Symmetry In Inorganic Chemistry

vi;ill.;122hal.;21c

Valency configuration of transition metal impurities in ZnO

We use the self-interaction corrected local spin-density approximation to investigate the ground state valency configuration of transition metal (TM = Mn, Co) impurities in n- and p-type ZnO. We find that in pure Zn1-xTMxO, the localized TM2+ configuration is energetically favored over the itinerant d-electron configuration of the local spin density (LSD) picture. Our calculations indicate furthermore that the (+/0) donor level is situated in the ZnO gap. Consequently, for n-type conditions, with the Fermi energy eF close to the conduction band minimum, TM remains in the 2+ charge state, while for p-type conditions, with eF close to the valence band maximum, the 3+ charge state is energetically preferred. In the latter scenario, modeled here by co-doping with N, the additional delocalized d-electron charge transfers into the entire states at the top of the valence band, and hole carriers will only exist, if the N concentration exceeds the TM impurity concentration