Electronic Structure of Copper Impurities in ZnO

We have measured the near infrared absorption, Zeeman effect, and electron spin resonance of Cu2+ ions introduced as a substitutional impurity into single-crystal ZnO. From the g values of the lowest Γ6 component of the T2 state (the ground state), gII=0.74 and g⊥=1.531, and from the g values of the Γ4Γ5 component of the E state, gII=1.63 and g⊥=0, we have determined the wave functions of Cu2+ in terms of an LCAO MO model in which overlap only with the first nearest neighbor oxygen ions is considered. These wave functions indicate that the copper 3d (t2) hole spends about 40% of its time in the oxygen orbitals, and that the copper t2 orbitals are expanded radially with respect to the e orbitals. Corroboration for the radial expansion of the t2 orbitals is obtained from an analysis of the hyperfine splitting. It is concluded from our model that the large values of the hyperfine constants, |A|=195×10^-4 cm^-1 and |B|=231×10^-4 cm^-1, are due to the contribution from the orbital motion of the t2 hole