Thermal Diffusion of Lithium Acceptors into ZnO Crystals

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Electron paramagnetic resonance (EPR) has been used to monitor the diffusion of lithium ions into single crystals of ZnO. The in-diffusion occurs when a crystal is embedded in LiF powder and then held in air at temperatures near 750degreesC for periods of time ranging up to 22 h. These added lithium ions occupy zinc sites and become singly ionized acceptors (because the material is initially n type). A corresponding reduction in the number of neutral shallow donors is observed with EPR. To monitor the lithium acceptors, we temporarily convert them to the EPR-active neutral acceptor state by exposure to laser light (325 nm or 442 nm) at low temperatures. Also, after each diffusion treatment, we monitor the EPR signal of singly ionized copper acceptors and the photo-induced EPR signal of neutral nitrogen acceptors. These nitrogen and copper impurities are initially present in the crystal, at trace levels, and are made observable by the thermal anneals. Infrared-absorption measurements at room temperature in the 2-10 mum region show that the concentration of free carriers decreases as lithium is added to the crystal. After 22 h at 750degreesC in the LiF powder, the free-carrier absorption is no longer present, and the crystal is semi-insulating.