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Positron lifetime spectroscopy was used to study native vacancy defects in semi-insulating silicon carbide. The material is shown to contain (i) vacancy clusters consisting of 4–5 missing atoms and (ii) Si vacancy related negatively charged defects. The total open volume bound to the clusters anticorrelates with the electrical resistivity both in as-grown and annealed material. Our results suggest that Si vacancy related complexes compensate electrically the as-grown material, but migrate to increase the size of the clusters during annealing, leading to loss of resistivity.

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