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Dielectric films of ZrBO were grown using thermal-CVD Zr(BH4)4-O2 gas system. Oxygen gas was activated by microwave to produce its radical. The grown film showed high barrier properties for Cu diffusion with a thickness of 50 nm. Typical side step coverage was over 60% for a 45-μm-deep and 7.5-aspect-ratio TSV with a high coverage of 67% at the bottom. We report ZrBO-CVD mechanism related to the coverage.