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The lower orbitals are filled first, then the higher ones. If an element has a filled valence orbital, the highest filled conduction band, then it won't conduct electricity well. If the valence and conduction band are the same, then it will conduct electricity. Semiconductors are the ones who have a partially filled valence orbital/band. This allows electrons from a current to hop on the atoms' electrons, to create the electrical flow through the band. The band gap, or distance from the valence band to the next conduction band is positively correlated with the electrons disability to conduct electricity...
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