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Amorphous silicon (a-Si) films were prepared by radio frequency magnetron sputtering. Spectroscopic ellipsometry (SE) was utilized to detect an ordered-structure fraction in a-Si. The SE analysis of a-Si films with different thicknesses (7.0–140.0 nm) demonstrates that no more than 2.81% of medium-range order exists in the samples, and interestingly, there is a thickness dependence of optical constants for a-Si in the range of 1.5–5.0 eV.