The band matching among layers of a TCO/β-FeSi2(n)/a-Si(i)/ c-Si(p)/ μc-Si(p ) solar cell is simulated by using the software AFORS-HET. The simulation result shows that the matching of the transparent conductive oxide with the n-type layer has a greater influence on the conversion efficiency, open-circuit voltage and fill factor of a solar cell. The conversion efficiency of the solar cell can be improved effectively through band matching. Since conduction band compensation can hinter the transport of minority carriers and interface state can accelerate the recombination of minority carriers, conduction band mismatching can be reduced. This is beneficial to the improvement of the conversion efficiency of solar cells. The interface electric field between substrate and back field can improve the conversion efficiency of solar cells.