Thickness-dependent change in the valence band offset of the SiO2/Si interface studied using synchrotron-radiation photoemission spectroscopy

We have studied the thickness-dependent change in the valence band offset (VBO) of the SiO2/Si(001) interface using synchrotron-radiation photoemission spectroscopy with soft and hard X-rays. The SiO2-film thickness (Tox) and X-ray irradiation time (tirrad) were systematically parameterized to distinguish between the “intrinsic” Tox effects in the VBOs and the “extrinsic” differential charging phenomena in SiO2 films on Si substrates. The results revealed that at a spontaneous time (tirrad ≈ 5 s) that suppresses the differential charging phenomena as much as possible, the experimental VBO abruptly increases as a function of Tox and gradually saturates to the traditional VBO value range determined by the internal photoemission and photoconduction measurements. This effect is not attributed to the differential charging phenomena, but rather it is attributed to the “intrinsic” Tox-dependent change in the VBO. The two possible physical behaviors include electronic polarization and image charge. We have derive...