用同步辐射光电子能谱测量了Ｓｉ／ＺｎＳ（１１１）及（１００）异质结的价带偏移ΔＥｖ．对于Ｓｉ／ＺｎＳ（１１１）及（１００）两界面，ΔＥｖ的实验结果均为（１９±０１）ｅＶ，与已有理论预期值相当符合，但与Ｍａｉｅｒｈｏｆｅｒ所报告的ＺｎＳ／Ｓｉ（１１１）异质结测量结果之间则存在明显差别．该实验结果表明对于Ｓｉ／ＺｎＳ极性界面，互逆性规则（ｃｏｍｍｕｔａｔｉｖｉｔｙｒｕｌｅ）可能不成立，就此进行了讨论． The valence band offset ΔEv of Si / ZnS (111) and (100) heterojunctions was measured by synchrotron radiation photoelectron spectroscopy. The experimental results of ΔEv for both Si / ZnS (111) and (100) interfaces are (19 ± 01) eV, which are in good agreement with the expected theoretical values. However, 111) there is a clear difference between the results of heterojunction measurement. The experimental results show that for the Si / ZnS polar interface, the commutativity rule may not be valid and was discussed.