Electronic, optoelectronic, and other functionalities of semiconductors are controlled by the nature and density of carriers, and the location of the Fermi energy. Developing strategies to tune these parameters holds the key to precise control over semiconductors properties. We propose that ligand exchange on superatoms can offer a systematic strategy to vary these properties. We demonstrate this by considering a WSe₂ surface doped with ligated metal chalcogenide Co₆Se₈(PEt₃)₆ clusters. These superatoms are characterized by valence quantum states that can readily donate multiple electrons. We find that the WSe₂ support binds more strongly to the Co₆Se₈ cluster than the PEt₃ ligand, so ligand exchange between the phosphine ligand and the WSe₂ support is energetically favorable. The metal chalcogenide superatoms serves as a donor that may transform the WSe₂ p-type film into an n-type semiconductor. The theoretical findings complement recent experiments where WSe₂ films with supported Co₆Se₈(PEt₃)₆ are indeed found to undergo a change in behavior from p- to n-type. We further show that by replacing the PEt₃ ligands by CO ligands, one can control the electronic character of the surface and deposited species.

半导体的电子，光电和其他功能受载流子的性质和密度以及费米能量的位置控制。开发调整这些参数的策略是精确控制半导体特性的关键。我们建议在超原子上进行配体交换可以提供一种改变这些性质的系统策略。我们通过考虑掺杂有连接金属硫属元素化物Co ₆ Se ₈（PEt ₃）₆簇的WSe ₂表面来证明这一点。这些超原子的特征是能轻易提供多个电子的价态量子态。我们发现WSe ₂支持物与Co ₆ Se的结合更牢固₈簇比PEt ₃配体簇，因此膦配体和WSe ₂载体之间的配体交换在能量上是有利的。金属硫属化物超原子用作供体，其可以将WSe ₂ p型膜转变为n型半导体。理论发现补充了最近的实验，在该实验中，确实发现了带有负载的Co ₆ Se ₈（PEt ₃）_6的WSe ₂膜的行为从p型转变为n型。我们进一步表明，通过用CO配体代替PEt ₃配体，可以控制表面和沉积物质的电子特性。