We studied heteroleptic Hf precursors with a linked amido-cyclopentadienyl ligand by density functional theory (DFT) calculation to enable high-temperature atomic layer deposition processes. The thermolysis and hydrolysis of Hf precursors were simulated to expect thermal stability and reactivity with hydroxyl groups. The effects of alkyl groups in the precursors were also investigated. We constructed the hydroxylated HfO₂ surface and then simulated the surface reactions of the precursors. The precursors with the linked ligand showed higher activation energies for thermolysis and lower activation energies for hydrolysis as compared with CpHf(NMe₂)₃. The precursors with the linked ligand also showed low activation energies for the serial ligand exchange reactions on the HfO₂ surface, significantly lower than those of CpHf(NMe₂)₃. Therefore, the DFT calculation suggests that the Hf precursors with the linked ligand are promising due to their thermal stability and reactivity better than CpHf(NMe₂)₃.

中文翻译：

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precursor前体与连接的酰胺基-环戊二烯基配体的表面反应：密度泛函理论研究

我们通过密度泛函理论（DFT）计算研究了具有连接的酰胺基-环戊二烯基配体的杂合Hf前体，以实现高温原子层沉积过程。模拟H的前体的热解和水解，以期望热稳定性和与羟基的反应性。还研究了烷基在前体中的作用。我们构建了羟基化的HfO ₂表面，然后模拟了前体的表面反应。与CpHf（NMe ₂）₃相比，具有连接配体的前体显示出较高的热分解活化能和较低的水解活化能。。具有连接的配体的前体在HfO ₂表面上也显示出较低的活化能，以进行连续的配体交换反应，远低于CpHf（NMe ₂）₃的活化能。因此，DFT计算表明，具有连接配体的Hf前体比CpHf（NMe ₂）_3具有更好的热稳定性和反应性，因此很有前途。