Jain Hardik, Poodt Paul
TNO/Holst Centre, 5656 AE Eindhoven, Netherlands.
Dalton Trans. 2021 May 4;50(17):5807-5818. doi: 10.1039/d1dt00623a.
The deposition rate and properties of MLD films are for a large part determined by what happens during the reactant exposure step. In some cases, however, the purge step is of equal importance, for example in MLD of alucone using trimethylaluminum (TMA) and ethylene glycol (EG). We show that infiltration of TMA into the alucone film followed by its continuous outgassing during the subsequent EG exposure step can lead to undesired CVD effects. To avoid the CVD effects, very long TMA purge times are required which in turn significantly impact the obtainable deposition rates. We also developed a kinetic model that correlates process parameters like reactant partial pressures, exposure times, purge time and deposition temperature to the CVD component in the film growth. We observed that the overall GPC decreases exponentially with TMA purge time attributed to the decreasing CVD component and after a long enough purge time reaches a steady-state value of growth only due to the MLD component. It was also observed that the CVD contributions reduced with decreasing partial pressure of TMA and increasing deposition temperature. With an intention to improve the outgassing efficiency of TMA, the influence of purge gas flow on the CVD growth component is also briefly discussed. Moreover, to mitigate the problem of infiltration, we show that a bulkier substitute of TMA like dimethylaluminum isopropoxide (DMAI) shows no infiltration and can improve the alucone deposition rate by at least an order of magnitude.
多层膜(MLD)的沉积速率和性质在很大程度上取决于反应物暴露步骤中发生的情况。然而,在某些情况下,吹扫步骤同样重要,例如在使用三甲基铝(TMA)和乙二醇(EG)进行铝酮的MLD过程中。我们表明,TMA渗透到铝酮膜中,随后在后续的EG暴露步骤中持续脱气,可能会导致不期望的化学气相沉积(CVD)效应。为了避免CVD效应,需要非常长的TMA吹扫时间,这反过来又会显著影响可获得的沉积速率。我们还开发了一个动力学模型,该模型将反应物分压、暴露时间、吹扫时间和沉积温度等工艺参数与膜生长中的CVD成分相关联。我们观察到,由于CVD成分的减少,总生长速率常数(GPC)随着TMA吹扫时间呈指数下降,并且在足够长的吹扫时间后,仅由于MLD成分而达到生长的稳态值。还观察到,随着TMA分压的降低和沉积温度的升高,CVD的贡献减少。为了提高TMA的脱气效率,还简要讨论了吹扫气体流量对CVD生长成分的影响。此外为了减轻渗透问题,我们表明,TMA的一种体积更大的替代物,如异丙醇二甲基铝(DMAI),不会发生渗透,并且可以将铝酮的沉积速率提高至少一个数量级。