Department of Chemical Engineering, Stanford University, Hillsboro, Oregon, USA.
ACS Nano. 2010 Jan 26;4(1):331-41. doi: 10.1021/nn901013r.
Nanoscale organic films are important for many applications. We report on a system of molecular layer deposition that allows for the deposition of conformal organic films with thickness and composition control at the subnanometer length scale. Nanoscale polyurea films are grown on silica substrates in a layer-by-layer fashion by dosing 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) in the gas phase. Ellipsometry measurements indicate that the film growth occurs at a constant growth rate, with film thicknesses consistent with molecular distances calculated using density functional theory. Characterization of the films by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy reveals formation of stable polyurea films with nearly stoichiometric composition, and transmission electron microscopy indicates that the films uniformly coat the substrate surface. Subnanometer control over the film composition was demonstrated using 2,2'-thiobis(ethylamine) (TBEA) as an alternate diamine to vary the composition of the films. By substituting TBEA for ED, blended films, with homogeneous composition through the film, and nanolaminates, with discrete layers of differing film chemistry, were created.
纳米有机薄膜在许多应用中都很重要。我们报告了一种分子层沉积系统,该系统允许在亚纳米长度尺度上进行具有厚度和组成控制的保形有机薄膜的沉积。通过在气相中计量 1,4-亚苯基二异氰酸酯(PDIC)和乙二胺(ED),在二氧化硅衬底上以逐层方式生长纳米级聚脲薄膜。椭圆测量表明,薄膜生长以恒定的生长速率进行,薄膜厚度与使用密度泛函理论计算的分子距离一致。傅里叶变换红外光谱和 X 射线光电子能谱的特性表明形成了具有近乎化学计量组成的稳定聚脲薄膜,透射电子显微镜表明薄膜均匀地覆盖了基底表面。通过使用 2,2'-硫代双(乙胺)(TBEA)作为替代二胺来控制薄膜的组成,可以实现亚纳米级的控制。通过用 TBEA 替代 ED,可以在薄膜中形成均匀组成的混合薄膜,以及具有不同薄膜化学性质的离散层的纳米层压板。