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.

The dehydrocoupling of the fluorinated secondary phosphine-borane adduct R2PH.BH3 (R = p-CF3C6H4) at 60 degrees C is catalyzed by the rhodium complex [{Rh(mu-Cl)(1,5-cod)}2] to give the four-membered chain R2PH-BH2-R2P-BH3. A mixture of the cyclic trimer [R2P-BH2]3 and tetramer [R2P-BH2]4 was obtained from the same reaction at a more elevated temperature of 100 degrees C. The analogous rhodium-catalyzed dehydrocoupling of the primary phosphine-borane adduct RPH2.BH3 at 60 degrees C gave the high molecular weight polyphosphinoborane polymer [RPH-BH2]n (Mw = 56,170, PDI = 1.67). The molecular weight was investigated by gel permeation chromatography and the compound characterized by multinuclear NMR spectroscopy. Interestingly, the electron-withdrawing fluorinated aryl substituents have an important influence on the reactivity as the dehydrocoupling process occurred efficiently at the mildest temperatures observed for phosphine-borane adducts to date. Thin films of polymeric [RPH-BH2]n (R = p-CF3C6H4) have also been shown to function as effective negative-tone resists towards electron beam (e-beam) lithography (EBL). The resultant patterned bars were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

High molecular weight, soluble, air- and moisture-stable, highly metallized (>25 wt% metal) polyferrocenylsilanes (PFS) [Fe(eta-C5H4)2Si(Me){Co2(CO)6C2Ph}]n (Co-PFS), [Fe(eta-C5H4)2Si(Me){Mo2-Cp2(CO)4C2Ph}]n (Mo-PFS), and [Fe(eta-C5H4)2Si(Me){Ni2Cp2C2Ph}]n (Ni-PFS) containing pendant cobalt, molybdenum, and nickel clusters, respectively, have been prepared via macromolecular clusterization of an acetylide-substituted PFS [Fe(eta-C5H4)2Si(Me)C(triple bond)CPh]n with [Co(2)(CO)8], [{MoCp(CO)(2)}2], or [{NiCp(CO)}2]. The extent of clusterization achieved was in the range of 70-75%. All three highly metallized polymers were demonstrated to function as negative-tone resists in electron-beam lithography, while Co-PFS and Mo-PFS were successfully patterned by UV-photolithography, allowing the fabrication of micron-sized bars, dots, and lines. These studies suggest that the highly metallized polymers may be useful in the fabrication of patterned arrays of alloy nanoparticles for both materials science and catalytic applications.

The reactions of AlMe3, BEt3, and ZnEt2 with toluene solutions of the copper(II) complexes [CuL2] {L = acetylacetonate (acac; 1), hexafluoroacetylacetonate (hfac; 2), N-isopropyl-β-ketiminate (acnac; 3), N,N-dimethyl-β-diketiminate (nacnac; 4), 2-pyrrolylaldehyde (PyrAld; 5), N-isopropyl-2-pyrrolylaldiminate (PyrIm iPr; 6a), N-ethyl-2-pyrrolylaldiminate (PyrImEt; 6b), and N-isopropyl-2-salicylaldiminate (IPSA; 7)} were investigated, and most combinations were found to deposit metal films or metal powder at 50 °C or less. SEM and XPS of metal films deposited on ruthenium showed a range of morphologies and compositions, including pure copper (excluding oxygen content after atmospheric exposure). These nonaqueous solution screening studies provided a rapid and convenient means to identify the most promising [CuIIL2] precursor/ER n co-reagent combinations for copper metal ALD/pulsed-CVD studies, and subsequent ALD/pulsed-CVD studies were performed using 6b in combination with AlMe3, BEt3 and ZnEt2. As in solution, the reactivity of these reagents (pulsed-CVD) followed the order ZnEt2 ≈ AlMe3 ≫ BEt3. Furthermore, at 120−150 °C, ZnEt2 was used successfully to deposit smooth, conductive films composed of copper with 8−15% Zn. On the basis of CVD studies with ZnEt2, zinc content appears to derive from a parasitic CVD process, which becomes more favorable above 120 °C, detracting from the goal of self-limiting deposition.