Preferred crystallographic orientation (texture) in thin films of technologically important materials frequently has a strong effect on the properties of these films and is important for stable surface properties. The deposition of organized molecular films of a poly‐perfluorodecylacrylate, poly‐(1H,1H,2H,2H‐perfluorodecyl acrylate) (p‐PFDA), by initiated chemical vapor deposition (iCVD) is described. The tendency of p‐PFDA to crystallize in a smectic B phase has been reported in films prepared from solution but not for those using a CVD technique. The degree of crystallinity and the preferred orientation of the perfluoro side chains, either parallel or perpendicular to the surface, are controlled by tuning the CVD process parameters (i.e., initiator to monomer flow rate ratio, filament temperature, and substrate temperature). Films with no observable X‐ray diffraction patterns are also achieved. The observed differences in crystal texture strongly impact the observed water contact angles (150° to 130°, advancing) and corresponding hysteresis behavior. Low hysteresis (<7°) is associated with high crystallinity, particularly when the orientation of the crystallites resulted in the perfluoro side groups being oriented parallel to the surface. The latter texture resulted in smoother film than the texture with the chains oriented perpendicular to the surface and this can be very advantageous for applications in which relatively smooth but still crystalline films are needed.

Clusters of methanol and ethanol formed above neat liquid samples were entrained in a supersonic jet of helium and probed in the expansion using 118 nm vacuum ultraviolet laser single-photon ionization/time-of-flight (TOF) mass spectrometry. Almost every cluster ion observed in the TOF mass spectra could be represented by the formula H(ROH)n+, where R=CH3 or C2H5, and n=1–5. Formation of these species is attributed to a well-established ionization pathway where each protonated (n−1)-mer originates from its n-mer neutral parent. Signals in the TOF mass spectra due to the protonated trimers H(CH3OH)3+ and H(CH3CH2OH)3+ were found to be the most intense and provides direct evidence that these particular cluster ions are “magic-number” structures. The possible relationships between the observed ion data and the neutral cluster vapor phase distributions are discussed. In this context, methanol and ethanol vapor cluster distributions at 298.15 K and at several pressures⩾the equilibrium vapor pressure were computed using the grand canonical Monte Carlo and molecular dynamics techniques. Lastly, differences between these experiments and the results of bimolecular reaction studies are discussed.

This report describes the preparation of superhydrophobic and oleophobic surfaces by grafting of poly(perfluorodecylacrylate) chains with initiated chemical vapor deposition on silicon substrates. The grafting enhances the formation of a semicrystalline phase. The crystalline structures reduce the polymer chain mobility, resulting in nonwetting surfaces with both water and mineral oil. On the contrary, the same contacting liquid easily wets the amorphous ungrafted polymer.

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To study the effect of an Si-Si bond on gas-phase reaction chemistry in the hot-wire chemical vapor deposition (HWCVD) process with a single source alkylsilane molecule, soft ionization with a vacuum ultraviolet wavelength of 118 nm was used with time-of-flight mass spectrometry to examine the products from the primary decomposition of hexamethyldisilane (HMDS) on a heated tungsten (W) filament and from secondary gas-phase reactions in a HWCVD reactor. It is found that both Si-Si and Si-C bonds break when HMDS decomposes on the W filament. The dominance of the breakage of Si-Si over Si-C bond has been demonstrated. In the reactor, the abstraction of methyl and H atom, respectively, from the abundant HMDS molecules by the dominant primary trimethylsilyl radicals produces tetramethylsilane (TMS) and trimethylsilane (TriMS). Along with TMS and TriMS, various other alkyl-substituted silanes (m/z = 160, 204, 262) and silyl-substituted alkanes (m/z = 218, 276, 290) are also formed from radical combination reactions. With HMDS, an increasing number of Si-Si bonds are found in the gas-phase reaction products aside from the Si-C bond which has been shown to be the major bond connection in the products when TMS is used in the same reactor. Three methyl-substituted 1,3-disilacyclobutane species (m/z = 116, 130, 144) are present in the reactor with HMDS, suggesting a more active involvement from the reactive silene intermediates.

The gas-phase reaction products of silacyclobutane (SCB) and 1, 1-dideuterio-silacyclobutane (SCB-d(2)) from a hot-wire chemical vapor deposition (HWCVD) chamber were diagnosed in situ using vacuum ultraviolet (VUV) laser single-photon ionization (SPI) coupled with time-of-flight (TOF) mass spectrometry. The SCB molecule was found to decompose at a filament temperature as low as 900 degrees C. Both Si- (silylene, methylsilylene, and silene) and C-containing (ethene and propene) species were produced from the SCB decomposition on the filament. Ethene and propene were detected by the mass spectrometer. It is demonstrated that the formation of ethene is favored over that of propene. The experimental study of hot-wire decomposition of SCB-d(2) shows that propene is most likely produced by a process that is initiated by a 1,2-H(D) migration to form n-propylsilylene, followed by an equilibration with silacyclopropane, which then decomposes to propene. The detection of ethene in our experiment indicates that a competitive route of fragmentation exists for SCB decomposition on the filament. It has been shown that this competitive route occurs without H/D scrambling. The highly reactive silylene, silene, and methylsilylene species produced from SCB decomposition underwent either insertion reactions into the Si-H bonds of the parent molecule or pi-type addition reaction across the double and triple CC bonds. The dimerization product of silene, 1,3-disilacyclobutane, at m/z = 88 was also observed.

The effect of the Si-H bond on the gas-phase reaction chemistry of trimethylsilane in the hot-wire chemical vapor deposition (HWCVD) process has been studied by examining its decomposition on a hot tungsten filament and the secondary gas-phase reactions in a reactor using a soft laser ionization source coupled with mass spectrometry. Trimethylsilane decomposes on the hot filament via Si-H and Si-CH(3) bond cleavages. A short-chain mechanism is found to dominate in the secondary reactions in the reactor. It has been shown that the hydrogen abstractions of both Si-H and C-H occur simultaneously, with the abstraction of Si-H being favored. Tetramethylsilane and hexamethyldisilane are the two major products formed from the radical recombination reactions in the termination steps. Three methyl-substituted disilacyclobutane molecules, i.e., 1,3-dimethyl-1,3-disilacyclobutane, 1,1,3-trimethyl-1,3-disilacyclobutane, and 1,1,3,3-tetramethyl-1,3-disilacyclobutane are also produced in reactor from the cycloaddition reactions of methyl-substituted silene species. Compared to tetramethylsilane and hexamethyldisilane, a common feature with trimethylsilane is that the short-chain mechanism still dominates. However, a more active involvement of the reactive silene intermediates has been found with trimethylsilane.

The decomposition of 1,1-dimethyl-1-silacyclobutane (DMSCB) on a heated tungsten filament has been studied using vacuum ultraviolet laser single photon ionization time-of-flight mass spectrometry. It is found that the decomposition of DMSCB on the W filament to form ethene and 1,1-dimethylsilene is a catalytic process. In addition, two other decomposition channels exist to produce methyl radicals via the Si-CH(3) bond cleavage and to form propene (or cyclopropane)/dimethylsilylene. It has been demonstrated that both the formation of ethene and that of propene are stepwise processes initiated by the cleavage of a ring C-C bond and a ring Si-C bond, respectively, to form diradical intermediates, followed by the breaking of the remaining central bonds in the diradicals. The formation of ethene via an initial cleavage of a ring C-C bond is dominant over that of propene via an initial cleavage of a ring Si-C bond. When the collision-free condition is voided, secondary reactions in the gas-phase produce various methyl-substituted 1,3-disilacyclobutane molecules. The dominant of all is found to be 1,1,3,3-tetramethyl-1,3-disilacyclobutane originated from the dimerization of 1,1-dimethylsilene.