Effects of photoirradiation in UV and VUV regions during plasma exposure to polymers

Interactions between photons irradiated from Ar-O₂ mixture plasmas and polymer surfaces were investigated on the basis of depth analyses of chemical bonding states in the nano-surface layer of polyethylene terephthalate (PET) films via hard X-ray photoelectron spectroscopy (HXPES) and conventional X-ray photoelectron spectroscopy (XPS). The PET films were exposed to photons from the Ar-O₂ mixture plasmas by covering the PET samples with MgF₂ and quartz windows as optical filters for evaluation of photoirradiation effects in ultraviolet (UV) and vacuum ultraviolet (VUV) regions. The HXPES results indicated that the degradation of the chemical bonding states due to photoirradiation in regions was insignificant in deeper regions up to about 50 nm from the surface. Whereas, conventional XPS analysis showed that CO bond, OCO bond and CO bond increased after photoirradiation in UV and VUV regions. These results suggest that the increase in oxygen functionalities (CO bond, OCO bond and CO bond) may be attributed to chemical reactions and/or terminations of scissed bonds via photodecompositions of the polymer with oxygen and/or OH species (oxygen molecules and radicals during plasma exposure and/or oxygen molecules and moisture after taking the PET samples out of the plasma reactor to the ambient air) in the vicinity of the sample surface.     

A vapor phase deposition of self-assembled monolayers: Vinyl-terminated films of volatile silanes on silicon oxide substrates

Vinyl-terminated self-assembled monolayers (SAMs) offer significant flexibility for further chemical modification and can serve as a versatile starting point for a tailoring of surface properties. A vapor phase deposition of such films would offer advantages in cases where the preparation from solution is not an option or not desired, for example in connection with silicon microstructures such as micro-electromechanical systems. We show that SAMs of 9-decenyltrichlorosilane (CH₂CH(CH₂)₈SiCl₃), 10-undecenyltrichlorosilane (CH₂CH(CH₂)₉SiCl₃), 14-pentadecenyltrichlorosilane (CH₂CH(CH₂)₁₃SiCl₃), decyltrichlorosilane (CH₃(CH₂)₉SiCl₃), and octadecanetrichlorosilane (CH₃(CH₂)₁₇SiCl₃) can be prepared both from solution and from the vapor phase. The resulting layers were compared by static contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy to determine their surface wettability, the film thickness, the smoothness and homogeneity of the respective films, and their chemical composition and each method gave films of comparable quality. Deposition of functionalized SAMs from the vapor phase is rare. Here we report the parameters for the preparation of well-ordered vinyl-terminated SAMs from the vapor phase.     

Preparation and characterization of silicate nanofilms doped with europium β-diketonate complexes

Films consisting of Eu³⁺ β-diketonate complexes were deposited onto glassy substrates by means of the spin- and dip-coating techniques, using different ion/ligand ratios. Absorption spectroscopy in the infrared region revealed the typical stretching bands of the SiOSi and SiOH bonds of the inorganic matrix as well as bands relative to the CO and CH symmetric vibration of β-diketone (dibenzoylmethane). The films displayed UV-visible absorption band at 350 nm, attributed to the organic ligand. Luminescence properties were studied by photoluminescence spectroscopy. Upon ligand excitation, the emission spectra exhibited the characteristic bands of the Eu³⁺ ion corresponding to the transition from the excited state ⁵D₀ to the ground state ⁷F_J. Scanning electron microscopy confirmed the formation of a film with average thickness ranging from 80 to 100 nm. The sol-gel process and the deposition techniques resulted in the effective formation of nanofilms, which opens up perspectives for their application in photonics.     

Surface characterization of plasma-treated and PEG-grafted PDMS for micro fluidic applications

The contact angle measurements have shown that polydimethyl siloxane (PDMS) surfaces treated by air plasma can recover up to about 40% of its hydrophobic nature in less than 20 min of air exposure. Therefore, poly(ethylene glycol) (PEG) silane was grafted after plasma treatment to permanently change the PDMS surface as hydrophilic in nature for micro fluidic application. The surface chemistry of plasma-treated and PEG-grafted PDMS substrate has been studied using X-ray photoelectron spectroscopy (XPS). The proportion of carbon atoms as C-Si and hydrocarbon decreased for both plasma-treated as well as PEG-grafted PDMS surfaces. The plasma treatment had increased the proportion of carbon atoms as CO and C(O)OX in C1s, whereas grafting of PEG silane decreased the proportion of C(O)OX and an increase in C-OX and CO functionalities. This is due to the interaction of OCH₃ on Si (in PEG silane) with C-OX and C(O)OX on plasma-treated PDMS by covalent bonding. Therefore, an increase in CO and C-OX functionalities and relative decrease in C(O)OX is expected. The plasma treatment of micro channels had increased the fluid velocity by a factor or four and similar measurements were observed in PEG grafted micro channel in PDMS chip. This indicates that the fluid velocity depends on the hydrophilic nature of substrate. The effect of nature of fluids on the fluid velocity in PDMS-based micro channel was also studied. It was observed that the fluid velocity was decreased with decreasing the pH values of the fluid.     

Bonding structure and optical properties of a-CNx:H films deposited in CH4-NH3 system

Hydrogenated amorphous carbon nitride (a-CN_x:H) films were deposited by plasma enhanced chemical vapor deposition (PECVD) in CH₄-NH₃ system. The chemical composition and bonding configuration were investigated by XPS and FTIR. The results indicated that both sp²CN and sp³CN bonds generally increased with the increase of the nitrogen concentration, and the N atoms bonded to C atoms through CN, CN and CN bonds. Remarkably, for FTIR spectra, two peaks (2125 and 2200 cm⁻¹) were obviously observed, corresponding to CN bond which was found to predominantly exist in the isonitrile structure. As more nitrogen atoms were incorporated, the optical band gap was found to vary from 1.8 to 2.5 eV. Finally, the conduction mechanisms were discussed at low and high temperature, respectively.