title: Covalent molecular assembly of oligoimide ultrathin films in supercritical and liquid solvent media.
abstract: An ultrathin film of oligoimide has been fabricated on amine-modified substrates of silicon and quartz through alternate layer-by-layer (LBL) assembly of pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (DDE), with interlayer links established by covalent bonds. The assembly was formed in supercritical carbon dioxide (SCCO2) and in solution (dimethyl acetamide, DMAc), and the imidization reaction was performed by thermal and chemical methods, in benzene and in the supercritical medium. X-ray photoelectron and UV-visible absorption spectroscopies, atomic force microscopy (AFM), and ellipsometry were employed to study the interfacial chemistry, growth, morphology, and thickness of the assembled film. XPS analysis confirmed the sequential deposition of PMDA and DDE through formation of amic acids. At each deposition step, surface functionalities for the assembly of the next layer were generated. The interfacial chemical reaction was almost complete in the SCF (supercritical fluid) medium, as compared to the conversions observed in conventional assembly. Both the PMDA and DDE molecules were assembled in an organized manner, resulting in uniform surface morphology. Uniform film growth was revealed from the increase of UV absorption intensity and film thickness. The overall growth and quality of the films in SCF medium were greater than that for films formed in DMAc. The results of this novel study show that an environmentally friendly solvent can be used to obtain mechanically robust and thermally stable ultrathin films with little loss of material during the imidization step. In contrast to conventional deposition of the molecular layers that utilizes liquid solvents, use of SCCO(2) avoids solvent effects and posttreatment for solvent removal, while ensuring facile transport during contact.
authors.affiliation: Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576.
authors.forename: Sreenivasa Reddy
authors.initials: SR
authors.lastname: Puniredd
authors.forename: M P
authors.initials: MP
authors.lastname: Srinivasan
mesh_terms: D001565:Benzoates / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D008567:Membranes, Artificial; D018625:Microscopy, Atomic Force / Q000379:methods; D015394:Molecular Structure; D010647:Phenyl Ethers / Q000737:chemistry*; D011312:Pressure; D011791:Quartz / Q000737:chemistry; D012680:Sensitivity and Specificity; D012825:Silicon / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013053:Spectrophotometry / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013499:Surface Properties; D014965:X-Rays
chemical_list: D001565:Benzoates; D008567:Membranes, Artificial; D010647:Phenyl Ethers; D012997:Solvents; D002245:Carbon Dioxide; D011791:Quartz; C015126:di-(4-aminophenyl)ether; C012019:pyromellitic dianhydride; D012825:Silicon