Organic Beam Epitaxy Using Controlled PMDA−ODA Coupling Reactions on Cu{110}

Abstract

Reflection−absorption infrared spectroscopy (RAIRS) has been used to study in detail, as a function of temperature and coverage, the interaction of pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) on the clean and oxygen-precovered Cu{110} surfaces. On the clean surface, both molecules show coverage-dependent reorientation from flat lying to upright species. The adsorption of PMDA on the clean surface leads to a ring-opening reaction of one of the anhydride group to produce a species with both carbonyl and carboxylate groups. The carbonyl group is lost into the gas phase above 350 K, with the resulting anhydride species bonded to the surface via the carboxylate group. The presence of preadsorbed oxygen also leads to the reaction of one of the anhydride groups, although in this case a dicarboxylate (phthalate) anhydride species is produced. The condensation reaction of 4,4-oxydianiline with the two PMDA-derived species has also been studied. It is shown that the PMDA−ODA oligomer can be grown layer by layer using controlled imide coupling reactions. The growth is monitored by IR spectroscopy.

Organic and inorganic–organic thin film structures by molecular layer deposition: A review

“…Yoshida et al [ 63 ] also modified the films electrically by using a scanning probe microscope and reported significant increases in the conductivity of the films. The precursor combination, PMDA+ODA, was also employed by Haq et al [ 65 ], who used reflection–absorption infrared spectroscopy to study the growth on Cu(110) surfaces as a function of temperature and coverage but did not discuss growth rates of the films. Also Miyamae et al [ 66 ] deposited thin films by using PMDA and ODA, but as PMDA was introduced to the reactor so that the pulsing of ODA was kept on, the growth process was not necessarily of the real MLD type.…”

Growth and Properties of Hybrid Organic‐Inorganic Metalcone Films Using Molecular Layer Deposition Techniques

“…Polyimide MLD using pyromellitic dianhydride (PMDA) and diamines as the reactants has also been studied by various surface science techniques 58–60. Electron energy loss investigations monitored the reaction between PMDA and 1,4‐phenylene diamine (PDA) and observed the initial formation of amic acid.…”

“…Electron energy loss investigations monitored the reaction between PMDA and 1,4‐phenylene diamine (PDA) and observed the initial formation of amic acid. The amic acid converted to the polyimide with the loss of H 2 O. Reflection‐absorption infrared spectroscopy was also used to monitor the growth of polyimide using PDMA and 4,4‐oxidianiline (ODA) reactants 59. Studies of polyimide MLD growth have observed temperature‐dependent linear growth rates 38.…”

Atomic/molecular layer deposited thin-film alloys of Ti-4,4′-oxydianiline hybrid–TiO2 with tunable properties

“…Since the pioneering works in the 1990s, [7][8][9][10][11][12] a number of MLD-grown organic polymers, e.g. polyamides, 8,10,13,14 polyimides, 12,[15][16][17] polyimide-amides, 18 polyurea, 19 polyurethane, 20 polythiourea, 21 polyester, 22 and polyazomethine, [23][24][25] have been reported. More recently, it was shown that the two techniques, ALD and MLD, can also be used in combination to produce inorganic-organic hybrid thin films.…”