RESUMO
We show that Al2O3 thin films, grown by atomic layer deposition (ALD) on polyester, are ultrabarriers with moisture permeation <10(-5) g-H2O/m2-day, as determined after aging for more than three years. We present evidence that the mechanism for gas permeation in ALD Al2O3 films is not due to pinholes, but that the onset of permeation occurs abruptly, analogous to electrical breakdown in oxide thin films. We show that the permeation onset time increases for thicker Al2O3 films and higher ALD process temperature, for which the hydrogen defect concentration in Al2O3 films is less. Further, we show that mild plasma treatment of the polyester, prior to ALD deposition of Al2O3, makes the surface more hydrophilic and reduces moisture permeation compared to an untreated surface. Similarly, ALD deposition on the bare or non-slip side of the polyester film is preferred for low permeation.
RESUMO
The reaction of Fe(II)(C5Me5)(C5H5), FeCpCp, with percyano acceptors, A [A = C4(CN)6 (hexacyanobutadiene), TCNQF4 (perfluoro-7,7,8,8-tetracyano-p-quinodimethane), and DDQ (2,3-dichloro-5,6-dicyanobenzoquinone)], results in formation of 1:1 charge-transfer salts of [Fe(III)CpCp]*]*+[A]*- composition. With A = TCNQ (7,7,8,8-tetracyano-p-quinodimethane) a 1:2 electron-transfer salt with FeCpCp forms. With A = TCNE (tetracyanoethylene) a pair of 1:1 salts as well as a pair of 2:3 salts of [FeCpCp]2[TCNE]3.S (S = CH2Cl2, THF) have been isolated and characterized by single-crystal X-ray diffraction. [FeCpCp][TCNE] consists of parallel 1-D.D(*+)A(*-)D(*+)A(*-)D(*+)A(*-). chains, while [FeCpCp][TCNE].MeCN has a herringbone array of D(*+)A2(2-)D(*+) dimers separated by solvent molecules. Although each [TCNE](-) is disordered, the diamagnetic [TCNE]2(2-) dimer is structurally different from those observed earlier with an intradimer separation of 2.79 A. The [TCNE](-) in the 2:3 [FeCpCp]2[TCNE]3.S exists as an eclipsed diamagnetic [TCNE]2(2-) dimer with an intradimer ethylene C.C separation of 2.833 and 2.903 A for the CH2Cl2- and THF-containing materials, respectively. The bond distances and angles for all the cations are essentially equivalent, and the distances are essentially equivalent to those previously reported for [FeCp2](*+) and [FeCp2](*+) cations. The average Fe-C5H5-ring and Fe-C5Me5-ring centroid distances are 1.71 and 1.69 A, respectively, which are 0.05 A longer than reported for Fe(II)CpCp. The one-electron reduction potential for Fe(II)CpCp is 0.11 V (vs SCE). The 5 K EPR of [FeCpCp](*+)[BF4](-) exhibits an axially symmetric powder pattern with g(parallel) = 4.36 and g(perpendicular) = 1.24, and the EPR parameters are essentially identical to those reported for ferrocenium and decamethylferrocenium. The high-temperature magnetic susceptibility for polycrystalline samples of these complexes can be fit by the Curie-Weiss law, chi = C/(T - theta), with low theta values and mu(eff) values from 2.08 to 3.43 mu(B), suggesting that the polycrystalline samples measured had varying degrees of orientation. [FeCpCp][TCNE] exhibits the highest effective moment of 3.43 mu(B)/Fe and weak ferromagnetic coupling, as evidenced from the theta of 3.3 K; however, unexpectedly, it does not magnetically order above 2 K. The formation of the four phases comprising FeCpCp and TCNE emphasizes the diversity of materials that may form and the present inability to predict neither solid-state compositions nor structure types.
RESUMO
The reaction of bis(benzene)vanadium with tetracyanoethylene, TCNE, affords an insoluble amorphous black solid that exhibits field-dependent magnetization and hysteresis at room temperature. The critical temperature could not be estimated as it exceeds 350 kelvin, the thermal decomposition temperature of the sample. The empirical composition of the reported material is V(TCNE)x.Y(CH(2)Cl(2)) with x approximately 2 and Y approximately 1/2. On the basis of the available magnetic and infrared data, threedimensional antiferromagnetic exchange of the donor and acceptor spins resulting in ferrimagnetic behavior appears to be the mode of magnetic coupling.
