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Aluminum-doped zinc oxide (AZO) films (70 nm thick) with dissimilar surface roughness were created on indium tin oxide coated glass and were used as electrodes for inverted organic solar cells. The photovoltaic performance of the devices depended strongly on the surface roughness of the AZO films. Increases in the surface root-mean-square roughness of AZO films from 2.5 to 10.9 nm enhanced power conversion efficiency from 0.5% to 1.4% due to increased contact area between electrode and active layer.

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The reactions of ethyl Y-phenyl chloro (1) and chlorothio (2) phosphates with X-anilines in acetonitrile at 55.0 degrees C are studied kinetically and theoretically. Kinetic results yield the primary kinetic isotope effects (k(H)/k(D) = 1.07-1.80 and 1.06-1.27 for 1 and 2, respectively) with deuterated aniline (XC(6)H(4)ND(2)) nucleophiles, and the cross-interaction constants rho(XY) = -0.60 and -0.28 for and , respectively. A concerted mechanism involving a partial frontside attack through a hydrogen-bonded, four-center-type transition state is proposed. The large rho(X) (rho(nuc) = -3.1 to -3.4) and beta(X) (beta(nuc) = 1.1-1.2) values seem to be characteristic of the anilinolysis of phosphates and thiophosphates with the Cl leaving group. Because of the relatively large size of the aniline nucleophile, the degree of steric hindrance could be the decisive factor that determines the direction of the nucleophilic attack to the phosphate and thiophosphate substrates with the relatively small-sized Cl leaving group.

Kinetic studies for the reactions of dimethyl chlorophosphate (1), dimethyl chlorothionophosphate (2), diethyl chlorophosphate (3), and diethyl chlorothionophosphate (4) with substituted (X) pyridines have been carried out in acetonitrile. The pyridinolyses of the P = O systems (1 and 3) show linear free energy correlations for substituent X variations, while those of the P = S systems (2 and 4) show biphasic concave upward Hammett and Brönsted plots with a break region between 3‐phenyl and 3‐methoxy pyridines. A concerted mechanism with both frontside and backside nucleophilic attack is proposed for the reactions of 1 and 3, but the fraction of a frontside attacks is somewhat larger than that of a backside attack. A concerted mechanism with a dominant backside nucleophilic attack for weakly basic pyridines and a concerted mechanism with a dominant frontside nucleophilic attack for strongly basic pyridines are proposed for the reactions of 2 and 4. The pyridinolysis rate does not depend solely on one major factor. The concave upward free energy relationship can be diagnostic of a change in the direction of the nucleophilic attack. Copyright © 2010 John Wiley & Sons, Ltd.