Self-assembly of zinc oxide thin films modified with tetrasulfonated metallophthalocyanines by one-step electrodeposition

被引:195
作者
Yoshida, T
Tochimoto, M
Schlettwein, D
Wöhrle, D
Sugiura, T
Minoura, H
机构
[1] Gifu Univ, Fac Engn, Dept Chem, Gifu 5011193, Japan
[2] Univ Bremen, Inst Angew & Phys Chem, D-28334 Bremen, Germany
[3] Univ Bremen, Inst Organ & Makromol Chem, D-28334 Bremen, Germany
关键词
D O I
10.1021/cm980619o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Cathodic electrodeposition in an aqueous mixed solution of zinc nitrate and water-soluble tetrasulfonated metallophthalocyanines (TSPcMs), in which M = Zn(II) (TSPcZn), AI(III)[OH] (TSPcAl), or Si(IV)[OH](2) (TSPcSi), resulted in a self-assembled growth of zinc oxide (ZnO) thin films whose surface is modified by TSPcMs. It has been found that the adsorption of TSPcM onto the growing surface of ZnO strongly affects the crystal growth and the orientation of the ZnO crystallites. The effect was most prominently seen with TSPcSi, creating a film looking like stacking disks aligned perpendicular to the substrate. Crystallographic studies by X-ray diffraction and TEM observation coupled with the selected area electron beam diffraction have revealed that; thin platelike crystals, whose planes and edges correspond to the (002) and (100) crystal faces, respectively, are aligned in the same orientation around the c-axis within the stacks. The evolution of this unique structure is interpreted as arising from the preferential adsorption of TSPcMs at the (002) planes, leading to film growth preferentially in the (100) direction. Optical analysis of the films also revealed high order in the interactions among TSPcMs. Because of the strong intermolecular attraction, TSPcZn forms multilayers of pi-stacking aggregates on ZnO as confirmed by the characteristic blueshift of the Q-band absorption. Thus, TSPcZn could be condensed at a very high concentration exceeding 1 M in the deposited film. These surface aggregates were completely removed by dipping the film in a solution of cationic detergent, cetyltrimethylammonium chloride, while only leaving surface-bound monomeric TSPcZn. By contrast, the aggregation was hindered for TSPcA1 and TSPcSi because of the presence of axially coordinated OH-, and monomeric adsorption was found in the electrodeposited films.
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页码:2657 / 2667
页数:11
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