Effects of ZnO Addition in In2O3 Ceramics: Defect Chemistry and Sintering Behavior

D.-H. Park, K.-Y. Son, J.-H. Lee, J.-J. Kim, J.-S. Lee Solid State Ionics, 172 (2004) 431-434

Transparent conducting oxides have a wide range of applications. In2 O3 is an n-type semiconductor. In order to increase its electrical conductivity and due to a steep rise in the price of indium in the last decade, metal cations, such as Sn and Zn, which also serve as sintering aids, are doped into it. Tin-doped indium oxide, in which ~6 % Sn forms a substitutional solution in In2 O3, is widely used in optical devices due to the high electrical conductivity and high transparency at visible light wavelengths [1]. Indium oxide has cubic bixbyte structure which is kept while doping. The coordination arrangement around the indium atoms is demonstrated in Figure 1. In this paper, Zn was chosen as the doping cation. ZnO and In2 O3 react at high temperatures (>1000C) to form a series of homologous compounds, ZnkIn2 Ok+3, where k is an integer as seen in Figure 2. The lattice parameterization, as well as XRD characterization, was done under O2 and N2 at several Zn concentrations. Electrical properties characterization and SEM images were also taken. Zn has shown to reach a solubility limit of 1% under oxygen and 0.5 under N2. Variations in the oxygen partial pressure and the sintering temperature were not conducted, and the material was evaluated in 100% O2 or N2 at 1300C. As known [2] changes in the lattice parameter correspond to the atomic radius (Zn+2r=0.074nm In+3r=0.080nm) in substitutional solid solutions. In accordance with that, the authors' remark on the reason for lattice parameter decrease at low sintering concentration in oxygen is suitable. The authors' conclusion regarding sintering under N2 is unclear. On the one hand it is noted that the interstitial solid solution is formed under N2, while on the other hand different assumptions are made, without a concluding remark that is in accordance with the result. It is noted that the interstitial solid solution of Zn+2 under N2 is expected to increase the carrier concentration as well as the conductivity, even though a decrease in those parameters can be observed in Figure 3 at 1% Zn. Adding more information to the chart at ascending Zn concentration would have been beneficial. Furthermore, it was not noted that another possible reason for the reduction in the carrier concentration at 0.5% Zn under O2 might stem from the higher probability of incorporation of Zn2+ ion into the In3+ sites together with higher oxidation probability. The valence state of Zn2+ is one lower than In3+ and the difference in the ionic radii could reduce the concentration of carriers and distort the host indium oxide [3]. It was remarked that low electrical characteristics of samples sintered in nitrogen are due to the porous structure of the material, although overall

(Figure 3) a significant difference between the two sintering atmospheres is not shown and at 1% Zn they seem to be very similar. Although the authors have shown the appearance of a solid solution following the sintering procedure with ZnO, the product does not appear to meet industry standards and does not serve as a potential candidate for a good transparent semiconductor. This is mainly because other researchers has accomplished to produce such TCO's containing up to 40% [4] of doped solid solution, when co-substituting 2In2 O3 with ZnO and SnO2.

Figures

Figure 1: The coordination arrangement around the indium atoms in the crystaline structure of Zinc Indium [5]

Figure 2: zinc oxide-indium oxide phase diagram[6]

Figure 3: Variation of the conductivity, the carrier concentration and the mobility as a function of Zn+2 content and sintering atmospheres.[7]

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