A. Maldonado


3 Undoped and Fluorine Doped Zinc Oxide (ZnO:F) Thin Films Deposited by Ultrasonic Chemical Spray: Effect of the Solution on the Electrical and Optical Properties

Authors: E. Chávez-Vargas, M. de la L. Olvera-Amador, A. Jimenez-Gonzalez, A. Maldonado


Undoped and fluorine doped zinc oxide (ZnO) thin films were deposited on sodocalcic glass substrates by the ultrasonic chemical spray technique. As the main goal is the manufacturing of transparent electrodes, the effects of both the solution composition and the substrate temperature on both the electrical and optical properties of ZnO thin films were studied. As a matter of fact, the effect of fluorine concentration ([F]/[F+Zn] at. %), solvent composition (acetic acid, water, methanol ratios) and ageing time, regarding solution composition, were varied. In addition, the substrate temperature and the deposition time, regarding the chemical spray technique, were also varied. Structural studies confirm the deposition of polycrystalline, hexagonal, wurtzite type, ZnO. The results show that the increase of ([F]/[F+Zn] at. %) ratio in the solution, decreases the sheet resistance, RS, of the ZnO:F films, reaching a minimum, in the order of 1.6 Ωcm, at 60 at. %; further increase in the ([F]/[F+Zn]) ratio increases the RS of the films. The same trend occurs with the variation in substrate temperature, as a minimum RS of ZnO:F thin films was encountered when deposited at TS= 450 °C. ZnO:F thin films deposited with aged solution show a significant decrease in the RS in the order of 100 ΩS. The transmittance of the films was also favorable affected by the solvent ratio and, more significantly, by the ageing of the solution. The whole evaluation of optical and electrical characteristics of the ZnO:F thin films deposited under different conditions, was done under Haacke’s figure of Merit in order to have a clear and quantitative trend as transparent conductors application.

Keywords: zinc oxide, ZnO:F, TCO, Haacke’s figure of Merit

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2 Influence of the Molar Concentration and Substrate Temperature on Fluorine-Doped Zinc Oxide Thin Films Chemically Sprayed

Authors: J. Ramirez, A. Maldonado, M. de la L. Olvera


The effect of both the molar concentration of the starting solution and the substrate temperature on the electrical, morphological, structural and optical properties of chemically sprayed fluorine-doped zinc oxide (ZnO:F) thin films deposited on glass substrates, is analyzed in this work. All the starting solutions employed were aged for ten days before the deposition. The results show that as the molar concentration increases, a decrease in the electrical resistivity values is obtained, reaching the minimum in films deposited from a 0.4 M solution at 500°C. A further increase in the molar concentration leads to a very slight increase in the resistivity. On the other hand, as the substrate temperature is increased, the resistivity decreases and a tendency towards to minimum value is evidenced; taking the molar concentration as parameter, minimum values are reached at 500°C. The attain of ZnO:F thin films, with a resistivity as low as 7.8×10-3 Ώcm (sheet resistance of 130 Ώ/☐ and film thickness of 600 nm) measured in as-deposited films is reported here for the first time. The concurrent effect of the high molar concentration of the starting solution, the substrate temperature values used, and the ageing of the starting solution, which might cause polymerization of the zinc ions with the fluorine species, enhance the electrical properties. The structure of the films is polycrystalline, with a (002) preferential growth. Molar concentration rules the surface morphology as at low concentration an hexagonal and porous structure is developed changing to a uniform compact and small grain size surface in the films deposited with the high molar concentrations.

Keywords: Thin Films, zinc oxide, chemical spray, TCO

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1 Nanostructured Fluorine Doped Zinc Oxide Thin Films Deposited by Ultrasonic Spray Pyrolisys Technique: Effect of Starting Solution Composition and Substrate Temperature on the Physical Characteristics

Authors: Esmeralda Chávez Vargas, M. de la L. Olvera, A. Maldonado


The doping it is believed as follows, at high concentration fluorine in ZnO: F films is incorporated to the lattice by substitution of O-2 ions by F-1 ions; at middle fluorine concentrations, F ions may form interstitials, whereas for low concentrations it is increased the carriers and mobility could be explained by the surface passivation effect of fluorine. ZnO:F thin films were deposited on sodocalcic glass substratesat 425 °C , 450°C, 475 during 8, 12, 15 min from a 0.2 M solution. Doping concentration in the starting solutions was varied, namely, [F]/[F+Zn] = 0, 5, 15, 30, 45, 60, and 90 at. %; solvent composition was varied as well, 100:100; 50:50; 100:50(acetic acid: water: methanol ratios, in volume). In this work it is reported the characterization results of fluorine doped zinc oxide (ZnO:F) thin films deposited by the ultrasonic spray pyrolysis technique, using zinc acetate and ammonium fluorine as Zn an F precursors, respectively. The effect of varying the fluorine concentration in the starting solutions, the solvent composition, and the ageing time of the starting solutions, on the electrical resistivity, optical transmittance, structure and surface morphology was analyzed. In order to have a quantitative evaluation of the ZnO:F thin films for its application as transparent electrodes, the Figure of Merit was estimated from the Haacke´s formula. After a thoroughly study, it can be found that optimal conditions for the deposition of transparent and conductive ZnO:F thin films on sodocalcic substrates, were as follows; substrate temperature: solution molar concentration 0.2, doping concentration in the starting solution of [F]/[Zn]= 60 at. %, (water content)/(acetic acid) in starting solution: [H2O/ CH3OH]= 50:50, substrate temperature: 450 °C. The effects of aging of the starting solution has also been analyzed thoroughly and it has been found a dramatic effect on the electric resistivity of the material, aged by 40 days, show an electrical resitivity as low as 120 Ω/□, with a transmittance around 80% in the visible range. X-ray diffraction spectra show a polycrystalline of ZnO (wurtzite structure) where the amount of fluorine doping affects to preferential orientation (002 plane). Therefore, F introduction in lattice is by the substitution of O-2 ions by F-1 ions. The results show that ZnO:F thin films are potentially adequate for application as transparent conductive oxide in thin film solar cells.

Keywords: Transparent Electrodes, zinc oxide, TCOs, ultrasonic spray pyrolysis, ZnO:F

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