Development and interface/surface characterization of titanium dioxide and zinc oxide electron-collection interlayer materials for organic solar cells.

摘要

My research on metal oxide electron-harvesting interlayers for organic solar cells was focused as three interrelated projects in this dissertation: i) development of a chemical vapor deposition (CVD) system for TiO 2 film; ii) an electrochemical methodology to evaluate ZnO thin film charge (hole) blocking ability; iii) the effects of plasma modifications on sol-gel ZnO and sol-gel ZnO/organic (active layer) interfaces. In i), we showed that nanoscale (12-36 nm) CVD TiO2 film deposited at 210 oC obtains properties of conformal growth, superior hole blocking ability, stoichiometric metal to oxide ratio. The introduction of CVD TiO2 film as an electron transport layer into organic solar cell significantly improves its J-V characteristics. The optimum TiO2 thickness in the OPV device applications was found to be 24 nm with a high fill factor (0.58) and power conversion efficiency (3.7%) obtained. In ii), simple electrochemical methods, i.e., cyclic voltammetry, impedance spectroscopy have been used to evaluate sol-gel derived ZnO (sg-ZnO) and sputtered ZnO (sp-ZnO) porosity and pinhole density. We showed that sg-ZnO with high surface area porous structure allows the probe molecules and poly-thiophene (P3HT) thin layer to direct contact ITO substrate, whereas sp-ZnO with dense structural property efficiently eliminates these electroactivities. This electrochemical property difference also directly reflects on the device shunt resistance (Rp), where we observed larger leakage current for the devices using sg-ZnO than that of devices using sp-ZnO. In iii), we demonstrated low power radio frequency (RF) O2 and Ar plasma treatments have significant impacts on sg-ZnO near-surface chemical compositions, which in turn influence the onset potential of sg-ZnO electron injection and its energetic alignment with electron acceptors, e.g., C60. Using UPS, we found the presence of localized mid-gap states near the Fermi-level of sg-ZnO, which induces the most favorable band bending and the largest vacuum level shift due to significant electron transfer from sg-ZnO to C60. As a result, the resultant solar cells show the best device performance. Upon the plasma treatments, the passivation effects eliminate the mid-gap state. Therefore, we observed less degree of band bending at ZnO/C60 interface and poorer device performance for the plasma treated sg-ZnO.