Adsorption and Thermal Stability of Ionic Liquid Multilayers on ZnO Surfaces

Ionic liquids (ILs) have been explored as a way of improving the performance of ZnO-based optoelectronic devices; however, there are few fundamental studies of the IL/ZnO interface. Here, the adsorption of the IL 1-octyl-3-methylimidazolium tetrafluoroborate [C8C1Im][BF4] on ZnO (0001) and ZnO (101¯0) has been studied using synchrotron-based soft X-ray photoelectron spectroscopy. The results indicate that [C8C1Im][BF4] is deposited intact on the ZnO (0001) surface; however, there is some dissociation of [BF4]− anions, resulting in boron atoms attaching to the oxygen atoms in the ZnO surface and forming B2O3. In contrast, the deposition of [C8C1Im][BF4] on the ZnO (101¯0) surface at −150 °C results in the appearance of more chemical environments in the spectra. We propose that the high temperature of the IL evaporator causes some conversion of [C8C1Im][BF4] to a carbene–borane adduct, resulting in the deposition of both the IL and adduct onto the ZnO surface. The adsorption and desorption of the analogous IL 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1Im][BF4] was investigated on ZnO (0001) using synchrotron-based soft X-ray photoelectron spectroscopy. The results indicate that [C4C1Im][BF4] is deposited largely intact at −150 °C and forms islands when heated to room temperature. When heated to over 80 °C, it begins to react with the ZnO surface and decomposes. This is a much lower temperature than the long-term thermal stability of the pure IL, quoted in the literature as ~400 °C, and of IL on powdered ZnO, quoted in the literature as ~300 °C. This indicates that the ZnO surface may catalyse the thermal decomposition of [C4C1Im][BF4] at lower temperatures. This is likely to have a negative impact on the potential use of ILs in ZnO-based photovoltaic applications, where operating temperatures can routinely reach 80 °C.