The comprehension of side effects caused by high-temperature thermal treatments in the design of (photo)electrodes is essential to achieve efficient and cost-effective devices for solar water splitting. This investigation explores the beneficial and damaging impacts of thermal treatments in the (photo)electrode design, unraveling the impact of self-diffusion and its consequences. The industrial-friendly polymeric precursor synthesis (PPS) method, which is known for its easy technological application, was chosen as the fabrication technique for hematite photoabsorbers. For substrate evaluation, two types of conductive glass substrates, aluminum borosilicate and quartz, both coated with fluorine-doped tin oxide (ABS/FTO and QTZ/FTO, respectively), were subjected to thermal treatments following the PPS protocol. Optical and structural analyses showed no significant alterations in substrate properties, whereas X-ray photoelectron spectroscopy (XPS) revealed the migration of silicon and calcium ions from the glass component to the FTO surface. This diffusion can be further mitigated by an oxide buffer layer. To track the potential ion diffusion on the photoabsorber surface and assess its effect on the photoelectrode performance, hematite was selected as the model material and deposited onto the glass substrates. From all the ions that could possibly migrate, only Si4+ and Ca2+ originating from the glass component, as well as Sn4+ from the fluorine-doped tin oxide (FTO), were detected on the surface of the hematite photoabsorber. Interestingly, the so-called "self-diffusion" of these ions did not result in any beneficial effect on the hematite photoelectrochemical response. Instead, intentional modifications showed more substantial impacts on the photoelectrochemical efficiency compared to unintentional self-diffusion. Therefore, "self-diffusion", which can unintentionally dope the hematite, is not sufficient to significantly impact the final photocurrent. These findings emphasize the importance of understanding the true effect of thermal treatments on the photoelectrode properties to unlock their full potential in photoelectrochemical applications.
Keywords: FTO; buffer layer; glass diffusion; hematite; photoelectrochemical; unintentional doping.