Unfolding the Challenges To Prepare Single Crystalline Complex Oxide Membranes by Solution Processing

The ability to prepare single crystalline complex oxide freestanding membranes has opened a new playground to access new phases and functionalities not available when they are epitaxially bound to the substrates. The water-soluble Sr₃Al₂O₆ (SAO) sacrificial layer approach has proven to be one of the most promising pathways to prepare a wide variety of single crystalline complex oxide membranes, typically by high vacuum deposition techniques. Here, we present solution processing, also named chemical solution deposition (CSD), as a cost-effective alternative deposition technique to prepare freestanding membranes identifying the main processing challenges and how to overcome them. In particular, we compare three different strategies based on interface and cation engineering to prepare CSD (00l)-oriented BiFeO₃ (BFO) membranes. First, BFO is deposited directly on SAO but forms a nanocomposite of Sr-Al-O rich nanoparticles embedded in an epitaxial BFO matrix because the Sr-O bonds react with the solvents of the BFO precursor solution. Second, the incorporation of a pulsed laser deposited La_0.7Sr_0.3MnO₃ (LSMO) buffer layer on SAO prior to the BFO deposition prevents the massive interface reaction and subsequent formation of a nanocomposite but migration of cations from the upper layers to SAO occurs, making the sacrificial layer insoluble in water and withholding the membrane release. Finally, in the third scenario, a combination of LSMO with a more robust sacrificial layer composition, SrCa₂Al₂O₆ (SC₂AO), offers an ideal building block to obtain (001)-oriented BFO/LSMO bilayer membranes with a high-quality interface that can be successfully transferred to both flexible and rigid host substrates. Ferroelectric fingerprints are identified in the BFO film prior and after membrane release. These results show the feasibility to use CSD as alternative deposition technique to prepare single crystalline complex oxide membranes widening the range of available phases and functionalities for next-generation electronic devices.