New angle for perovskite research

Perovskite materials offer the potential for cheaper optoelectronic devices such as solar cells. Of these, the formamidinium (FA)-based FAPbI3 crystal is one of the most promising – it has a bandgap close to ideal and is very thermally stable. However, photoactive cubic (α)-FAPbI3 perovskite phase is highly unstable and quickly transforms into the non-perovskite yellow phase at room temperature in ambient atmosphere, which affects the performance of photovoltaic devices. Alloying of FA-based perovskite with caesium, methylammonium (MA) cations or a combination of both can keep the perovskite in its more efficient phase at lower temperatures. However, this can give patchy results, leading to power losses.

In work recently published in Science, researchers from the University of Cambridge Department of Chemical Engineering and Biotechnology (CEB) and the Cavendish Laboratory investigated the crystal structure of the alloyed perovskite materials to understand why adding cations improved their performance. Their results show that cation alloying induces a minor octahedral tilt that keeps the perovskite material in its highly efficient phase, and is a step towards commercial production of stable and efficient perovskite-based solar cells. 

A small distortion makes a big difference

Formamidinium (FA)-based perovskites have much better thermal stability than the methylammonium (MA)-based absorber layers commonly used in early perovskite-based solar cells. FAPbI3 is a particularly promising material, but its photoactive phase is only stable at high temperatures (above 150ºC) in inert atmosphere. It transitions to a hexagonal phase with poor optoelectronic performance at lower temperatures.  

It has been shown empirically that alloying FAPbI3 with methylammonium (MA) cations or caesium (or both) improves stability. However, although this approach led to record efficiencies, the mechanism underlying it was not fully understood. It also produces uneven materials with patches of instability that lead to performance losses. 

Co-lead author Tiarnan Doherty was a PhD student at the Cavendish Laboratory and is now an Oppenheimer Fellow in CEB. He says:

We wanted to investigate the atomic structure of the alloyed perovskite materials, but they’re very sensitive to damage. So we brought the samples to ePSIC for high-resolution electron microscopy with a low electron dose. We also used nano X-ray diffraction on beamline I14. That beamline has very sensitive detectors, which allowed us to achieve our results using low X-ray exposures.

Read more on the Diamond website

Image: Artist’s impression of formamidinium (FA)-based crystal

Credit: Tiarnan Doherty, University of Cambridge