Researchers at Georgia Institute of Technology have developed a new low-temperature solution printing technique that allows fabrication of high-efficiency perovskite solar cells with large crystals intended to minimise current-robbing grain boundaries. The meniscus-assisted solution printing (MASP) technique boosts power conversion efficiencies to nearly 20% by controlling crystal size and orientation.
According to the researchers the process, which uses parallel plates to create a meniscus of ink containing the metal halide perovskite precursors, could be scaled up to rapidly generate large areas of dense crystalline film on a variety of substrates, including flexible polymers. Operating parameters for the fabrication process were chosen by using a detailed kinetics study of perovskite crystals observed throughout their formation and growth cycle.
It is known that perovskites offesr an attractive alternative to traditional materials for capturing electricity from light, but existing fabrication techniques typically produce small crystalline grains whose boundaries can trap the electrons produced when photons strike the materials.
Existing production techniques for preparing large-grained perovskite films typically require higher temperatures, which is not favourable for polymer materials used as substrates - which could help lower the fabrication costs and enable flexible perovskite solar cells.
To address this So Lin, Research Scientist Ming He and colleagues decided to try a new approach that relies on capillary action to draw perovskite ink into a meniscus formed between two nearly parallel plates approximately 300 microns apart. The bottom plate moves continuously, allowing solvent to evaporate at the meniscus edge to form crystalline perovskite. As the crystals form, fresh ink is drawn into the meniscus using the same physical process that forms a coffee ring on an absorbent surface such as paper.
To establish the optimal rate for moving the plates, the distance between plates and the temperature applied to the lower plate, the researchers studied the growth of perovskite crystals during MASP. Using movies taken through an optical microscope to monitor the grains, they discovered that the crystals first grow at a quadratic rate, but slow to a linear rate when they began to impinge on their neighbours.
The MASP process generates relatively large crystals - 20 to 80 microns in diameter - that cover the substrate surface. Having a dense structure with fewer crystals minimises the gaps that can interrupt the current flow, and reduces the number of boundaries that can trap electrons and holes and allow them to recombine.
Using films produced with the MASP process, the researchers have built solar cells that have power conversion efficiencies averaging 18 percent - with some as high as 20 percent. The cells have been tested with more than 100 hours of operation without encapsulation.
Doctor-blading is one of the conventional perovskite fabrication techniques in which higher temperatures are used to evaporate the solvent. Lin and his colleagues heated their substrate to only about 60 degrees Celsius, which would be potentially compatible with polymer substrate materials.
So far, the researchers have produced centimetre-scale samples, but they believe the process could be scaled up and applied to flexible substrates, potentially facilitating roll-to-roll continuous processing of the perovskite materials. That could help lower the cost of producing solar cells and other optoelectronic devices.
Among the next steps are fabricating the films on polymer substrates, and evaluating other unique properties (e.g., thermal and piezotronic) of the material.
Zhiqun Lin, a professor in the School of Materials Science and Engineering at the Georgia Institute of Technology, said, "We used a meniscus-assisted solution printing technique at low temperature to craft high quality perovskite films with much improved optoelectronic performance," Lin add "We began by developing a detailed understanding of crystal growth kinetics that allowed us to know how the preparative parameters should be tuned to optimize fabrication of the films."
Lin explained "Because solvent evaporation triggers the transport of precursors from the inside to the outside, perovskite precursors accumulate at the edge of the meniscus and form a saturated phase." Lin added, "This saturated phase leads to the nucleation and growth of crystals. Over a large area, we see a flat and uniform film having high crystallinity and dense growth of large crystals."
Lin continued, "When the crystals run into their neighbors, that affects their growth. We found that all of the grains we studied followed similar growth dynamics and grew into a continuous film on the substrate. The stability of our MASP film is improved because of the high quality of the crystals. The meniscus-assisted solution printing technique would have advantages for flexible solar cells and other applications requiring a low-temperature continuous fabrication process. We expect the process could be scaled up to produce high throughput, large-scale perovskite films."
Meniscus-assisted solution printing of large-grained perovskite films for high-efficiency solar cells
Ming He | Bo Li | Xun Cui | Beibei Jiang | Yanjie He | Yihuang Chen | Daniel O’Neil | Paul Szymanski | Mostafa A. EI-Sayed | Jinsong Huang | Zhiqun LinNature Communications 8, Article number: 16045 (2017) | doi:10.1038/ncomms16045
Received: 19 October 2016 | Accepted: 23 May 2017 | Published online: 07 July 2017
Abstract
Control over morphology and crystallinity of metal halide perovskite films is of key importance to enable high-performance optoelectronics. However, this remains particularly challenging for solution-printed devices due to the complex crystallization kinetics of semiconductor materials within dynamic flow of inks. Here we report a simple yet effective meniscus-assisted solution printing (MASP) strategy to yield large-grained dense perovskite film with good crystallization and preferred orientation. Intriguingly, the outward convective flow triggered by fast solvent evaporation at the edge of the meniscus ink imparts the transport of perovskite solutes, thus facilitating the growth of micrometre-scale perovskite grains. The growth kinetics of perovskite crystals is scrutinized by in situ optical microscopy tracking to understand the crystallization mechanism. The perovskite films produced by MASP exhibit excellent optoelectronic properties with efficiencies approaching 20% in planar perovskite solar cells. This robust MASP strategy may in principle be easily extended to craft other solution-printed perovskite-based optoelectronics.