Controlling Homogenous Spherulitic Crystallization for High-Efficiency Planar Perovskite Solar Cells Fabricated under Ambient High-Humidity Conditions.

The influence of precursor solution properties, fabrication environment, and antisolvent properties on the microstructural evolution of perovskite films is reported. First, the impact of fabrication environment on the morphology of methyl ammonium lead iodide (MAPbI3 ) perovskite films with various Lewis-base additives is reported. Second, the influence of antisolvent properties on perovskite film microstructure is investigated using antisolvents ranging from nonpolar heptane to highly polar water. This study shows an ambient environment that accelerates crystal growth at the expense of nucleation and introduces anisotropies in crystal morphology. The use of antisolvents enhances nucleation but also influences ambient moisture interaction with the precursor solution, resulting in different crystal morphology (shape, size, dispersity) in different antisolvents. Crystal morphology, in turn, dictates film quality. A homogenous spherulitic crystallization results in pinhole-free films with similar microstructure irrespective of processing environment. This study further demonstrates propyl acetate, an environmentally benign antisolvent, which can induce spherulitic crystallization under ambient environment (52% relative humidity, 25 °C). With this, planar perovskite solar cells with ≈17.78% stabilized power conversion efficiency are achieved. Finally, a simple precipitation test and in situ crystallization imaging under an optical microscope that can enable a facile a priori screening of antisolvents is shown.

The first demonstration of entirely roll-to-roll fabricated perovskite solar cell modules under ambient room conditions.

The rapid development of organic-inorganic hybrid perovskite solar cells has resulted in laboratory-scale devices having power conversion efficiencies that are competitive with commercialised technologies. However, hybrid perovskite solar cells are yet to make an impact beyond the research community, with translation to large-area devices fabricated by industry-relevant manufacturing methods remaining a critical challenge. Here we report the first demonstration of hybrid perovskite solar cell modules, comprising serially-interconnected cells, produced entirely using industrial roll-to-roll printing tools under ambient room conditions. As part of this development, costly vacuum-deposited metal electrodes are replaced with printed carbon electrodes. A high-throughput experiment involving the analysis of batches of 1600 cells produced using 20 parameter combinations enabled rapid optimisation over a large parameter space. The optimised roll-to-roll fabricated hybrid perovskite solar cells show power conversion efficiencies of up to 15.5% for individual small-area cells and 11.0% for serially-interconnected cells in large-area modules. Based on the devices produced in this work, a cost of ~0.7 USD W-1 is predicted for a production rate of 1,000,000 m² per year in Australia, with potential for further significant cost reductions.

Fully Roll-to-Roll Processed Efficient Perovskite Solar Cells via Precise Control on the Morphology of PbI2:CsI Layer.

Perovskite solar cells (PSCs) have attracted tremendous attention as a promising alternative candidate for clean energy generation. Many attempts have been made with various deposition techniques to scale-up manufacturing. Slot-die coating is a robust and facile deposition technique that can be applied in large-area roll-to-roll (R2R) fabrication of thin film solar cells with the advantages of high material utilization, low cost and high throughput. Herein, we demonstrate the encouraging result of PSCs prepared by slot-die coating under ambient environment using a two-step sequential process whereby PbI2:CsI is slot-die coated first followed by a subsequent slot-die coating of organic cations containing solution. A porous PbI2:CsI film can promote the rapid and complete transformation into perovskite film. The crystallinity and morphology of perovskite films are significantly improved by optimizing nitrogen blowing and controlling substrate temperature. A power conversion efficiency (PCE) of 18.13% is achieved, which is promising for PSCs fabricated by two-step fully slot-die-coated devices. Furthermore, PSCs with a 1 cm2 area yield a champion PCE of 15.10%. Moreover, a PCE of 13.00% is obtained on a flexible substrate by the roll-to-roll (R2R) coating, which is one of the highest reported cells with all layers except for metal electrode fabricated by R2R process under ambient condition.

Spontaneous Formation of a Ligand-Based 2D Capping Layer on the Surface of Quasi-2D Perovskite Films.

Two-dimensional (2D) Ruddlesden-Popper phase perovskites (RPPs) are attracting growing attention for photovoltaic applications due to their enhanced stability compared to three-dimensional (3D) perovskites. The superior tolerance of 2D RPPs films to moisture and oxygen is mainly attributed to the hydrophobic nature of the introduced long-chain spacer cations (ligands). In this work, it is revealed that a thin capping layer, consisting of self-assembled butylammonium ligands, is spontaneously formed on the top surface of a quasi-2D perovskite film prepared by conventional one-step hot casting. Based on morphological and crystallographic analyses of both the top/bottom surfaces and the interior of quasi-2D perovskite films, the formation process of the 2D capping layer and the assembly of RPPs, comprising both large and small slab thickness (large-n, small-n), is elucidated. The vertical orientation of RPPs that is required for sufficient charge transport for 2D perovskite solar cells (PSCs) is further verified. We propose that the surface capping layer is directly responsible for the long-term stability of 2D PSCs. This work provides detailed insight into the microstructure of quasi-2D RPPs films that should assist the development of strategies for unlocking the full potential of 2D perovskites for high-performance PSCs and other solid-state electronic devices.

Beyond Fullerenes: Indacenodithiophene-Based Organic Charge-Transport Layer toward Upscaling of Low-Cost Perovskite Solar Cells.

Phenyl-C61-butyric acid methyl ester (PCBM) is universally used as the electron-transport layer (ETL) in the low-cost inverted planar structure of perovskite solar cells (PeSCs). PCBM brings tremendous challenges in upscaling of PeSCs using industry-relevant methods due to its aggregation behavior, which undermines the power conversion efficiency and stability. Herein, we highlight these, seldom reported, challenges with PCBM. Furthermore, we investigate the potential of nonfullerene indacenodithiophene (IDT)-based molecules by employing a commercially available variant, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3- d:2',3'- d']- s-indaceno[1,2- b:5,6- b'] dithiophene (ITIC), as a PCBM replacement in ambient-processed PeSCs. Films fabrication by laboratory-based spin-coating and industry-relevant slot-die coating methods are compared. Although similar power-conversion efficiencies are achieved with both types of ETL in a simple device structure fabricated by spin-coating, the nanofibriller morphology of ITIC compared to the aggregated morphology of PCBM films enables improved mechanical integrity and stability of ITIC devices. Upon slot-die coating, the aggregation of PCBM is exacerbated, leading to significantly lower power-conversion efficiency of devices than spin-coated PCBM as well as slot-die-coated ITIC devices. Our results clearly indicate that IDT-based molecules have great potential as an ETL in PeSCs, offering superior properties and upscaling compatibility than PCBM. Thus, we present a short summary of recently emerged nonfullerene IDT-based molecules from the field of organic solar cells and discuss their scope in PeSCs as electron or hole-transport layer.

Comparative Indoor and Outdoor Degradation of Organic Photovoltaic Cells via Inter-laboratory Collaboration.

We report on the degradation of organic photovoltaic (OPV) cells in both indoor and outdoor environments. Eight different research groups contributed state of the art OPV cells to be studied at Pomona College. Power conversion efficiency and fill factor were determined from IV curves collected at regular intervals over six to eight months. Similarly prepared devices were measured indoors, outdoors, and after dark storage. Device architectures are compared. Cells kept indoors performed better than outdoors due to the lack of temperature and humidity extremes. Encapsulated cells performed better due to the minimal oxidation. Some devices showed steady aging but many failed catastrophically due to corrosion of electrodes not active device layers. Degradation of cells kept in dark storage was minimal over periods up to one year.

High-Volume Processed, ITO-Free Superstrates and Substrates for Roll-to-Roll Development of Organic Electronics.

The fabrication of substrates and superstrates prepared by scalable roll-to-roll methods is reviewed. The substrates and superstrates that act as the flexible carrier for the processing of functional organic electronic devices are an essential component, and proposals are made about how the general availability of various forms of these materials is needed to accelerate the development of the field of organic electronics. The initial development of the replacement of indium-tin-oxide (ITO) for the flexible carrier materials is described and a description of how roll-to-roll processing development led to simplification from an initially complex make-up to higher performing materials through a more simple process is also presented. This process intensification through process simplification is viewed as a central strategy for upscaling, increasing throughput, performance, and cost reduction.

Silver front electrode grids for ITO-free all printed polymer solar cells with embedded and raised topographies, prepared by thermal imprint, flexographic and inkjet roll-to-roll processes.

Semitransparent front electrodes for polymer solar cells, that are printable and roll-to-roll processable under ambient conditions using different approaches, are explored in this report. The excellent smoothness of indium-tin-oxide (ITO) electrodes has traditionally been believed to be difficult to achieve using printed front grids, as surface topographies accumulate when processing subsequent layers, leading to shunts between the top and bottom printed metallic electrodes. Here we demonstrate how aqueous nanoparticle based silver inks can be employed as printed front electrodes using several different roll-to-roll techniques. We thus compare hexagonal silver grids prepared using either roll-to-roll inkjet or roll-to-roll flexographic printing. Both inkjet and flexo grids present a raised topography and were found to perform differently due to only the conductivity of the obtained silver grid. The raised topographies were compared with a roll-to-roll thermally imprinted grid that was filled with silver in a roll-to-roll process, thus presenting an embedded topography. The embedded grid and the flexo grid were found to perform equally well, with the flexographic technique currently presenting the fastest processing and the lowest silver use, whereas the embedded grid presents the maximally achievable optical transparency and conductivity. Polymer solar cells were prepared in the same step, using roll-to-roll slot-die coating of zinc oxide as the electron transport layer, poly-3-hexylthiophene:phenyl-C(61)-butyric acid methyl ester (P3HT:PCBM) as the active layer and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the top electrode, along with a flat bed screen printed silver grid. The power conversion efficiency (PCE) obtained for large area devices (6 cm(2)) was 1.84%, 0.79% and 1.72%, respectively, for thermally imprinted, inkjet and flexographic silver grids, tested outside under the real sun. Central to all three approaches was that they employed environmentally friendly solvents, i.e. water based nanoparticle silver inks.