Modeling and Fundamental Dynamics of Vacuum, Gas, and Antisolvent Quenching for Scalable Perovskite Processes.

Hybrid perovskite photovoltaics (PVs) promise cost-effective fabrication with large-scale solution-based manufacturing processes as well as high power conversion efficiencies. Almost all of today's high-performance solution-processed perovskite absorber films rely on so-called quenching techniques that rapidly increase supersaturation to induce a prompt crystallization. However, to date, there are no metrics for comparing results obtained with different quenching methods. In response, the first quantitative modeling framework for gas quenching, anti-solvent quenching, and vacuum quenching is developed herein. Based on dynamic thickness measurements in a vacuum chamber, previous works on drying dynamics, and commonly known material properties, a detailed analysis of mass transfer dynamics is performed for each quenching technique. The derived models are delivered along with an open-source software framework that is modular and extensible. Thereby, a deep understanding of the impact of each process parameter on mass transfer dynamics is provided. Moreover, the supersaturation rate at critical concentration is proposed as a decisive benchmark of quenching effectiveness, yielding ≈ 10-3 - 10-1s-1 for vacuum quenching, ≈ 10-5 - 10-3s-1 for static gas quenching, ≈ 10-2 - 100s-1 for dynamic gas quenching and ≈ 102s-1 for antisolvent quenching. This benchmark fosters transferability and scalability of hybrid perovskite fabrication, transforming the "art of device making" to well-defined process engineering.

Controlling Thin Film Morphology Formation during Gas Quenching of Slot-Die Coated Perovskite Solar Modules.

Transferring record power conversion efficiency (PCE) >25% of spin coated perovskite solar cells (PSCs) from the laboratory scale to large-area photovoltaic modules requires significant advances in scalable fabrication techniques. In this work, we demonstrate the fundamental interrelation between drying dynamics of slot-die coated precursor solution thin films and the quality of resulting slot-die coated gas-quenched polycrystalline perovskite thin films. Well-defined drying conditions are established using a temperature-stabilized, movable table and a flow-controlled, oblique impinging slot nozzle purged with nitrogen. The accurately deposited solution thin film on the substrate is recorded by a tilted CCD camera, allowing for in situ monitoring of the perovskite thin film formation. With the tracking of crystallization dynamics during the drying process, we identify the critical process parameters needed for the design of optimal drying and gas quenching systems. In addition, defining different drying regimes, we derive practical slot jet adjustments preventing gas backflow and demonstrate large-area, homogeneous, and pinhole-free slot-die coated perovskite thin films that result in solar cells with PCEs of up to 18.6%. Our study reveals key interrelations of process parameters, e.g., the gas flow and drying velocity, and the exact crystallization position with the morphology formation of fabricated thin films, resulting in a homogeneous performance of corresponding 50 × 50 mm2 solar minimodules (17.2%) with only minimal upscaling loss. In addition, we validate a previously developed model on the drying dynamics of perovskite thin films on small-area slot-die coated areas of ≥100 cm2. The study provides methodical guidelines for the design of future slot-die coating setups and establishes a step forward to a successful transfer of solution processes towards industrial-scale deposition systems beyond brute force optimization.

Drying and Coating of Perovskite Thin Films: How to Control the Thin Film Morphology in Scalable Dynamic Coating Systems.

Hybrid perovskite photovoltaics combine high performance with the ease of solution processing. However, to date, a poor understanding of morphology formation in coated perovskite precursor thin films casts doubt on the feasibility of scaling-up laboratory-scale solution processes. Oblique slot jet drying is a widely used scalable method to induce fast crystallization in perovskite thin films, but deep knowledge and explicit guidance on how to control this dynamic method are missing. In response, we present a quantitative model of the drying dynamics under oblique slot jets. Using this model, we identify a simple criterion for successful scaling of perovskite solution printing and predict coating windows in terms of air velocity and web speed for reproducible fabrication of perovskite solar cells of ∼15% in power conversion efficiency─in direct correlation with the morphology of fabricated thin films. These findings are a corner stone toward scaling perovskite fabrication from simple principles instead of trial and error optimization.

Coated and Printed Perovskites for Photovoltaic Applications.

Hybrid organic-inorganic metal halide perovskite semiconductors provide opportunities and challenges for the fabrication of low-cost thin-film photovoltaic devices. The opportunities are clear: the power conversion efficiency (PCE) of small-area perovskite photovoltaics has surpassed many established thin-film technologies. However, the large-scale solution-based deposition of perovskite layers introduces challenges. To form perovskite layers, precursor solutions are coated or printed and these must then be crystallized into the perovskite structure. The nucleation and crystal growth must be controlled during film formation and subsequent treatments in order to obtain high-quality, pin-hole-free films over large areas. A great deal of understanding regarding material engineering during the perovskite film formation process has been gained through spin-coating studies. Based on this, significant progress has been made on transferring material engineering strategies to processes capable of scale-up, such as blade coating, spray coating, inkjet printing, screen printing, relief printing, and gravure printing. Here, an overview is provided of the strategies that led to devices deposited by these scalable techniques with PCEs as high as 21%. Finally, the opportunities to fully close the shrinking gap to record spin-coated solar cells and to scale these efficiencies to large areas are highlighted.

Effect of Crystal Grain Orientation on the Rate of Ionic Transport in Perovskite Polycrystalline Thin Films.

In this work, we examine the effect of microstructure on ion-migration-induced photoluminescence (PL) quenching in methylammonium lead iodide perovskite films. Thin films were fabricated by two methods: spin-coating, which results in randomly oriented perovskite grains, and zone-casting, which results in aligned grains. As an external bias is applied to these films, migration of ions causes a quenching of the PL signal in the vicinity of the anode. The evolution of this PL-quenched zone is less uniform in the spin-coated devices than in the zone-cast ones, suggesting that the relative orientation of the crystal grains plays a significant role in the migration of ions within polycrystalline perovskite. We simulate this effect via a simple Ising model of ionic motion across grains in the perovskite thin film. The results of this simulation align closely with the observed experimental results, further solidifying the correlation between crystal grain orientation and the rate of ionic transport.