An Equalized Flow Velocity Strategy for Perovskite Colloidal Particles in Flexible Perovskite Solar Cells.

The non-uniform distribution of colloidal particles in perovskite precursor results in an imbalanced response to the shear force during flexible printing process. Herein, it is observed that the continuous disordered migration occurring in perovskite inks significantly contributes to the enlargement of colloidal particles size and diminishes the crystallization activity of the inks. Therefore, a molecular encapsulation architecture by glycerol monostearate to mitigate colloidal particles collisions in the precursor ink, while simultaneously homogenizing the size distribution of perovskite colloids to minimize their diffusion disparities, is devised. The utilization of colloidal particles with a molecular encapsulation structure enables the achievement of uniform deposition during the printing process, thereby effectively balancing the crystallization rate and phase transition in the film and facilitating homogeneous crystallization of perovskite films. The large-area flexible perovskite device (1.01 cm2 and 100 cm2) fabricated through printing processes, achieves an efficiency of 24.45% and 15.87%, respectively, and manifests superior environmental stability, maintaining an initial efficiency of 91% after being stored in atmospheric ambiences for 150 days (unencapsulated). This work demonstrates that the dynamic evolution process of colloidal particles in both the precursor ink and printing process represents a crucial stride toward achieving uniform crystallization of perovskite films.

In-Situ Polymer Framework Strategy Enabling Printable and Efficient Perovskite Solar Cells by Mitigating "Coffee Ring" Effect.

Organic-inorganic hybrid perovskites are considered ideal candidates for future photovoltaic applications due to their excellent photovoltaic properties. Although solution-printed manufacturing has shown inherent potential for the low-cost, high-throughput production of thin-film semiconductor electronics, the high-quality and high-reproducibility deposition of large-area perovskite remains a bottleneck that restricts their commercialization due to the droplet coffee-ring effect (CRE). In this study, these issues are addressed by introducing an in situ polymer framework. The 3D framework formed by spontaneous cross-linking improves the precursor viscosity and homogenizes its heat diffusion coefficient, counteracting the lateral capillary flow of the colloidal particles and anchoring their flocculent movement. Thus, the Marangoni convection intensity is properly controlled to ensure high-quality perovskite films, which significantly enhances reproducibility in printing efficient photovoltaics by mitigating the CRE. Subsequently, the perovskite solar cells and modules achieve power conversion efficiencies of 23.94 and 17.53%, and exhibit positive environmental stability, retaining over 90 and 78% efficiency after storage for 2500 and 1600 h, respectively. This work may serves as a foundation for exploring precursor rheology to match the homogeneous deposition requirements of perovskite photovoltaics and facilitating the advancement of their printing manufacturing and commercialization transition.

Modulation of Colloidal Assembly Behavior Enables Printable Low-Dimensional Perovskite Photovoltaics.

The multiple quantum wells (QWs) distribution in low-dimensional perovskite films hinders charge transport due to the fundamental difficulty of controlling crystal growth from precursor solutions, yielding poorly homogeneous low-dimensional perovskite solar cells (PSCs), especially in upscaling fabrication. Here, efficient low-dimensional PSCs are realized by modulating the colloidal assembly behavior in the precursor solution to induce intermediate structures. In combination with in situ liquid time-of-flight secondary ion mass spectrometry, the assembly behavior of organic cations involved lead iodide-dominated colloidal soft framework is visualized by investigating the precursor species differences under hydrogen bonding interactions. Subsequently, solid-state reactions emerge and the formamidine (FA)-based perovskite films exhibit significantly suppressed multiple QWs distribution. Encouragingly, the FA device (n=9, by meniscus-assisted coating) achieves a power conversion efficiency (PCE) of 20.28 % for a size of 0.04 cm2 and a PCE of 15.35 % for a mini-module of 16.94 cm2 with superior stability.

Uncovering Aging Chemistry of Perovskite Precursor Solutions and Anti-aging Mechanism of Additives.

The aging of precursor solutions is the major stumbling block for the commercialization of perovskite solar cells (PSCs). Herein, for the first time we used the state-of-the-art in situ liquid time-of-flight secondary ion mass spectrometry to molecularly explore the perovskite precursor solution chemistry. We identified that the methylammonium and formamidinium cations and the I- anion are the motivators of the aging chemistry. Further, we introduced two kinds of Lewis bases, triethyl phosphate (TP) and ethyl ethanesulfonate (EE), as new additives in the solution and unraveled that both of them can protect the reactive cations from aging through weak interactions. Significantly, TP is superior to EE in enhancing long-term solution stability as it can well-maintain the internal interaction structures within the solution phase. The PSC derived from a fresh TP-doped solution delivered a high power conversion efficiency of 23.06 %, 92.23 % of which remained in that from a 21-day-old solution.

A Bionic Interface to Suppress the Coffee-Ring Effect for Reliable and Flexible Perovskite Modules with a Near-90% Yield Rate.

The inhomogeneity, poor interfacial contact, and pinholes caused by the coffee-ring effect severely affect the printing reliability of flexible perovskite solar cells (PSCs). Herein, inspired by the bio-glue of barnacles, a bionic interface layer (Bio-IL) of NiOx /levodopa is introduced to suppress the coffee-ring effect during printing perovskite modules. The coordination effect of the sticky functional groups in Bio-IL can pin the three-phase contact line and restrain the transport of perovskite colloidal particles during the printing and evaporation process. Moreover, the sedimentation rate of perovskite precursor is accelerated due to the electrostatic attraction and rapid volatilization from an extraordinary wettability. The superhydrophilic Bio-IL affords an even spread over a large-area substrate, which boosts a complete and uniform liquid film for heterogeneous nucleation as well as crystallization. Perovskite films on different large-area substrates with negligible coffee-ring effect are printed. Consequently, inverted flexible PSCs and perovskite solar modules achieve a high efficiency of 21.08% and 16.87%, respectively. This strategy ensures a highly reliable reproducibility of printing PSCs with a near 90% yield rate.