Crystallization Kinetics and Morphology Control of Formamidinium–Cesium Mixed‐Cation Lead Mixed‐Halide Perovskite via Tunability of the Colloidal Precursor Solution

The meteoric rise of the field of perovskite solar cells has been fueled by the ease with which a wide range of high‐quality materials can be fabricated via simple solution processing methods. However, to date, little effort has been devoted to understanding the precursor solutions, and the role of additives such as hydrohalic acids upon film crystallization and final optoelectronic quality. Here, a direct link between the colloids concentration present in the [HC(NH₂)₂]_0.83Cs_0.17Pb(Br_0.2I_0.8)₃ precursor solution and the nucleation and growth stages of the thin film formation is established. Using dynamic light scattering analysis, the dissolution of colloids over a time span triggered by the addition of hydrohalic acids is monitored. These colloids appear to provide nucleation sites for the perovskite crystallization, which critically impacts morphology, crystal quality, and optoelectronic properties. Via 2D X‐ray diffraction, highly ordered and textured crystals for films prepared from solutions with lower colloidal concentrations are observed. This increase in material quality allows for a reduction in microstrain along with a twofold increase in charge‐carrier mobilities leading to values exceeding 20 cm² V^?1 s^?1. Using a solution with an optimized colloidal concentration, devices that reach current–voltage measured power conversion efficiency of 18.8% and stabilized efficiency of 17.9% are fabricated.     

Controlling Nucleation and Growth of Metal Halide Perovskite Thin Films for High‐Efficiency Perovskite Solar Cells

Metal halide perovskite thin films can be crystallized via a broad range of solution‐based routes. However, the quality of the final films is strongly dependent upon small changes in solution composition and processing parameters. Here, this study demonstrates that a fractional substitution of PbCl₂ with PbI₂ in the 3CH₃NH₃I:PbCl₂ mixed‐halide starting solution has a profound influence upon the ensuing thin‐film crystallization. The presence of PbI₂ in the precursor induces a uniform distribution of regular quadrilateral‐shaped CH₃NH₃PbI₃ perovskite crystals in as‐cast films, which subsequently grow to form pinhole‐free perovskite films with highly crystalline domains. With this new formulation of 3CH₃NH₃I:0.98PbCl₂:0.02PbI₂, this study achieves a 19.1% current–voltage measured power conversion efficiency and a 17.2% stabilized power output in regular planar heterojunction solar cells.     

醋酸铅添加剂在印刷钙钛矿太阳能电池中的应用

印刷钙钛矿太阳能电池采用无机介孔骨架包覆有机无机杂化钙钛矿材料的器件结构,制备工艺简单,原材料成本低廉,且稳定性优异.然而,在介孔骨架中均匀沉积高质量的钙钛矿材料存在一定困难.本研究通过在典型钙钛矿材料甲胺铅碘(MAPbI3)前驱液中引入醋酸铅(Pb(Ac)2)作为添加剂,加快钙钛矿晶体的成核从而改善其在介孔骨架中的生...     

基于形核结晶调控的钙钛矿太阳电池印刷制造的研究进展

目的 有机–无机杂化钙钛矿太阳电池以其优异的光电转换性能和低成本溶液加工等优势受到了科研工作者和产业界人士的广泛关注,文中着眼于解决把实验室的旋涂研发工艺转换为可大规模重复生产的工艺这一直接挑战。方法 印刷制造技术具有低成本、大规模、高产率、适用于柔性基底等优点,是应对该挑战的有效手段。深入梳理和总结印刷制造中钙钛矿薄膜的形核与结晶过程,对于印刷高质量钙钛矿薄膜和实现大面积高效钙钛矿太阳电池制造至关重要。结论 分析了钙钛矿形核结晶的热力学与动力学基本理论,从钙钛矿形核结晶调控这一角度出发,对各类印刷工艺制造大面积钙钛矿薄膜及光伏器件的研究现状做出相应评价,认为“升级制备技术、创新材料体系、改善稳定性能”三步走将掀起钙钛矿产业化的新浪潮。     

Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. To investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH₃NH₃PbBr₃) is varied, and changes are mapped in both their elemental composition and photoluminescence. Synchrotron‐based nanoprobe X‐ray fluorescence (nano‐XRF) with 250 nm resolution reveals quasi‐reversible field‐assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH₃NH₃PbBr₃. A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy‐mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field‐assisted ionic migration in a model hybrid‐perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.     

Position- and Orientation-Controlled Growth of Wulff-Shaped Colloidal Crystals Engineered with DNA

Colloidal crystals have emerged as promising candidates for building optical microdevices. Techniques now exist for synthesizing them with control over their nanoscale features (e.g., particle compositions, sizes, shapes, and lattice parameters and symmetry); however, the ability to tune macroscale structural features, such as the relative positions of crystals to one another and lattice orientations, has yet to be realized. Here, inspiration is drawn from epitaxial growth strategies in atomic crystallization, and patterned substrates are prepared that, when used in conjunction with DNA-mediated nanoparticle crystallization, allow for control over individual Wulff-shaped crystal growth, location, and orientation. In addition, the approach allows exquisite control over the patterned substrate/crystal lattice mismatch, something not yet realized for any epitaxy process. This level of structural control is a significant step toward realizing complex, integrated devices with colloidal crystal components, and this approach provides a model system for further exploration in epitaxy systems.     

Directed Self‐Assembly of Star‐Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism

Exploring the ordering mechanism and dynamics of self‐assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self‐assembling mechanism and kinetics of silicon‐containing 3‐arm star‐block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self‐assembly using topographically patterned substrates. The ordering process of the star‐block copolymer within fabricated topographic patterns with PS‐functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well‐ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self‐assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top‐down and bottom‐up approaches.