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Title: Autonomous Nanocrystal Doping by Self‐Driving Fluidic Micro‐Processors
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Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Intelligent Systems
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Metal cation‐doped lead halide perovskite (LHP) quantum dots (QDs) with photoluminescence quantum yields (PLQYs) higher than unity, due to quantum cutting phenomena, are an important building block of the next‐generation renewable energy technologies. However, synthetic route exploration and development of the highest‐performing QDs for device applications remain challenging. In this work, Smart Dope is presented, which is a self‐driving fluidic lab (SDFL), for the accelerated synthesis space exploration and autonomous optimization of LHP QDs. Specifically, the multi‐cation doping of CsPbCl3QDs using a one‐pot high‐temperature synthesis chemistry is reported. Smart Dope continuously synthesizes multi‐cation‐doped CsPbCl3QDs using a high‐pressure gas‐liquid segmented flow format to enable continuous experimentation with minimal experimental noise at reaction temperatures up to 255°C. Smart Dope offers multiple functionalities, including accelerated mechanistic studies through digital twin QD synthesis modeling, closed‐loop autonomous optimization for accelerated QD synthetic route discovery, and on‐demand continuous manufacturing of high‐performing QDs. Through these developments, Smart Dope autonomously identifies the optimal synthetic route of Mn‐Yb co‐doped CsPbCl3QDs with a PLQY of 158%, which is the highest reported value for this class of QDs to date. Smart Dope illustrates the power of SDFLs in accelerating the discovery and development of emerging advanced energy materials.

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  3. Abstract

    Despite the groundbreaking advancements in the synthesis of inorganic lead halide perovskite (LHP) nanocrystals (NCs), stimulated from their intriguing size‐, composition‐, and morphology‐dependent optical and optoelectronic properties, their formation mechanism through the hot‐injection (HI) synthetic route is not well‐understood. In this work, for the first time, in‐flow HI synthesis of cesium lead iodide (CsPbI3) NCs is introduced and a comprehensive understanding of the interdependent competing reaction parameters controlling the NC morphology (nanocube vs nanoplatelet) and properties is provided. Utilizing the developed flow synthesis strategy, a change in the CsPbI3NC formation mechanism at temperatures higher than 150 °C, resulting in different CsPbI3morphologies is revealed. Through comparison of the flow‐ versus flask‐based synthesis, deficiencies of batch reactors in reproducible and scalable synthesis of CsPbI3NCs with fast formation kinetics are demonstrated. The developed modular flow chemistry route provides a new frontier for high‐temperature studies of solution‐processed LHP NCs and enables their consistent and reliable continuous nanomanufacturing for next‐generation energy technologies.

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  4. Abstract

    Mechanistic studies of the morphology of lead halide perovskite nanocrystals (LHP‐NCs) are hampered by a lack of generalizable suitable synthetic strategies and ligand systems. Here, the synthesis of zwitterionic CsPbBr3NCs is presented with controlled anisotropy using a proposed “surface‐selective ligand pairs” strategy. Such a strategy provides a platform to systematically study the binding affinity of capping ligand pairs and the resulting LHP morphologies. By using zwitterionic ligands (ZwL) with varying structures, majority ZwL‐capped LHP NCs with controlled morphology are obtained, including anisotropic nanoplatelets and nanorods, for the first time. Combining experiments with density functional theory calculations, factors that govern the ligand binding on the different surface facets of LHP‐NCs are revealed, including the steric bulkiness of the ligand, the number of binding sites, and the charge distance between binding moieties. This study provides guidance for the further exploration of anisotropic LHP‐NCs.

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  5. Abstract

    Lead halide perovskite (LHP) nanocrystals (NCs) have recently garnered enhanced development efforts from research disciplines owing to their superior optical and optoelectronic properties. These materials, however, are unlike conventional quantum dots, because they possess strong ionic character, labile ligand coverage, and overall stability issues. As a result, the system as a whole is highly dynamic and can be affected by slight changes of particle surface environment. Specifically, the surface ligand shell of LHP NCs has proven to play imperative roles throughout the lifetime of a LHP NC. Recent advances in engineering and understanding the roles of surface ligand shells from initial synthesis, through postsynthetic processing and device integration, finally to application performances of colloidal LHP NCs are covered here.

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