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Cu 2− x S nanocrystals can serve as templates and intermediates in the synthesis of a wide range of nanocrystals through seeded growth, cation exchange, and/or catalytic growth. This versatility can facilitate and accelerate the search for environmentally benign nanocrystals of high performance with variable shapes, sizes, and composition. However, expanding the compositional space via Cu 2− x S nanocrystals while achieving necessary uniformity requires an improved understanding of the growth mechanisms. Herein we address several unusual and previously unexplained aspects of the growth of CuGaS 2 nanorods from Cu 2− x S seeds as an example. In particular, we address the origin of the diverse morphologies which manifest from a relatively homogeneous starting mixture. We find that CuGaS 2 nanorods start as Cu 2− x S/CuGaS 2 Janus particles, the majority of which have a {101̄2}/{101̄2} interface that helps to minimize lattice strain. We propose a mechanism that involves concurrent seed growth and cation exchange (CSC), where epitaxial growth of the Cu 2− x S seed, rather than the anticipated catalytic or seeded growth of CuGaS 2 , occurs along with cation exchange that converts growing Cu 2− x S to CuGaS 2 . This mechanism can explain the incorporation of the large number of anions needed to account for the order-of-magnitude volume increase upon CuGaS 2 rod growth (which cannot be accounted for by the commonly assumed catalytic growth mechanism) and variations in morphology, including the pervasive tapering and growth direction change. Insights from the CSC growth mechanism also help to explain a previously puzzling phenomenon of regioselective nucleation of CuInSe 2 on kinked CuGaS 2 nanorods. 

Colloidal semiconductor nanocrystals with tunable optical and electronic properties are opening up exciting opportunities for high-performance optoelectronics, photovoltaics, and bioimaging applications. Identifying the optimal synthesis conditions and screening of synthesis recipes in search of efficient synthesis pathways to obtain nanocrystals with desired optoelectronic properties, however, remains one of the major bottlenecks for accelerated discovery of colloidal nanocrystals. Conventional strategies, often guided by limited understanding of the underlying mechanisms remain expensive in both time and resources, thus significantly impeding the overall discovery process. In response, an autonomous experimentation platform is presented as a viable approach for accelerated synthesis screening and optimization of colloidal nanocrystals. Using a machine-learning-based predictive synthesis approach, integrated with automated flow reactor and inline spectroscopy, indium phosphide nanocrystals are autonomously synthesized. Their polydispersity for different target absorption wavelengths across the visible spectrum is simultaneously optimized during the autonomous experimentation, while utilizing minimal self-driven experiments (less than 50 experiments within 2 days). Starting with no-prior-knowledge of the synthesis, an ensemble neural network is trained through autonomous experiments to accurately predict the reaction outcome across the entire synthesis parameter space. The predicted parameter space map also provides new nucleation-growth kinetic insights to achieve high monodispersity in size of colloidal nanocrystals. 

Over the past decade, colloidal quantum dot solar cells (CQD-SCs) have been developed rapidly, with their performances reaching over 16% power conversion efficiency. Accompanied by the development in materials engineering (CQD surface chemistry) and device physics (structures and defect engineering), CQD-SCs are moving towards commercialization. A broad overview of the requirements for commercialization is thus timely and imperative. Broad comprehension of structure engineering, upscaling techniques, stability and the manufacturing cost of CQD-SCs is necessary and should be established. In this review, the development of device structures is presented with their corresponding charge transfer mechanisms. Then, we overview the upscaling methods for the mass production of CQD-SCs. Comparisons between each of the upscaling techniques suggest the most advanced process close to industrialization. In addition, we have investigated the origin of the photovoltaic (PV) performance degradation. The possible degradation sources are categorized according to external environmental factors. Moreover, strategies for improving the stability of CQD-SCs are presented. In the conclusion, we have reviewed the cost-effectiveness of CQD-SCs in terms of the niche PV market. Step-wise manufacturing cost analysis for the commercial CQD-SCs is presented. In the conclusion, the future direction for environment-friendly CQD-SCs is discussed. 

Abstract Patterning of quantum dots (QDs) is essential for many, especially high‐tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2‐vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3‐mercaptopropionic acid and patterned poly(2‐vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti‐counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.