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1. Solution-phase synthesis of group 3–5 transition metal chalcogenide inorganic nanomaterials

   https://doi.org/10.1039/D3CC01731A  

   Zilevu, Daniel; Creutz, Sidney E. (July 2023, Chemical Communications)

   The versatility of early transition metal chalcogenide nanomaterials, including chalcogenide perovskites, has attracted enormous attention for a variety of applications, such as photovoltaics, photocatalysis, and optoelectronic devices. These nanomaterials exhibit unique electronic and optical properties, allowing for a broad range of applications, depending on their chemical composition and crystal structure. However, solution-phase synthesis of early transition metal chalcogenide nanocrystals is challenging due, in part, to their high crystallization energy and oxophilicity. In this feature article, we explore various synthetic routes reported for inorganic ternary and binary sulfide and selenide nanomaterials that include transition metals from groups 3, 4, and 5. By systematically comparing different synthetic approaches, we identify trends and insights into the chemistry of these chalcogenide nanomaterials. 

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2. Scalable nanomanufacturing of chalcogenide inks: a case study on thermoelectric V–VI nanoplates

   https://doi.org/10.1039/d1ta05858d  

   Zeng, Minxiang; Xie, Hongyao; Saeidi-Javash, Mortaza; Tanvir, A.N.M.; Du, Yipu; Chen, Jiahao; Kanatzidis, Mercouri G.; Zhang, Yanliang (October 2021, Journal of Materials Chemistry A)

   null (Ed.)

   Solution-processed semiconducting main-group chalcogenides (MMCs) have attracted increasing research interest for next-generation device technologies owing to their unique nanostructures and superior properties. To achieve the full potential of MMCs, the development of highly universal, scalable, and sustainable synthesis and processing methods of chalcogenide particles is thus becoming progressively more important. Here we studied scalable factors for the synthesis of two-dimensional (2D) V–VI chalcogenide nanoplates (M 2 Q 3  : M = Sb, Bi; Q = Se, Te) and systematically investigated their colloidal behaviour and chemical stability. Based on a solvent engineering technique, we demonstrated scale-up syntheses of MMCs up to a 900% increase of batch size compared with conventional hydrazine-based gram-level syntheses, and such a scalable approach is highly applicable to various binary and ternary MMCs. Furthermore, we studied the stability of printable chalcogenide nanoparticle inks with several formulation factors including solvents, additives, and pH values, resulting in inks with high chemical stability (>4 months). As a proof of concept, we applied our solution-processed chalcogenide particles to multiple additive manufacturing methods, confirming the high printability and processability of MMC inks. The ability to combine the top-down designing freedom of additive manufacturing with bottom-up scalable synthesis of chalcogenide particles promises great opportunities for large-scale design and manufacturing of chalcogenide-based functional devices for broad application. 

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3. Determination of adsorption-controlled growth windows of chalcogenide perovskites

   https://doi.org/10.1557/mrc.2018.10  

   Filippone, Stephen A.; Sun, Yi-Yang; Jaramillo, R. (March 2018, MRS Communications)

   Ternary sulfides and selenides in the distorted-perovskite structure (“chalcogenide perovskites”) are predicted by theory to be semiconductors with a band gap in the visible-to-infrared and may be useful for optical, electronic, and energy conversion technologies. Here we use computational thermodynamics to predict the pressure–temperature phase diagrams for select chalcogenide perovskites. Our calculations incorporate formation energies calculated by density functional theory, and empirical estimates of heat capacities. We highlight the windows of thermodynamic equilibrium between solid chalcogenide perovskites and the vapor phase at high temperature and very low pressure. These results can guide the adsorption-limited growth of ternary chalcogenides by molecular beam epitaxy. 

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4. Chalcogenide Perovskite Thin Films with Controlled Phases for Optoelectronics

   https://doi.org/10.1002/adfm.202309514  

   Yu, Zhonghai; Hui, Haolei; West, Damien; Zhang, Han; Sun, Yiyang; Kong, Sen; Zhang, Yin; Deng, Chenhua; Yang, Sen; Zhang, Shengbai; et al (November 2023, Advanced Functional Materials)

   Abstract Chalcogenide perovskites have emerged as promising semiconductor materials due to their appealing properties, including tunable bandgaps, high absorption coefficients, reasonable carrier lifetimes and mobilities, excellent chemical stability, and environmentally benign nature. However, beyond the well‐studied BaZrS₃, reports on chalcogenide perovskite thin films with diverse compositions are scarce. In this study, the realization of four different types of chalcogenide perovskite thin films with controlled phases, through CS₂annealing of amorphous chalcogenide precursor films deposited by pulsed laser deposition (PLD), is reported. This achievement is guided by a thorough theoretical investigation of the phase stability of chalcogenide perovskites. Upon crystallization in the distorted perovskite phase, all materials exhibit photoluminescence (PL) with peak positions in the visible range, consistent with their expected bandgap values. However, the full‐width‐at‐half‐maximum (FWHM) of the PL spectra varies significantly across these materials, ranging from 99 meV for SrHfS₃to 231 meV for BaHfS₃. The difference is attributed to the difference in kinetic barriers between local structural motifs for the Sr and Ba compounds. The findings underscore the promise of chalcogenide perovskite thin films as an alternative to traditional halide perovskites for optoelectronic applications, while highlighting the challenges in optimizing their synthesis and performance. 

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5. Effects of the Chalcogenide Identity in N ‐Aryl Phenochalcogenazine Photoredox Catalysts

   https://doi.org/10.1002/cctc.202200485  

   Corbin, Daniel_A; Cremer, Christopher; Puffer, Katherine_O; Newell, Brian_S; Patureau, Frederic_W; Miyake, Garret_M (July 2022, ChemCatChem)

   Abstract Phenochalcogenazines such as phenoxazines and phenothiazines have been widely employed as photoredox catalysts (PCs) in small molecule and polymer synthesis. However, the effect of the chalcogenide in these catalysts has not been fully investigated. In this work, a series of four phenochalcogenazines is synthesized to understand how the chalcogenide impacts catalyst properties and performance. Increasing the size of the chalcogenide is found to distort the PC structure, ultimately impacting the properties of each PC. For example, larger chalcogenides destabilize the PC radical cation, possibly resulting in catalyst degradation. In addition, PCs with larger chalcogenides experience increased reorganization during electron transfer, leading to slower electron transfer. Ultimately, catalyst performance is evaluated in organocatalyzed atom transfer radical polymerization and a photooxidation reaction for C(sp²)−N coupling. Results from these experiments highlight that a balance of PC properties is most beneficial for catalysis, including a long‐lived excited state, a stable radical cation, and a low reorganization energy. 

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