Digenite Nanosheets Synthesized by Thermolysis of Layered Copper-Alkanethiolate Frameworks

Bryks, Whitney; Lupi, Eduardo; Ngo, Charles; Tao, Andrea R.

doi:10.1021/jacs.6b08264

Cited by 25 publications

(39 citation statements)

References 56 publications

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“…The strong and broad NIR absorption bands observed in the spectra of the product CIS/ZnS HNCs obtained by using injection methods II and III ( Figure S3 ) are assigned to localized surface plasmon resonances (LSPR), which are often observed in Cu-chalcogenide NCs. 9 , 24 , 25 LSPR bands involve excess charge carriers, which are due to stoichiometry deviations, typically Cu-vacancies, which lead to excess holes in the valence band. 9 , 24 However, LSPRs due to In-vacancies have also been reported.…”

Section: Results and Discussionmentioning

confidence: 99%

“… 9 , 24 , 25 LSPR bands involve excess charge carriers, which are due to stoichiometry deviations, typically Cu-vacancies, which lead to excess holes in the valence band. 9 , 24 However, LSPRs due to In-vacancies have also been reported. 25 These observations imply that methods II and III lead to product HNCs that are rich in cation (Cu or In) vacancies, in contrast to method IV.…”

Section: Results and Discussionmentioning

confidence: 99%

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Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

et al. 2018

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Synthesis protocols for anisotropic CuInX2 (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX2 lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS2/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS2 NCs used as seeds are obtained by topotactic partial Cu+ for In3+ cation exchange in template Cu2–xS NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS2 seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS2 seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

et al. 2018

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“…NIR absorption bands similar to those displayed in the spectra of the template Cu 2– x Se NCs ( Figure 3 ) are commonly observed for Cu-chalcogenide NCs and have been ascribed to localized surface plasmon resonances due to excess charge carriers (typically valence band holes originating from Cu vacancies). 1 , 2 , 35 The NIR absorption bands are no longer present in the absorption spectra of the product NCs obtained from the CE reactions, indicating the absence of Cu vacancies and the successful conversion of the template Cu 2– x Se NCs into either CdSe or CuInSe 2 NCs, through Cu + for Cd 2+ or partial, self-limited Cu + for In 3+ CE, respectively.…”

Section: Resultsmentioning

confidence: 99%

Anisotropic 2D Cu_2–xSe Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe₂ Nanoparticles

et al. 2018

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We present the synthesis of colloidal anisotropic Cu2–xSe nanocrystals (NCs) with excellent size and shape control, using the unexplored phosphine-free selenium precursor 1-dodecaneselenol (DDSe). This precursor forms lamellar complexes with Cu(I) that enable tailoring the NC morphology from 0D polyhedral to highly anisotropic 2D shapes. The Cu2–xSe NCs are subsequently used as templates in postsynthetic cation exchange reactions, through which they are successfully converted to CdSe and CuInSe2 quantum dots, nanoplatelets, and ultrathin nanosheets. The shape of the template hexagonal nanoplatelets is preserved during the cation exchange reaction, despite a substantial reorganization of the anionic sublattice, which leads to conversion of the tetragonal umangite crystal structure of the parent Cu2–xSe NCs into hexagonal wurtzite CdSe and CuInSe2, accompanied by a change of both the thickness and the lateral dimensions of the nanoplatelets. The crystallographic transformation and reconstruction of the product NCs are attributed to a combination of the unit cell dimensionalities of the parent and product crystal phases and an internal ripening process. This work provides novel tools for the rational design of shape-controlled colloidal anisotropic Cu2–xSe NCs, which, besides their promising optoelectronic properties, also constitute a new family of cation exchange templates for the synthesis of shape-controlled NCs of wurtzite CdSe, CuInSe2, and other metal selenides that cannot be attained through direct synthesis approaches. Moreover, the insights provided here are likely applicable also to the direct synthesis of shape-controlled NCs of other metal selenides, since DDSe may be able to form lamellar complexes with several other metals.

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“…Later (2016), Bryks et al demonstrated a similar Cl-assisted synthetic strategy for ultrathin Cu 9 S 5 nanosheets. 308 …”

Section: Semiconductor Nanocrystalsmentioning

confidence: 99%

The Many “Facets” of Halide Ions in the Chemistry of Colloidal Inorganic Nanocrystals

2018

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Over the years, scientists have identified various synthetic “handles” while developing wet chemical protocols for achieving a high level of shape and compositional complexity in colloidal nanomaterials. Halide ions have emerged as one such handle which serve as important surface active species that regulate nanocrystal (NC) growth and concomitant physicochemical properties. Halide ions affect the NC growth kinetics through several means, including selective binding on crystal facets, complexation with the precursors, and oxidative etching. On the other hand, their presence on the surfaces of semiconducting NCs stimulates interesting changes in the intrinsic electronic structure and interparticle communication in the NC solids eventually assembled from them. Then again, halide ions also induce optoelectronic tunability in NCs where they form part of the core, through sheer composition variation. In this review, we describe these roles of halide ions in the growth of nanostructures and the physical changes introduced by them and thereafter demonstrate the commonality of these effects across different classes of nanomaterials.

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Digenite Nanosheets Synthesized by Thermolysis of Layered Copper-Alkanethiolate Frameworks

Cited by 25 publications

References 56 publications

Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Anisotropic 2D Cu_2–xSe Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe₂ Nanoparticles

The Many “Facets” of Halide Ions in the Chemistry of Colloidal Inorganic Nanocrystals

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Digenite Nanosheets Synthesized by Thermolysis of Layered Copper-Alkanethiolate Frameworks

Cited by 25 publications

References 56 publications

Near-Infrared-Emitting CuInS2/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Near-Infrared-Emitting CuInS2/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Anisotropic 2D Cu2–xSe Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe2 Nanoparticles

The Many “Facets” of Halide Ions in the Chemistry of Colloidal Inorganic Nanocrystals

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Product

Resources

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Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Anisotropic 2D Cu_2–xSe Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe₂ Nanoparticles