In situ formation of reactive sulfide precursors in the one-pot, multigram synthesis of Cu2ZnSnS4 nanocrystals

Anthony S R Chesman, Joel van Embden, Noel William Duffy, Nathan A S Webster, Jacek Jaroslaw Jasieniak

Research output: Contribution to journalArticleResearchpeer-review

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Abstract

Herein we outline a general one-pot method to produce large quantities of compositionally tunable, kesterite Cu2ZnSnS4 (CZTS) nanocrystals (NCs) through the decomposition of in situ generated metal sulfide precursors. This method uses air stable precursors and should be applicable to the synthesis of a range of metal sulfides. We examine the formation of the ligands, precursors, and particles in turn. Direct reaction of CS2 with the aliphatic primary amines and thiols that already constitute the reaction mixture is used to produce ligands in situ. Through the use of 1H and 13C nuclear magnetic resonance, Fourier transform infrared spectroscopy, and optical absorption spectroscopy, we elucidate the formation of the resulting oleyldithiocarbamate and dodecyltrithiocarbonate ligands. The decomposition of their corresponding metal complexes at temperatures of 100 C yields nuclei with a size of 1-2 nm, with further growth facilitated by the decomposition of dodecanethiol. In this way the nucleation and growth stages of the reaction are decoupled, allowing for the generation of NCs at high concentrations. Using in situ X-ray diffraction, we monitor the evolution of our reactions, thus enabling a real-time glimpse into the formation of Cu2ZnSnS4 NCs. For completeness, the surface chemistry and the electronic structure of the resulting CZTS NCs are studied.
Original languageEnglish
Pages (from-to)1712 - 1720
Number of pages9
JournalCrystal Growth and Design
Volume13
Issue number4
DOIs
Publication statusPublished - 2013
Externally publishedYes

Cite this

Chesman, Anthony S R ; van Embden, Joel ; Duffy, Noel William ; Webster, Nathan A S ; Jasieniak, Jacek Jaroslaw. / In situ formation of reactive sulfide precursors in the one-pot, multigram synthesis of Cu2ZnSnS4 nanocrystals. In: Crystal Growth and Design. 2013 ; Vol. 13, No. 4. pp. 1712 - 1720.
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abstract = "Herein we outline a general one-pot method to produce large quantities of compositionally tunable, kesterite Cu2ZnSnS4 (CZTS) nanocrystals (NCs) through the decomposition of in situ generated metal sulfide precursors. This method uses air stable precursors and should be applicable to the synthesis of a range of metal sulfides. We examine the formation of the ligands, precursors, and particles in turn. Direct reaction of CS2 with the aliphatic primary amines and thiols that already constitute the reaction mixture is used to produce ligands in situ. Through the use of 1H and 13C nuclear magnetic resonance, Fourier transform infrared spectroscopy, and optical absorption spectroscopy, we elucidate the formation of the resulting oleyldithiocarbamate and dodecyltrithiocarbonate ligands. The decomposition of their corresponding metal complexes at temperatures of 100 C yields nuclei with a size of 1-2 nm, with further growth facilitated by the decomposition of dodecanethiol. In this way the nucleation and growth stages of the reaction are decoupled, allowing for the generation of NCs at high concentrations. Using in situ X-ray diffraction, we monitor the evolution of our reactions, thus enabling a real-time glimpse into the formation of Cu2ZnSnS4 NCs. For completeness, the surface chemistry and the electronic structure of the resulting CZTS NCs are studied.",
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In situ formation of reactive sulfide precursors in the one-pot, multigram synthesis of Cu2ZnSnS4 nanocrystals. / Chesman, Anthony S R; van Embden, Joel; Duffy, Noel William; Webster, Nathan A S; Jasieniak, Jacek Jaroslaw.

In: Crystal Growth and Design, Vol. 13, No. 4, 2013, p. 1712 - 1720.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - In situ formation of reactive sulfide precursors in the one-pot, multigram synthesis of Cu2ZnSnS4 nanocrystals

AU - Chesman, Anthony S R

AU - van Embden, Joel

AU - Duffy, Noel William

AU - Webster, Nathan A S

AU - Jasieniak, Jacek Jaroslaw

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AB - Herein we outline a general one-pot method to produce large quantities of compositionally tunable, kesterite Cu2ZnSnS4 (CZTS) nanocrystals (NCs) through the decomposition of in situ generated metal sulfide precursors. This method uses air stable precursors and should be applicable to the synthesis of a range of metal sulfides. We examine the formation of the ligands, precursors, and particles in turn. Direct reaction of CS2 with the aliphatic primary amines and thiols that already constitute the reaction mixture is used to produce ligands in situ. Through the use of 1H and 13C nuclear magnetic resonance, Fourier transform infrared spectroscopy, and optical absorption spectroscopy, we elucidate the formation of the resulting oleyldithiocarbamate and dodecyltrithiocarbonate ligands. The decomposition of their corresponding metal complexes at temperatures of 100 C yields nuclei with a size of 1-2 nm, with further growth facilitated by the decomposition of dodecanethiol. In this way the nucleation and growth stages of the reaction are decoupled, allowing for the generation of NCs at high concentrations. Using in situ X-ray diffraction, we monitor the evolution of our reactions, thus enabling a real-time glimpse into the formation of Cu2ZnSnS4 NCs. For completeness, the surface chemistry and the electronic structure of the resulting CZTS NCs are studied.

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