General Synthetic Approach to Heterostructured Nanocrystals Based on Noble Metals and I-VI, II-VI, and I-III-VI Metal Chalcogenides

Solid metal precursors (alloys or monometals) can serve both as a starting template and as a source material for chemical transformation to metal chalcogenides. Herein, we develop a simple solution-based strategy to obtain highly monodisperse noble-metal-based heterostructured nanocrystals from such precursor seeds. By utilizing chemical and structural inhomogeneity of these metal seeds, in this work, we have synthesized a total of five 1 VI (Ag2S, Ag2Se, Ag3AuS2, Ag3AuSe2, and Cu9S5), three II-VI (CdS, CdSe, and CuSe), and four I-III-VI (AgInS2, AgInSe2, CuInS2, and CuInSe2) chalcogenides, together with their fifteen associated heterodimers (Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, Au-Ag3AuSe2, Au-AgInS2, Au-AgInSe2, Au-CdS, Au-CdSe, Ag-Ag2S, Ag-AgInS2, Au-Cu9S5, Au-CuInS2, Au-CuSe, Au-CuInSe2, and Pt-AgInS2) to affirm the process generality. Briefly, by adding elemental sulfur or selenium to AuAg alloy seeds and tuning the reaction conditions, we can readily obtain phase-pure Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, and Au-Ag3AuSe2 heterostructures. Similarly, we can also fabricate Au-AgInS2 and Au-AgInSe2 heterostructures from the AuAg seeds by adding sulfur/selenium and indium precursors. Furthermore, by partial or full conversion of Ag seeds, we can prepare both single-phase Ag chalcogenide nanocrystals and Ag-based heterostructures. To demonstrate wide applicability of this strategy, we have also synthesized Au-based binary and ternary Cu chalcogenide (Au-Cu9S5, Au-CuSe, Au-CuInS2, and Au-CuInSe2) heterostructures from alloy seeds of AuCu and Pt chalcogenides (e.g., Pt-AgInS2) from alloy seeds of PtAg. The structure and composition of the above products have been confirmed with X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy methods. A kinetic investigation of the formation mechanism of these heterostructures is brought forward using Au-AgInS2 and Ag-CuInS2 as model examples.