Versatile Colloidal Syntheses of Metal Chalcogenide Nanoparticles from Elemental Precursors Using Amine-Thiol Chemistry
Versatile Colloidal Syntheses of Metal Chalcogenide Nanoparticles from Elemental Precursors Using Amine-Thiol Chemistry
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DOI：
10.1021/acs.chemmater.9b03401
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发表时间：
2019-11-12
影响因子：
8.6
通讯作者：
Agrawal, Rakesh
中科院分区：
文献类型：
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作者：
Deshmukh, Swapnil D.;Ellis, Ryan G.;Agrawal, Rakesh
胶体金属硫族化物纳米颗粒已经成为一种有前途的无肼路线，用于制造溶液处理的电子器件。虽然已经为这些纳米材料开发了各种各样的合成途径，但典型的胶体合成依赖于使用金属盐作为前体，其含有阴离子杂质，例如卤化物、硝酸盐、乙酸盐等，其可以掺入并改变靶向纳米颗粒的电性质。在这份报告中，胺硫醇化学的最新进展及其独特的能力，以溶解纯金属，硫族元素，和金属硫族化物的金属硫族化物纳米粒子的制造扩展。在将单胺和二硫醇添加到元素Cu、In、Ga、Sn、Zn、Se或金属硫属元素化物如Cu 2S和Ag 2S时，容易形成烷基铵金属硫醇盐物质。然后将这些物质直接用于合成胶体纳米颗粒，而不需要任何额外的纯化。研究了一种这样的代表性烷基铵硫醇盐物质的热分解途径，验证了仅形成金属硫属化物和挥发性副产物，提供了一种灵活的路线，以获得组成均匀、相纯和无阴离子杂质的胶体纳米颗粒。从这些前体开发合成方法以产生二元、三元和四元材料的纯相胶体纳米颗粒及其合金，包括In 2S 3、（InxGa 1-x）（2）S-3、CuInS 2、CuIn（SxSe 1-x）（2）、Cu（InxGa 1-x）S-2、Cu 2 ZnSnS 4和AgInS 2。成功的合成与各种实验方法，如加热，热注射，微波辅助溶剂热反应也被证明，显示了这种新的合成路线的灵活性和更大的范围。
Colloidal metal chalcogenide nanoparticles have emerged as a promising hydrazine-free route for the fabrication of solution processed electronic devices. While a wide variety of synthetic pathways have been developed for these nanomaterials, typical colloidal syntheses rely on the use of metal salts as precursors, which contain anionic impurities such as halides, nitrates, acetates, and so forth, that may incorporate and alter the electrical properties of the targeted nanoparticles. In this report, the recent advances in aminethiol chemistry and its unique ability to dissolve pure metals, chalcogens, and metal chalcogenides is expanded upon for the fabrication of metal chalcogenide nanoparticles. Alkylammonium metal thiolate species are easily formed upon addition of monoamine and dithiol to elemental Cu, In, Ga, Sn, Zn, Se, or metal chalcogenides such as Cu2S and Ag2S. These species were then used directly for the synthesis of colloidal nanoparticles without the need for any additional purification. The thermal decomposition pathway of one such representative alkylammonium inetal thiolate species was studied, verifying that only metal chalcogenides and volatile byproducts are formed, providing a flexible route to compositionally uniform, phase pure, and anionic impurity-free colloidal nanoparticles. Synthetic methods were developed from these precursors to yield pure phase colloidal nanoparticles of binary, ternary, and quaternary materials and their alloys including In2S3, (InxGa1-x)(2)S-3, CuInS2, CuIn(SxSe1-x)(2), Cu(InxGa1-x)S-2, Cu2ZnSnS4, and AgInS2. Successful synthesis with various experimental methods such as heat up, hot injection, and microwave assisted solvothermal reactions were also demonstrated, showing the flexibility and greater scope for this new synthesis route.