Cation Exchange on Colloidal Copper Selenide Nanosheets: A Route to Two-Dimensional Metal Selenide Nanomaterials
Cation Exchange on Colloidal Copper Selenide Nanosheets: A Route to Two-Dimensional Metal Selenide Nanomaterials
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胶体硒化铜纳米片上的阳离子交换：二维金属硒化物纳米材料的途径
DOI：
10.1039/d1tc04815e
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发表时间：
2021
影响因子：
6.4
通讯作者：
Eychmüller
中科院分区：
文献类型：
--
作者：
Shamraienko;Spittel;Hübner;Samadi Khoshkhoo;Georgi;Borchert;K. B. L;Schwarz;Lesnyak;Eychmüller
我们报道了一种基于阳离子交换（CE）反应的二维PbSe，HgSe，ZnSe，SnSe和Cu-Zn-Sn-Se（CZTSe）纳米材料的合成路线。这种方法包括两个步骤：首先合成六方晶系，最大可达几微米，但大约。5 nm厚的CuSe纳米片（NS），随后是主体铜离子与所需客体阳离子（Pb 2+、Hg 2+、Zn 2+或Sn 4+）的CE。在CZTSe的情况下，可以同时添加两种客体阳离子，因为客体阳离子比率和反应时间的变化可以导致各种组成。温和的反应条件允许保留母体NS的尺寸和2D形状，伴随着它们的晶体结构的相应变化。我们进一步证明，CuSe NS的晶体结构可以重新排列，即使没有在三正辛基膦的存在下添加客体阳离子。因此，所获得的NS进一步进行配体交换反应，以便用紧凑的碘离子和硫离子取代其表面上的绝缘大体积有机分子，这是将纳米材料应用于（光）电子器件的关键步骤。将所得NS分散体通过喷涂到市售叉指型铂电极上加工成薄膜。光响应测量的PbSe和CZTSe NS-膜证明了它们作为光敏材料在光探测或光化学中的应用潜力。
We report a synthesis route to two-dimensional PbSe, HgSe, ZnSe, SnSe, and Cu–Zn–Sn–Se (CZTSe) nanomaterials based on cation exchange (CE) reactions. This approach includes two steps: it starts with the synthesis of hexagonal, up to several micrometers large yet approx. 5 nm-thick CuSe nanosheets (NSs), followed by CE of the host copper ions with the desired guest cation (Pb2+, Hg2+, Zn2+, or Sn4+). In the case of CZTSe, both guest cations can be added simultaneously since the variation of the guest cation ratio and reaction time can lead to various compositions. Mild reaction conditions allow for a preservation of the size and the 2D shape of the parent NSs accompanied by corresponding changes in their crystal structure. We furthermore demonstrate that the crystal structure of CuSe NSs can be rearranged even without addition of guest cations in the presence of tri-n-octylphosphine. Thus, the obtained NSs were further subjected to ligand exchange reactions in order to replace insulating bulky organic molecules on their surface with compact iodide and sulfide ions, a step crucial for the application of nanomaterials in (opto)electronic devices. The resulting NS dispersions were processed into thin films by spray-coating onto commercially available interdigitated platinum electrodes. Light response measurements of PbSe and CZTSe NS-films demonstrated their potential for applications as light-sensitive materials in photodetection or photovoltaics.