Yang Jingjing, Russell Jake C, Tao Songsheng, Lessio Martina, Wang Feifan, Hartnett Alaina C, Peurifoy Samuel R, Doud Evan A, O'Brien Evan S, Gadjieva Natalia, Reichman David R, Zhu Xiaoyang, Crowther Andrew C, Billinge Simon J L, Roy Xavier, Steigerwald Michael L, Nuckolls Colin
Department of Chemistry, Columbia University, New York, NY, USA.
Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY, USA.
Nat Chem. 2021 Jun;13(6):607-613. doi: 10.1038/s41557-021-00680-8. Epub 2021 Apr 26.
In atomic solids, substitutional doping of atoms into the lattice of a material to form solid solutions is one of the most powerful approaches to modulating its properties and has led to the discovery of various metal alloys and semiconductors. Herein we have prepared solid solutions in hierarchical solids that are built from atomically precise clusters. Two geometrically similar metal chalcogenide clusters, CoSe(PEt) and CrTe(PEt), were combined as random substitutional mixture, in three different ratios, in a crystal lattice together with fullerenes. This does not alter the underlying crystalline structure of the [cluster][C] material, but it influences its electronic and magnetic properties. All three solid solutions showed increased electrical conductivities compared with either the Co- or Cr-based parent material, substantially so for two of the Co:Cr ratios (up to 100-fold), and lowered activation barriers for electron transport. We attribute this to the existence of additional energy states arising from the materials' structural heterogeneity, which effectively narrow transport gaps.
在原子固体中，将原子替代掺杂到材料晶格中以形成固溶体是调节其性能的最有效方法之一，并促成了各种金属合金和半导体的发现。在此，我们制备了由原子精确簇构建的分级固体中的固溶体。将两个几何形状相似的金属硫族化物簇CoSe(PEt)和CrTe(PEt)作为随机替代混合物，以三种不同比例与富勒烯一起在晶格中组合。这不会改变[簇][C]材料的潜在晶体结构，但会影响其电子和磁性特性。与基于Co或Cr的母体材料相比，所有三种固溶体的电导率均有所提高，对于两种Co:Cr比例而言大幅提高（高达100倍），并且降低了电子传输的活化能垒。我们将此归因于材料结构异质性产生的额外能态的存在，这有效地缩小了传输间隙。
