Hole-Doping to a Cu(I)-Based Semiconductor with an Isovalent Cation: Utilizing a Complex Defect as a Shallow Acceptor
Hole-Doping to a Cu(I)-Based Semiconductor with an Isovalent Cation: Utilizing a Complex Defect as a Shallow Acceptor
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DOI：
10.1021/jacs.2c06283
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发表时间：
2022-09-14
影响因子：
15
通讯作者：
Hosono, Hideo
中科院分区：
文献类型：
--
作者：
Matsuzaki, Kosuke;Tsunoda, Naoki;Hosono, Hideo
Cu（I）基半导体中的p型掺杂对于太阳能电池光吸收剂和空穴传输材料以改善器件性能是关键的。杂质掺杂是克服由本征缺陷控制的空穴浓度的本征限制的基本技术。在这里，我们报告说，碱金属杂质是突出的p型掺杂剂的Cu（I）为基础的阳离子缺乏空穴导体。当与Cu+在主晶格中的尺寸失配增加时，这些等价杂质优先位于间隙位置，与组分Cu阳离子相互作用，形成稳定的杂质-缺陷复合物。我们证明了Cs杂质在γ-CuI半导体中增强了单晶和薄膜在10（13）-10（19）cm（-3）范围内的空穴浓度可控性。第一性原理计算表明，Cs杂质形成的杂质缺陷复合物，作为浅受主导致p型导电性增加。这种等价掺杂提供了一种通过杂质与天然缺陷的相互作用来控制掺杂到阳离子缺陷半导体中的方法。
p-Type doping in Cu(I)-based semiconductors is pivotal for solar cell photoabsorbers and hole transport materials to improve the device performance. Impurity doping is a fundamental technology to overcome the intrinsic limits of hole concentration controlled by native defects. Here, we report that alkali metal impurities are prominent p-type dopants for the Cu(I)-based cation-deficient hole conductors. When the size mismatch with Cu+ in the host lattice is increased, these isovalent impurities are preferentially located at interstitial positions to interact with the constituent Cu cations, forming stable impurity-defect complexes. We demonstrate that the Cs impurity in gamma-CuI semiconductors enhances hole concentration controllability for single crystals and thin films in the range of 10(13)-10(19) cm(-3). First-principles calculations indicate that the Cs impurity forms impurity-defect complexes that act as shallow acceptors leading to the increased p-type conductivity. This isovalent doping provides an approach for controlled doping into cation-deficient semiconductors through an interaction of impurities with native defects.