Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S
Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S
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DOI：
10.1002/anie.201501532
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发表时间：
2015-07-06
影响因子：
16.6
通讯作者：
Rao, C. N. R.
中科院分区：
文献类型：
--
作者：
Kouser, Summayya;Lingampalli, S. R.;Rao, C. N. R.
与阳离子取代不同，金属氧化物和硫化物等无机材料中的阴离子取代有望带来电子结构和性能的重大变化。为了探索这一重要方面，我们进行了第一性原理DFT计算，以确定P和Cl的取代对六方和立方结构的CdS和ZnS性能的影响，并表明与阳离子强键合的三价磷的子带出现在价带正上方的能隙中，导致能隙减小并增强介电性能。实验上，已经可以替代六方CdS和ZnS中的P和Cl。正如理论预测的那样，掺杂显着降低了带隙。在 N 和 F 共取代立方 ZnS 中观察到带隙的类似减小。这种阴离子取代有助于改善 CdS 半导体结构的析氢，并可能带来其他应用。
Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first-principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub-band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co-substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well.