论文标题

在溅射Cuins $ {_ 2} $的稳定和亚稳态阶段的实验和理论研究

Experimental and theoretical study of stable and metastable phases in sputtered CuInS${_2}$

论文作者

Larsen, Jes K., Sopiha, Kostiantyn V., Persson, Clas, Platzer-Björkman, Charlotte, Edoff, Marika

论文摘要

由于潜在的串联太阳能电池中的潜在应用,近年来,Chalcopyrite Cu(in Ga)s $ {_ 2} $在近年来引起了兴趣。在这一贡献中,采用了合并的理论和实验方法来研究在库因$ {_ 2} $(CIS)薄膜中形成的稳定和亚稳态的相。从头开始计算以获得顺式多型和相关化合物的形成能,X射线衍射模式和拉曼光谱。鉴定了具有锌 - 蓝色和Wurtzite衍生的晶格的多个顺式结构,其XRD/拉曼模式显示出包含重叠的特征,这可能导致错误识别。通过二进制靶标的溅射,随后是高温硫化的两步方法,将具有从铜到铜的成分组成的薄膜合成。发现使用这种方法生长材料时形成了几种顺式多晶型物。在Cu-poor材料中,首次在溅射的薄膜中观察到Wurtzite顺式,以及辣椒顺式Cis和Cuau订购的顺式。一旦形成了wurtzite s阶段,就很难将其转化为稳定的金黄铁矿多晶型物。 Cuin $ {_ 5} $ s $ {_ 8} $,nains $ {_ 2} $可容纳在cis polymorphs的同时。有人认为,亚稳态的多晶型物是通过前体的化写计量法稳定的,因此需要严格的组成控制。

The chalcopyrite Cu(In,Ga)S${_2}$ has gained renewed interest in recent years due to the potential application in tandem solar cells. In this contribution, a combined theoretical and experimental approach is applied to investigate stable and metastable phases forming in CuInS${_2}$ (CIS) thin films. Ab initio calculations are performed to obtain formation energies, X-ray diffraction patterns, and Raman spectra of CIS polytypes and related compounds. Multiple CIS structures with zinc-blende and wurtzite-derived lattices are identified and their XRD/Raman patterns are shown to contain overlapping features, which could lead to misidentification. Thin films with compositions from Cu-rich to Cu-poor are synthesized with a two-step approach based on sputtering from binary targets followed by high-temperature sulfurization. It is discovered that several CIS polymorphs are formed when growing the material with this approach. In the Cu-poor material, wurtzite CIS is observed for the first time in sputtered thin films along with chalcopyrite CIS and CuAu-ordered CIS. Once the wurtzite CIS phase has formed, it is difficult to convert into the stable chalcopyrite polymorph. CuIn${_5}$S${_8}$ and NaInS${_2}$ accommodating In-excess are found alongside the CIS polymorphs. It is argued that the metastable polymorphs are stabilized by off-stoichiometry of the precursors, hence tight composition control is required.

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