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首页> 外文期刊>Chemistry: A European journal >ZnSe Etching of Zn-Rich Cu_2ZnSnSe_4: An Oxidation Route for Improved Solar-Cell Efficiency
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ZnSe Etching of Zn-Rich Cu_2ZnSnSe_4: An Oxidation Route for Improved Solar-Cell Efficiency

机译：富锌Cu_2ZnSnSe_4的ZnSe蚀刻：改善太阳能电池效率的氧化途径

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Cu_2ZnSnSe_4 kesterite compounds are some of the most promising materials for low-cost thin-film photo-voltaics. However, the synthesis of absorbers for high-performing devices is still a complex issue. So far, the best devices rely on absorbers grown in a Zn-rich and Cu-poor environment. These off-stoichiometric conditions favor the presence of a ZnSe secondary phase, which has been proved to be highly detrimental for device performance. Therefore, an effective method for the selective removal of this phase is important. Previous attempts to remove this phase by using acidic etching or highly toxic organic compounds have been reported but so far with moderate impact on device performance. Herein, a new oxidizing route to ensure efficient removal of ZnSe is presented based on treatment with a mixture of an oxidizing agent and a mineral acid followed by treatment in an aqueous Na_2S solution. Three different oxidizing agents were tested: H_2O_2, KMnO_4, and K_2Cr_2O_7, combined with different concentrations of H_2SO_4. With all of these agents Se~(2-) from the ZnSe surface phase is selectively oxidized to Se~0, forming an elemental Se phase, which is removed with the subsequent etching in Na_2S. Using KMnO_4 in a H_2SO_4-based medium, a large improvement on the conversion efficiency of the devices is observed, related to an improvement of all the optoelectronic parameters of the cells. Improvement of short-circuit current density (J_(sc)) and series resistance is directly related to the selective etching of the ZnSe surface phase, which has a demonstrated current-blocking effect. In addition, a significant improvement of open-circuit voltage (V_(OC)). shunt resistance (R_(sh)), and fill factor (FF) are attributed to a passivation effect of the kesterite absorber surface resulting from the chemical processes, an effect that likely leads to a reduction of non-radiative-recombination states density and a subsequent improvement of the p-n junction.
机译：Cu_2ZnSnSe_4硅藻土化合物是低成本薄膜光伏最有希望的材料。然而，用于高性能装置的吸收剂的合成仍然是一个复杂的问题。到目前为止，最好的设备依赖于在富锌和贫铜环境中生长的吸收器。这些非化学计量的条件有利于ZnSe次级相的存在，事实证明，该相对器件性能非常有害。因此，有选择地去除该相的有效方法很重要。已经报道了通过使用酸性蚀刻或剧毒有机化合物去除该相的先前尝试，但是到目前为止对器件性能具有中等影响。在本文中，提出了一种新的氧化途径，以确保有效地去除ZnSe，这是基于用氧化剂和无机酸的混合物进行处理，然后在Na_2S水溶液中进行处理。测试了三种不同的氧化剂：H_2O_2，KMnO_4和K_2Cr_2O_7，以及不同浓度的H_2SO_4。使用所有这些试剂，ZnSe表面相中的Se〜（2-）被选择性氧化为Se〜0，形成元素Se相，随后在Na_2S中进行蚀刻将其去除。在基于H_2SO_4的介质中使用KMnO_4，可以观察到器件转换效率的大幅提高，这与电池所有光电参数的提高有关。短路电流密度（J_（sc））和串联电阻的提高与ZnSe表面相的选择性刻蚀直接相关，这具有已证明的电流阻挡作用。另外，显着改善了开路电压（V_（OC））。分流电阻（R_（sh））和填充因数（FF）归因于化学过程导致的硅藻土吸收体表面的钝化效应，这种效应很可能导致非辐射复合态密度的降低和pn结的后续改进。

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