RESUMEN
High-crystalline-quality absorbers with fewer defects are crucial for further improvement of open-circuit voltage (VOC) and efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. However, the preparation of high-quality CZTSSe absorbers remains challenging due to the uncontrollability of the selenization reaction and the complexity of the required selenization environment for film growth. Herein, a novel segmented control strategy for the selenization environment, specifically targeting the evaporation area of Se, to regulate the selenization reactions and improve the absorber quality is proposed. The large evaporation area of Se in the initial stage of the selenization provides a great evaporation and diffusion flux for Se, which facilitates rapid phase transition reactions and enables the attainment of a single-layer thin film. The reduced evaporation area of Se in the later stage creates a soft-selenization environment for grain growth, effectively suppressing the loss of Sn and promoting element homogenization. Consequently, the mitigation of Sn-related deep-level defects on the surface and in the bulk induced by element imbalance is simultaneously achieved. This leads to a significant improvement in nonradiative recombination suppression and carrier collection enhancement, thereby enhancing the VOC. As a result, the CZTSSe device delivers an impressive efficiency of 13.77% with a low VOC deficit.
RESUMEN
Kesterites, Cu2ZnSn(SxSe1- x)4 (CZTSSe), solar cells suffer from severe open-circuit voltage (VOC) loss due to the numerous secondary phases and defects. The prevailing notion attributes this issue to Sn-loss during the selenization. However, this work unveils that, instead of Sn-loss, elemental inhomogeneity caused by Cu-directional diffusion toward Mo(S,Se)2 layer is the critical factor in the formation of secondary phases and defects. This diffusion decreases the Cu/(Zn+Sn) ratio to 53% at the bottom fine-grain layer, increasing the Sn-/Zn-related bulk defects. By suppressing the Cu-directional diffusion with a blocking layer, the crystal quality is effectively improved and the defect density is reduced, leading to a remarkable photovoltaic coversion efficiency (PCE) of 14.9% with a VOC of 576 mV and a certified efficiency of 14.6%. The findings provide insights into element inhomogeneity, holding significant potential to advance the development of CZTSSe solar cells.
RESUMEN
The post-heating treatment of the CZTSSe/CdS heterojunction can enhance the interfacial properties of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. In this regard, a two-step annealing method was developed to enhance the heterojunction quality for the first time. That is, a low-temperature (90 °C) process was introduced before the high-temperature treatment, and 12.3% efficiency of CZTSSe solar cells was achieved. Further investigation revealed that the CZTSSe/CdS heterojunction band alignment with a smaller spike barrier can be realized by the two-step annealing treatment, which assisted in carrier transportation and reduced the charge recombination loss, thus enhancing the open-circuit voltage (VOC) and fill factor (FF) of the devices. In addition, the two-step annealing could effectively avoid the disadvantages of direct high-temperature treatment (such as more pinholes on CdS films and excess element diffusion), improve the CdS crystallization, and decrease the defect densities within the device, especially interfacial defects. This work provides an effective method to improve the CZTSSe/CdS heterojunction properties for efficient kesterite solar cells.