Junsu Han

Ge-doped CIGSe absorbers were fabricated using a two-step process of depositing sputtered stacked Ge-doped CIGSe precursors and selenization annealing. The effects of Ge doping on the crystallinity as well as defects of CIGSe absorbers and the performance of CIGSe buffer-free solar cells were investigated. The results show that Ge doping significantly promotes the grain growth of CIGSe absorbers. Due to Ge loss via volatilization during selenization annealing, Ge residue is undetectable in Ge-doped absorbers. Ge doping offers an effective approach to improve CIGSe crystallinity without introducing notable impurity phases or Ge-related defects. However, Ge doping also induces Se loss, and excessive Se vacancy defects adversely affect the performance of the absorber. In addition, Ge doping increases the contact potential difference at CIGSe grain boundaries and is beneficial for reducing carrier recombination at these sites. Analysis of recombination rates in Ge-doped CIGSe buffer-free solar cells reveals that the combined effects of enhanced crystallinity and optimized electrical properties at grain boundaries effectively suppress the recombination in the space charge region, at the interface, and in the quasi-neutral region, leading to improved device performance.

The tunable bandgap of CIGSe has established bandgap engineering as a pivotal research direction for advancing the efficiency frontiers of solar cells. In particular, the proposal of the V-shaped bandgap gradient has motivated extensive efforts to achieve precise control over elemental composition and spatial distribution within the absorber layer. Against this backdrop, this review systematically classifies active control strategies—such as surface sulfurization, Ga grading, and Ag alloying—according to their doping mechanisms and the resulting bandgap profiles. It further evaluates emerging profiles, including the “hockey-stick” distribution, against the conventional V-shaped benchmark, and explores future pathways for bandgap engineering in next-generation, high-efficiency photovoltaic devices. Further improvements in photovoltaic efficiency can effectively boost power generation and lower solar power costs, providing a practical solution to future energy and environmental challenges.

Recombination is one of the main factors that cause the large open‐circuit voltage deficit (V_{oc, def}) in Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells. To mitigate this issue, an effective strategy is developed to suppress the recombinations in CZTSe devices by doping Ge in the absorber. A certified efficiency of 14.67%(total area: 0.3143 cm², without an anti‐reflective layer) was achieved in optimally Ge‐doped CZTSe solar cells. In addition to promoting the grain growth, Ge doping induces more pronounced downward band‐bending, effectively passivating GBs and suppressing recombination in the quasi neutral region (QNR). While optimal Ge doping reduces the number of Cu_Zn defects, excessive Ge doping leads to additional Sn loss, resulting in the formation of deep‐level defects such as V_Sn. Furthermore, the incorporation of Ge resulted in the formation of residual SnSe_x secondary phases near the rear interface, highlighting the need for precise cation ratio adjustments in the precursor films. This work reveals the mechanism underlying Ge doping, demonstrating it potential to mitigate the high recombination velocity at GBs, providing a pathway for achieving high‐efficiency CZTSe solar cells.