Shifting the Paradigm: A Functional Hole‐Selective Transport Layer for Chalcopyrite Solar Cells

High‐efficiency Cu(In,Ga)Se₂ solar cells rely on Ga grading to mitigate back surface recombination. However, the inhomogeneous absorber has drawbacks, including increased non‐radiative loss and inadequate absorption. Therefore, literatures demand a paradigm shift of using a hole‐transport layer to passivate the back surface. Herein, a functional hole‐transport layer is demonstrated as an alternative to Ga grading. The novel hole‐transport layer is prepared as a double‐layer: co‐evaporated CuGaSe₂ covered by solution combustion synthesis prepared In₂O₃. As demonstrated by micrographs, elemental mapping, and photoluminescence spectroscopy, the oxide layer improves thermal stability and prevents Ga diffusion. However, during the absorber deposition, a complete ion exchange of In and Ga converts CuGaSe₂/In₂O₃ into CuInSe₂/GaO_x. Incorporating this hole‐transport layer in co‐evaporated nongraded CuInSe₂ solar cells leads to significantly increased minority carrier lifetime from 5 to 113 ns, yielding an 80 meV improvement in quasi‐Fermi‐level splitting. The devices exhibit improved open‐circuit voltage, as well as a promising fill factor of over 71%, indicating good hole‐transport properties. In these results, the passivation effect and good hole‐transport properties of the hole‐transport layer are experimentally demonstrated. Thus, high‐efficiency solar cells can be achieved by using a functional hole‐transport layer without relying on Ga grading.