Pd(II)/Pd(IV) redox shuttle to suppress vacancy defects at grain boundaries for efficient kesterite solar cells

Abstract

Charge loss at grain boundaries of kesterite Cu2ZnSn(S, Se)4 polycrystalline absorbers is an important cause limiting the performance of this emerging thin-film solar cell. Herein, we report a Pd element assisted reaction strategy to suppress atomic vacancy defects in GB regions. The Pd, on one hand in the form of PdSex compounds, can heterogeneously cover the GBs of the absorber film, suppressing Sn and Se volatilization loss and the formation of their vacancy defects (i.e. VSn and VSe), and on the other hand, in the form of Pd(II)/Pd(IV) redox shuttle, can assist the capture and exchange of Se atoms, thus contributing to eliminating the already-existing VSe defects within GBs. These collective effects have effectively reduced charge recombination loss and enhanced p-type characteristics of the kesterite absorber. As a result, high-performance kesterite solar cells with a total-area efficiency of 14.5% (certified at 14.3%) have been achieved.

Improving the performance of kesterite solar cells by solution germanium alloying

“…Previous reports have shown that Cu + –Sn 4+ -based solutions have great advantages in the fabrication of high-quality CZTSSe absorbers due to the unique direct phase transformation crystallization mechanism. 5,21,22 Introducing Ag + or Cd 2+ into kesterite through Cu + –Sn 4+ based DMSO solution has shown great success in precise control of alloying concentration, suppressing deep defects/band tailing, and improving device performance. 23,24…”