Pure-sulfide kesterite Cu 2 ZnSnS 4 (CZTS)-based thin-film solar cell has been emerging as a promising cost-effective thin-film photovoltaic (PV) technology, enjoying its Earth-abundant and ecofriendly constituents, thermodynamically stable structure, combined with the ideal bandgap perfectly matching with solar spectrum, and the compatibility with both rigid and flexible substrates. [1][2][3][4][5][6] These compelling features endow this PV technology huge potential for application of various scenes in the future, including wearable and portable PV power sources, building-integrated PVs (BIPVs) at curved building surfaces, and sustainable power sources for internet of things (IOT). [7,8] Moreover, pure-sulfide CZTS is also one of the most promising candidates as the top cell for silicon-based tandem solar cells, potentially triggering further technological evolution for largescale deployment of PV technologies. [9][10][11] Nevertheless, the current status of CZTS thin-film solar cells suffers from a much more open-circuit voltage (V OC ) loss than low-bandgap Cu 2 ZnSnS,Se 4 (CZTSSe) solar cells. [3,12,13] Besides the more severe bandgap/potential fluctuation and shorter photoluminescence (PL) decay time (related to real minority carrier lifetime), [14][15][16] the unfavorable "cliff"-like conduction band offset (CBO) at CZTS/CdS heterojunction interface is well believed to be a serious limiting factor to the V OC of CZTS solar cells. [17][18][19][20] To address this issue, alternative buffer materials with wide bandgap and a suitable conduction band edge have been screened, among which (Zn,Cd)S and (Zn,Sn)O are the most successful materials, allowing a great V OC boost up to 100 mV. [18,19] Nevertheless, the V OC of CZTS solar cells with a bandgap of 1.5 eV is still limited to be below 750 mV, far lower than that of the moderate CdTe solar cells with a similar recombination bandgap (1.45 eV) and low minority carrier lifetime (1À2 ns), let alone the "cliff"-like CBO at the CdTe/CdS interface. [21][22][23][24] Results of SunsÀV OC measurements for these cells configured with (Zn,Sn)O or (Zn,Cd)S buffer layer have revealed that J 02 (representing nonradiative recombination at the heterojunction region) is still 5 orders of magnitude larger than J 01 (representing nonradiative recombination in the quasineutral bulk region) (10 À7 A cm À2 for J 02 vs. 10 À12 A cm À2 for J 01 ). [18,19] This verifies that the V OC of pure-sulfide CZTS solar cells is still currently limited by nonradiative recombination in the heterojunction interface region, even though the unfavorable "cliff-like" CBO has been avoided, indicating that other important interface recombination mechanisms may persist and are yet to be properly recognized.