Although it has been reported that grain boundaries have not to adversely affect solar cell characteristics in CIGS and halide perovskite solar cell, nevertheless, an effective strategy for efficient carrier management in a CZTS layer is to make the grain size not too small. Generally, grain boundary control is a key concern for polycrystalline thin-film solar cells. [5][6][7][8][9][10][11] A light absorber consisting of small grains can degrade the device performance due to the vertical current flow through the multiple grain boundaries. Current and voltage loss can derive from nonradiative recombination of electrons and holes and scattering at grain boundaries. In fact, CZTSSe solar cells with efficiencies above 12% have a grain size over micrometer scale. [12][13][14][15] Generally, as the annealing temperature and time increase, the grain size increases. The efficiency is expected to decrease when the temperature and annealing time are increased due to the decomposition of CZTSSe by Mo [16,17] and the increase in the MoSSe thickness [16] and Sn loss. [18] Therefore, a liquid-assisted grain growth (LGG) method could be a good method for increasing the grain size at low temperatures over a short time while suppressing the Sn loss, growth of MoSSe and CZTSSe decomposition by Mo. The liquid phase that exists during grain growth plays a role as a diffusion path necessary for material movement such that grain growth more effectively occurs. [19] To date, liquid-assisted grain growth (LGG) has been achieved by controlling the partial pressure of chalcogen vapor to form a liquid phase at the grain boundary of CZTSSe nanoparticles. [7,20] Liquid Cu-Se causes LGG in a Cu-rich composition, and the vapor-liquidsolid (VLS) model has been adopted; [21,22] similarly, LGG might occur in the GeSe 2 -Se system. [23][24][25] Additionally, LGG can occur through the eutectic reaction of the Na-Se system; [24][25][26][27] a similar eutectic reaction can occur in other alkali-chalcogen (AX) systems (AX; A = Li, Na, K, Cs, Rb; X = Se, Te). [28] In addition, LGG might occur due to liquid phase generation upon the addition of dopants, such as Sb 2 S 3 , [29] CuSbS 2 , [29] and NaSb 5 S 8 ; [29] similar eutectic reactions can occur in other similar systems (ASb 5 X 8 ; A = Li, Na, K, and Cs, Rb; X = S, Se, and Te). [28] Additionally, LGG can occur with Ag substitution due to the Ag-related alloy. [30] The similarity is the liquid phase formation due to the existence of the eutectic reaction point (Solid A + Solid B → Liquid) or the liquidus line at the process Herein, a liquid-assisted grain growth (LGG) mechanism for a vacuumprocessed Cu 2 ZnSn(S 1−x Se x ) 4 (CZTSSe) absorber that is enabled by the presence of a liquid phase containing predominantly Cu, Sn, and Se (L-CTSe) is suggested to explain the large grain size of up to ≈6 µm obtained at low temperatures, such as 480 °C. In this system, LGG plays a key role in achieving a large grain CZTSSe absorber, but the residual L-CTSe, a key factor in LGG, deteriorates the device performa...