Quaternary Cu₂ZnSnS₄ (CZTS) nanocrystalline thin films were in situ grown on FTO coated conductive glass by a low cost solvothermal method. The effect of the reaction time and the concentration of precursor solution on the purity and morphologies of the deposited thin films was studied. The morphology, crystal structure and composition of the deposited thin films were characterized by scanning electron microscope, high resolution transmission electron microscope, X-ray diffraction, Raman spectroscopy and energy-dispersive X-ray spectroscopy. The pure wurtzite CZTS nanoparticles can be formed as the reaction time is 20 h. The film prepared at the optimized precursor solution concentration has uniform thickness, smooth surface and tight binding between the nanoparticles. The performance of the deposited CZTS thin films used as the counter electrode for dye-sensitized solar cells (DSSCs) was evaluated by measuring photocurrent density-voltage curves of DSSCs, electrochemical impedance spectroscopies and Tafel polarization curves of the symmetric cells. Photoelectric conversion efficiency of DSSC based on the optimized CZTS counter electrode reached 6.19%. The excellent photoelectric performance is attributed to the better surface morphology and conductive skeleton of the prepared CZTS thin film. The in situ solvothermal preparation method of the CZTS thin films for counter electrode of DSSCs is green, low cost and simple.

季Cu ₂ ZnSnS ₄（CZTS）纳米晶体薄膜通过低成本溶剂热法在FTO涂层导电玻璃上原位生长。研究了反应时间和前驱体溶液浓度对沉积薄膜纯度和形貌的影响。通过扫描电子显微镜，高分辨率透射电子显微镜，X射线衍射，拉曼光谱和能量色散X射线光谱表征了沉积薄膜的形态，晶体结构和组成。反应时间为20 h时，可以形成纯纤锌矿CZTS纳米颗粒。以最佳前体溶液浓度制备的薄膜具有均匀的厚度，光滑的表面和纳米颗粒之间的紧密结合。通过测量DSSC的光电流密度-电压曲线，电化学阻抗谱和对称电池的Tafel极化曲线，评估了用作染料敏化太阳能电池（DSSC）对电极的CZTS薄膜沉积性能。基于优化的CZTS对电极的DSSC的光电转换效率达到6.19％。优异的光电性能归因于所制备的CZTS薄膜的更好的表面形态和导电骨架。DSSCs对电极用CZTS薄膜的原位溶剂热制备方法绿色环保，成本低廉，操作简便。基于优化的CZTS对电极的DSSC的光电转换效率达到6.19％。优异的光电性能归因于所制备的CZTS薄膜的更好的表面形态和导电骨架。用于DSSCs对电极的CZTS薄膜的原位溶剂热制备方法绿色环保，成本低廉，简单。基于优化的CZTS对电极的DSSC的光电转换效率达到6.19％。优异的光电性能归因于所制备的CZTS薄膜的更好的表面形态和导电骨架。用于DSSCs对电极的CZTS薄膜的原位溶剂热制备方法绿色环保，成本低廉，简单。