PbI2 thin film crystallization control is prerequisite of high-quality perovskite layer for the sequentially solution-processed perovskite solar cells. According to the present invention, an efficient-and-simple method has been developed by adding halogen acid additive to improve perovskite thin-film quality and an efficiency of at least 15.2% is obtained. This approach improves coverage, uniformity and stability of pervoskite thin-film. In addition, a nanofiber scaffold is incorporated into the perovskite layer so as to reduce the amount of grain boundaries, thus substantially reducing electron recombination within these boundaries.