Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells (all-PSCs). To overcome this obstacle, the sequential deposition method is used to fabricate the photoactive layers of all-PSCs comprising a polymer donor PTzBI-oF and a polymer acceptor PS1. The film morphology can be manipulated by incorporating amounts of a dibenzyl ether additive into the PS1 layer. Detailed morphology investigations by grazing incidence wide-angle X-ray scattering and a transmission electron microscope reveal that the combination merits of sequential deposition and DBE additive can render favorable crystalline properties as well as phase separation for PTzBI-oF:PS1 blends. Consequently, the optimized all-PSCs delivered an enhanced power conversion efficiency (PCE) of 15.21% along with improved carrier extraction and suppressed charge recombination. More importantly, the optimized all-PSCs remain over 90% of their initial PCEs under continuous thermal stress at 65 °C for over 500 h. This work validates that control over microstructure morphology via a sequential deposition process is a promising strategy for fabricating highly efficient and stable all-PSCs.

聚（3，4-乙烯二氧噻吩）∶聚（苯乙烯磺酸盐）（PEDOT∶PSS）作为热门空穴传输材料之一，被广泛应用于各种光电子器件中。为提高其导电性，高沸点溶剂常常被直接添加到PEDOT∶PSS溶液中，然而这同时会造成溶剂残留，给器件带来明显的漏电流。而在以往的报道中，并未见有效利用更易去除的低沸点溶剂。在本工作中，我们发现使用异丙醇、乙醇和丙酮三种低沸点溶剂对PEDOT∶PSS薄膜进行先滴加后旋涂处理后，相应的P3HT∶PC₆₁BM聚合物太阳能电池（PSCs）性能得到了改善。尤其在异丙醇处理后，电池短路电流密度从8.15 mA/cm²提高到9.17 mA/cm²，能量转换效率达到3.5%，相比参比器件提升了18.6%，同时未引起器件的漏电流增加。分析后发现处理后的PEDOT∶PSS薄膜中PEDOT链和PSS链发生相分离，表面形貌发生改变，透光能力和导电性得到增强。同时，通过溶剂处理尤其异丙醇处理后，PEDOT∶PSS的空穴传输能力显著上升。这些结果表明，低沸点溶剂可以通过这种方法被有效地利用，从而改善PEDOT∶PSS薄膜的光电性能。

Solution processible photovoltaics (PV) are poised to play an important role in scalable manufacturing of low-cost solar cells. Electrospray is uniquely suited for fabricating PVs due to its several desirable characteristics of an ideal manufacturing process such as compatibility with roll-to-roll production processes, tunability and uniformity of droplet size, capability of operating at atmospheric pressure, and negligible material waste and nano structures. This review begins with an introduction of the fundamentals and unique properties of electrospray. We put emphasis on the evaporation time and residence time that jointly affect the deposition outcome. Then we review the efforts of electrospray printing polymer solar cells, perovskite solar cells, and dye sensitized solar cells. Collectively, these results demonstrate the advantages of electrospray for solution processed PV. Electrospray has also exhibited the capability of producing uniform films as well as nanostructured and even multiscale films. So far, the electrospray has been found to improve active layer morphology, and create devices with efficiencies comparable with that of spin-coating. Finally, we discuss challenges and research opportunities that enable electrospray to become a mainstream technique for industrial scale production.