摘要： A series of POM-based dyes with triphenylamine electron donor group, cyanoacrylic acid electron acceptor group and different π linkers of thiophene derivatives are systematically investigated to analyze the influence of rigidified bithiophene with fastening atoms (C and N) on the performance of dye-sensitized solar cells (DSSCs) based on density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The interfacial electron transfer (IET) processes are evaluated, which is less investigated previously. We can see that the electron in dyes 2, 4 and 5 are almost completely injected after 100 fs, thus leading to the fast IET. Dye 2 not only has lower interaction energy for most stable dimer configuration than dye 1, but also has larger short-circuit photocurrent density JSC and open-circuit photovoltage VOC, resulting from the insertion of POM group. Compared with dye 3 containing 2,2'-bithiophene π linker, its two counterparts (dyes 4 and 5) with rigidified bithiophene π linkers tend to accelerate IET process as well as retard the electron recombination, thus improve the performance of DSSCs. In particular, dye 4 with rigidified bithiophene π linker fastening by C atom would obtain the larger JSC and VOC than that of dye 5 with N atom rigidified bithiophene π linker.