Here, an investigation of three-dimensional (3D) morphologies for bulk heterojunction (BHJ) films based on regioregular poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) is reported Based on the results, it is demonstrated that optimized post-treatment, such as solvent annealing, forces the PCBM molecules to migrate or diffuse toward the top surface of the BHJ composite films, which induces a new vertical component distribution favorable for enhancing the internal quantum efficiency (eta(IQE)) of the devices. To the 3D BHJ morphology, novel time-of-flight secondary-ion mass spectroscopy studies are employed along with conventional methods, such as UV-vis absorption, X-ray diffraction, and high-resolution transmission electron microscopy studies. The eta(IQE) of the devices are also compared after solvent annealing for different times, which performance of BHJ polymer solar cells. In addition, the fabrication of high performance P3HT:PCBM solar cells using the optimized solvent-annealing method is reported, and these cells show a mean power-conversion efficiency of 4.12% under AM 1.5G illumination conditions at an intensity of 100 mW cm(-2).