Correlation between Hierarchical Structure and Processing Control of Large-area Spray-coated Polymer Solar Cells toward High Performance.

The formation mechanism of a spray-coated film is different from that of a spin-coated film. This study employs grazing incidence small- and wide-angle X-ray Scattering (GISAXS and GIWAXS, respectively) quantitatively and systematically to investigate the hierarchical structure and phase-separated behavior of a spray-deposited blend film. The formation of PCBM clusters involves mutual interactions with both the P3HT crystal domains and droplet boundary. The processing control and the formed hierarchical structure of the active layer in the spray-coated polymer/fullerene blend film are compared to those in the spin-coated film. How the different post-treatments, such as thermal and solvent vapor annealing, tailor the hierarchical structure of the spray-coated films is quantitatively studied. Finally, the relationship between the processing control and tailored BHJ structures and the performance of polymer solar cell devices is established here, taking into account the evolution of the device area from 1 × 0.3 and 1 × 1 cm(2). The formation and control of the special networks formed by the PCBM cluster and P3HT crystallites, respectively, are related to the droplet boundary. These structures are favorable for the transverse transport of electrons and holes.

Mechanism and control of the structural evolution of a polymer solar cell from a bulk heterojunction to a thermally unstable hierarchical structure.

We simultaneously employed grazing incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS) techniques to quantitatively study the structural evolution and kinetic behavior of poly(3-hexylthiophene) (P3HT) crystallization, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) aggregation and amorphous P3HT/PCBM domains from a bulk heterojunction (BHJ) to a thermally unstable structure. The independent phase separation regimes on the nanoscale (∼10 nm), mesoscale (∼100 nm) and macroscale (∼µm) are revealed for the first time. Bis-PCBM molecules as inhibitors incorporated into the P3HT/PCBM blend films were adopted as a case study of a control strategy for improving the thermal stability of P3HT/PCBM solar cell. The detailed information on the formation, growth, transformation and mutual interaction between different phases during the hierarchical structural evolution of P3HT/PCBM:xbis-PCBM (x = 8-100%) blend films are presented herein. This systematic study proposes the mechanisms of thermal instability for a polymer/fullerene-based solar cell. We demonstrate a new fundamental concept that the structural evolution and thermal stability of mesoscale amorphous P3HT/PCBM domains during heating are the origin of controlling thermal instability rather than those of nanoscale thermally-stable BHJ structures. It leads to a low-cost and easy-fabrication control strategy for effectively tailoring the hierarchical morphology against thermal instability from molecular to macro scales. The optimum treatment achieving high thermal stability, control of mesoscale domains, can be effectively designed. It is independent of the original BHJ nanostructure design of a polymer/fullerene-based solar cell with high performance. It advances the general knowledge on the thermal instability directly arising from the nanoscale structure.

Distribution of crystalline polymer and fullerene clusters in both horizontal and vertical directions of high-efficiency bulk heterojunction solar cells.

In this study, we used (i) synchrotron grazing-incidence small-/wide-angle X-ray scattering to elucidate the crystallinity of the polymer PBTC12TPD and the sizes of the clusters of the fullerenes PC61BM and ThC61BM and (ii) transmission electron microscopy/electron energy loss spectroscopy to decipher both horizontal and vertical distributions of fullerenes in PBTC12TPD/fullerene films processed with chloroform, chlorobenzene and dichlorobezene. We found that the crystallinity of the polymer and the sizes along with the distributions of the fullerene clusters were critically dependent on the solubility of the polymer in the processing solvent when the solubility of fullerenes is much higher than that of the polymer in the solvent. In particular, with chloroform (CF) as the processing solvent, the polymer and fullerene units in the PBTC12TPD/ThC61BM layer not only give rise to higher crystallinity and a more uniform and finer fullerene cluster dispersion but also formed nanometer scale interpenetrating network structures and presented a gradient in the distribution of the fullerene clusters and polymer, with a higher polymer density near the anode and a higher fullerene density near the cathode. As a result of combined contributions from the enhanced polymer crystallinity, finer and more uniform fullerene dispersion and gradient distributions, both the short current density and the fill factor for the device incorporating the CF-processed active layer increase substantially over that of the device incorporating a dichlorobenzene-processed active layer; the resulting power conversion efficiency of the device incorporating the CF-processed active layer was enhanced by 46% relative to that of the device incorporating a dichlorobenzene-processed active layer.

Nanoparticle-tuned self-organization of a bulk heterojunction hybrid solar cell with enhanced performance.

We demonstrate here that the nanostructure of poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PCBM) bulk heterojunction (BHJ) can be tuned by inorganic nanoparticles (INPs) for enhanced solar cell performance. The self-organized nanostructural evolution of P3HT/PCBM/INPs thin films was investigated by using simultaneous grazing-incidence small-angle X-ray scattering (GISAXS) and grazing-incidence wide-angle X-ray scattering (GIWAXS) technique. Including INPs into P3HT/PCBM leads to (1) diffusion of PCBM molecules into aggregated PCBM clusters and (2) formation of interpenetrating networks that contain INPs which interact with amorphous P3HT polymer chains that are intercalated with PCBM molecules. Both of the nanostructures provide efficient pathways for free electron transport. The distinctive INP-tuned nanostructures are thermally stable and exhibit significantly enhanced electron mobility, external quantum efficiency, and photovoltaic device performance. These gains over conventional P3HT/PCBM directly result from newly demonstrated nanostructure. This work provides an attractive strategy for manipulating the phase-separated BHJ layers and also increases insight into nanostructural evolution when INPs are incorporated into BHJs.

Quantitative nanoorganized structural evolution for a high efficiency bulk heterojunction polymer solar cell.

We have developed an improved small-angle X-ray scattering (SAXS) model and analysis methodology to quantitatively evaluate the nanostructures of a blend system. This method has been applied to resolve the various structures of self-organized poly(3-hexylthiophene)/C61-butyric acid methyl ester (P3HT/PCBM) thin active layer in a solar cell from the studies of both grazing-incidence small-angle X-ray scattering (GISAXS) and grazing-incidence X-ray diffraction (GIXRD). Tuning the various length scales of PCBM-related structures by a different annealing process can provide a flexible approach and better understanding to enhance the power conversion of the P3HT/PCBM solar cell. The quantitative structural characterization by this method includes (1) the mean size, volume fraction, and size distribution of aggregated PCBM clusters, (2) the specific interface area between PCBM and P3HT, (3) the local cluster agglomeration, and (4) the correlation length of the PCBM molecular network within the P3HT phase. The above terms are correlated well with the device performance. The various structural evolutions and transformations (growth and dissolution) between PCBM and P3HT with the variation of annealing history are demonstrated here. This work established a useful SAXS approach to present insight into the modeling of the morphology of P3HT/PCBM film. In situ GISAXS measurements were also conducted to provide informative details of thermal behavior and temporal evolution of PCBM-related structures during phase separation. The results of this investigation significantly extend the current knowledge of the relationship of bulk heterojunction morphology to device performance.