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

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

Reaction Kinetics and Formation Mechanism of TiO₂ Nanorods in Solution: An Insight into Oriented Attachment

The reaction kinetics and formation mechanism of oriented attachment for shaped nanoparticles in solution are not well-understood. We present the reaction kinetics and formation mechanism of organic-capped anatase TiO₂ nanorods in solution as a case study for the oriented attachment process using small-angle X-ray scattering (SAXS) and transmission electronic microscopy. The SAXS analysis qualitatively and quantitatively provides in-depth understanding of the mechanism, including the structural evolution, interparticle interaction, and spatial orientation of nanoparticles developed from nanodots to nanorods during the nucleation, isotropic, and anisotropic growth steps. The present study demonstrates the growth details of oriented attachment of nanoparticles in solution. An ordered lamellar structure in the solution is constructed by the balance of interaction forces among surface ligands, functional groups, and solvent molecules serving as a natural template. The template allows the alignment of spherical nanoparticles into ordered chain arrays and facilitates simultaneous transformation from spherical to rod shape via proximity attachment. The proposed model reveals an insight into the oriented attachment mechanism. This multistep formation mechanism of TiO₂ nanorods in solution can provide the fundamental understanding of how to tune the shape of nanoparticles and further control the aggregation of spatial nanorod networks in solution

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

Small- and Wide-Angle X-ray Scattering Characterization of Bulk Heterojunction Polymer Solar Cells with Different Fullerene Derivatives

The aim of this study is to quantitatively investigate the effect of different fullerene type (PC₆₀BM and PC₇₀BM) on various morphological structures and power conversion efficiency (PCE) in the bulk heterojunction (BHJ) P3HT/PC_<i>x</i>BM solar cells. The solar cells are fabricated by spin coating without thermal annealing. The quantitative investigations of three-dimensional self-organized nanostructures are performed by using combined grazing-incidence small- and wide-angle X-ray scattering technique (GISAXS/GIWAXS). Two types of nanostructures are observed due to the phase separation in the BHJ films during the processing. They include (1) intercalated PC_<i>x</i>BM molecules around boundary of P3HT crystalline domain and within amorphous domain and (2) aggregated PC_<i>x</i>BM clusters in PC_<i>x</i>BM domains. The lamellar spacing of P3HT crystalline domains in P3HT/PC₇₀BM is larger than that in P3HT/PC₆₀BM. This result indicates more interfacial areas are generated between PC₇₀BM and P3HT at the molecular scale for more efficient charge separation. On the other hand, the size, volume fraction, partial attachment, and spatial distribution of PC₆₀BM clusters are larger than that of PC₇₀BM clusters, which reveals more efficient electron transport in P3HT/PC₆₀BM. We deduce the correlation between nanostructures and PCE (3.25% and 2.64%, respectively, for P3HT/PC₇₀BM and P3HT/PC₆₀BM). The structure of fullerene intercalated with P3HT rather than the size of fullerene cluster plays a major role in the PCE performance of BHJ solar cell without thermal annealing