Chun-Jen Su

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.

Bi-hierarchical nanostructures of donor–acceptor copolymer and fullerene for high efficient bulk heterojunction solar cells

Solvent additive processing has become the most effective method to tune the nanostructure of donor–acceptor (D–A) type copolymer/fullerene bulk heterojunctions (BHJs) solar cells for improving power conversion efficiencies. However, to date qualitative microscopic observations reveal discrepant results on the effects of solvent additives. Here, we present quantitative evolution of bi-hierarchical nanostructure of D–A copolymers and fullerenes by employing grazing-incidence small/wide angle X-ray scattering (GISAXS/GIWAXS) techniques and [2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]/[6,6]-phenyl-C71-butyric acid methyl ester (PCPDTBT/PCBM) BHJ as model materials. An accurate GISAXS model analysis is established herein for revealing the distinctive bi-hierarchical nanostructures from molecular level to a scale of hundreds of nanometers. The mechanisms of hierarchical formation and mutual influence between PCPDTBT and PCBM domains are proposed to correlate with photovoltaic properties. These results provide a comprehensive interpretation in respect to previous studies on the nanostructures of D–A copolymer/fullerene BHJs. It is helpful for optimum structural design and associated synthesis improvement for achieving high efficiency BHJ solar cells.

Insight into Evolution, Processing and Performance of Multi-length-scale Structures in Planar Heterojunction Perovskite Solar Cells.

The structural characterization correlated to the processing control of hierarchical structure of planar heterojunction perovskite layer is still incomplete due to the limitations of conventional microscopy and X-ray diffraction. This present study performed the simultaneously grazing-incidence small-angle scattering and wide-angle scattering (GISAXS/GIWAXS) techniques to quantitatively probe the hierarchical structure of the planar heterojunction perovskite solar cells. The result is complementary to the currently microscopic study. Correlation between the crystallization behavior, crystal orientation, nano- and meso-scale internal structure and surface morphology of perovskite film as functions of various processing control parameters is reported for the first time. The structural transition from the fractal pore network to the surface fractal can be tuned by the chloride percentage. The GISAXS/GIWAXS measurement provides the comprehensive understanding of concurrent evolution of the film morphology and crystallization correlated to the high performance. The result can provide the insight into formation mechanism and rational synthesis design.

Insights into solvent vapor annealing on the performance of bulk heterojunction solar cells by a quantitative nanomorphology study

Bulk heterojunctions (BHJ) represent the most promising structures for high efficiency polymer solar cells and their morphologies can be finely tuned by post-treatments such as thermal annealing and solvent vapor annealing. Though extensive studies have shown improved power conversion efficiencies by tuning the treating parameters of both treatments, substantial knowledge of how the BHJ morphologies evolve with various solvent vapors related to photovoltaic characteristics and differ from those with thermal annealing is still limited. Herein we employed simultaneous grazing incidence wide and small angle X-ray scattering (GIWAXS/GISAXS) to systematically investigate the changes in morphology of a poly(3-hexylthiophene)/C61-butyric acid methyl ester (P3HT–PCBM) BHJ manipulated by solvent vapor annealing using different solvents. Solvents with different solubility, i.e. non-solvent, poor solvent and good solvent were studied. Distinctive morphologies were quantitatively resolved among these solvent vapor-annealed BHJs and their evolutions during processing are interpreted. The resolved morphologies can clearly explain the subtle variations in photovoltaic characteristics of open circuit voltage (Voc), short circuit current (Jsc) and fill factor (FF) related to the working mechanism of the BHJ, i.e. carrier generation, carrier transportation and recombination. This work provides fundamental new insights into how the BHJ morphologies and photovoltaic characteristics can be flexibly tailored by solvent vapor annealing using various kinds of solvent vapors.

Hierarchical i–p and i–n porous heterojunction in planar perovskite solar cells

A hierarchical pore network in planar CH3NH3PbI3 perovskite is demonstrated herein. Quantitative characterizations by grazing incidence small angle X-ray scattering (GISAXS) with modeling and complementary microscopic observations provide insight at various length scales. It is a pore structure comprised of nano-scaled primary pores aggregating into meso-scaled fractal networks within the perovskite layer. Its structural evolution and mechanistic interpretation are explored with respect to different preparation methods/steps. The time-of-flight secondary ion mass spectrometer (TOF-SIMS) results suggest the infiltration of hole transporting materials (HTM) or electron transporting materials (ETM) deposited on top at different length scales. The inter-penetrating perovskite/HTM or perovskite/ETM form i–p or i–n one-sided porous heterojunctions, respectively, over the typically regarded planar-stacked heterojunction. They show distinctive photovoltaic characteristics and behaviors in which the large i–n interfaces at the nanoscale lead to highly efficient, hysteresis-free and reliable solar cell devices. The morphology–performance correlation is helpful for associated design of device architecture and processing toward higher efficiency and stability.

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 cm2. 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.