Circular dichroism spectroscopy is essential for structural characterization of proteins and chiral nanomaterials. Chiral structures from plasmonic materials have extraordinary strong circular dichroism effects compared to their molecular counterparts. While being extensively investigated, the comprehensive account of circular dichroism effects consistent with other plasmonic phenomena is still missing. Here we investigated the circular differential scattering of a simple chiral plasmonic system, a twisted side-by-side Au nanorod dimer, using single-particle circular dichroism spectroscopy complimented with electromagnetic simulations. This approach enabled us to quantify the effects of structural symmetry breaking, namely, size-mismatch between the constituent Au nanorods and large twist angles on the resulting circular differential scattering spectrum. Our results demonstrate that, if only scattering is considered as measured by dark-field spectroscopy, a homodimer of Au nanorods with similar sizes produces a circular differential scattering line shape that is different from the bisignate response of the corresponding conventional CD spectrum, which measures extinction, that is, the sum of scattering and absorption. On the other hand, symmetry breaking in a heterodimer with Au nanorods with different sizes yields a bisignate circular differential scattering line shape. In addition, we provide a general method for correcting linear dichroism artifacts arising from slightly elliptically polarized light in a typical dark-field microscope, as is necessary especially when measuring highly anisotropic nanostructures, such as side-by-side nanorods. This work lays the foundation for understanding absorption and scattering contributions to the CD line shape of single chiroplasmonic nanostructures free from ensemble-averaging, especially important for self-assembled chiral nanostructures that usually exist as both enantiomers.
Any new solar photovoltaic (PV) technology must reach low production costs to compete with today's marketleading crystalline silicon and commercial thin-film PV technologies. Colloidal quantum dots (QDs) could open up new applications by enabling lightweight and flexible PV modules. However, the cost of synthesizing nanocrystals at the large scale needed for PV module production has not previously been investigated. Based on our experience with commercial QD scale-up, we develop a Monte Carlo model to analyze the cost of synthesizing lead sulfide and metal halide perovskite QDs using 8 different reported synthetic methods. We also analyze the cost of solution-phase ligand exchange for preparing deposition-ready PbS QD inks, as well as the manufacturing cost for roll-to-roll solution-processed PV modules using these materials. We find that present QD synthesis costs are prohibitively high for PV applications, with median costs of 11 to 59 $ per g for PbS QDs (0.15 to 0.84 $ per W for a 20% efficient cell) and 73 $ per g for CsPbI 3 QDs (0.74 $ per W). QD ink preparation adds 6.3 $ per g (0.09 $ per W). In total, QD materials contribute up to 55% of the total module cost, making even roll-to-roll-processed QDPV modules significantly more expensive than silicon PV modules. These results suggest that the development of new low-cost synthetic methods is critically important for the commercial relevance of QD photovoltaics. Using our cost model, we identify strategies for reducing synthetic cost and propose a cost target of 5 $ per g to move QD solar cells closer to commercial viability. Broader contextColloidal quantum dots (QDs) have been widely investigated as an avenue toward ultra-low-cost solar photovoltaics (PV), alongside organics and metal halide perovskites. It is often implicitly assumed-and explicitly stated-that QD-based PV technologies can reach low cost because they employ low-cost, abundant elements and low-temperature, high-throughput manufacturing processes. However, this argument holds true only if QDs can be synthesized at low cost-materials dictate the module cost floor. Here we report the first detailed analysis of the cost of large-scale QD synthesis for PV applications. Our Monte Carlo approach constitutes a complete cost modeling framework for QD photovoltaics, from raw precursors to finished modules. We find that QD synthesis is prohibitively expensive today, highlighting the importance of synthetic cost for the commercial viability of QD solar technologies and guiding further research toward promising synthetic directions.
The authors would like to thank the two anonymous reviewers for their insightful and constructive comments that improved the quality of our work as well as the Ministry of Economic Affairs and Climate Policy of the Netherlands for its financial support enabling the research behind this publication.
Ultra‐lightweight and flexible solar cells are desired for many potential applications, such as self‐powered aviation, wearable electronics, and the Internet of things. PbS quantum dots (QDs) are good candidates for this purpose due to their low‐cost and low‐temperature processing. In this work, a thin layer of parylene (1 µm) is deposited on a poly(ethylene teraphthalate) (PET) substrate using chemical vapor deposition (CVD) and is employed as a flexible substrate for PbS QDs solar cell. Here, the commonly used ITO electrode in the QDs photovoltaics (PVs) is replaced by CVD‐graphene and its wettability issue is addressed using a thin layer of oxidative CVD poly(3,4‐ethylene dioxythiophene) (oCVD PEDOT), which also works as second hole transporting layer in the device. Inverted PbS QDs device is fabricated on PET/parylene/graphene/oCVD PEDOT stack and finally by removing the PET substrate, an ultra‐lightweight PbS QDs solar cell is achieved. Using this architecture, a power conversion efficiency (PCE) of 7.1% and a power‐per‐weight of 12.3 W g−1 are achieved. Additionally, the QDs device on graphene shows good flexibility as compared to the device on PET/ITO. This work highlights the advantages of oCVD PEDOT and CVD‐graphene for the fabrication of flexible and ultralight weight photostatics.
Intensive research of hybrid metal-halide perovskite materials for use as photoactive materials has resulted in an unmatched increase in the power conversion efficiency of perovskite photovoltaics (PVs) over the last couple of years. Now that lab-fabricated perovskite devices rival the efficiency of silicon PVs, the next challenge of scalable mass manufacturing of large perovskite PV panels remains to be solved. For that purpose, it is still unclear which manufacturing method will provide the lowest processing cost and highest quality solar cells. Vapor deposition has been proven to work well for perovskites as a controllable and repeatable thin-film deposition technique but with processing speeds currently too slow to adequately lower the production costs. Addressing this challenge, in the present work, we demonstrate a high-speed vapor transport processing technique in a custom-built reactor that produces high-quality perovskite films with unprecedented deposition speed exceeding 1 nm/s, over 10× faster than previous vapor deposition demonstrations. We show that the semiconducting perovskite films produced with this method have excellent crystallinity and optoelectronic properties with 10 ns charge carrier lifetime, enabling us to fabricate the first photovoltaic devices made by perovskite vapor transport deposition. Our experiments are guided by computational fluid dynamics simulations that also predict that this technique could lead to deposition rates on the order of micrometers per second. This, in turn, could enable cost-effective scalable manufacturing of the perovskite-based solar technologies.
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