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Organic solar cells utilize an energy-level offset to generate free charge carriers. Although a very small energy-level offset increases the open-circuit voltage, it remains unclear how exactly charge generation is affected. Here we investigate organic solar cell blends with highest occupied molecular orbital energy-level offsets (∆EHOMO) between the donor and acceptor that range from 0 to 300 meV. We demonstrate that exciton quenching at a negligible ∆EHOMO takes place on timescales that approach the exciton lifetime of the pristine materials, which drastically limits the external quantum efficiency. We quantitatively describe this finding via the Boltzmann stationary-state equilibrium between charge-transfer states and excitons and further reveal a long exciton lifetime to be decisive in maintaining an efficient charge generation at a negligible ∆EHOMO. Moreover, the Boltzmann equilibrium quantitatively describes the major reduction in non-radiative voltage losses at a very small ∆EHOMO. Ultimately, highly luminescent near-infrared emitters with very long exciton lifetimes are suggested to enable highly efficient organic solar cells. Donor–acceptor systems with low energy-level offset enable high power efficiency in organic solar cells yet it is unclear what drives charge generation. Classen et al. show that long exciton lifetimes enable efficient exciton splitting and thus generation of free charges while also suppressing voltage losses.

Organic solar cells utilize an energy-level offset to generate free charge carriers. Although a very small energy-level offset increases the open-circuit voltage, it remains unclear how exactly charge generation is affected. Here we investigate organic solar cell blends with highest occupied molecular orbital energy-level offsets (∆EHOMO) between the donor and acceptor that range from 0 to 300 meV. We demonstrate that exciton quenching at a negligible ∆EHOMO takes place on timescales that approach the exciton lifetime of the pristine materials, which drastically limits the external quantum efficiency. We quantitatively describe this finding via the Boltzmann stationary-state equilibrium between charge-transfer states and excitons and further reveal a long exciton lifetime to be decisive in maintaining an efficient charge generation at a negligible ∆EHOMO. Moreover, the Boltzmann equilibrium quantitatively describes the major reduction in non-radiative voltage losses at a very small ∆EHOMO. Ultimately, highly luminescent near-infrared emitters with very long exciton lifetimes are suggested to enable highly efficient organic solar cells. Donor–acceptor systems with low energy-level offset enable high power efficiency in organic solar cells yet it is unclear what drives charge generation. Classen et al. show that long exciton lifetimes enable efficient exciton splitting and thus generation of free charges while also suppressing voltage losses.

AbstractThe preparation of nanomaterials for energy applications such as intercalation batteries and materials that can act as substrates for water oxidation is a subject of major interest nowadays. In this work, we report the deposition of Prussian blue (PB) and its cobalt analogue (CoPBA) on mesoporous titania thin films (MTTF) using the successive ionic layer adsorption reaction (SILAR) technique under soft conditions. A bifunctional ligand, 1,10‐phenanthroline‐5,6‐dione (pd), was used to functionalize the titania surface and promote the growth of PB and CoPBA. The resulting PB@MTTF and CoPBA@MTTF nanocomposites were characterized using several techniques and it was determined that PB and CoPBA grow in a controlled and sequential manner, maintaining the mesoporous architecture. Both PB@MTTF and CoPBA@MTTF demonstrated very good electroactive properties, while CoPBA@MTTF exhibited water oxidation capabilities. The flexibility of this PBA@MTTF platform allows the incorporation of any labile transition metal ion or fragment into the structure of the coordination polymer embedded into a mesoporous matrix, opening the door for (photo)electrochemical devices and catalysts.

AbstractThe preparation of nanomaterials for energy applications such as intercalation batteries and materials that can act as substrates for water oxidation is a subject of major interest nowadays. In this work, we report the deposition of Prussian blue (PB) and its cobalt analogue (CoPBA) on mesoporous titania thin films (MTTF) using the successive ionic layer adsorption reaction (SILAR) technique under soft conditions. A bifunctional ligand, 1,10‐phenanthroline‐5,6‐dione (pd), was used to functionalize the titania surface and promote the growth of PB and CoPBA. The resulting PB@MTTF and CoPBA@MTTF nanocomposites were characterized using several techniques and it was determined that PB and CoPBA grow in a controlled and sequential manner, maintaining the mesoporous architecture. Both PB@MTTF and CoPBA@MTTF demonstrated very good electroactive properties, while CoPBA@MTTF exhibited water oxidation capabilities. The flexibility of this PBA@MTTF platform allows the incorporation of any labile transition metal ion or fragment into the structure of the coordination polymer embedded into a mesoporous matrix, opening the door for (photo)electrochemical devices and catalysts.

This review highlights the importance of controlling the crystallization dynamics for the deposition of high-quality photovoltaic perovskite layers on larger-area coatings.

This review highlights the importance of controlling the crystallization dynamics for the deposition of high-quality photovoltaic perovskite layers on larger-area coatings.

Humic-like substances (HULIS) account for a major redox-active fraction of biomass burning organic aerosols (BBOA). During atmospheric transport, fresh acidic BB-HULIS in droplets and humid aerosols are subject to neutralization and pH-modified aging process. In this study, solutions containing HULIS isolated from wood smoldering emissions were first adjusted with NaOH and NH3 to pH values in the range of 3.6-9.0 and then aged under oxic dark conditions. Evolution of HULIS oxidative potential (OP) and total peroxide content (equivalent H2O2 concentration, H2O2eq) were measured together with the changes in solution absorbance and chemical composition. Notable immediate responses such as peroxide generation, HULIS autoxidation, and an increase in OP and light absorption were observed under alkaline conditions. Initial H2O2eq, OP, and absorption increased exponentially with pH, regardless of the alkaline species added. Dark aging further oxidized the HULIS and led to pH-dependent toxic and chemical changes, exhibiting an alkaline-facilitated initial increase followed by a decrease of OP and H2O2eq. Although highly correlated with HULIS OP, the contributions of H2O2eq to OP are minor but increased both with solution pH and dark aging time. Alkalinity-assisted autoxidation of phenolic compounds and quinoids with concomitant formation of H2O2 and other alkalinity-favored peroxide oxidation reactions are proposed here for explaining the observed HULIS OP and chemical changes in the dark. Our findings suggest that alkaline neutralization of fresh BB-HULIS represents a previously overlooked peroxide source and pathway for modifying aerosol redox-activity and composition. Additionally, these findings imply that the lung fluid neutral environment can modify the OP and peroxide content of inhaled BB-HULIS. The results also suggest that common separation protocols of HULIS using base extraction methods should be treated with caution when evaluating and comparing their composition, absorption, and relative toxicity.

Humic-like substances (HULIS) account for a major redox-active fraction of biomass burning organic aerosols (BBOA). During atmospheric transport, fresh acidic BB-HULIS in droplets and humid aerosols are subject to neutralization and pH-modified aging process. In this study, solutions containing HULIS isolated from wood smoldering emissions were first adjusted with NaOH and NH3 to pH values in the range of 3.6-9.0 and then aged under oxic dark conditions. Evolution of HULIS oxidative potential (OP) and total peroxide content (equivalent H2O2 concentration, H2O2eq) were measured together with the changes in solution absorbance and chemical composition. Notable immediate responses such as peroxide generation, HULIS autoxidation, and an increase in OP and light absorption were observed under alkaline conditions. Initial H2O2eq, OP, and absorption increased exponentially with pH, regardless of the alkaline species added. Dark aging further oxidized the HULIS and led to pH-dependent toxic and chemical changes, exhibiting an alkaline-facilitated initial increase followed by a decrease of OP and H2O2eq. Although highly correlated with HULIS OP, the contributions of H2O2eq to OP are minor but increased both with solution pH and dark aging time. Alkalinity-assisted autoxidation of phenolic compounds and quinoids with concomitant formation of H2O2 and other alkalinity-favored peroxide oxidation reactions are proposed here for explaining the observed HULIS OP and chemical changes in the dark. Our findings suggest that alkaline neutralization of fresh BB-HULIS represents a previously overlooked peroxide source and pathway for modifying aerosol redox-activity and composition. Additionally, these findings imply that the lung fluid neutral environment can modify the OP and peroxide content of inhaled BB-HULIS. The results also suggest that common separation protocols of HULIS using base extraction methods should be treated with caution when evaluating and comparing their composition, absorption, and relative toxicity.