Search

Integrating benzo-18-crown-6-ether at interfaces between perovskite and hole transport layer achieves dual-functionality: lead ion sequestration and robust interfacial passivation, enhancing stability and efficiency of perovskite solar cell.

Understanding the fundamental origin of morphological degradation in non-fullerene acceptor-based organic solar cells is challenging. In the April 2021 issue of Nature Materials, Ghasemi et al. reveal that the most thermodynamically unstable and low-miscibility systems with high Flory-Huggins interaction parameter (χ) exhibit the most kinetically stable (low diffusion) morphology for superior device operation stability under thermal stress.

A bulk-heterojunction (BHJ) structure of organic semiconductor blend is widely used in photon-to-electron converting devices such as organic photodetectors (OPD) and photovoltaics (OPV). However, the impact of the molecular structure on the interfacial electronic states and optoelectronic properties of the constituent organic semiconductors is still unclear, limiting further development of these devices for commercialization. Herein, the critical role of donor molecular structure on OPD performance is identified in highly intermixed BHJ blends containing a small-molecule donor and C60acceptor. Blending introduces a twisted structure in the donor molecule and a strong coupling between donor and acceptor molecules. This results in ultrafast exciton separation (<1 ps), producing bound (binding energy ∼135 meV), localized (∼0.9 nm), and highly emissive interfacial charge transfer (CT) states. These interfacial CT states undergo efficient dissociation under an applied electric field, leading to highly efficient OPDs in reverse bias but poor OPVs. Further structural twisting and molecular-scale aggregation of the donor molecules occur in blends upon thermal annealing just above the transition temperature of 150 °C at which donor molecules start to reorganize themselves without any apparent macroscopic phase-segregation. These subtle structural changes lead to significant improvements in charge transport and OPD performance, yielding ultralow dark currents (∼10–10A cm–2), 2-fold faster charge extraction (in μs), and nearly an order of magnitude increase in effective carrier mobility. Our results provide molecular insights into high-performance OPDs by identifying the role of subtle molecular structural changes on device performance and highlight key differences in the design of BHJ blends for OPD and OPV devices.

Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

Wavelength-selective harvesting by organic solar cells (OSCs) has attracted significant research attention due to the unique potential of these materials for smart photovoltaic window applications. Here, a visibly transparent OSC is demonstrated by utilizing both near-infrared (NIR)-absorbing polymer donor and nonfullerene acceptor (NFA) materials with narrow optical band gaps of less than 1.4 eV. Despite the substantial overlap in absorption spectra between the donor and acceptor, sufficient lowest unoccupied molecular orbital (LUMO) and highest occupied molecule orbital (HOMO) energy offsets for efficient charge separation with concurrent very low voltage losses yield a power conversion efficiency (PCE) of 9.13%. Moreover, with the introduction of an ultrathin Ag film (8 nm) as a transparent top electrode, semitransparent OSCs exhibit an excellent dual-side photovoltaic performance of 5.7 and 3.9% under bottom and top illumination, respectively, with high transmittance reaching 60% at wavelengths from 400 to 600 nm. This approach is expected to provide a new perspective in developing the highly efficient and transparent OSCs.

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2evolution rate of over 60,000?µmol?h-1?g-1under 350 to 800?nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux.

The side-chain directions in nonfullerene acceptors (NFAs) strongly influence the intermolecular interactions in NFAs; however, the influence of these side chains on the morphologies and charge carrier dynamics of Y6-based acceptors remains underexplored. In this study, we synthesize four distinct Y6-based acceptors, i.e., meta-HOP–Y6-F (mF), meta-HOP–Y6-Cl (mCl), para-HOP–Y6-F (pF), and para-HOP–Y6-Cl (pCl), with outer side chains of alkoxy-2-ethylhexyl attached at the metaor parapositions. Devices containing the meta-position acceptors blended with the polymer donor PM6 achieve power conversion efficiencies (PCEs) at least 1.27-fold higher than those of devices containing para-position acceptors. The enhanced performance can be attributed to the formation of donor–acceptor domains that are advantageous for charge carrier generation, transport, and collection. This is due to variations in phase aggregation that result from steric hindrance effects at the meta- and para-position acceptors. As a result, meta-position acceptors with lower steric hindrance improved π–π and lamellar stacking, whereas the para-position acceptors encountered excessive steric hindrance, reducing their photovoltaic efficiencies. Additionally, the meta-position acceptors demonstrate long charge carrier lifetimes, which suppress recombination in the charge transfer state and promote efficient charge separation. These results underline the critical role of side-chain direction in optimizing Y6-based acceptors for improving photovoltaic performance.

Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure–property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.

A sequential deposition method, along with independent additive processing, regulates vertical phase separation in photoactive layers. GIWAXS analysis indicates enhanced depth-wise phase separation in SD structures, reducing charge-transfer state recombination and extending charge carrier lifetime.

A series of naphthalene diimide (NDI)-based small molecules were synthesized as nonfullerene acceptors and incorporated in all-small-molecule solar cells. Three NDI-based small molecules, NDICN-T, NDICN-BT, and NDICN-TVT, were designed with different linkers between two NDI units to induce the different conjugation length and modulate the geometric structures of the NDI dimers. The small NDI-based dimer electron acceptors with slip-stacked structures that facilitate π–π stacking interactions and/or hinder excessive aggregation exhibited different morphological behaviors, such as miscibility or crystallinity in bulk heterojunction blends with 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (DTS-F) electron donors. The photovoltaic devices prepared with NDICN-TVT gave the highest power conversion efficiency (PCE) of 3.01%, with an open-circuit voltage (Voc) of 0.75 V, a short-circuit current density (Jsc) of 7.10 mA cm–2, and a fill factor of 56.2%, whereas the DTS-F:NDICN-T and DTS-F:NDICN-BT devices provided PCEs of 1.81 and 0.13%, respectively. Studies of the charge-generation properties, charge-transfer dynamics, and charge-transport properties for understanding the structure–property relations revealed that DTS-F:NDICN-TVT blend films with well-developed domains and well-ordered crystalline structures performed well, whereas an excessive miscibility between DTS-F and NDICN-BT disrupted the crystallinity of the material and yielded a poor device performance.

To investigate the influence of donor molecule crystallinity on photovoltaic performance in all-small-molecule solar cells, two dithieno[2,3-d:2′,3′-d′]-benzo[1,2-b:4,5-b′]dithiophene (DTBDT)-based small molecules, denoted as DTBDT-Rho and DTBDT-S-Rho and incorporating different side chains, are synthesized and characterized. The photovoltaic properties of solar cells made of these DTBDT-based donor molecules are systemically studied with the [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) fullerene acceptor and the O-IDTBR nonfullerene acceptor to study the aggregation behavior and crystallinity of the donor molecules in both blends. Morphological analyses and a charge carrier dynamics study are carried out simultaneously to derive structure–property relationships and address the requirements of all-small-molecule solar cells. This study reveals exciton decay loss driven by large-scale phase separation of the DTBDT molecules to be a crucial factor limiting photocurrent generation in the all-small-molecule solar cells incorporating O-IDTBR. In the all-small-molecule blends, DTBDT domains with dimensions greater than 100 nm limit the exciton migration to the donor–acceptor interface, whereas blends with PC71BM exhibit homogeneous phase separation with smaller domains than in the O-IDTBR blends. The significant energy losses in nonfullerene-based devices lead to decreased Jscand fill factor values and unusual decrease in Vocvalues. These results indicate the modulation of phase separation to be important for improving the photovoltaic performances of all-small-molecule blends. In addition, the enhanced molecular aggregation of DTBDT-S-Rho with the alkylthio side chain leads to higher degrees of phase separation and unfavorable charge transfer, which are mainly responsible for the relatively low photocurrent when using DTBDT-S-Rho compared with that when using DTBDT-Rho. On the other hand, this enhanced molecular aggregation improves the crystallinity of DTBDT-S-Rho and results in its increased hole mobility.

The molecular packing structures of two conjugated polymers based on alkoxy naphthalene, one with cyano-substituents and one without, have been investigated to determine the effects of electron-withdrawing cyano-groups on the performance of bulk-heterojunction solar cells. The substituted cyano-groups facilitate the self-assembly of the polymer chains, and the cyano-substituted polymer:PC71BM blend exhibits enhanced exciton dissociation to PC71BM. Moreover, the electron-withdrawing cyano-groups lower the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of the conjugated polymer, which leads to a higher open circuit voltage (VOC) and a lower energy loss during electron transfer from the donor to the acceptor. A bulk-heterojunction device fabricated with the cyano-substituted polymer:PC71BM blend has a higher VOC(0.89 V), a higher fill factor (FF) (51.4%), and a lower short circuit current (JSC) (7.4 mA/cm2) than that of the noncyano-substituted polymer:PC71BM blend under AM 1.5G illumination with an intensity of 100 mW cm–2. Thus, the cyano-substitution of conjugated polymers may be an effective strategy for optimizing the domain size and crystallinity of the polymer:PC71BM blend, and for increasing VOCby tuning the HOMO and LUMO energy levels of the conjugated polymer.

Solution‐processed small‐molecule bulk heterojunction photovoltaic cells are fabricated by using [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) as electron acceptor and triisopropylsilylethynyl anthracene (TIPSAnt) derivatives substituted with naphthalene (TIPSAntNa) and bithiophene (TIPSAntBT) as electron donors. In contrast to TIPS–pentacene, the TIPSAnt derivatives are not susceptible to Diels–Alder reactions with PCBM when processed in solution, as confirmed by UV/Vis measurements. Photoluminescence quenching measurements show exciton diffusion lengths of 5 and 3 nm for TIPSAntBT and TIPSAntNa, respectively. Blending TIPSAntBT and TIPSAntNa with PCBM (1:1, 1:2, 1:3, and 1:4 weight ratios) produces films that possess adequate hole and electron mobilities. The morphological changes that result from varying the blending ratio range from obvious phase‐segregated crystalline domains at a 1:1 ratio to homogeneous, nearly amorphous phases at a 1:4 ratio. Bulk heterojunction solar cells prepared by using a TIPSAntBT:PCBM blend reach power conversion efficiencies as high as 1.4 %.

Limited light absorption beyond the UV region and rapid photocarrier recombination are critical impediments for the improved photocatalytic performance of carbon quantum dots (CQDs) under visible-light irradiation. Herein, we demonstrate single-step microwave-assisted syntheses of O-CQDs (typical CQDs terminated by carboxylic and hydroxyl functional groups) from a sucrose precursor and Cl-doped CQDs (Cl-CQDs) from a sucralose precursor in short reaction times and without using obligatory strong acids for Cl doping. The doping of Cl into the CQDs is observed to widen the absorption range and facilitate an enhanced separation of photoexcited charge carriers, which is confirmed by the results of optical absorption, photothermal response, and pump-probe ultrafast transient absorption spectroscopy measurements of the O-CQDs and Cl-CQDs. The photoexcited charge carriers with their longer lifetimes in Cl-CQDs enabled the quick degradation of methylene blue dye, rapid conversion of Ag+ions to metallic Ag nanoparticles on the CQD surfaces, and reduction of GO to a well-dispersed rGO through the photoelectron transfer reactions under visible-light irradiation. The facile Cl doping strategy, hybridization of Ag nanoparticles or rGO to CQDs, and the elevated charge separation mechanism would open up new avenues in designing CQD-based materials for futuristic applications.

Minimizing the energy offset between the lowest exciton and charge-transfer (CT) states is a widely employed strategy to suppress the energy loss (Eg/q – VOC) in polymer:non-fullerene acceptor (NFA) organic solar cells (OSCs). In this work, transient absorption spectroscopy is employed to determine CT state lifetimes in a series of low energy loss polymer:NFA blends. The CT state lifetime is observed to show an inverse energy gap law dependence and decreases as the energy loss is reduced. This behavior is assigned to increased mixing/hybridization between these CT states and shorter-lived singlet excitons of the lower gap component as the energy offset ΔECT-S1is reduced. This study highlights how achieving longer exciton and CT state lifetimes has the potential for further enhancement of OSC efficiencies.