Anomalous Correlation between Thermal Conductivity and Elastic Modulus in Two-Dimensional Hybrid Metal Halide Perovskites.

Device-level implementation of soft materials for energy conversion and thermal management demands a comprehensive understanding of their thermal conductivity and elastic modulus to mitigate thermo-mechanical challenges and ensure long-term stability. Thermal conductivity and elastic modulus are usually positively correlated in soft materials, such as amorphous macromolecules, which poses a challenge to discover materials that are either soft and thermally conductive or hard and thermally insulative. Here, we show anomalous correlations of thermal conductivity and elastic modulus in two-dimensional (2D) hybrid organic-inorganic perovskites (HOIP) by engineering the molecular interactions between organic cations. By replacing conventional alkyl-alkyl and aryl-aryl type organic interactions with mixed alkyl-aryl interactions, we observe an enhancement in elastic modulus with a reduction in thermal conductivity. This anomalous dependence provides a route to engineer thermal conductivity and elastic modulus independently and a guideline to search for better thermal management materials. Further, introducing chirality into the organic cation induces a molecular packing that leads to the same thermal conductivity and elastic modulus regardless of the composition across all half-chiral 2D HOIPs. This finding provides substantial leeway for further investigations in chiral 2D HOIPs to tune optoelectronic properties without compromising thermal and mechanical stability.

Precisely Controlling Polymer Acceptors with Weak Intramolecular Charge Transfer Effect and Superior Coplanarity for Efficient Indoor All-Polymer Solar Cells with over 27% Efficiency.

Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

Optimized Incorporation of Furan into Diketopyrrolopyrrole-Based Conjugated Polymers for Organic Field-Effect Transistors.

Flexible electronics have received considerable attention in the past decades due to their promising application in rollable display screens, wearable devices, implantable devices, and other electronic applications. In particular, conjugated polymers are favored for flexible electronics due to their mechanical flexibility and potential for solution-processed fabrication techniques, such as blade-coating, roll-to-roll printing, and high-throughput printing allowing for high-performance transistor devices. Thiophene is the prevailing conjugated unit to construct these conjugated polymers due to its favorable electronic properties. On the other hand, furans are among the few conjugated moieties that are easily derived from bio renewable resources. To promote sustainability, we selectively introduced furan into the conjugated backbone of a high-mobility polymer scaffold and systematically studied the effect on the microstructure and charge transport. We show that partially and selectively replacing thiophene units with furan can yield nearly comparable performance compared to the all-thiophene polymer. This strategy offers an improvement in the sustainability of the polymer by incorporating bio-sourced furan without sacrificing the high-performance characteristics. Meanwhile, polymers with incorrect or complete furan incorporation show reduced mobilities. This work serves to develop coherent structure-morphology-performance relationships; such knowledge will establish guidelines for the future development of sustainable, furan-based conjugated materials.

The role of interfacial donor-acceptor percolation in efficient and stable all-polymer solar cells.

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor-acceptor (D-A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D-A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D-A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device "burn-in" loss upon solar illumination.

Precise synthesis and photovoltaic properties of giant molecule acceptors.

Series of giant molecule acceptors DY, TY and QY with two, three and four small molecule acceptor subunits are synthesized by a stepwise synthetic method and used for systematically investigating the influence of subunit numbers on the structure-property relationship from small molecule acceptor YDT to giant molecule acceptors and to polymerized small molecule acceptor PY-IT. Among these acceptors-based devices, the TY-based film shows proper donor/acceptor phase separation, higher charge transfer state yield and longer charge transfer state lifetime. Combining with the highest electron mobility, more efficient exciton dissociation and lower charge carrier recombination properties, the TY-based device exhibits the highest power conversion efficiency of 16.32%. These results indicate that the subunit number in these acceptors has significant influence on their photovoltaic properties. This stepwise synthetic method of giant molecule acceptors will be beneficial to diversify their structures and promote their applications in high-efficiency and stable organic solar cells.

Auxiliary sequential deposition enables 19%-efficiency organic solar cells processed from halogen-free solvents.

High-efficiency organic solar cells are often achieved using toxic halogenated solvents and additives that are constrained in organic solar cells industry. Therefore, it is important to develop materials or processing methods that enabled highly efficient organic solar cells processed by halogen free solvents. In this paper, we report an innovative processing method named auxiliary sequential deposition that enables 19%-efficiency organic solar cells processed by halogen free solvents. Our auxiliary sequential deposition method is different from the conventional blend casting or sequential deposition methods in that it involves an additional casting of dithieno[3,2-b:2',3'-d]thiophene between the sequential depositions of the donor (D18-Cl) and acceptor (L8-BO) layers. The auxiliary sequential deposition method enables dramatic performance enhancement from 15% to over 18% compared to the blend casting and sequential deposition methods. Furthermore, by incorporating a branched-chain-engineered acceptor called L8-BO-X, device performance can be boosted to over 19% due to increased intermolecular packing, representing top-tier values for green-solvent processed organic solar cells. Comprehensive morphological and time-resolved characterizations reveal that the superior blend morphology achieved through the auxiliary sequential deposition method promotes charge generation while simultaneously suppressing charge recombination. This research underscores the potential of the auxiliary sequential deposition method for fabricating highly efficient organic solar cells using environmentally friendly solvents.

Additive-free molecular acceptor organic solar cells processed from a biorenewable solvent approaching 15% efficiency.

We report on the use of molecular acceptors (MAs) and donor polymers processed with a biomass-derived solvent (2-methyltetrahydrofuran, 2-MeTHF) to facilitate bulk heterojunction (BHJ) organic photovoltaics (OPVs) with power conversion efficiency (PCE) approaching 15%. Our approach makes use of two newly designed donor polymers with an opened ring unit in their structures along with three molecular acceptors (MAs) where the backbone and sidechain were engineered to enhance the processability of BHJ OPVs using 2-MeTHF, as evaluated by an analysis of donor-acceptor (D-A) miscibility and interaction parameters. To understand the differences in the PCE values that ranged from 9-15% as a function of composition, the surface, bulk, and interfacial BHJ morphologies were characterized at different length scales using atomic force microscopy, grazing-incidence wide-angle X-ray scattering, resonant soft X-ray scattering, X-ray photoelectron spectroscopy, and 2D solid-state nuclear magnetic resonance spectroscopy. Our results indicate that the favorable D-A intermixing that occurs in the best performing BHJ film with an average domain size of ∼25 nm, high domain purity, uniform distribution and enhanced local packing interactions - facilitates charge generation and extraction while limiting the trap-assisted recombination process in the device, leading to high effective mobility and good performance.

Study of Glass Formation and Crystallization Kinetics in a 2D Metal Halide Perovskite Using Ultrafast Calorimetry.

While crystalline 2D metal halide perovskites (MHPs) represent a well-celebrated semiconductor class, supporting applications in the fields of photovoltaics, emitters, and sensors, the recent discovery of glass formation in an MHP opens many new opportunities associated with reversible glass-crystalline switching, with each state offering distinct optoelectronic properties. However, the previously reported [S-(-)-1-(1-naphthyl)ethylammonium]2PbBr4 perovskite is a strong glass former with sluggish glass-crystal transformation time scales, pointing to a need for glassy MHPs with a broader range of compositions and crystallization kinetics. Herein we report glass formation for low-melting-temperature 1-MeHa2PbI4 (1-MeHa = 1-methyl-hexylammonium) using ultrafast calorimetry, thereby extending the range of MHP glass formation across a broader range of organic (fused ring to branched aliphatic) and halide (bromide to iodide) compositions. The importance of a slight loss of organic and hydrogen iodide components from the MHP in stabilizing the glassy state is elucidated. Furthermore, the underlying kinetics of glass-crystal transformation, including activation energies, crystal growth rate, Angell plot, and fragility index, is studied using a combination of kinetic, thermodynamic, and rheological modeling techniques. An inferred fast crystal growth rate of 0.21 m/s for 1-MeHa2PbI4 shows promise toward suitability in extended application spaces, for example, in metamaterials, nonvolatile memory, and optical and neuromorphic computing devices.

Introducing a Phenyl End Group in the Inner Side Chains of A-DA'D-A Acceptors Enables High-Efficiency Organic Solar Cells Processed with Nonhalogenated Solvent.

Power conversion efficiency (PCE) of organic solar cells (OSCs) processed by nonhalogenated solvents is unsatisfactory due to the unfavorable morphology. Herein, two new small molecule acceptors (SMAs) Y6-Ph and L8-Ph are synthesized by introducing a phenyl end group in the inner side chains of the SMAs of Y6 and L8-BO, respectively, for overcoming the excessive aggregation of SMAs in the long-time film forming processed by nonhalogenated solvents. First, the effect of the film forming time on the aggregation property and photovoltaic performance of Y6, L8-BO, Y6-Ph, and L8-Ph is studied by using the commonly used solvents: chloroform (CF) (rapid film forming process) and chlorobenzene (CB) (slow film forming process). It is found that Y6- and L8-BO-based OSCs exhibit a dramatic drop in PCE from CF- to CB-processed devices owing to the large phase separation, while the Y6-Ph and L8-Ph based OSCs show obviously increased PCEs Furthermore, L8-Ph-based OSCs processed by nonhalogenated solvent o-xylene (o-XY) achieved a high PCE of 18.40% with an FF of 80.11%. The results indicate that introducing a phenyl end group in the inner side chains is an effective strategy to modulate the morphology and improve the photovoltaic performance of the OSCs processed by nonhalogenated solvents.

Unveiling re-entrant phase behavior and crystalline-amorphous interactions in semi-conducting polymer:small molecule blends.

It has been reported recently that conjugated polymer:small molecule systems might exhibit complex, re-entrant phase behavior with hourglass or closed-loop miscibility gaps due to an 'apparent' lower critical solution temperature branch. However, the study did not firmly establish if the observations were reflecting equilibrium or not. To assure that the observed shapes of the binodals via a mixing experiment represent local near-equilibrium conditions that capture complex molecular interactions or equation-of-state effects, we present here the liquidus and the binodal for the exact same systems, i.e., PTB7-Th:PC61BM, PffBT4T-C9C13:PC71BM and PTB7-Th:EH-IDTBR, with the liquidus measured via a demixing experiment with long annealing time of days to weeks. We observe that the binodal displayed consistent trends with the liquidus, revealing an underlying thermodynamic and not microstructural or kinetic cause behind the complex phase behavior. Our results highlight the need for a novel, sufficiently complex physical model for understanding these non-trivial phase diagrams of semi-conducting materials. We also discover that the composition difference (Δϕ) between liquidus and binodal reflects the crystalline-amorphous interaction, exhibiting a linear relationship with the binodal composition (ϕb,polymer), i.e., Δϕ increases as χaa decreases. This possibly provides a new approach for obtaining the crystalline-amorphous interaction parameter χca(T) beyond the commonly used melting point depression method, which estimates χca near the melting temperature Tm of the crystalline component. The capability of obtaining χca(T) over a more extended temperature range may encourage more extensive studies and facilitate the understanding of χca in general, but particularly for all the novel non-fullerene acceptors that are able to crystallize.