Chemistry of Materials最新文献

{"title":"Effect of a Two-Step Temperature-Swing Synthesis on Coarse-Grained LiNiO2 Secondary Particles Characterized by Scanning Transmission Electron Microscopy","authors":"Thomas Demuth, Philipp Kurzhals, Shamail Ahmed, Felix Riewald, Michael Malaki, Johannes Haust, Andreas Beyer, Jürgen Janek, Kerstin Volz","doi":"10.1021/acs.chemmater.5c00108","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00108","url":null,"abstract":"To enhance the range of electric vehicles, research is focused on increasing the nickel content in cathode active materials (CAM), which leads to higher practically achievable specific capacities. As a result, the material LiNiO₂ (LNO) has attracted significant interest. In this study, a two-step temperature swing synthesis is employed to produce LNO secondary particles with large primary grains as CAM for solid-state batteries (SSBs). The synthesis involves sintering the material at 800 °C for 1 h, followed by an annealing step at a lower temperature for 6 h. Different batches of annealed LNO, using temperatures of 600 and 700 °C, are compared with unannealed LNO, utilizing various transmission electron microscopy (TEM) techniques. The annealing step contributes to smoother particle surfaces, reduced residual lithium species on particle surfaces, and increased lithium occupancy in the crystal lattice, resulting in higher discharge capacity during the initial cycles. However, higher annealing temperatures also lead to the formation of a thin rock-salt layer on the surface and internal misorientation, likely caused by thermal residual stress during cooling. These effects are more pronounced in the sample annealed at 700 °C compared to 600 °C. Despite the potential drawbacks associated with these factors, LNO annealed at 700 °C achieves the highest discharge capacity, indicating that the benefits of annealing outweigh its disadvantages, at least during the initial cycles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"130 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Moisture-Stable Argyrodites with High Ionic Conductivity via Crystal Structure Engineering: Li6+xMxAs1–xS5I (M = Ge, Sn)","authors":"Jihun Roh, Joowon Kim, Hyungjin Lee, Namgyu Do, Jeyne Lyoo, Alicia María Manjón-Sanz, Ginga Kitahara, Shuki Torii, Seung-Tae Hong","doi":"10.1021/acs.chemmater.5c00125","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00125","url":null,"abstract":"Sulfide solid electrolytes (SSEs) are promising alternatives to liquid electrolytes in lithium-ion batteries due to their high ionic conductivity and reduced flammability. However, their chemical instability under humid conditions poses significant challenges. This study introduces a substitution series, Li_6+<i>x</i>M_<i>x</i>As_1–<i>x</i>S₅I (M = Ge, Sn), adopting an argyrodite-type structure with high ionic conductivity and moisture stability. Among these, Li_6.333Ge_0.333As_0.667S₅I achieves ∼3 mS cm^–1 at 303 K, an improvement of 3 orders of magnitude over pristine Li₆AsS₅I. Powder X-ray and neutron diffraction patterns reveal additional lithium-ion sites enhancing 3D diffusion pathways, significantly lowering the activation energy. Li_6.333Ge_0.333As_0.667S₅I also demonstrates superior moisture stability, releasing minimal toxic H₂S gas (70 ppm) after exposure to 27% relative humidity at 303 K for 1 h, outperforming Li₆PS₅Cl (160 ppm). Additionally, it retains ∼70% of its initial discharge capacity over 40 cycles of galvanostatic testing (In/InLi/Li_6.333Ge_0.333As_0.667S₅I/TiS₂). However, cycling beyond the electrochemical stability window leads to capacity fading. These findings provide insights into the interplay between crystal structure, ionic conductivity, and moisture stability, offering a pathway to high-performance solid electrolytes for next-generation all-solid-state batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Moisture-Stable Argyrodites with High Ionic Conductivity via Crystal Structure Engineering: Li6+xMxAs1–xS5I (M = Ge, Sn)","authors":"Jihun Roh,&nbsp;Joowon Kim,&nbsp;Hyungjin Lee,&nbsp;Namgyu Do,&nbsp;Jeyne Lyoo,&nbsp;Alicia María Manjón-Sanz,&nbsp;Ginga Kitahara,&nbsp;Shuki Torii and Seung-Tae Hong*,&nbsp;","doi":"10.1021/acs.chemmater.5c0012510.1021/acs.chemmater.5c00125","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00125https://doi.org/10.1021/acs.chemmater.5c00125","url":null,"abstract":"<p >Sulfide solid electrolytes (SSEs) are promising alternatives to liquid electrolytes in lithium-ion batteries due to their high ionic conductivity and reduced flammability. However, their chemical instability under humid conditions poses significant challenges. This study introduces a substitution series, Li_6+<i>x</i>M_<i>x</i>As_1–<i>x</i>S₅I (M = Ge, Sn), adopting an argyrodite-type structure with high ionic conductivity and moisture stability. Among these, Li_6.333Ge_0.333As_0.667S₅I achieves ∼3 mS cm^–1 at 303 K, an improvement of 3 orders of magnitude over pristine Li₆AsS₅I. Powder X-ray and neutron diffraction patterns reveal additional lithium-ion sites enhancing 3D diffusion pathways, significantly lowering the activation energy. Li_6.333Ge_0.333As_0.667S₅I also demonstrates superior moisture stability, releasing minimal toxic H₂S gas (70 ppm) after exposure to 27% relative humidity at 303 K for 1 h, outperforming Li₆PS₅Cl (160 ppm). Additionally, it retains ∼70% of its initial discharge capacity over 40 cycles of galvanostatic testing (In/InLi/Li_6.333Ge_0.333As_0.667S₅I/TiS₂). However, cycling beyond the electrochemical stability window leads to capacity fading. These findings provide insights into the interplay between crystal structure, ionic conductivity, and moisture stability, offering a pathway to high-performance solid electrolytes for next-generation all-solid-state batteries.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3720–3732 3720–3732"},"PeriodicalIF":7.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tannic Acid-Programmed Hydroxyapatite Biomineralization Enables Bilayered Bone-Mimetic Hydrogels for Mandibular Regeneration","authors":"Yongxi Luo, Jiahao Lin, Xinmiao Luo, Guangbing Luo, Jianyong Zou, Liu Cai, Yutong He, Xiaozhong Qiu, Huiyong Xu","doi":"10.1021/acs.chemmater.5c00840","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00840","url":null,"abstract":"The effective restoration of mandibular defects continues to pose a significant clinical challenge. Although biomimetic hydrogels have shown potential in bone tissue engineering, existing approaches fail to simultaneously replicate the hierarchical architecture of native bone and dynamically regulate the osteogenic niche. This study presents a bioinspired hydrogel system engineered through green hydrogen-bond cross-linking integrated with tannic acid-mediated gradient mineralization, achieving precise emulation of cortical–trabecular bone interfaces across multiple scales. The hydrogel demonstrates multifunctional therapeutic capabilities, including targeted recruitment of bone marrow mesenchymal stem cells, synchronized modulation of oxidative stress, transition of M1 macrophages to M2 macrophages, broad-spectrum antimicrobial activity, and potent osteogenic differentiation. Through spatiotemporal control of microenvironmental cues, the construct establishes a self-regulating repair niche that coordinates angiogenesis and osteogenesis. In vivo evaluation utilizing a rat mandibular defect model confirmed the hydrogel’s efficacy in enhancing osseous regeneration and restoring biomechanical competence. This work pioneers a structural-dynamic dual-regulation strategy, advancing translational solutions for complex craniofacial reconstruction.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural Distortions and Uniaxial Negative Thermal Expansion in the Polar Dion–Jacobson Oxide RbNdTa2O7","authors":"P. Neenu Lekshmi, E. Lora da Silva, P. Rocha-Rodrigues, John S. O. Evans, João Horta Belo, Pedro Silva de Sousa, Alicia María Manjón-Sanz, António M. dos Santos, Armandina M. L. Lopes, João Pedro Araújo","doi":"10.1021/acs.chemmater.5c00137","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00137","url":null,"abstract":"We provide deeper insight into the crystal structures, sequential structural phase transitions (<i>I2cm</i> → <i>Cmce</i> → <i>I</i>4/<i>mcm</i> → <i>P</i>4/<i>mmm</i>), thermal expansion, and electronic properties of the <i>n</i> = 2 Dion–Jacobson polar oxide RbNdTa₂O₇, through X-ray powder diffraction, neutron powder diffraction, Raman studies, and density functional theory calculations. We observed a uniaxial negative thermal expansion (NTE) across the first-order transition, <i>I2cm</i> → <i>Cmce</i>, where the unit cell contracts along the <i>c-</i>axis, which is driven by a contraction of the NdTa₂O₆ layer. This NTE occurs within the temperature range of the first-order phase transition and contrasts with the corkscrew mechanism typically observed in Ruddlesden–Popper phases. In RbNdTa₂O₇, the <i>I2cm</i> (hybrid improper ferroelectric) → <i>Cmce</i> (antipolar) transition involves crucial changes in the bond lengths of Nd and Ta polyhedra, coupled with polar to antipolar displacement of the Nd ions, leading to a net contraction in the NdTa₂O₆ layer along the <i>c-</i>axis, while preserving the overall octahedral tilting magnitude. This transition highlights the intricate interplay between the Nd and Ta coordination and the associated TaO₆ distortions. Temperature-dependent Raman spectra analysis further confirms the first-order structural transition and associated NTE, providing evidence for increased bond stiffness across this transition. Additionally, using neutron powder diffraction, we have determined that the transition <i>I</i>4/<i>mcm</i> → <i>P</i>4/<i>mmm</i> occurs at approximately 1150 K. Finally, we have calculated from DFT + <i>U</i>, the partial density of states, the energy bandgaps, and effective masses of the charge carriers of the polar ground structure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"80 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tannic Acid-Programmed Hydroxyapatite Biomineralization Enables Bilayered Bone-Mimetic Hydrogels for Mandibular Regeneration","authors":"Yongxi Luo,&nbsp;Jiahao Lin,&nbsp;Xinmiao Luo,&nbsp;Guangbing Luo,&nbsp;Jianyong Zou,&nbsp;Liu Cai,&nbsp;Yutong He*,&nbsp;Xiaozhong Qiu* and Huiyong Xu*,&nbsp;","doi":"10.1021/acs.chemmater.5c0084010.1021/acs.chemmater.5c00840","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00840https://doi.org/10.1021/acs.chemmater.5c00840","url":null,"abstract":"<p >The effective restoration of mandibular defects continues to pose a significant clinical challenge. Although biomimetic hydrogels have shown potential in bone tissue engineering, existing approaches fail to simultaneously replicate the hierarchical architecture of native bone and dynamically regulate the osteogenic niche. This study presents a bioinspired hydrogel system engineered through green hydrogen-bond cross-linking integrated with tannic acid-mediated gradient mineralization, achieving precise emulation of cortical–trabecular bone interfaces across multiple scales. The hydrogel demonstrates multifunctional therapeutic capabilities, including targeted recruitment of bone marrow mesenchymal stem cells, synchronized modulation of oxidative stress, transition of M1 macrophages to M2 macrophages, broad-spectrum antimicrobial activity, and potent osteogenic differentiation. Through spatiotemporal control of microenvironmental cues, the construct establishes a self-regulating repair niche that coordinates angiogenesis and osteogenesis. In vivo evaluation utilizing a rat mandibular defect model confirmed the hydrogel’s efficacy in enhancing osseous regeneration and restoring biomechanical competence. This work pioneers a structural-dynamic dual-regulation strategy, advancing translational solutions for complex craniofacial reconstruction.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3853–3869 3853–3869"},"PeriodicalIF":7.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bulky Cation-Modified Interfaces for Thermally Stable Lead Halide Perovskite Solar Cells","authors":"Sakshi Sharma, Carlo A. R. Perini, Courtney Brea, Sarah Wieghold, Ruipeng Li, Letian Dou, Antonio Facchetti, Guoxiang Hu, Juan-Pablo Correa-Baena","doi":"10.1021/acs.chemmater.4c03468","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03468","url":null,"abstract":"Charged conjugated organic molecules offer promising prospects for reducing nonradiative recombination at interfaces in perovskite solar cells, while protecting the active layer from moisture. However, several studies have shown that the heat-induced diffusion of these cations leads to irreversible solar cell degradation. Passivation molecules for perovskite can reconstruct the film surface into lower-dimensional phases when exposed to thermal stress, impeding charge extraction and affecting the photoconversion efficiency (PCE) of devices. In this work, we study how molecular interactions between passivation molecules and 3D CsFAPbI₃ perovskite impact stability and charge extraction at the perovskite/hole transport layer interfaces. Two model π-conjugated molecules are studied: 2-([2,2′-bithiophen]-5-yl)ethan-1-aminium iodide (2TI) and 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quaterthiophen]-5-yl)ethan-1-ammonium iodide (4TmI). We demonstrate that the speed of surface layer reconstruction under thermal stress can be controlled by the cation size and correlate these structural changes with the solar cell performance and stability. Devices treated with 2TI and 4TmI achieve PCEs over 21% and maintain their performance under thermal stress. Our findings demonstrate that thermal stability in PSCs can be achieved via the design engineering of passivation agents, offering a blueprint for developing next-generation passivation molecules.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"50 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bulky Cation-Modified Interfaces for Thermally Stable Lead Halide Perovskite Solar Cells","authors":"Sakshi Sharma,&nbsp;Carlo A. R. Perini*,&nbsp;Courtney Brea,&nbsp;Sarah Wieghold,&nbsp;Ruipeng Li,&nbsp;Letian Dou,&nbsp;Antonio Facchetti,&nbsp;Guoxiang Hu and Juan-Pablo Correa-Baena*,&nbsp;","doi":"10.1021/acs.chemmater.4c0346810.1021/acs.chemmater.4c03468","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03468https://doi.org/10.1021/acs.chemmater.4c03468","url":null,"abstract":"<p >Charged conjugated organic molecules offer promising prospects for reducing nonradiative recombination at interfaces in perovskite solar cells, while protecting the active layer from moisture. However, several studies have shown that the heat-induced diffusion of these cations leads to irreversible solar cell degradation. Passivation molecules for perovskite can reconstruct the film surface into lower-dimensional phases when exposed to thermal stress, impeding charge extraction and affecting the photoconversion efficiency (PCE) of devices. In this work, we study how molecular interactions between passivation molecules and 3D CsFAPbI₃ perovskite impact stability and charge extraction at the perovskite/hole transport layer interfaces. Two model π-conjugated molecules are studied: 2-([2,2′-bithiophen]-5-yl)ethan-1-aminium iodide (2TI) and 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴-quaterthiophen]-5-yl)ethan-1-ammonium iodide (4TmI). We demonstrate that the speed of surface layer reconstruction under thermal stress can be controlled by the cation size and correlate these structural changes with the solar cell performance and stability. Devices treated with 2TI and 4TmI achieve PCEs over 21% and maintain their performance under thermal stress. Our findings demonstrate that thermal stability in PSCs can be achieved via the design engineering of passivation agents, offering a blueprint for developing next-generation passivation molecules.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3676–3684 3676–3684"},"PeriodicalIF":7.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c03468","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advanced Multifunctional Electrocatalysts: Integrating DFT and Machine Learning for OER, HER, and ORR Reactions","authors":"Swetarekha Ram, Albert S. Lee, Seung-Cheol Lee, Satadeep Bhattacharjee","doi":"10.1021/acs.chemmater.4c03213","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03213","url":null,"abstract":"Expanding MXene applications in energy conversion and storage offers a promising approach to developing robust, multifunctional electrocatalysts. Progress in electrochemical energy systems is strongly dependent on effective catalysts for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). In this study, we used density functional theory (DFT) to investigate transition-metal-based single-atom catalysts (TM_SA) supported on Mo₂CS₂ MXene. Our findings revealed that the bifunctional overpotential for Ni_SA is 0.44 V for water splitting and 1.11 V for metal–air batteries, showcasing excellent catalytic performance. Volcano plots, based on Gibbs free energy changes for the intermediates OH*, O*, and OOH*, density of states and crystal orbital Hamilton population (COHP) effectively illustrate these results. Additionally, we utilized a multitask machine learning (MTL) approach to predict overpotentials for OER + HER and OER + ORR in the context of water splitting and metal–air batteries, respectively. Using the Sure Independence Screening and Sparsifying Operator (SISSO) method, we identified meaningful descriptors associated with catalytic activity. The key features influencing the adsorption behavior were found to include the shift of the d-band center and the difference in Bader charge upon the adsorption of O* and OH* on the TM_SA–MXene interface. This comprehensive study underscores the significant potential of Mo₂CS₂–Ni_SA as multifunctional electrocatalysts and offers crucial theoretical insights for the development of advanced catalysts capable of facilitating OER, ORR, and HER.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"20 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning the Solubility Parameters of Conjugated Polymers via Side-Chain Engineering for All-Polymer Solar Cells","authors":"Justin Neu,&nbsp;Jiyeon Oh,&nbsp;Subhrangsu Mukherjee,&nbsp;Somayeh Kashani,&nbsp;Zixuan Chen,&nbsp;Saidikrom Mardiev,&nbsp;Harald Ade and Wei You*,&nbsp;","doi":"10.1021/acs.chemmater.5c0051510.1021/acs.chemmater.5c00515","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00515https://doi.org/10.1021/acs.chemmater.5c00515","url":null,"abstract":"<p >Bulk heterojunction (BHJ) all-polymer solar cells (all-PSCs) have garnered significant attention as a promising solution for harnessing clean, renewable solar energy due to their merits of mechanical flexibility, morphological stability, and compatibility with large-scale solution-based manufacturing processes. Extensive efforts have been devoted toward controlling and optimizing the miscibility and morphology of polymer blends to enhance the performance of all-PSCs. Herein, we systematically explore molecular structure-miscibility-device efficiency relationships in all-PSCs. Specifically, the Hansen solubility parameters (HSPs) of representative donor and acceptor polymers were broken down into their backbone and side chain contributions. The effects of nonpolar or polar side chains on the resulting solubility parameters are correlated to empirically and experimentally determined HSPs as the different side chains were shown to significantly influence the resulting HSPs of the conjugated polymers. Furthermore, the HSP framework enabled miscibility predictions between polymer blends, which were verified by experimental determinations of miscibility via contact angle and Atomic Force Microscopy (AFM) measurements. Differences in photovoltaic performance between the four blend systems can be directly attributed to alterations in the side chains. This work establishes coherent structure-solubility parameter correlations by showing that as guided by the HSP framework, the miscibility between donor and acceptor polymers can be predictively manipulated via side-chain engineering, creating opportunities to pursue improvements in device efficiency and stability.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3788–3798 3788–3798"},"PeriodicalIF":7.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}