Chemistry of Materials最新文献

{"title":"Lattice-Matched Heterogeneous Nucleation Eliminates Defective Buried Interfaces in Halide Perovskites","authors":"Paramvir Ahlawat, Cecilia Clementi, Felix Musil, Maria-Andreea Filip, M. Ibrahim Dar","doi":"10.1021/acs.chemmater.4c03034","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03034","url":null,"abstract":"Advancements in the formation of metal halide perovskite semiconductors have led to solar cells and light-emitting devices with efficiencies exceeding 25%. To push these performances beyond theoretical limits and achieve long-term stability, a fundamental understanding of the structural evolution at the interface between perovskites and charge-transporting materials is essential. In this study, we perform molecular dynamics simulations to investigate the atomic-scale processes involved in the nucleation and growth of cesium lead bromide perovskite on commonly used oxide interfaces. Our results reveal that the perovskite crystallizes through a heteroepitaxial mechanism, which can induce the formation of dislocations, voids, and defects at the buried interface as well as grain boundaries within the bulk crystal. From simulations, we find that the lattice-matched interfaces promote epitaxially ordered growth of the perovskite, potentially mitigating defect formation at the interface. Eliminating these defects could arguably pave the way for achieving the long-term stability required for high-efficiency perovskite solar cells and light-emitting diodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599621","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":"Driving Thermoelectric Optimization in AgSbTe2 via Design of Experiments and Machine Learning","authors":"Jan-Hendrik Pöhls*,&nbsp;Chun-Wan Timothy Lo,&nbsp;Marissa MacIver,&nbsp;Yu-Chih Tseng and Yurij Mozharivskyj*,&nbsp;","doi":"10.1021/acs.chemmater.5c0002210.1021/acs.chemmater.5c00022","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00022https://doi.org/10.1021/acs.chemmater.5c00022","url":null,"abstract":"<p >Systemic optimization of thermoelectric materials is arduous due to their conflicting electrical and thermal properties. A strategy based on Design of Experiments and machine learning is developed to optimize the thermoelectric efficiency of AgSb_1+<i>x</i>Te_2+<i>y</i>, an established thermoelectric. From eight experiments, high thermoelectric performance in AgSb_1.021Te_2.04 is revealed with a peak and average thermoelectric figure of merit of 1.61 ± 0.24 at 600 K and 1.18 ± 0.18 (300–623 K), respectively, which is &gt;30% higher than the best literature values for AgSb_1+<i>x</i>Te_2+<i>y</i>. Ag deficiency and suppression of secondary phases in AgSb_1.021Te_2.04 improve the electrical properties and reduce the thermal conductivity (∼0.4 W m^–1 K^–1). Our strategy is implemented into an open-source graphical user interface, and it can be used to optimize the methodologies, properties, and processes across different scientific fields.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2281–2289 2281–2289"},"PeriodicalIF":7.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678448","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":"Enhanced Electrochromic Smart Windows Based on Supramolecular Viologen Tweezers","authors":"Jaume Ramon Otaegui,&nbsp;Silvia Mena,&nbsp;Jovelt M. Dorsainvil,&nbsp;Gonzalo Guirado,&nbsp;Daniel Ruiz-Molina,&nbsp;Jordi Hernando*,&nbsp;Jonathan C. Barnes* and Claudio Roscini*,&nbsp;","doi":"10.1021/acs.chemmater.4c0317410.1021/acs.chemmater.4c03174","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03174https://doi.org/10.1021/acs.chemmater.4c03174","url":null,"abstract":"<p >Extending the spectral response of viologen-based electrochromic devices to the near-infrared region is essential to enhance their performance for smart window applications. Although synthetic and formulation modifications have been proposed to achieve this goal, these strategies always come at the expense of deteriorating the electrochromic behavior of the system. To overcome this limitation, herein we exploited the supramolecular chemistry of viologen molecular tweezers, which undergo an intramolecular dimerization process upon reduction that leads to broad light absorption through the visible and near-infrared spectra. We observed this behavior to take place at low concentrations in a variety of electrolytic media, including solid-state ionogels that could be applied to the fabrication of electrochromic devices. Better spectral response, lower operation voltage, and higher stability were measured for these devices relative to analogous systems based on viologen monomers. As a result, when used as electrochromic smart windows, the viologen tweezer-based devices exhibited enhanced modulation of solar heat gain with reduced energy consumption, thereby demonstrating the potential of viologen supramolecular chemistry to rationally improve the performance of electrochromic devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2220–2229 2220–2229"},"PeriodicalIF":7.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678449","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":"Opening the Hysteresis Loop in MAB Magnets: Experimental and Computational Studies of CrMn4SiB2 and Mo0.8Mn4.2SiB2","authors":"Shola E. Adeniji,&nbsp;Alexei A. Belik,&nbsp;Takao Mori and Boniface P. T. Fokwa*,&nbsp;","doi":"10.1021/acs.chemmater.5c0018710.1021/acs.chemmater.5c00187","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00187https://doi.org/10.1021/acs.chemmater.5c00187","url":null,"abstract":"<p >This study presents the synthesis and magnetic characterization of two quaternary MAB phases: CrMn₄SiB₂ and Mo_0.8Mn_4.2SiB₂. Using a refined synthesis method, we successfully produced single-phase compounds, overcoming previous challenges associated with impurity phases. Both compounds crystallize in the tetragonal space group <i>I</i>4/<i>mcm</i>, with Mo demonstrating distinct site preferences in Mo_0.8Mn_4.2SiB₂. Magnetic measurements indicate the presence of long-range ferromagnetic interactions, with Curie temperatures (<i>T</i>_C) of approximately 270 K for CrMn₄SiB₂ and 340 K for Mo_0.8Mn_4.2SiB₂. Field-dependent magnetization measurements indicate a saturation magnetization (<i>M</i>_s) of 5.128 μ_B/f.u. (at 5 K) for CrMn₄SiB₂ and 6.214 μ_B/f.u. (at 5 K) and 3.692 μ_B/f.u. (at 300 K) for Mo_0.8Mn_4.2SiB₂. The introduction of Mo or Cr in the ternary parent compound Mn₅SiB₂, opens a hysteresis for the first time in this class of T2 phases, with intrinsic coercivities of <i>H</i>_c = 5.57 kA/m for CrMn₄SiB₂ and 6.53 kA/m for Mo_0.8Mn_4.2SiB₂. Density functional theory (DFT) calculations confirm the ferromagnetic ordering while the magnetocrystalline anisotropy energy (MAE) calculations show that CrMn₄SiB₂ and MoMn₄SiB₂ have in-plane anisotropy with higher MAE values than Mn₅SiB₂, thus confirming experimental findings. This research not only introduces a synthesis pathway toward single-phase T2-based quaternary materials, but it also opens an avenue toward MAB-based permanent magnets.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2349–2357 2349–2357"},"PeriodicalIF":7.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.5c00187","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678611","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":"Fermi-Level Interstitial Electron Contributions: A Key Mechanism Driving Magnetism in Electrides","authors":"Jiahao Yu, Kun Li, Hideo Hosono, Junjie Wang","doi":"10.1021/acs.chemmater.5c00158","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00158","url":null,"abstract":"Electrides, a unique class of ionic materials, are distinguished by their exceptional properties, such as low work functions, making them highly versatile for a broad range of applications. Remarkably, some electrides exhibit magnetism, even in the absence of conventional magnetic elements. However, the underlying mechanisms governing their magnetic properties require further investigation, which will enable the development of magnetic electrides that are not primarily limited to modifying materials with magnetic elements. In this study, we demonstrate that the proportion of interstitial electrons contributing to states near the Fermi level is a critical factor in the emergence of magnetism in electrides. Leveraging this insight, we successfully designed and identified a series of magnetic electrides, including Ca₃YNbSi₃ and Sr₂₄P₁₅F, without reliance on known magnetic prototypes. This strategy and the accompanying theoretical framework present a flexible and powerful approach, potentially expanding the frontiers of magnetic electrides research.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"68 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599760","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":"Enhanced Electrochromic Smart Windows Based on Supramolecular Viologen Tweezers","authors":"Jaume Ramon Otaegui, Silvia Mena, Jovelt M. Dorsainvil, Gonzalo Guirado, Daniel Ruiz-Molina, Jordi Hernando, Jonathan C. Barnes, Claudio Roscini","doi":"10.1021/acs.chemmater.4c03174","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03174","url":null,"abstract":"Extending the spectral response of viologen-based electrochromic devices to the near-infrared region is essential to enhance their performance for smart window applications. Although synthetic and formulation modifications have been proposed to achieve this goal, these strategies always come at the expense of deteriorating the electrochromic behavior of the system. To overcome this limitation, herein we exploited the supramolecular chemistry of viologen molecular tweezers, which undergo an intramolecular dimerization process upon reduction that leads to broad light absorption through the visible and near-infrared spectra. We observed this behavior to take place at low concentrations in a variety of electrolytic media, including solid-state ionogels that could be applied to the fabrication of electrochromic devices. Better spectral response, lower operation voltage, and higher stability were measured for these devices relative to analogous systems based on viologen monomers. As a result, when used as electrochromic smart windows, the viologen tweezer-based devices exhibited enhanced modulation of solar heat gain with reduced energy consumption, thereby demonstrating the potential of viologen supramolecular chemistry to rationally improve the performance of electrochromic devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"22 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608245","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":"Opening the Hysteresis Loop in MAB Magnets: Experimental and Computational Studies of CrMn4SiB2 and Mo0.8Mn4.2SiB2","authors":"Shola E. Adeniji, Alexei A. Belik, Takao Mori, Boniface P. T. Fokwa","doi":"10.1021/acs.chemmater.5c00187","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00187","url":null,"abstract":"This study presents the synthesis and magnetic characterization of two quaternary MAB phases: CrMn₄SiB₂ and Mo_0.8Mn_4.2SiB₂. Using a refined synthesis method, we successfully produced single-phase compounds, overcoming previous challenges associated with impurity phases. Both compounds crystallize in the tetragonal space group <i>I</i>4/<i>mcm</i>, with Mo demonstrating distinct site preferences in Mo_0.8Mn_4.2SiB₂. Magnetic measurements indicate the presence of long-range ferromagnetic interactions, with Curie temperatures (<i>T</i>_C) of approximately 270 K for CrMn₄SiB₂ and 340 K for Mo_0.8Mn_4.2SiB₂. Field-dependent magnetization measurements indicate a saturation magnetization (<i>M</i>_s) of 5.128 μ_B/f.u. (at 5 K) for CrMn₄SiB₂ and 6.214 μ_B/f.u. (at 5 K) and 3.692 μ_B/f.u. (at 300 K) for Mo_0.8Mn_4.2SiB₂. The introduction of Mo or Cr in the ternary parent compound Mn₅SiB₂, opens a hysteresis for the first time in this class of T2 phases, with intrinsic coercivities of <i>H</i>_c = 5.57 kA/m for CrMn₄SiB₂ and 6.53 kA/m for Mo_0.8Mn_4.2SiB₂. Density functional theory (DFT) calculations confirm the ferromagnetic ordering while the magnetocrystalline anisotropy energy (MAE) calculations show that CrMn₄SiB₂ and MoMn₄SiB₂ have in-plane anisotropy with higher MAE values than Mn₅SiB₂, thus confirming experimental findings. This research not only introduces a synthesis pathway toward single-phase T2-based quaternary materials, but it also opens an avenue toward MAB-based permanent magnets.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"68 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599623","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":"Lattice-Matched Heterogeneous Nucleation Eliminates Defective Buried Interfaces in Halide Perovskites","authors":"Paramvir Ahlawat*,&nbsp;Cecilia Clementi,&nbsp;Felix Musil,&nbsp;Maria-Andreea Filip and M. Ibrahim Dar,&nbsp;","doi":"10.1021/acs.chemmater.4c0303410.1021/acs.chemmater.4c03034","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03034https://doi.org/10.1021/acs.chemmater.4c03034","url":null,"abstract":"<p >Advancements in the formation of metal halide perovskite semiconductors have led to solar cells and light-emitting devices with efficiencies exceeding 25%. To push these performances beyond theoretical limits and achieve long-term stability, a fundamental understanding of the structural evolution at the interface between perovskites and charge-transporting materials is essential. In this study, we perform molecular dynamics simulations to investigate the atomic-scale processes involved in the nucleation and growth of cesium lead bromide perovskite on commonly used oxide interfaces. Our results reveal that the perovskite crystallizes through a heteroepitaxial mechanism, which can induce the formation of dislocations, voids, and defects at the buried interface as well as grain boundaries within the bulk crystal. From simulations, we find that the lattice-matched interfaces promote epitaxially ordered growth of the perovskite, potentially mitigating defect formation at the interface. Eliminating these defects could arguably pave the way for achieving the long-term stability required for high-efficiency perovskite solar cells and light-emitting diodes.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2177–2191 2177–2191"},"PeriodicalIF":7.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678658","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":"Fermi-Level Interstitial Electron Contributions: A Key Mechanism Driving Magnetism in Electrides","authors":"Jiahao Yu,&nbsp;Kun Li,&nbsp;Hideo Hosono and Junjie Wang*,&nbsp;","doi":"10.1021/acs.chemmater.5c0015810.1021/acs.chemmater.5c00158","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00158https://doi.org/10.1021/acs.chemmater.5c00158","url":null,"abstract":"<p >Electrides, a unique class of ionic materials, are distinguished by their exceptional properties, such as low work functions, making them highly versatile for a broad range of applications. Remarkably, some electrides exhibit magnetism, even in the absence of conventional magnetic elements. However, the underlying mechanisms governing their magnetic properties require further investigation, which will enable the development of magnetic electrides that are not primarily limited to modifying materials with magnetic elements. In this study, we demonstrate that the proportion of interstitial electrons contributing to states near the Fermi level is a critical factor in the emergence of magnetism in electrides. Leveraging this insight, we successfully designed and identified a series of magnetic electrides, including Ca₃YNbSi₃ and Sr₂₄P₁₅F, without reliance on known magnetic prototypes. This strategy and the accompanying theoretical framework present a flexible and powerful approach, potentially expanding the frontiers of magnetic electrides research.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2339–2348 2339–2348"},"PeriodicalIF":7.2,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678451","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":"Driving Thermoelectric Optimization in AgSbTe2 via Design of Experiments and Machine Learning","authors":"Jan-Hendrik Pöhls, Chun-Wan Timothy Lo, Marissa MacIver, Yu-Chih Tseng, Yurij Mozharivskyj","doi":"10.1021/acs.chemmater.5c00022","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00022","url":null,"abstract":"Systemic optimization of thermoelectric materials is arduous due to their conflicting electrical and thermal properties. A strategy based on Design of Experiments and machine learning is developed to optimize the thermoelectric efficiency of AgSb_1+<i>x</i>Te_2+<i>y</i>, an established thermoelectric. From eight experiments, high thermoelectric performance in AgSb_1.021Te_2.04 is revealed with a peak and average thermoelectric figure of merit of 1.61 ± 0.24 at 600 K and 1.18 ± 0.18 (300–623 K), respectively, which is &gt;30% higher than the best literature values for AgSb_1+<i>x</i>Te_2+<i>y</i>. Ag deficiency and suppression of secondary phases in AgSb_1.021Te_2.04 improve the electrical properties and reduce the thermal conductivity (∼0.4 W m^–1 K^–1). Our strategy is implemented into an open-source graphical user interface, and it can be used to optimize the methodologies, properties, and processes across different scientific fields.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599620","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}