Chemistry of Materials最新文献

{"title":"Rotator Phases in Chemically Recyclable Oligocyclobutanes","authors":"Hang Zhang,&nbsp;Shawn M. Maguire,&nbsp;Cherish Nie,&nbsp;Rodney D. Priestley,&nbsp;Paul J. Chirik,&nbsp;Richard A. Register,&nbsp;Emily C. Davidson and Michael A. Webb*,&nbsp;","doi":"10.1021/acs.chemmater.4c0257610.1021/acs.chemmater.4c02576","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02576https://doi.org/10.1021/acs.chemmater.4c02576","url":null,"abstract":"<p >Rotator phases are rotationally disordered yet crystalline stable states found in many materials. The presence of a rotator phase leads to unique properties that influence processing methods and offer potential applications in areas such as thermal energy storage, lubrication, and sensing. Recently, a novel family of chemically recyclable oligomers, (1,<i>n</i>′-divinyl)oligocyclobutane (DVOCB(<i>n</i>)), has shown evidence of rotator phases. This study combines experimental characterization and molecular dynamics simulations to confirm and elucidate the rotator phases in DVOCB(<i>n</i>). Compared with well-studied <i>n</i>-alkanes, DVOCB(<i>n</i>) exhibits distinct structural, thermodynamic, and dynamical characteristics. The crystal-to-rotator phase transition of DVOCB(<i>n</i>) involves a shift from stretched to isotropic hexagonal lamellar packing, captured by a rotational order parameter tracking local chain orientations orthogonal to the chain axis. Unlike <i>n</i>-alkanes, where rotational relaxation times are constant and long in the crystal phase before dropping dramatically during the crystal-to-rotator phase transition, relaxation times decrease more gradually upon heating in DVOCB(<i>n</i>), including continuously throughout the transition. This behavior is attributed to its unique enchained-ring architecture, which allows for semi-independent rotation of chain segments that promotes overall rotational disorder. This work provides a fundamental understanding of rotator phases in DVOCB(<i>n</i>) and highlights differences from those of conventional materials. The analyses and insights herein will inform future studies and applications of DVOCB(<i>n</i>) as well as other materials with rotator phases.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11596–11605 11596–11605"},"PeriodicalIF":7.2,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843848","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":"Exploring the Links between Structural Distortions, Orbital Ordering, and Multipolar Magnetic Ordering in Double Perovskites Containing Re(VI) and Os(VII)","authors":"Victor da Cruz Pinha Barbosa, Dalini D. Maharaj, Zachery W. Cronkright, Ye Wang, Rong Cong, Erick Garcia, Arneil P. Reyes, Jiaqiang Yan, Clemens Ritter, Vesna F. Mitrović, Bruce D. Gaulin, John E. Greedan, Patrick M. Woodward","doi":"10.1021/acs.chemmater.4c02135","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02135","url":null,"abstract":"A combination of high-resolution powder diffraction techniques and solid-state NMR has been employed to explore the links between crystal structure, orbital ordering, and magnetism in three isostructural double perovskites containing transition metal ions with a 5d¹ configuration. In Ba₂ZnReO₆, both neutron and synchrotron X-ray powder diffraction data reveal a cubic-to-tetragonal transition at 23 K that breaks the degeneracy of the t_2g orbitals and leads to a pattern of orbital ordering that stabilizes magnetic ordering when the sample is cooled below 16 K. Similar behavior is observed in Ba₂MgReO₆, with an orbital ordering temperature of 33 K and a magnetic ordering temperature of 18 K. Prior theoretical works suggest that the pattern of orbital order seen in the <i>P</i>4₂/<i>mnm</i> space group is needed to stabilize the heavily canted antiferromagnetism of these compounds. Unfortunately, powder diffraction data is not sensitive enough to differentiate between the <i>I</i>4/<i>mmm</i> and <i>P</i>4₂/<i>mnm</i> structural models, as the distortions are too subtle to be unambiguously identified from either neutron or synchrotron X-ray powder diffraction methods. In contrast, both diffraction and ⁷Li NMR data indicate that Ba₂LiOsO₆ retains the cubic structure down to 1.7 K. The antiferromagnetic ground state and lack of any sign of orbital ordering in Ba₂LiOsO₆ provide compelling evidence that the electronically driven tetragonal distortion seen in Ba₂ZnReO₆, and Ba₂MgReO₆ is intimately linked to the magnetic ordering seen in those compounds. The absence of magnetic reflections in high intensity neutron powder diffraction data collected on Ba₂MgReO₆ strongly suggests ordering of multipolar moments on Re(VI), likely ferro-octupolar ordering.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"15 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752905","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":"Rotator Phases in Chemically Recyclable Oligocyclobutanes","authors":"Hang Zhang, Shawn M. Maguire, Cherish Nie, Rodney D. Priestley, Paul J. Chirik, Richard A. Register, Emily C. Davidson, Michael A. Webb","doi":"10.1021/acs.chemmater.4c02576","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02576","url":null,"abstract":"Rotator phases are rotationally disordered yet crystalline stable states found in many materials. The presence of a rotator phase leads to unique properties that influence processing methods and offer potential applications in areas such as thermal energy storage, lubrication, and sensing. Recently, a novel family of chemically recyclable oligomers, (1,<i>n</i>′-divinyl)oligocyclobutane (DVOCB(<i>n</i>)), has shown evidence of rotator phases. This study combines experimental characterization and molecular dynamics simulations to confirm and elucidate the rotator phases in DVOCB(<i>n</i>). Compared with well-studied <i>n</i>-alkanes, DVOCB(<i>n</i>) exhibits distinct structural, thermodynamic, and dynamical characteristics. The crystal-to-rotator phase transition of DVOCB(<i>n</i>) involves a shift from stretched to isotropic hexagonal lamellar packing, captured by a rotational order parameter tracking local chain orientations orthogonal to the chain axis. Unlike <i>n</i>-alkanes, where rotational relaxation times are constant and long in the crystal phase before dropping dramatically during the crystal-to-rotator phase transition, relaxation times decrease more gradually upon heating in DVOCB(<i>n</i>), including continuously throughout the transition. This behavior is attributed to its unique enchained-ring architecture, which allows for semi-independent rotation of chain segments that promotes overall rotational disorder. This work provides a fundamental understanding of rotator phases in DVOCB(<i>n</i>) and highlights differences from those of conventional materials. The analyses and insights herein will inform future studies and applications of DVOCB(<i>n</i>) as well as other materials with rotator phases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752906","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":"Solution-Phase Synthesis of Platinum-Decorated Hydrogen Tungsten Bronzes for Hydrogen Atom Transfer from Oxides to Molecules","authors":"Noah P. Holzapfel, Matthew Chagnot, Payman Sharifi Abdar, Jay R. Paudel, Ethan J. Crumlin, James R. McKone, Veronica Augustyn","doi":"10.1021/acs.chemmater.4c02814","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02814","url":null,"abstract":"Hydrogen bronzes can be used as hydrogen donors for the broad class of reactions involving proton-coupled electron transfer (PCET). Here, we describe a method to prepare platinum-decorated hydrogen tungsten bronzes, Pt@H_<i>x</i>WO₃·<i>n</i>H₂O with <i>n</i> = 0, 1, and 2, by reacting the pristine oxides at modest temperatures with a mild reducing agent, H₃PO₂, and H₂PtCl₆ in an aqueous solution. We explored the tunability and kinetics of this reaction and compared it with that of archetypal gas–solid hydrogen spillover. We demonstrate that the identity of the noble metal affects the extent of bronze reduction. This suggests that the mechanism proceeds via the adsorption of a hydrogen-atom species on the noble metal. Finally, we explored the ability of the Pt-decorated hydrogen tungsten bronzes to hydrogenate a model H⁺/e^– acceptor, 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The bronze phases return to their fully oxidized states along with the subsequent reduction of TEMPO to TEMPOH. Overall, this work demonstrates a solution-phase method to obtain hydrogen bronzes, which can then be used to perform hydrogen transfer reactions, providing a pathway for the use of extended transition metal oxides as stoichiometric reagents for broad classes of hydrogenation reactions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"47 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752907","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":"Anionic Disorder and Its Impact on the Surface Electronic Structure of Oxynitride Photoactive Semiconductors","authors":"Anna Hartl, Ján Minár, Procopios Constantinou, Vladimir Roddatis, Fatima Alarab, Arnold M. Müller, Christof Vockenhuber, Thorsten Schmitt, Daniele Pergolesi, Thomas Lippert, Vladimir N. Strocov, Nick A. Shepelin","doi":"10.1021/acs.chemmater.4c01832","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01832","url":null,"abstract":"The conversion of solar energy into chemical energy, stored in the form of hydrogen, bears enormous potential as a sustainable fuel for powering emerging technologies. Photoactive oxynitrides are promising materials for splitting water into molecular oxygen and hydrogen. However, one of the issues limiting widespread commercial use of oxynitrides is degradation during operation. While recent studies have shown the loss of nitrogen, its relation to reduced efficiency has not been directly and systematically addressed with experiments. In this study, we demonstrate the impact of the anionic stoichiometry of BaTaO_<i>x</i>N_<i>y</i> on its electronic structure and functional properties. Through experimental ion scattering, electron microscopy, and photoelectron spectroscopy investigations, we determine the anionic composition ranging from the bulk toward the surface of BaTaO_<i>x</i>N_<i>y</i> thin films. This further serves as input for band structure computations modeling the substitutional disorder of the anion sites. Combining our experimental and computational approaches, we reveal the depth-dependent elemental composition of oxynitride films, resulting in downward band bending and the loss of semiconducting character toward the surface. Extending beyond idealized systems, we demonstrate the relation between the electronic properties of real oxynitride photoanodes and their performance, providing guidelines for engineering highly efficient photoelectrodes and photocatalysts for clean hydrogen production.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752902","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":"Area-Selective Molecular Layer Deposition of Alucone on Photoresist for Enhanced Pattern Transfer","authors":"Long Liu,&nbsp;Yue Zhang,&nbsp;Wenda Bao,&nbsp;Weixuan Zeng,&nbsp;Xiaoyun Yu*,&nbsp;Jiayi Chen and Shisheng Xiong*,&nbsp;","doi":"10.1021/acs.chemmater.4c0252110.1021/acs.chemmater.4c02521","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02521https://doi.org/10.1021/acs.chemmater.4c02521","url":null,"abstract":"<p >Multilayer mask dry etching is commonly used for pattern transfer on industrial lines to reduce the semiconductor component size. One of the challenges is the need for improved photoresists (PRs) that combine high resolution and etch selectivity with low complexity and material cost. Here, an alternative masking approach using area-selective molecular layer deposition (AS-MLD) has been shown to improve the etch resistance and pattern transfer accuracy. This technology enables the selective deposition of alucone into prepatterned PR areas or a class of PRs rich in ester groups like poly(methyl methacrylate) (PMMA), avoiding the deposition on the silicon-based substrate. The AS-MLD minimizes feature size variation and reduces edge placement errors. In this work, the mechanism of selective deposition of alucone on PMMA and the inhibition mechanism on Si-based substrates were investigated in detail. The alucone-PMMA demonstrates considerable resistance to high-energy fluorine plasma etching. Compared to the original PMMA, the etch resistance is improved by 85 times and the etch selectivity between alucone-PMMA-trimmed and SiON or SiO₂ can reach as high as 52 or 32, respectively. By improving film uniformity and thickness control, this method simplifies the manufacturing process, increases production efficiency, and reduces costs. Our approach addresses the urgent need for improved deposition selectivity and resolution in extreme ultraviolet (EUV) lithography and is an important step toward achieving reliable and high-performance semiconductor devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11583–11595 11583–11595"},"PeriodicalIF":7.2,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843920","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":"Area-Selective Molecular Layer Deposition of Alucone on Photoresist for Enhanced Pattern Transfer","authors":"Long Liu, Yue Zhang, Wenda Bao, Weixuan Zeng, Xiaoyun Yu, Jiayi Chen, Shisheng Xiong","doi":"10.1021/acs.chemmater.4c02521","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02521","url":null,"abstract":"Multilayer mask dry etching is commonly used for pattern transfer on industrial lines to reduce the semiconductor component size. One of the challenges is the need for improved photoresists (PRs) that combine high resolution and etch selectivity with low complexity and material cost. Here, an alternative masking approach using area-selective molecular layer deposition (AS-MLD) has been shown to improve the etch resistance and pattern transfer accuracy. This technology enables the selective deposition of alucone into prepatterned PR areas or a class of PRs rich in ester groups like poly(methyl methacrylate) (PMMA), avoiding the deposition on the silicon-based substrate. The AS-MLD minimizes feature size variation and reduces edge placement errors. In this work, the mechanism of selective deposition of alucone on PMMA and the inhibition mechanism on Si-based substrates were investigated in detail. The alucone-PMMA demonstrates considerable resistance to high-energy fluorine plasma etching. Compared to the original PMMA, the etch resistance is improved by 85 times and the etch selectivity between alucone-PMMA-trimmed and SiON or SiO₂ can reach as high as 52 or 32, respectively. By improving film uniformity and thickness control, this method simplifies the manufacturing process, increases production efficiency, and reduces costs. Our approach addresses the urgent need for improved deposition selectivity and resolution in extreme ultraviolet (EUV) lithography and is an important step toward achieving reliable and high-performance semiconductor devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"84 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753154","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":"Composition Governed Structure Evolution and Thermoelectric Properties in Eu(Li1–2xZnx)Sb (0< x < 0.5) Zintl Phases","authors":"Zhenlei Yuan,&nbsp;Kefeng Liu,&nbsp;Qian Liu,&nbsp;Xiao-Cun Liu and Sheng-Qing Xia*,&nbsp;","doi":"10.1021/acs.chemmater.4c0225810.1021/acs.chemmater.4c02258","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02258https://doi.org/10.1021/acs.chemmater.4c02258","url":null,"abstract":"<p >In this report, a new series of Zintl phases, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb (0 &lt; <i>x</i> &lt; 0.5), was discovered and investigated. These phases exhibit rich structural chemistry and notable thermoelectric properties. For the structures of Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb, three classes of analogues have been identified, which can be best represented by the well-known TiNiSi, LiGaGe, and ZrBeSi types, respectively. Interestingly, the structures of Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb phases are strongly dependent on the compositions varied with Li/Zn ratios. As a result, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb features a highly complex polyanionic framework as well as inherently low thermal conductivity. In addition to the converged band structures and improved effective mass, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb materials exhibit excellent thermoelectric performance. Demonstrated by Eu(Li_0.5Zn_0.25)Sb, exceptionally low thermal conductivity has been confirmed generally below 0.5 W/(m K), which led to a remarkable figure of merit (ZT) of 1.12 at 823 K. This value is about 14 times the maximum experimental ZT reported for the isotypic LiZnSb material. These results could bring new understandings on the structure-and-property correlations within the Zintl-phase-based thermoelectric materials since previously the performance of the p-type LiZnSb material was rather difficult to optimize. Besides, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb phases established a very significant connection among the well-known TiNiSi, LiGaGe, and ZrBeSi structures, which classify three important thermoelectric Zintl systems represented by EuLiSb, LiZnSb, and EuZn_0.5Sb.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11529–11540 11529–11540"},"PeriodicalIF":7.2,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843919","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":"Anionic Disorder and Its Impact on the Surface Electronic Structure of Oxynitride Photoactive Semiconductors","authors":"Anna Hartl,&nbsp;Ján Minár,&nbsp;Procopios Constantinou,&nbsp;Vladimir Roddatis,&nbsp;Fatima Alarab,&nbsp;Arnold M. Müller,&nbsp;Christof Vockenhuber,&nbsp;Thorsten Schmitt,&nbsp;Daniele Pergolesi,&nbsp;Thomas Lippert,&nbsp;Vladimir N. Strocov* and Nick A. Shepelin*,&nbsp;","doi":"10.1021/acs.chemmater.4c0183210.1021/acs.chemmater.4c01832","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01832https://doi.org/10.1021/acs.chemmater.4c01832","url":null,"abstract":"<p >The conversion of solar energy into chemical energy, stored in the form of hydrogen, bears enormous potential as a sustainable fuel for powering emerging technologies. Photoactive oxynitrides are promising materials for splitting water into molecular oxygen and hydrogen. However, one of the issues limiting widespread commercial use of oxynitrides is degradation during operation. While recent studies have shown the loss of nitrogen, its relation to reduced efficiency has not been directly and systematically addressed with experiments. In this study, we demonstrate the impact of the anionic stoichiometry of BaTaO_<i>x</i>N_<i>y</i> on its electronic structure and functional properties. Through experimental ion scattering, electron microscopy, and photoelectron spectroscopy investigations, we determine the anionic composition ranging from the bulk toward the surface of BaTaO_<i>x</i>N_<i>y</i> thin films. This further serves as input for band structure computations modeling the substitutional disorder of the anion sites. Combining our experimental and computational approaches, we reveal the depth-dependent elemental composition of oxynitride films, resulting in downward band bending and the loss of semiconducting character toward the surface. Extending beyond idealized systems, we demonstrate the relation between the electronic properties of real oxynitride photoanodes and their performance, providing guidelines for engineering highly efficient photoelectrodes and photocatalysts for clean hydrogen production.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 23","pages":"11393–11403 11393–11403"},"PeriodicalIF":7.2,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c01832","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843606","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":"Composition Governed Structure Evolution and Thermoelectric Properties in Eu(Li1–2xZnx)Sb (0< x < 0.5) Zintl Phases","authors":"Zhenlei Yuan, Kefeng Liu, Qian Liu, Xiao-Cun Liu, Sheng-Qing Xia","doi":"10.1021/acs.chemmater.4c02258","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02258","url":null,"abstract":"In this report, a new series of Zintl phases, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb (0 &lt; <i>x</i> &lt; 0.5), was discovered and investigated. These phases exhibit rich structural chemistry and notable thermoelectric properties. For the structures of Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb, three classes of analogues have been identified, which can be best represented by the well-known TiNiSi, LiGaGe, and ZrBeSi types, respectively. Interestingly, the structures of Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb phases are strongly dependent on the compositions varied with Li/Zn ratios. As a result, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb features a highly complex polyanionic framework as well as inherently low thermal conductivity. In addition to the converged band structures and improved effective mass, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb materials exhibit excellent thermoelectric performance. Demonstrated by Eu(Li_0.5Zn_0.25)Sb, exceptionally low thermal conductivity has been confirmed generally below 0.5 W/(m K), which led to a remarkable figure of merit (ZT) of 1.12 at 823 K. This value is about 14 times the maximum experimental ZT reported for the isotypic LiZnSb material. These results could bring new understandings on the structure-and-property correlations within the Zintl-phase-based thermoelectric materials since previously the performance of the p-type LiZnSb material was rather difficult to optimize. Besides, Eu(Li_{1–2<i>x</i>}Zn_<i>x</i>)Sb phases established a very significant connection among the well-known TiNiSi, LiGaGe, and ZrBeSi structures, which classify three important thermoelectric Zintl systems represented by EuLiSb, LiZnSb, and EuZn_0.5Sb.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"21 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753153","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}