Tin iodide phosphide (SnIP), the first atomic-scale one-dimensional (1D) double-helical inorganic semiconductor, has triggered growing interest due to its high structural flexibility, excellent electron mobility, and remarkable optical properties. Chemical vapor transport reaction has been the sole approach to growing SnIP crystals, though it suffers from time-consumption (∼2–3 weeks) and low yield. Inspired by its unique structure and properties, advancing rapid growth of SnIP crystals with a high yield is crucial. Herein, a systematic series of experiments have been designed to search the suitable synthesis conditions, viz., temperature gradient and temperature variations as well as precursors amount and ampule lengths to achieve the optimal conditions for the synthesis of SnIP crystals. Three transport agents, namely, SnI2, SnI4, and I2, were analyzed and compared, and SnI2 was deemed the most suitable agent for SnIP crystal growth. The optimal synthetic route enables high-yield (up to 84%) and high-quality SnIP crystals at a maximum temperature of 600 °C within only 10 days. Additionally, a comprehensive exploration of liquid-phase exfoliation of SnIP crystals is investigated to screen the optimal solvent in terms of the total surface tensions and polar/dispersive component ratios. It is demonstrated that cyclohexane can effectively isolate as-grown SnIP crystals into SnIP nanowires (NWs), boasting a high aspect ratio exceeding 950. The exfoliated NWs show smooth surfaces and clear signatures of the 1D SnIP helix. These findings shed light on the future applications of double-helical SnIP crystals in flexible electronics, mechanical sensors, and semiconductor devices.
{"title":"Rapid Chemical Vapor Transport Growth of Inorganic Double Helix Tin Iodide Phosphide Crystals with Increased Yield and Their Liquid-Phase Exfoliation","authors":"Mudussar Ali, Bowen Zhang, Wujia Chen, Kezheng Tao, Qiang Li, Qingfeng Yan","doi":"10.1021/acs.chemmater.4c01162","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01162","url":null,"abstract":"Tin iodide phosphide (SnIP), the first atomic-scale one-dimensional (1D) double-helical inorganic semiconductor, has triggered growing interest due to its high structural flexibility, excellent electron mobility, and remarkable optical properties. Chemical vapor transport reaction has been the sole approach to growing SnIP crystals, though it suffers from time-consumption (∼2–3 weeks) and low yield. Inspired by its unique structure and properties, advancing rapid growth of SnIP crystals with a high yield is crucial. Herein, a systematic series of experiments have been designed to search the suitable synthesis conditions, viz., temperature gradient and temperature variations as well as precursors amount and ampule lengths to achieve the optimal conditions for the synthesis of SnIP crystals. Three transport agents, namely, SnI<sub>2</sub>, SnI<sub>4</sub>, and I<sub>2</sub>, were analyzed and compared, and SnI<sub>2</sub> was deemed the most suitable agent for SnIP crystal growth. The optimal synthetic route enables high-yield (up to 84%) and high-quality SnIP crystals at a maximum temperature of 600 °C within only 10 days. Additionally, a comprehensive exploration of liquid-phase exfoliation of SnIP crystals is investigated to screen the optimal solvent in terms of the total surface tensions and polar/dispersive component ratios. It is demonstrated that cyclohexane can effectively isolate as-grown SnIP crystals into SnIP nanowires (NWs), boasting a high aspect ratio exceeding 950. The exfoliated NWs show smooth surfaces and clear signatures of the 1D SnIP helix. These findings shed light on the future applications of double-helical SnIP crystals in flexible electronics, mechanical sensors, and semiconductor devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489826","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}
Pub Date : 2024-07-02DOI: 10.1021/acs.chemmater.4c00056
Jia Wen Song, Yuan Gao, Yi Bang Ou, Xiang Tao Luo, Xing Yu Chen, Wen Ya Wang, Ying Wang, Shu Ya Wu, Xiao Qiang Liu, Xiao Li Zhu, He Tian, Xiang Ming Chen
The role of incommensurate (IC) modulation in the evolution of the pinched polarization–electric field (P–E) hysteresis loops has been investigated and discussed based on the structure and polarization evolution in Ba4(Sm1–xLax)2Ti4Nb6O30 tetragonal tungsten bronzes. The relaxor behavior in the La-rich compound is accompanied by an IC modulation structure. Introduction of smaller Sm in the system increases the driving force for the transition from an IC modulation structure to a commensurate superstructure, which coupled with the ferroelectric transition in the middle composition with x = 0.5. In the Sm-rich compounds, the IC modulation structure reappears as a metastable state to balance the structural instability caused by the too small average ionic radius of the rare-earth ion; meanwhile, the field-induced transition from the IC modulation structure to the commensurate superstructure is confirmed by selected area electron diffraction using an in situ bias technique as the structural origin for the pinched P–E loops. A phase diagram has been established by combining the ferroelectric phase transition and the modulation structure transition, and a new region with both very small A-site size (A1 + A2)/2 and A1-site tolerance factor (tA1) related to the ferroelectric compounds with pinched P–E loops (pinched FE) was added into the previously reported crystal-chemical framework (Chem. Mater.2015,27, 3250–3261). The present work expands the composition–structure–property relationships in tungsten bronze ferroelectrics by including the recently reported “pinched FE” and meanwhile extends the composition manipulation ranges from the crossover between relaxor and normal ferroelectrics to ferroelectrics with pinched P–E loops.
根据 Ba4(Sm1-xLax)2Ti4Nb6O30 四方钨青铜的结构和极化演化，研究并讨论了非通量（IC）调制在捏合极化-电场（P-E）磁滞环演化中的作用。富含 La 的化合物中的弛豫器行为伴随着 IC 调制结构。在体系中引入较小的 Sm 增加了从 IC 调制结构过渡到相称上层结构的驱动力，这与 x = 0.5 的中间成分中的铁电转换相耦合。在富含钐的化合物中，集成电路调制结构作为一种可转移状态重新出现，以平衡稀土离子平均离子半径过小造成的结构不稳定性；同时，利用原位偏置技术进行的选区电子衍射证实了由场诱导的集成电路调制结构向相称上层结构的转变是挤压 P-E 环的结构起源。结合铁电相变和调制结构转变建立了相图，并在之前报道的晶体-化学框架（Chem. Mater. 2015, 27, 3250-3261）中加入了一个新的区域，该区域同时具有极小的 A 位尺寸 (A1 + A2)/2 和 A1 位公差因子 (tA1)，与具有捏合 P-E 环（捏合 FE）的铁电化合物有关。本研究将最近报道的 "捏合 FE "纳入其中，从而扩展了钨青铜铁电的成分-结构-性质关系，同时将成分操纵范围从弛豫铁电和正常铁电之间的交叉扩展到具有捏合 P-E 环的铁电。
{"title":"Role of Incommensurate Modulation in Ba4(Sm1–xLax)2Ti4Nb6O30 Tetragonal Tungsten Bronzes","authors":"Jia Wen Song, Yuan Gao, Yi Bang Ou, Xiang Tao Luo, Xing Yu Chen, Wen Ya Wang, Ying Wang, Shu Ya Wu, Xiao Qiang Liu, Xiao Li Zhu, He Tian, Xiang Ming Chen","doi":"10.1021/acs.chemmater.4c00056","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00056","url":null,"abstract":"The role of incommensurate (IC) modulation in the evolution of the pinched polarization–electric field (<i>P</i>–<i>E</i>) hysteresis loops has been investigated and discussed based on the structure and polarization evolution in Ba<sub>4</sub>(Sm<sub>1–<i>x</i></sub>La<sub><i>x</i></sub>)<sub>2</sub>Ti<sub>4</sub>Nb<sub>6</sub>O<sub>30</sub> tetragonal tungsten bronzes. The relaxor behavior in the La-rich compound is accompanied by an IC modulation structure. Introduction of smaller Sm in the system increases the driving force for the transition from an IC modulation structure to a commensurate superstructure, which coupled with the ferroelectric transition in the middle composition with <i>x</i> = 0.5. In the Sm-rich compounds, the IC modulation structure reappears as a metastable state to balance the structural instability caused by the too small average ionic radius of the rare-earth ion; meanwhile, the field-induced transition from the IC modulation structure to the commensurate superstructure is confirmed by selected area electron diffraction using an in situ bias technique as the structural origin for the pinched <i>P</i>–<i>E</i> loops. A phase diagram has been established by combining the ferroelectric phase transition and the modulation structure transition, and a new region with both very small <i>A</i>-site size (A1 + A2)/2 and A1-site tolerance factor (<i>t</i><sub>A1</sub>) related to the ferroelectric compounds with pinched <i>P</i>–<i>E</i> loops (pinched FE) was added into the previously reported crystal-chemical framework (<i>Chem. Mater.</i> <b>2015,</b> <i>27,</i> 3250–3261). The present work expands the composition–structure–property relationships in tungsten bronze ferroelectrics by including the recently reported “pinched FE” and meanwhile extends the composition manipulation ranges from the crossover between relaxor and normal ferroelectrics to ferroelectrics with pinched <i>P</i>–<i>E</i> loops.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489791","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}
Pub Date : 2024-07-01DOI: 10.1021/acs.chemmater.4c01246
Gang Han, Robin M. Studer, Moonjoo Lee, Katherine Mizrahi Rodriguez, Justin J. Teesdale, Zachary P. Smith
Polyamide thin-film nanocomposite (TFN) membranes provide a promising pathway to alleviate the trade-off between water permeability and selectivity of conventional thin-film composite (TFC) membranes. However, the fabrication of defect-free TFN membranes with enhanced permselectivity remains a challenge due to the formation of defects at the polyamide–filler interface and from filler agglomeration. In this study, a facile interfacial modification strategy was demonstrated to effectively mitigate particle agglomeration and enhance the interaction between the polyamide with the filler particles using UiO-66-NH2 nanoparticles as the probe fillers, leading to the formation of TFN membranes with excellent interfacial compatibility and selectivity toward both salt ions and small neutral molecules. The TFN membrane with an optimized particle loading shows high rejections of 97.0–99.2% to NaCl, MgCl2, Na2SO4, and MgSO4 with a water flux greater than 4.0 L m–2 h–1 at a relatively low pressure of 150 psi, which represents a ≥23.0% increase in salt rejections relative to the TFC benchmark. Additionally, the TFN membranes show great potential for effectively discriminating small neutral contaminants such as boric acid (H3BO3) at a pH value of 7.5, outperforming the commercial TFC membrane benchmark at the same testing conditions. The structural stability of the TFN membranes was confirmed by performing a continuous performance test of 480 h. These findings demonstrate that enhanced size screening for various species can be achieved by TFN membranes based on the engineered interfacial structure of the porous fillers, and the reported method represents an advancement in addressing permselectivity limitations in classic TFNs through a multifaceted yet generalizable approach of reducing particle agglomeration and creating compatible polymer–filler interfaces. We believe this strategy can be applied broadly with different filler systems, enabling TFNs to address a wide variety of unmet separation needs.
{"title":"Engineering Interfacial Structure and Channels of Polyamide Thin-Film Nanocomposite Membranes to Enhance Permselectivity for Water Purification","authors":"Gang Han, Robin M. Studer, Moonjoo Lee, Katherine Mizrahi Rodriguez, Justin J. Teesdale, Zachary P. Smith","doi":"10.1021/acs.chemmater.4c01246","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01246","url":null,"abstract":"Polyamide thin-film nanocomposite (TFN) membranes provide a promising pathway to alleviate the trade-off between water permeability and selectivity of conventional thin-film composite (TFC) membranes. However, the fabrication of defect-free TFN membranes with enhanced permselectivity remains a challenge due to the formation of defects at the polyamide–filler interface and from filler agglomeration. In this study, a facile interfacial modification strategy was demonstrated to effectively mitigate particle agglomeration and enhance the interaction between the polyamide with the filler particles using UiO-66-NH<sub>2</sub> nanoparticles as the probe fillers, leading to the formation of TFN membranes with excellent interfacial compatibility and selectivity toward both salt ions and small neutral molecules. The TFN membrane with an optimized particle loading shows high rejections of 97.0–99.2% to NaCl, MgCl<sub>2</sub>, Na<sub>2</sub>SO<sub>4</sub>, and MgSO<sub>4</sub> with a water flux greater than 4.0 L m<sup>–2</sup> h<sup>–1</sup> at a relatively low pressure of 150 psi, which represents a ≥23.0% increase in salt rejections relative to the TFC benchmark. Additionally, the TFN membranes show great potential for effectively discriminating small neutral contaminants such as boric acid (H<sub>3</sub>BO<sub>3</sub>) at a pH value of 7.5, outperforming the commercial TFC membrane benchmark at the same testing conditions. The structural stability of the TFN membranes was confirmed by performing a continuous performance test of 480 h. These findings demonstrate that enhanced size screening for various species can be achieved by TFN membranes based on the engineered interfacial structure of the porous fillers, and the reported method represents an advancement in addressing permselectivity limitations in classic TFNs through a multifaceted yet generalizable approach of reducing particle agglomeration and creating compatible polymer–filler interfaces. We believe this strategy can be applied broadly with different filler systems, enabling TFNs to address a wide variety of unmet separation needs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489686","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}
Pub Date : 2024-07-01DOI: 10.1021/acs.chemmater.4c01090
Suvodeep Sen, Niladri Sekhar Karan, Narayan Pradhan
The burgeoning fascination for plasmonic nanomaterials has been stimulated by their emerging applications in energy, medicine, and several optoelectronic technologies. The plasmonic properties of nanomaterials are engineered by various parameters that primarily include architecture (size and shape), composition, and dielectricity of the local environment. The pursuit to innovate the distinctive physicochemical functionalities of plasmonic nanostructures is conceivably addressed by precisely engineered nanoheterostructures (NHCs) because of their compositional and structural versatility. Often, heterostructuring manifests strong light–matter interactions that translate into plasmon–plasmon resonance coupling effects, forming dual plasmonic heterostructures (DPHs). Such exquisite structural control down to the nanometer level requires detailed understanding, aptly designed guidelines, and synthetic tools. In this review, first a brief fundamental knowledge about surface plasmonic resonance is discussed and then a detailed understanding of the interference phenomenon arising due to heterostructuring two plasmonic nano-objects is presented. The synthesis, plasmonic features, and diverse applications of different DPHs, from metal–metal to metal–semiconductor, are discussed at length in this review. Building on the current status of plasmon coupling in semiconductor–semiconductor and other NHCs and their interfacial energy/charge transfer mechanisms, the final part of the review summarizes the topic by shedding light on the research niche that provides direction for future prospects.
{"title":"Synthesis Innovations and Applications of Dual Plasmonic Heteronanostructures: Fundamentals to Future Horizons","authors":"Suvodeep Sen, Niladri Sekhar Karan, Narayan Pradhan","doi":"10.1021/acs.chemmater.4c01090","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01090","url":null,"abstract":"The burgeoning fascination for plasmonic nanomaterials has been stimulated by their emerging applications in energy, medicine, and several optoelectronic technologies. The plasmonic properties of nanomaterials are engineered by various parameters that primarily include architecture (size and shape), composition, and dielectricity of the local environment. The pursuit to innovate the distinctive physicochemical functionalities of plasmonic nanostructures is conceivably addressed by precisely engineered nanoheterostructures (NHCs) because of their compositional and structural versatility. Often, heterostructuring manifests strong light–matter interactions that translate into plasmon–plasmon resonance coupling effects, forming dual plasmonic heterostructures (DPHs). Such exquisite structural control down to the nanometer level requires detailed understanding, aptly designed guidelines, and synthetic tools. In this review, first a brief fundamental knowledge about surface plasmonic resonance is discussed and then a detailed understanding of the interference phenomenon arising due to heterostructuring two plasmonic nano-objects is presented. The synthesis, plasmonic features, and diverse applications of different DPHs, from metal–metal to metal–semiconductor, are discussed at length in this review. Building on the current status of plasmon coupling in semiconductor–semiconductor and other NHCs and their interfacial energy/charge transfer mechanisms, the final part of the review summarizes the topic by shedding light on the research niche that provides direction for future prospects.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489744","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}
Pub Date : 2024-07-01DOI: 10.1021/acs.chemmater.4c00345
Nuno M. Fortunato, Xiaoqing Li, Stephan Schönecker, Ruiwen Xie, Andreas Taubel, Franziska Scheibel, Ingo Opahle, Oliver Gutfleisch, Hongbin Zhang
Due to their versatile composition and customizable properties, A2BC Heusler alloys have found applications in magnetic refrigeration, magnetic shape memory effects, permanent magnets, and spintronic devices. The discovery of all-d-metal Heusler alloys with improved mechanical properties compared to those containing main group elements presents an opportunity to engineer Heusler alloys for energy-related applications. Using high-throughput density-functional theory calculations, we screened magnetic all-d-metal Heusler compounds and identified 686 (meta)stable compounds. Our detailed analysis revealed that the inverse Heusler structure is preferred when the electronegativity difference between the A and B/C atoms is small, contrary to conventional Heusler alloys. Additionally, our calculations of Pugh ratios and Cauchy pressures demonstrated that ductile and metallic bonding are widespread in all-d-metal Heuslers, supporting their enhanced mechanical behavior. We identified 49 compounds with a double-well energy surface based on Bain path calculations and magnetic ground states, indicating their potential as candidates for magnetocaloric and shape memory applications. Furthermore, by calculating the free energies, we propose that 11 compounds exhibit structural phase transitions and suggest isostructural substitutions to enhance the magnetocaloric effect.
{"title":"High-Throughput Screening of All-d-Metal Heusler Alloys for Magnetocaloric Applications","authors":"Nuno M. Fortunato, Xiaoqing Li, Stephan Schönecker, Ruiwen Xie, Andreas Taubel, Franziska Scheibel, Ingo Opahle, Oliver Gutfleisch, Hongbin Zhang","doi":"10.1021/acs.chemmater.4c00345","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00345","url":null,"abstract":"Due to their versatile composition and customizable properties, A<sub>2</sub>BC Heusler alloys have found applications in magnetic refrigeration, magnetic shape memory effects, permanent magnets, and spintronic devices. The discovery of all-<i>d</i>-metal Heusler alloys with improved mechanical properties compared to those containing main group elements presents an opportunity to engineer Heusler alloys for energy-related applications. Using high-throughput density-functional theory calculations, we screened magnetic all-<i>d</i>-metal Heusler compounds and identified 686 (meta)stable compounds. Our detailed analysis revealed that the inverse Heusler structure is preferred when the electronegativity difference between the A and B/C atoms is small, contrary to conventional Heusler alloys. Additionally, our calculations of Pugh ratios and Cauchy pressures demonstrated that ductile and metallic bonding are widespread in all-<i>d</i>-metal Heuslers, supporting their enhanced mechanical behavior. We identified 49 compounds with a double-well energy surface based on Bain path calculations and magnetic ground states, indicating their potential as candidates for magnetocaloric and shape memory applications. Furthermore, by calculating the free energies, we propose that 11 compounds exhibit structural phase transitions and suggest isostructural substitutions to enhance the magnetocaloric effect.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489824","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}
Pub Date : 2024-07-01DOI: 10.1021/acs.chemmater.4c01040
Marcel Junige, Steven M. George
Selectivity was examined between SiO2 and SiNx during thermal atomic layer etching (ALE) and spontaneous etching. Thermal ALE of SiO2 and SiNx was explored using sequential trimethylaluminum (TMA) and hydrogen fluoride (HF) with reactant exposures of 3 Torr for 45 s at 275 °C. SiO2 thermal ALE achieved an etch per cycle (EPC) of 0.20 Å/cycle and near-ideal synergy up to 95%. SiNx thermal ALE exhibited a higher EPC of 1.06 Å/cycle. The selectivity factor was ∼5:1 for SiNx etching compared to SiO2 etching (preferential SiNx removal) during thermal ALE using TMA and HF. Spontaneous etching was then quantified using repeated exposures of HF vapor alone at 3 Torr and 275 °C. SiO2 spontaneous etching was minor at an etch rate of 0.03 Å/min, enabling near-ideal synergy for SiO2 thermal ALE. In contrast, major SiNx spontaneous etching displayed an etch rate of 1.72 Å/min and predominated over SiNx thermal ALE. The selectivity factor was ∼50:1 for SiNx spontaneous etching compared to SiO2 spontaneous etching using an HF pressure of 3 Torr. This selective SiNx spontaneous etching was attributed to F– surface species during HF exposures. NH3 codosing with HF was then examined during thermal ALE and spontaneous etching. Thermal ALE of SiO2 and SiNx was examined using sequential TMA and HF + NH3 codosing with reactant exposures of 3 Torr for 45 s at 275 °C. SiO2 thermal ALE with HF + NH3 codosing had a high EPC of 8.83 Å/cycle. In contrast, SiNx thermal ALE with HF + NH3 codosing was negligible. The selectivity factor was reversed and much higher at >1000:1 for SiO2 etching compared to SiNx etching (preferential SiO2 removal) during thermal ALE with HF + NH3 codosing. Rapid SiO2 spontaneous etching with HF + NH3 codosing at 3 Torr had an etch rate of 27.50 Å/min. In contrast, SiNx spontaneous etching with HF + NH3 codosing produced a very low etch rate of 0.02 Å/min. The selectivity factor was >1000:1 for SiO2 spontaneous etching compared to SiNx spontaneous etching with HF + NH3 codosing. This selective SiO2 spontaneous etching was attributed to HF2– surface species during HF + NH3 exposures. These studies revealed that the NH3 coadsorbate during HF exposures modified the active etch species and dramatically influenced the etch selectivity between SiO2 and SiNx. Reciprocal etch selectivity should be important for the selective removal of SiO2 or SiNx in com
{"title":"Selectivity between SiO2 and SiNx during Thermal Atomic Layer Etching Using Al(CH3)3/HF and Spontaneous Etching Using HF and Effect of HF + NH3 Codosing","authors":"Marcel Junige, Steven M. George","doi":"10.1021/acs.chemmater.4c01040","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01040","url":null,"abstract":"Selectivity was examined between SiO<sub>2</sub> and SiN<sub><i>x</i></sub> during thermal atomic layer etching (ALE) and spontaneous etching. Thermal ALE of SiO<sub>2</sub> and SiN<sub><i>x</i></sub> was explored using sequential trimethylaluminum (TMA) and hydrogen fluoride (HF) with reactant exposures of 3 Torr for 45 s at 275 °C. SiO<sub>2</sub> thermal ALE achieved an etch per cycle (EPC) of 0.20 Å/cycle and near-ideal synergy up to 95%. SiN<sub><i>x</i></sub> thermal ALE exhibited a higher EPC of 1.06 Å/cycle. The selectivity factor was ∼5:1 for SiN<sub><i>x</i></sub> etching compared to SiO<sub>2</sub> etching (preferential SiN<sub><i>x</i></sub> removal) during thermal ALE using TMA and HF. Spontaneous etching was then quantified using repeated exposures of HF vapor alone at 3 Torr and 275 °C. SiO<sub>2</sub> spontaneous etching was minor at an etch rate of 0.03 Å/min, enabling near-ideal synergy for SiO<sub>2</sub> thermal ALE. In contrast, major SiN<sub><i>x</i></sub> spontaneous etching displayed an etch rate of 1.72 Å/min and predominated over SiN<sub><i>x</i></sub> thermal ALE. The selectivity factor was ∼50:1 for SiN<sub><i>x</i></sub> spontaneous etching compared to SiO<sub>2</sub> spontaneous etching using an HF pressure of 3 Torr. This selective SiN<sub><i>x</i></sub> spontaneous etching was attributed to F<sup>–</sup> surface species during HF exposures. NH<sub>3</sub> codosing with HF was then examined during thermal ALE and spontaneous etching. Thermal ALE of SiO<sub>2</sub> and SiN<sub><i>x</i></sub> was examined using sequential TMA and HF + NH<sub>3</sub> codosing with reactant exposures of 3 Torr for 45 s at 275 °C. SiO<sub>2</sub> thermal ALE with HF + NH<sub>3</sub> codosing had a high EPC of 8.83 Å/cycle. In contrast, SiN<sub><i>x</i></sub> thermal ALE with HF + NH<sub>3</sub> codosing was negligible. The selectivity factor was reversed and much higher at >1000:1 for SiO<sub>2</sub> etching compared to SiN<sub><i>x</i></sub> etching (preferential SiO<sub>2</sub> removal) during thermal ALE with HF + NH<sub>3</sub> codosing. Rapid SiO<sub>2</sub> spontaneous etching with HF + NH<sub>3</sub> codosing at 3 Torr had an etch rate of 27.50 Å/min. In contrast, SiN<sub><i>x</i></sub> spontaneous etching with HF + NH<sub>3</sub> codosing produced a very low etch rate of 0.02 Å/min. The selectivity factor was >1000:1 for SiO<sub>2</sub> spontaneous etching compared to SiN<sub><i>x</i></sub> spontaneous etching with HF + NH<sub>3</sub> codosing. This selective SiO<sub>2</sub> spontaneous etching was attributed to HF<sub>2</sub><sup>–</sup> surface species during HF + NH<sub>3</sub> exposures. These studies revealed that the NH<sub>3</sub> coadsorbate during HF exposures modified the active etch species and dramatically influenced the etch selectivity between SiO<sub>2</sub> and SiN<sub><i>x</i></sub>. Reciprocal etch selectivity should be important for the selective removal of SiO<sub>2</sub> or SiN<sub><i>x</i></sub> in com","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489829","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}
Pub Date : 2024-06-30DOI: 10.1021/acs.chemmater.4c01089
Jihun Roh, Hyojin Kim, Hyungjin Lee, Hyeri Bu, Alicia Manjón-Sanz, Hyungsub Kim, Seung-Tae Hong
Safety concerns regarding organic-based liquid electrolytes in Li-ion batteries have led to extensive research on lithium-ion conductors. Despite cost-effectiveness, thio-silicate Li4SiS4 has been overlooked owing to unclear crystallographic information. This study clarifies the crystal structures and electrochemical properties of two Li4SiS4 polymorphs and their aliovalent substitution series, i.e., Li4–xSi1–xSbxS4. Our findings indicate that the polymorphs differ primarily in their SiS4 tetrahedra stacking configurations, with the high-temperature phase being more orderly than the low-temperature phase. However, they exhibit similar ionic-transport properties, indicating that the tetrahedra stacking minimally affects Li-ion mobility. We found that the dense packing of Li in these structures restricts ion movement, necessitating the creation of Li vacancies through the aliovalent substitution of Sb5+ for Si4+ to enhance Li mobility. The substitution series Li4–xSi1–xSbxS4 with x = 0.15 exhibited a 10-fold conductivity increase, signifying the influence of Li vacancies on ionic transport. Cyclic voltammetry confirmed the suitability of Li3.85Si0.85Sb0.15S4 as a solid electrolyte for all-solid-state batteries. This study suggests that the ionic conductivity in Li4SiS4 depends more on Li-ion concentration than on SiS4 tetrahedra stacking, providing strategic insights for developing more efficient solid-state battery materials.
{"title":"Unraveling Polymorphic Crystal Structures of Li4SiS4 for All-Solid-State Batteries: Enhanced Ionic Conductivity via Aliovalent Sb Substitution","authors":"Jihun Roh, Hyojin Kim, Hyungjin Lee, Hyeri Bu, Alicia Manjón-Sanz, Hyungsub Kim, Seung-Tae Hong","doi":"10.1021/acs.chemmater.4c01089","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01089","url":null,"abstract":"Safety concerns regarding organic-based liquid electrolytes in Li-ion batteries have led to extensive research on lithium-ion conductors. Despite cost-effectiveness, thio-silicate Li<sub>4</sub>SiS<sub>4</sub> has been overlooked owing to unclear crystallographic information. This study clarifies the crystal structures and electrochemical properties of two Li<sub>4</sub>SiS<sub>4</sub> polymorphs and their aliovalent substitution series, i.e., Li<sub>4–<i>x</i></sub>Si<sub>1–<i>x</i></sub>Sb<sub><i>x</i></sub>S<sub>4</sub>. Our findings indicate that the polymorphs differ primarily in their SiS<sub>4</sub> tetrahedra stacking configurations, with the high-temperature phase being more orderly than the low-temperature phase. However, they exhibit similar ionic-transport properties, indicating that the tetrahedra stacking minimally affects Li-ion mobility. We found that the dense packing of Li in these structures restricts ion movement, necessitating the creation of Li vacancies through the aliovalent substitution of Sb<sup>5+</sup> for Si<sup>4+</sup> to enhance Li mobility. The substitution series Li<sub>4–<i>x</i></sub>Si<sub>1–<i>x</i></sub>Sb<sub><i>x</i></sub>S<sub>4</sub> with <i>x</i> = 0.15 exhibited a 10-fold conductivity increase, signifying the influence of Li vacancies on ionic transport. Cyclic voltammetry confirmed the suitability of Li<sub>3.85</sub>Si<sub>0.85</sub>Sb<sub>0.15</sub>S<sub>4</sub> as a solid electrolyte for all-solid-state batteries. This study suggests that the ionic conductivity in Li<sub>4</sub>SiS<sub>4</sub> depends more on Li-ion concentration than on SiS<sub>4</sub> tetrahedra stacking, providing strategic insights for developing more efficient solid-state battery materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489781","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}
Pub Date : 2024-06-28DOI: 10.1021/acs.chemmater.4c00576
Yateng Wang, Bianca Baldassarri, Jiahong Shen, Jiangang He, Chris Wolverton
Perovskite oxides have been extensively studied for their wide range of compositions and structures, as well as their valuable properties for various applications. Expanding from single-perovskite ABO3 to double-perovskite A2BB′O6 significantly enhances the ability to tailor specific physical and chemical properties. However, the vast number of potential compositions of A2BB′O6 makes it impractical to explore all of them experimentally. In this study, we conducted high-throughput calculations to systematically investigate the structures and stabilities of 4900 A2BB′O6 compositions (with A = Ca, Sr, Ba, and La; B and B′ representing metal elements) through over 42 000 density functional theory (DFT) calculations. Our analysis lead to the discovery of more than 1500 new A2BB′O6 compounds, with over 1100 of them exhibiting double perovskite structures, predominantly in the space group. By leveraging the high-throughput dataset, we developed machine learning models that achieved mean absolute errors of 0.0422 and 0.0329 eV/atom for formation energy and decomposition energy, respectively. Using these models, we identified 803 stable or metastable compositions beyond the chemical space covered in our initial calculations, with 612 of them having DFT-validated decomposition energies below 0.1 eV/atom, resulting in a success rate of 76.2%. This study delineates the stability landscape of A2BB′O6 compounds and offers new insights for exploration of these materials.
{"title":"Landscape of Thermodynamic Stabilities of A2BB′O6 Compounds","authors":"Yateng Wang, Bianca Baldassarri, Jiahong Shen, Jiangang He, Chris Wolverton","doi":"10.1021/acs.chemmater.4c00576","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00576","url":null,"abstract":"Perovskite oxides have been extensively studied for their wide range of compositions and structures, as well as their valuable properties for various applications. Expanding from single-perovskite <i>AB</i>O<sub>3</sub> to double-perovskite <i>A</i><sub>2</sub><i>BB</i>′O<sub>6</sub> significantly enhances the ability to tailor specific physical and chemical properties. However, the vast number of potential compositions of <i>A</i><sub>2</sub><i>BB</i>′O<sub>6</sub> makes it impractical to explore all of them experimentally. In this study, we conducted high-throughput calculations to systematically investigate the structures and stabilities of 4900 <i>A</i><sub>2</sub><i>BB</i>′O<sub>6</sub> compositions (with <i>A</i> = Ca, Sr, Ba, and La; <i>B</i> and <i>B</i>′ representing metal elements) through over 42 000 density functional theory (DFT) calculations. Our analysis lead to the discovery of more than 1500 new <i>A</i><sub>2</sub><i>BB</i>′O<sub>6</sub> compounds, with over 1100 of them exhibiting double perovskite structures, predominantly in the space group. By leveraging the high-throughput dataset, we developed machine learning models that achieved mean absolute errors of 0.0422 and 0.0329 eV/atom for formation energy and decomposition energy, respectively. Using these models, we identified 803 stable or metastable compositions beyond the chemical space covered in our initial calculations, with 612 of them having DFT-validated decomposition energies below 0.1 eV/atom, resulting in a success rate of 76.2%. This study delineates the stability landscape of <i>A</i><sub>2</sub><i>BB</i>′O<sub>6</sub> compounds and offers new insights for exploration of these materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463596","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}
Ionic covalent organic framework (iCOF) materials are providing a potential platform to develop next-generation electro-responsive smart materials because of ion movement-induced interfacial polarization. However, it is challenging to achieve strong interfacial polarization while reducing electrode polarization due to the nature of pure ions as charge carriers in iCOF. In this article, we developed a mixed ionic–electronic covalent organic framework (ieCOF), which can overcome this challenge. This ieCOF was prepared by thermal cracking of task-specific ionic liquids. It shows that ieCOF is composed of a positively charged slight-carbonized framework attracted with fluoric counteranions. Through changing the heating target temperature, ieCOF with different ion contents and different carbonized level frameworks can be obtained. We find that compared with the ion-dominated system, the mixed ionic–electronic ieCOF can achieve a stronger interfacial polarization but a weaker electrode polarization. Consequently, the ieCOF has a higher electro-responsive electrorheological (ER) effect but lower leaking current density. In particular, increasing the temperature can promote the interfacial polarization intensity, resulting in a higher ER effect. The present result shows that ieCOF can provide a platform to design and develop high-performance electro-responsive smart materials.
{"title":"Mixed Ionic–Electronic Covalent Organic Frameworks as a Platform for High-Performance Electro-Responsive Smart Materials","authors":"Ruijing Ma, Wuyang Nie, Yudong Wang, Xufeng Hu, Xiaopeng Zhao, Jianbo Yin","doi":"10.1021/acs.chemmater.4c01052","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01052","url":null,"abstract":"Ionic covalent organic framework (iCOF) materials are providing a potential platform to develop next-generation electro-responsive smart materials because of ion movement-induced interfacial polarization. However, it is challenging to achieve strong interfacial polarization while reducing electrode polarization due to the nature of pure ions as charge carriers in iCOF. In this article, we developed a mixed ionic–electronic covalent organic framework (ieCOF), which can overcome this challenge. This ieCOF was prepared by thermal cracking of task-specific ionic liquids. It shows that ieCOF is composed of a positively charged slight-carbonized framework attracted with fluoric counteranions. Through changing the heating target temperature, ieCOF with different ion contents and different carbonized level frameworks can be obtained. We find that compared with the ion-dominated system, the mixed ionic–electronic ieCOF can achieve a stronger interfacial polarization but a weaker electrode polarization. Consequently, the ieCOF has a higher electro-responsive electrorheological (ER) effect but lower leaking current density. In particular, increasing the temperature can promote the interfacial polarization intensity, resulting in a higher ER effect. The present result shows that ieCOF can provide a platform to design and develop high-performance electro-responsive smart materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463619","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}
Pub Date : 2024-06-28DOI: 10.1021/acs.chemmater.4c00535
Shichen Sun, Xi Yang, Aidan Billings, Kevin Huang
The unique technical merits of aqueous zinc-ion batteries (AZIBs) have attracted significant interest in the development of grid-scale energy storage technologies in the past decade. However, the development of AZIBs is severely hampered by the poor cycle stability, which exclusively stems from the electrolyte/electrode interactions. To address this issue, knowledge of the bulk properties of electrolytes, a pivotal component of AZIBs, is needed. Unfortunately, there still exists a significant gap in the data and understanding of these properties. This study investigates the concentration-dependent bulk properties of Zn-salt solution electrolytes through a combined experimental and theoretical approach. Key bulk properties such as pH, conductivity, water activity, hydrogen bonding, and electrochemical stability of five Zn-salt solutions are systematically studied as a function of concentration through a suite of experiments and theoretically interpreted by quantum chemistry calculations, molecular dynamics, and a tailored solvation model considering multispecies ion–ion and ion–molecule interactions. The model-produced theoretical results agree well with the experimental data. The revealed theoretical insights offer valuable fundamental guidance for future electrolyte discovery and understanding/mitigating degradation mechanisms in AZIBs.
{"title":"Understanding the Critical Bulk Properties of Zn-Salt Solution Electrolytes for Aqueous Zn-Ion Batteries","authors":"Shichen Sun, Xi Yang, Aidan Billings, Kevin Huang","doi":"10.1021/acs.chemmater.4c00535","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00535","url":null,"abstract":"The unique technical merits of aqueous zinc-ion batteries (AZIBs) have attracted significant interest in the development of grid-scale energy storage technologies in the past decade. However, the development of AZIBs is severely hampered by the poor cycle stability, which exclusively stems from the electrolyte/electrode interactions. To address this issue, knowledge of the bulk properties of electrolytes, a pivotal component of AZIBs, is needed. Unfortunately, there still exists a significant gap in the data and understanding of these properties. This study investigates the concentration-dependent bulk properties of Zn-salt solution electrolytes through a combined experimental and theoretical approach. Key bulk properties such as pH, conductivity, water activity, hydrogen bonding, and electrochemical stability of five Zn-salt solutions are systematically studied as a function of concentration through a suite of experiments and theoretically interpreted by quantum chemistry calculations, molecular dynamics, and a tailored solvation model considering multispecies ion–ion and ion–molecule interactions. The model-produced theoretical results agree well with the experimental data. The revealed theoretical insights offer valuable fundamental guidance for future electrolyte discovery and understanding/mitigating degradation mechanisms in AZIBs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463684","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}
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