Pub Date : 2024-12-03DOI: 10.1021/accountsmr.4c0030310.1021/accountsmr.4c00303
Priyam Ghosh, and , Parameswar Krishnan Iyer*,
Alzheimer’s disease (AD) is a complex neurological disorder with a progressive nature, posing challenges in diagnosis and treatment. It is characterized by the formation of Aβ plaques and neurofibrillary tangles (NFTs), which have been the focus of clinical diagnosis and treatment. Despite decades of research, the elusive nature of AD has made it difficult to develop widely recognized diagnostic and treatment methods. However, recent advances have led to new diagnostic and therapeutic techniques targeting Aβ and tau. These technologies aim to address gaps in our understanding by targeting biomarkers using multifunctional fluorescent organic-molecule-based theranostics. There is a leading hypothesis that Aβ and its oligomers are crucial pathogenic features in AD-afflicted brains. Metals found in Aβ plaques have been linked to AD, contributing to oxidative stress and stabilizing toxic Aβ oligomers. Drug research is addressing AD’s diverse toxicity, including protein aggregation, metal toxicity, oxidative stress, mitochondrial damage, and neuroinflammation. Drug development is adopting multifaceted approaches, focusing on the intricate interaction of AD contributors. Diverse diagnostic techniques and innovative drug development tactics are crucial for AD diagnosis and therapy advances.
This Account is focused on analyzing the interaction between fluorescent molecular probes in the context of AD theranostics. It explores their design methods, imaging techniques, and therapeutic applications to develop innovative approaches for diagnosing and treating AD, thereby contributing to the advancement of precision medicine in neurodegenerative disorders. The first section explains the pathological factors associated with AD, while the second part discusses recently identified multifunctional fluorescent compounds as therapeutic and diagnostic targets. We also delve into the multifunctional probes developed in our laboratory over the past decade for the purpose of AD theranostics. The subsequent section covers small molecule and conjugated polymer (CP) chemistry, design, and functions. Our research aims to shed light on AD development by studying the link between Aβ, metal ions, and particularly metal-Aβ interactions. We utilize multifunctional fluorescent molecular probes to target metal-Aβ species, modulate interaction, and guide aggregation into nontoxic, off-pathway aggregates. These multipotent ligands reduce oxidative stress by preventing the production of reactive intermediate species (RIS) from redox-active metal-Aβ. Ongoing research aims to enhance fluorescent compounds for early and accurate detection of AD and to prevent its associated causes. We also explore current challenges and potential methods for developing multifunctional probes for AD theranostics. This Account aims to aid readers in understanding the multifaceted nature of AD and the development of novel multifunctional molecules that target its multifaceted toxicity.
{"title":"Multifunctional Fluorescent Probes Unveiling Complex Pathways in Alzheimer’s Disease Pathogenesis","authors":"Priyam Ghosh, and , Parameswar Krishnan Iyer*, ","doi":"10.1021/accountsmr.4c0030310.1021/accountsmr.4c00303","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00303https://doi.org/10.1021/accountsmr.4c00303","url":null,"abstract":"<p >Alzheimer’s disease (AD) is a complex neurological disorder with a progressive nature, posing challenges in diagnosis and treatment. It is characterized by the formation of Aβ plaques and neurofibrillary tangles (NFTs), which have been the focus of clinical diagnosis and treatment. Despite decades of research, the elusive nature of AD has made it difficult to develop widely recognized diagnostic and treatment methods. However, recent advances have led to new diagnostic and therapeutic techniques targeting Aβ and tau. These technologies aim to address gaps in our understanding by targeting biomarkers using multifunctional fluorescent organic-molecule-based theranostics. There is a leading hypothesis that Aβ and its oligomers are crucial pathogenic features in AD-afflicted brains. Metals found in Aβ plaques have been linked to AD, contributing to oxidative stress and stabilizing toxic Aβ oligomers. Drug research is addressing AD’s diverse toxicity, including protein aggregation, metal toxicity, oxidative stress, mitochondrial damage, and neuroinflammation. Drug development is adopting multifaceted approaches, focusing on the intricate interaction of AD contributors. Diverse diagnostic techniques and innovative drug development tactics are crucial for AD diagnosis and therapy advances.</p><p >This Account is focused on analyzing the interaction between fluorescent molecular probes in the context of AD theranostics. It explores their design methods, imaging techniques, and therapeutic applications to develop innovative approaches for diagnosing and treating AD, thereby contributing to the advancement of precision medicine in neurodegenerative disorders. The first section explains the pathological factors associated with AD, while the second part discusses recently identified multifunctional fluorescent compounds as therapeutic and diagnostic targets. We also delve into the multifunctional probes developed in our laboratory over the past decade for the purpose of AD theranostics. The subsequent section covers small molecule and conjugated polymer (CP) chemistry, design, and functions. Our research aims to shed light on AD development by studying the link between Aβ, metal ions, and particularly metal-Aβ interactions. We utilize multifunctional fluorescent molecular probes to target metal-Aβ species, modulate interaction, and guide aggregation into nontoxic, off-pathway aggregates. These multipotent ligands reduce oxidative stress by preventing the production of reactive intermediate species (RIS) from redox-active metal-Aβ. Ongoing research aims to enhance fluorescent compounds for early and accurate detection of AD and to prevent its associated causes. We also explore current challenges and potential methods for developing multifunctional probes for AD theranostics. This Account aims to aid readers in understanding the multifaceted nature of AD and the development of novel multifunctional molecules that target its multifaceted toxicity.</p>","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"89–103 89–103"},"PeriodicalIF":14.0,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-27DOI: 10.1021/accountsmr.4c00236
Xueqiu Zheng, Yi Zhou, Yunfan Guo
Figure 1. Schematic diagram of structure, synthesis, properties and performance of Janus TMDCs. Reproduced with permission from refs (2−5). Copyright 2021 The Authors, 2021 American Chemical Society, 2023 The Authors, 2017 American Chemical Society. Figure 2. Structures of Janus TMDCs and their heterostructures. (a) Lattice structures of monolayer 1T’ MoSSe and 2H MoSSe. (b) Schematic illustration of the topological band inversion of 1T’ MoSSe (left) and 2H MoSSe (right). Reproduced with permission from ref (4). Copyright 2023 The Authors. (c) Schematic illustration of a monolayer lateral multi-heterostructure composed with MoS<sub>2</sub>-Janus MoSSe-Janus MoSeS-MoSe<sub>2</sub>. (d) Kelvin probe force microscope image of monolayer lateral multi-heterostructure composed of MoS<sub>2</sub>–MoSSe-MoSeS-MoSe<sub>2</sub>. Reproduced with permission from ref (2). Copyright 2021 The Authors. (e) Schematic illustration of MoSSe/MoS<sub>2</sub> vertical heterostructure. (f) Optical microscopy (OM) images of Janus heterostructures with AA, AB, AAA, AAB, and ABA stacking modes. Scale bars: 4 μm. Scale bars: 1.2 μm. Reproduced with permission from ref (6). Copyright 2020 American Chemical Society. Figure 3. Synthesis of Janus TMDCs and their lateral heterostructures. (a) Contrast of activation energy barriers between RT-ALS strategy (red) and conventional substitution in high temperature (blue). (b) Raman spectra of pristine monolayer MoS<sub>2</sub>, Janus MoSSe, and converted MoSe<sub>2</sub>. (c) Spatially resolved Raman mapping for A<sub>1g</sub> mode intensity of a monolayer multi-heterostructure made with MoS<sub>2</sub>–MoSSe-MoSeS-MoSe<sub>2</sub>. Reproduced with permission from ref (2). Copyright 2021 The Authors. Figure 4. Properties and potential applications of Janus TMDCs. (a) HHG image of 1T’ MoSSe observed by CCD camera. (b) Left: schematic illustration of angle-resolved SHG setup measuring out-of-plane dipole of Janus MoSSe. Right: angle-dependent SHG intensity ratio between <i>p</i> and <i>s</i> polarization (I<sub>p</sub> and I<sub>s</sub>) in 1T’ MoSSe, 2H MoSSe, and 2H MoS<sub>2</sub>. Reproduced with permission from ref (4). Copyright 2023 The Authors. (c) Calculated volcano curve of hydrogen evolution reaction (HER) of various catalysts, including Janus WSSe. Reproduced with permission from ref (13). Copyright 2018 American Chemical Society. (d) DFT calculation of shift current susceptibility tensor element σ<sub><i>xzx</i></sub><sup>(2)</sup> and σ<sub><i>zxx</i></sub><sup>(2)</sup>. The dark (red) blue curve indicates shift current for Janus MoSeS (MoSSe) monolayer. Reproduced with permission from ref (15). Copyright 2022 American Chemical Society. <b>Xueqiu Zheng</b> received her B.S. Degree in Department of Chemistry in Zhejiang University in 2023. She is a Master degree candidate in Department of Chemistry in Zhejiang University currently. Her research focuses on the controllable synthesis of Janus TMDCs and their heterostructur
{"title":"Symmetry Manipulation of Two-Dimensional Semiconductors by Janus Structure","authors":"Xueqiu Zheng, Yi Zhou, Yunfan Guo","doi":"10.1021/accountsmr.4c00236","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00236","url":null,"abstract":"Figure 1. Schematic diagram of structure, synthesis, properties and performance of Janus TMDCs. Reproduced with permission from refs (2−5). Copyright 2021 The Authors, 2021 American Chemical Society, 2023 The Authors, 2017 American Chemical Society. Figure 2. Structures of Janus TMDCs and their heterostructures. (a) Lattice structures of monolayer 1T’ MoSSe and 2H MoSSe. (b) Schematic illustration of the topological band inversion of 1T’ MoSSe (left) and 2H MoSSe (right). Reproduced with permission from ref (4). Copyright 2023 The Authors. (c) Schematic illustration of a monolayer lateral multi-heterostructure composed with MoS<sub>2</sub>-Janus MoSSe-Janus MoSeS-MoSe<sub>2</sub>. (d) Kelvin probe force microscope image of monolayer lateral multi-heterostructure composed of MoS<sub>2</sub>–MoSSe-MoSeS-MoSe<sub>2</sub>. Reproduced with permission from ref (2). Copyright 2021 The Authors. (e) Schematic illustration of MoSSe/MoS<sub>2</sub> vertical heterostructure. (f) Optical microscopy (OM) images of Janus heterostructures with AA, AB, AAA, AAB, and ABA stacking modes. Scale bars: 4 μm. Scale bars: 1.2 μm. Reproduced with permission from ref (6). Copyright 2020 American Chemical Society. Figure 3. Synthesis of Janus TMDCs and their lateral heterostructures. (a) Contrast of activation energy barriers between RT-ALS strategy (red) and conventional substitution in high temperature (blue). (b) Raman spectra of pristine monolayer MoS<sub>2</sub>, Janus MoSSe, and converted MoSe<sub>2</sub>. (c) Spatially resolved Raman mapping for A<sub>1g</sub> mode intensity of a monolayer multi-heterostructure made with MoS<sub>2</sub>–MoSSe-MoSeS-MoSe<sub>2</sub>. Reproduced with permission from ref (2). Copyright 2021 The Authors. Figure 4. Properties and potential applications of Janus TMDCs. (a) HHG image of 1T’ MoSSe observed by CCD camera. (b) Left: schematic illustration of angle-resolved SHG setup measuring out-of-plane dipole of Janus MoSSe. Right: angle-dependent SHG intensity ratio between <i>p</i> and <i>s</i> polarization (I<sub>p</sub> and I<sub>s</sub>) in 1T’ MoSSe, 2H MoSSe, and 2H MoS<sub>2</sub>. Reproduced with permission from ref (4). Copyright 2023 The Authors. (c) Calculated volcano curve of hydrogen evolution reaction (HER) of various catalysts, including Janus WSSe. Reproduced with permission from ref (13). Copyright 2018 American Chemical Society. (d) DFT calculation of shift current susceptibility tensor element σ<sub><i>xzx</i></sub><sup>(2)</sup> and σ<sub><i>zxx</i></sub><sup>(2)</sup>. The dark (red) blue curve indicates shift current for Janus MoSeS (MoSSe) monolayer. Reproduced with permission from ref (15). Copyright 2022 American Chemical Society. <b>Xueqiu Zheng</b> received her B.S. Degree in Department of Chemistry in Zhejiang University in 2023. She is a Master degree candidate in Department of Chemistry in Zhejiang University currently. Her research focuses on the controllable synthesis of Janus TMDCs and their heterostructur","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"8 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-25DOI: 10.1021/accountsmr.4c0027010.1021/accountsmr.4c00270
Zejun Li*, Zhi Zhang and Jiong Lu*,
Layered materials bound by weak van der Waals (vdW) interactions offer a rich platform for exploring intriguing fundamental science in the two-dimensional (2D) limit and advancing technological innovations. Transition from bulk to 2D geometry results in profound alterations in electronic structures and crystallographic symmetries, giving rise to a plethora of novel physical effects and functionalities. Due to their atomic-scale thinness, 2D materials with a high specific surface area enable post-processing chemical modification of their basal planes to further regulate their intrinsic physical properties. Moreover, the interfacial effects induced by surface modifications can modulate properties without altering the original lattice, facilitating the emergence of novel electronic phases and exotic quantum phenomena. Consequently, extensive research is delving into surface modifications of 2D materials, paving the way to further expand the research fields of 2D materials.
Notably, layered materials also feature a subnanometer-sized vdW gap between adjacent layers, enabling the incorporation of guest species and evoking a new type of surface modification called vdW gap engineering, without the need for pre-exfoliation into 2D structures. Unlike postprocessing surface modifications, direct vdW gap engineering protects guest species within the layers from environmental degradation, fostering stable guest–host structures with enhanced environmental stability. Additionally, the confined vdW gap engineering prompts electronic interactions between guest species and host materials, resulting in new physics and functionalities that cannot be achieved through traditional surface modifications. Furthermore, vdW gap engineering also enables the creation of a new class of hybrid vdW superlattices with highly adaptable structural motifs, harnessing the synergistic effects of guest species and host materials.
This Account highlights recent advancements in vdW gap engineering of 2D materials from our group and other researchers. We focus on three key aspects of vdW gap engineering including the design and synthesis of low-dimensional materials, modulation of phase transitions, and fabrication of hybrid superlattices. Specifically, we provide a comprehensive overview of current vdW gap engineering methodologies such as intercalation, interlayer growth, and direct chemical growth. Various forms of host–guest interactions and their underlying mechanisms are introduced along with the exciting physical properties and functional applications. Finally, we outline the present challenges and future prospects for vdW gap engineering of 2D materials. We emphasize the crucial role of in situ characterization techniques and machine learning in advancing vdW gap engineering studies as well as potential new research directions that could open new frontiers in creating artificial vdW materials for technological innovations.
{"title":"van der Waals Gap Engineering of Emergent Two-Dimensional Materials","authors":"Zejun Li*, Zhi Zhang and Jiong Lu*, ","doi":"10.1021/accountsmr.4c0027010.1021/accountsmr.4c00270","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00270https://doi.org/10.1021/accountsmr.4c00270","url":null,"abstract":"<p >Layered materials bound by weak van der Waals (vdW) interactions offer a rich platform for exploring intriguing fundamental science in the two-dimensional (2D) limit and advancing technological innovations. Transition from bulk to 2D geometry results in profound alterations in electronic structures and crystallographic symmetries, giving rise to a plethora of novel physical effects and functionalities. Due to their atomic-scale thinness, 2D materials with a high specific surface area enable post-processing chemical modification of their basal planes to further regulate their intrinsic physical properties. Moreover, the interfacial effects induced by surface modifications can modulate properties without altering the original lattice, facilitating the emergence of novel electronic phases and exotic quantum phenomena. Consequently, extensive research is delving into surface modifications of 2D materials, paving the way to further expand the research fields of 2D materials.</p><p >Notably, layered materials also feature a subnanometer-sized vdW gap between adjacent layers, enabling the incorporation of guest species and evoking a new type of surface modification called vdW gap engineering, without the need for pre-exfoliation into 2D structures. Unlike postprocessing surface modifications, direct vdW gap engineering protects guest species within the layers from environmental degradation, fostering stable guest–host structures with enhanced environmental stability. Additionally, the confined vdW gap engineering prompts electronic interactions between guest species and host materials, resulting in new physics and functionalities that cannot be achieved through traditional surface modifications. Furthermore, vdW gap engineering also enables the creation of a new class of hybrid vdW superlattices with highly adaptable structural motifs, harnessing the synergistic effects of guest species and host materials.</p><p >This Account highlights recent advancements in vdW gap engineering of 2D materials from our group and other researchers. We focus on three key aspects of vdW gap engineering including the design and synthesis of low-dimensional materials, modulation of phase transitions, and fabrication of hybrid superlattices. Specifically, we provide a comprehensive overview of current vdW gap engineering methodologies such as intercalation, interlayer growth, and direct chemical growth. Various forms of host–guest interactions and their underlying mechanisms are introduced along with the exciting physical properties and functional applications. Finally, we outline the present challenges and future prospects for vdW gap engineering of 2D materials. We emphasize the crucial role of in situ characterization techniques and machine learning in advancing vdW gap engineering studies as well as potential new research directions that could open new frontiers in creating artificial vdW materials for technological innovations.</p>","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"52–63 52–63"},"PeriodicalIF":14.0,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-25DOI: 10.1021/accountsmr.4c00270
Zejun Li, Zhi Zhang, Jiong Lu
Layered materials bound by weak van der Waals (vdW) interactions offer a rich platform for exploring intriguing fundamental science in the two-dimensional (2D) limit and advancing technological innovations. Transition from bulk to 2D geometry results in profound alterations in electronic structures and crystallographic symmetries, giving rise to a plethora of novel physical effects and functionalities. Due to their atomic-scale thinness, 2D materials with a high specific surface area enable post-processing chemical modification of their basal planes to further regulate their intrinsic physical properties. Moreover, the interfacial effects induced by surface modifications can modulate properties without altering the original lattice, facilitating the emergence of novel electronic phases and exotic quantum phenomena. Consequently, extensive research is delving into surface modifications of 2D materials, paving the way to further expand the research fields of 2D materials.
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Pub Date : 2024-11-25DOI: 10.1021/accountsmr.4c00268
Soyun Joo, Uichang Jeong, Chaewon Gong, Seungbum Hong
Microscopy has long expanded humanity’s understanding of the microscopic world, transcending limitations of the naked eye. The atomic force microscope (AFM), in particular, marks a major advancement in this field, enabling nanoscale investigations of materials through direct physical probing of their surface. Unlike traditional microscopes that use light or electrons, AFM’s unique methodology allows for both imaging on the atomic scale and precise manipulation of a material’s mechanical, electrical, and chemical properties. A key advantage also lies in its capacity for multimodal analysis, where multiple properties can be simultaneously measured to provide comprehensive insights into material behavior.
{"title":"Bridging Mechanical and Electrical Analyses in AFM: Advances, Techniques, and Applications","authors":"Soyun Joo, Uichang Jeong, Chaewon Gong, Seungbum Hong","doi":"10.1021/accountsmr.4c00268","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00268","url":null,"abstract":"Microscopy has long expanded humanity’s understanding of the microscopic world, transcending limitations of the naked eye. The atomic force microscope (AFM), in particular, marks a major advancement in this field, enabling nanoscale investigations of materials through direct physical probing of their surface. Unlike traditional microscopes that use light or electrons, AFM’s unique methodology allows for both imaging on the atomic scale and precise manipulation of a material’s mechanical, electrical, and chemical properties. A key advantage also lies in its capacity for multimodal analysis, where multiple properties can be simultaneously measured to provide comprehensive insights into material behavior.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-25DOI: 10.1021/accountsmr.4c0026810.1021/accountsmr.4c00268
Soyun Joo, Uichang Jeong, Chaewon Gong and Seungbum Hong*,
<p >Microscopy has long expanded humanity’s understanding of the microscopic world, transcending limitations of the naked eye. The atomic force microscope (AFM), in particular, marks a major advancement in this field, enabling nanoscale investigations of materials through direct physical probing of their surface. Unlike traditional microscopes that use light or electrons, AFM’s unique methodology allows for both imaging on the atomic scale and precise manipulation of a material’s mechanical, electrical, and chemical properties. A key advantage also lies in its capacity for multimodal analysis, where multiple properties can be simultaneously measured to provide comprehensive insights into material behavior.</p><p >In the current landscape of miniaturizing electronics and optimizing energy materials, the interplay between mechanical and electrical properties has gained particular importance. The precise integration of these properties is vital for advancing nanotechnology, and AFM allows the elucidation of these effects on the nanoscale. This is especially relevant for multifunctional materials that respond to both mechanical and electrical stimuli, and as surface properties exert a pronounced influence on material behavior at reduced scales, the capabilities of the AFM have informed the design and characterization of many smart, dielectric, and energy materials over the past decades.</p><p >In this article, we present our group’s recent works on the integration of mechanical and electrical analyses using AFM-based characterization techniques. We begin by tracing the progression from early piezoresponse force microscopy (PFM) studies, which investigated domain growth and switching characteristics in ferroelectric films, as well as the surface charge dynamics of polar domains. Based on these foundations, we introduce a surface scraping-based method of imaging─charge gradient microscopy─for rapid characterization of these domains and showcase a novel three-dimensional lithography technique that exploits asymmetric wear rates of up and down domains. This method underscores the strongly coupled interactions between the mechanical and electrical properties of dielectrics, with the potential for scaling to device-relevant dimensions.</p><p >The discussion then transitions from piezoelectric electromechanical dynamics to ionic electrochemical phenomena, where electrical stimuli similarly induce mechanical surface deformations detectable by an AFM tip. We explore a multimodal approach in electrochemical strain microscopy (ESM) to investigate functional components in composite materials, demonstrating how friction mapping can be employed to identify specific material components. Additionally, we introduce mechanically and electrically modulated spectroscopy techniques, including nanoindentation, PFM hysteresis, and current–voltage spectroscopy, emphasizing the potential of spectroscopic methods to be customized for eliciting targeted material response. Fina
{"title":"Bridging Mechanical and Electrical Analyses in AFM: Advances, Techniques, and Applications","authors":"Soyun Joo, Uichang Jeong, Chaewon Gong and Seungbum Hong*, ","doi":"10.1021/accountsmr.4c0026810.1021/accountsmr.4c00268","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00268https://doi.org/10.1021/accountsmr.4c00268","url":null,"abstract":"<p >Microscopy has long expanded humanity’s understanding of the microscopic world, transcending limitations of the naked eye. The atomic force microscope (AFM), in particular, marks a major advancement in this field, enabling nanoscale investigations of materials through direct physical probing of their surface. Unlike traditional microscopes that use light or electrons, AFM’s unique methodology allows for both imaging on the atomic scale and precise manipulation of a material’s mechanical, electrical, and chemical properties. A key advantage also lies in its capacity for multimodal analysis, where multiple properties can be simultaneously measured to provide comprehensive insights into material behavior.</p><p >In the current landscape of miniaturizing electronics and optimizing energy materials, the interplay between mechanical and electrical properties has gained particular importance. The precise integration of these properties is vital for advancing nanotechnology, and AFM allows the elucidation of these effects on the nanoscale. This is especially relevant for multifunctional materials that respond to both mechanical and electrical stimuli, and as surface properties exert a pronounced influence on material behavior at reduced scales, the capabilities of the AFM have informed the design and characterization of many smart, dielectric, and energy materials over the past decades.</p><p >In this article, we present our group’s recent works on the integration of mechanical and electrical analyses using AFM-based characterization techniques. We begin by tracing the progression from early piezoresponse force microscopy (PFM) studies, which investigated domain growth and switching characteristics in ferroelectric films, as well as the surface charge dynamics of polar domains. Based on these foundations, we introduce a surface scraping-based method of imaging─charge gradient microscopy─for rapid characterization of these domains and showcase a novel three-dimensional lithography technique that exploits asymmetric wear rates of up and down domains. This method underscores the strongly coupled interactions between the mechanical and electrical properties of dielectrics, with the potential for scaling to device-relevant dimensions.</p><p >The discussion then transitions from piezoelectric electromechanical dynamics to ionic electrochemical phenomena, where electrical stimuli similarly induce mechanical surface deformations detectable by an AFM tip. We explore a multimodal approach in electrochemical strain microscopy (ESM) to investigate functional components in composite materials, demonstrating how friction mapping can be employed to identify specific material components. Additionally, we introduce mechanically and electrically modulated spectroscopy techniques, including nanoindentation, PFM hysteresis, and current–voltage spectroscopy, emphasizing the potential of spectroscopic methods to be customized for eliciting targeted material response. Fina","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"17–27 17–27"},"PeriodicalIF":14.0,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1021/accountsmr.4c00355
Zaki N. Zahran, Yuta Tsubonouchi, Debraj Chandra, Masayuki Yagi
Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies. Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction (toward water splitting systems). Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology. Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting, semiconducting, and insulating and diverse catalytic properties at their surface depending on the exposing facet, as well as physical and chemical robustness under ambient conditions. We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors. We have developed an easy preparation technique of mono- and multimetallic oxide films, termed the “mixed metal-imidazole casting (MiMIC) method”, by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand, followed by calcination. The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions, because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films. In this Account, we expound synthesis and characterization of a variety of mono- and multimetallic oxide films using the MiMIC method and its application to electro- and photoelectrocatalysis for water splitting and oxygen reduction, which are important key reactions in future sustainable technology. The adherability of these films onto the electrode surface is prominent although their morphology, crystallinity, and nanostructures depend on the metal oxide materials, which is one of the important factors to induce high performance of the metal oxide films for electro- and photoelectrocatalysis. Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice, and a structure-directing agent for the anisotropic crystallization, as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate. These findings surely expand material development to a great extent, by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.
将可再生能源转化为有用的化学品和燃料的电化学和光电化学过程对未来的可持续技术至关重要。可再生能源转换需要多电子氧化还原反应催化剂,如水氧化和还原(用于水分离系统)。开发高效的多电子氧化还原反应催化剂是当前科学和技术领域面临的巨大挑战。金属氧化物具有导电、半导电和绝缘等多种电子特性,其表面的催化特性因暴露面而异,而且在环境条件下具有物理和化学稳定性,因此被广泛应用于各种光子和电子设备。我们希望在简单铸造和煅烧的基础上,开发出一种可用于大规模生产金属氧化物薄膜的简便技术,采用一种通过前驱体中金属中心的配体来控制金属氧化物薄膜的形成和生长的策略。我们开发了一种简便的单金属和多金属氧化物薄膜制备技术,称为 "混合金属-咪唑浇铸(MiMIC)法",通过在甲醇/咪唑衍生物作为配体的混合溶剂中浇铸含有组分金属盐的前驱体溶液或悬浮液,然后进行煅烧,在各种电极基底上紧密生成金属氧化物薄膜。MiMIC 方法的通用性鼓励我们寻找新的金属氧化物薄膜作为多电子氧化还原反应的高效催化剂,因为在集流电极上形成的薄膜的刚性附着性是评估金属氧化物薄膜催化性能的必要条件。在本报告中,我们阐述了利用 MiMIC 方法合成和表征各种单金属和多金属氧化物薄膜,并将其应用于电催化和光电催化的水分离和氧还原反应,这些反应是未来可持续发展技术的重要关键反应。虽然这些薄膜的形态、结晶度和纳米结构取决于金属氧化物材料,但它们在电极表面的附着性非常突出,这是促使金属氧化物薄膜在电催化和光催化中发挥高性能的重要因素之一。研究发现,咪唑衍生物可作为金属氧化物晶格中 N 掺杂的氮源、各向异性结晶的结构引导剂,以及构成纳米颗粒的粘合剂,从而使薄膜在基底上具有刚性附着性。这些发现不仅改变了金属成分,还通过掺杂代表性元素和控制金属氧化物薄膜的晶面,实现了能带工程,从而在很大程度上拓展了材料开发领域。
{"title":"Material Hunting of Advanced Metal Oxide Films for Electro- and Photoelectrocatalysis Using a Mixed Metal-Imidazole Casting (MiMIC) Method","authors":"Zaki N. Zahran, Yuta Tsubonouchi, Debraj Chandra, Masayuki Yagi","doi":"10.1021/accountsmr.4c00355","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00355","url":null,"abstract":"Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies. Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction (toward water splitting systems). Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology. Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting, semiconducting, and insulating and diverse catalytic properties at their surface depending on the exposing facet, as well as physical and chemical robustness under ambient conditions. We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors. We have developed an easy preparation technique of mono- and multimetallic oxide films, termed the “mixed metal-imidazole casting (MiMIC) method”, by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand, followed by calcination. The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions, because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films. In this Account, we expound synthesis and characterization of a variety of mono- and multimetallic oxide films using the MiMIC method and its application to electro- and photoelectrocatalysis for water splitting and oxygen reduction, which are important key reactions in future sustainable technology. The adherability of these films onto the electrode surface is prominent although their morphology, crystallinity, and nanostructures depend on the metal oxide materials, which is one of the important factors to induce high performance of the metal oxide films for electro- and photoelectrocatalysis. Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice, and a structure-directing agent for the anisotropic crystallization, as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate. These findings surely expand material development to a great extent, by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Topotactic transformations between related crystal structures, involving etching, replacement, and intercalation, are increasingly recognized in the design and tuning of material properties. These transformations reveal the fundamental principles of material structural changes, paving the way for creating novel materials with unique properties. Layered materials readily undergo structural or compositional changes due to their stacked atomic layers and bonding features. MAX phases, as nonvan der Waals (non-vdW) layered compounds, exhibit distinctive elemental compositions and bonding characters that make them suitable for topotactic transformations. A notable example is the typical transformation from MAX phases to MXenes, a new addition to two-dimensional (2D) materials, through A-site etching within MAX phases. In turn, the 2D structure of MXenes further promoted versatile topotactic transformations utilizing the interlayer space and tunable surfaces. This Account comprehensively reviews the topotactic transformation in MXenes and MAX phases, covering aspects from chemical etching to versatile chemical editing. We commence with an analysis of MAX phase degradation, examining the corrosion resistance of MAX phases in liquid metals and molten salts, which is crucial for their application as nuclear materials. This leads us to introduce the novel concept of precise A-site etching in MAX phases, which has paved the way for the groundbreaking discovery of 2D MXene. Given the important effect of etching methods on MXenes, we then delve into the various etching methods employed in preparing MXene and explore the detailed processes and mechanisms behind each method. Additionally, we highlight the recent advancements made by our research group regarding the Lewis acidic molten salt (LAMS) method. This method utilizes LAMSs as etching agents to selectively etch the A-site atomic layer, creating opportunities for the subsequent intercalation of atoms or anions to achieve isomorphous replacement of A-site atoms and surface modification with novel terminations. The strong oxidation ability of LAMSs also offers versatility in selectively etching A-site atomic species, particularly confined to the Al element. The LAMS method shows potential for synthesizing and controlling the structure of MXene and MAX phases, albeit with limitations. Its success depends on the properties of LAMSs, which must facilitate both etching and intercalation. However, some LAMSs are unsuitable due to their low redox potential, low boiling points, and instability at high temperatures. Therefore, we propose a versatile chemical scissor-mediated structural editing strategy. This strategy decouples etching from intercalation, using Lewis acidic cations or reduced metal atoms as chemical scissors to create space between MX sublayers, allowing atoms or anions to diffuse and enable topotactic transitions. This approach has facilitated the intercalation of various A-site atoms, expanded MXen
在设计和调整材料特性的过程中,人们越来越认识到相关晶体结构之间涉及蚀刻、置换和插层的拓扑结构转化。这些转变揭示了材料结构变化的基本原理,为创造具有独特性能的新型材料铺平了道路。层状材料由于其原子层的堆叠和键合特征,很容易发生结构或成分的变化。MAX 相作为非范德华(non-vdW)层状化合物,表现出独特的元素组成和键合特征,使其适合拓扑转化。一个显著的例子是,通过 MAX 相内的 A 位蚀刻,从 MAX 相转化为 MXenes(二维(2D)材料的新成员)的典型转化。反过来,MXenes 的二维结构进一步促进了利用层间空间和可调表面的多功能拓扑转化。本开户绑定手机领体验金全面回顾了 MXenes 和 MAX 相中的拓扑转变,涵盖了从化学蚀刻到多功能化学编辑等各个方面。我们首先分析了 MAX 相的降解,研究了 MAX 相在液态金属和熔盐中的耐腐蚀性,这对于它们作为核材料的应用至关重要。由此,我们引入了在 MAX 相中精确蚀刻 A 位的新概念,这为二维 MXene 的突破性发现铺平了道路。鉴于蚀刻方法对 MXene 的重要影响,我们将深入探讨制备 MXene 所采用的各种蚀刻方法,并探索每种方法背后的详细过程和机制。此外,我们还重点介绍了我们研究小组最近在路易斯酸熔盐(LAMS)方法方面取得的进展。这种方法利用路易斯酸性熔盐作为蚀刻剂,选择性地蚀刻 A 位原子层,为随后的原子或阴离子插层创造机会,从而实现 A 位原子的同构置换,并通过新型端点对表面进行修饰。LAMS 的强氧化能力还为选择性蚀刻 A 位原子层提供了多功能性,特别是局限于铝元素。LAMS 方法显示出合成和控制 MXene 和 MAX 相结构的潜力,尽管有其局限性。它的成功取决于 LAMS 的特性,LAMS 必须同时促进蚀刻和插层。然而,一些 LAMS 因其氧化还原电位低、沸点低以及在高温下不稳定而不适用。因此,我们提出了一种以化学剪刀为媒介的多功能结构编辑策略。这种策略将蚀刻与插层分离开来,利用路易斯酸性阳离子或还原金属原子作为化学剪刀,在 MX 亚层之间创造空间,允许原子或阴离子扩散,实现拓扑转变。这种方法促进了各种 A 位原子的插层,扩大了 MXene 表面终止的选择范围,甚至通过将终止去除与原子插层相结合,使二维 MXene 转变为三维 MAX 相。最后,我们对这些材料中拓扑结构转化的未来发展提出了见解,旨在激励这一领域取得进一步的创新进展。深入了解拓扑结构转化过程有望拓宽层状材料的应用领域,为相关领域的进步奠定坚实的基础。
{"title":"Layered Transition Metal Carbides/Nitrides: From Chemical Etching to Chemical Editing","authors":"Haoming Ding, Youbing Li, Mian Li, Zhifang Chai, Qing Huang","doi":"10.1021/accountsmr.4c00250","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00250","url":null,"abstract":"Topotactic transformations between related crystal structures, involving etching, replacement, and intercalation, are increasingly recognized in the design and tuning of material properties. These transformations reveal the fundamental principles of material structural changes, paving the way for creating novel materials with unique properties. Layered materials readily undergo structural or compositional changes due to their stacked atomic layers and bonding features. MAX phases, as nonvan der Waals (non-vdW) layered compounds, exhibit distinctive elemental compositions and bonding characters that make them suitable for topotactic transformations. A notable example is the typical transformation from MAX phases to MXenes, a new addition to two-dimensional (2D) materials, through A-site etching within MAX phases. In turn, the 2D structure of MXenes further promoted versatile topotactic transformations utilizing the interlayer space and tunable surfaces. This Account comprehensively reviews the topotactic transformation in MXenes and MAX phases, covering aspects from chemical etching to versatile chemical editing. We commence with an analysis of MAX phase degradation, examining the corrosion resistance of MAX phases in liquid metals and molten salts, which is crucial for their application as nuclear materials. This leads us to introduce the novel concept of precise A-site etching in MAX phases, which has paved the way for the groundbreaking discovery of 2D MXene. Given the important effect of etching methods on MXenes, we then delve into the various etching methods employed in preparing MXene and explore the detailed processes and mechanisms behind each method. Additionally, we highlight the recent advancements made by our research group regarding the Lewis acidic molten salt (LAMS) method. This method utilizes LAMSs as etching agents to selectively etch the A-site atomic layer, creating opportunities for the subsequent intercalation of atoms or anions to achieve isomorphous replacement of A-site atoms and surface modification with novel terminations. The strong oxidation ability of LAMSs also offers versatility in selectively etching A-site atomic species, particularly confined to the Al element. The LAMS method shows potential for synthesizing and controlling the structure of MXene and MAX phases, albeit with limitations. Its success depends on the properties of LAMSs, which must facilitate both etching and intercalation. However, some LAMSs are unsuitable due to their low redox potential, low boiling points, and instability at high temperatures. Therefore, we propose a versatile chemical scissor-mediated structural editing strategy. This strategy decouples etching from intercalation, using Lewis acidic cations or reduced metal atoms as chemical scissors to create space between MX sublayers, allowing atoms or anions to diffuse and enable topotactic transitions. This approach has facilitated the intercalation of various A-site atoms, expanded MXen","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p >Topotactic transformations between related crystal structures, involving etching, replacement, and intercalation, are increasingly recognized in the design and tuning of material properties. These transformations reveal the fundamental principles of material structural changes, paving the way for creating novel materials with unique properties. Layered materials readily undergo structural or compositional changes due to their stacked atomic layers and bonding features. MAX phases, as nonvan der Waals (non-vdW) layered compounds, exhibit distinctive elemental compositions and bonding characters that make them suitable for topotactic transformations. A notable example is the typical transformation from MAX phases to MXenes, a new addition to two-dimensional (2D) materials, through A-site etching within MAX phases. In turn, the 2D structure of MXenes further promoted versatile topotactic transformations utilizing the interlayer space and tunable surfaces. This Account comprehensively reviews the topotactic transformation in MXenes and MAX phases, covering aspects from chemical etching to versatile chemical editing. We commence with an analysis of MAX phase degradation, examining the corrosion resistance of MAX phases in liquid metals and molten salts, which is crucial for their application as nuclear materials. This leads us to introduce the novel concept of precise A-site etching in MAX phases, which has paved the way for the groundbreaking discovery of 2D MXene. Given the important effect of etching methods on MXenes, we then delve into the various etching methods employed in preparing MXene and explore the detailed processes and mechanisms behind each method. Additionally, we highlight the recent advancements made by our research group regarding the Lewis acidic molten salt (LAMS) method. This method utilizes LAMSs as etching agents to selectively etch the A-site atomic layer, creating opportunities for the subsequent intercalation of atoms or anions to achieve isomorphous replacement of A-site atoms and surface modification with novel terminations. The strong oxidation ability of LAMSs also offers versatility in selectively etching A-site atomic species, particularly confined to the Al element. The LAMS method shows potential for synthesizing and controlling the structure of MXene and MAX phases, albeit with limitations. Its success depends on the properties of LAMSs, which must facilitate both etching and intercalation. However, some LAMSs are unsuitable due to their low redox potential, low boiling points, and instability at high temperatures. Therefore, we propose a versatile chemical scissor-mediated structural editing strategy. This strategy decouples etching from intercalation, using Lewis acidic cations or reduced metal atoms as chemical scissors to create space between MX sublayers, allowing atoms or anions to diffuse and enable topotactic transitions. This approach has facilitated the intercalation of various A-site atoms, expanded
{"title":"Layered Transition Metal Carbides/Nitrides: From Chemical Etching to Chemical Editing","authors":"Haoming Ding, Youbing Li, Mian Li, Zhifang Chai and Qing Huang*, ","doi":"10.1021/accountsmr.4c0025010.1021/accountsmr.4c00250","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00250https://doi.org/10.1021/accountsmr.4c00250","url":null,"abstract":"<p >Topotactic transformations between related crystal structures, involving etching, replacement, and intercalation, are increasingly recognized in the design and tuning of material properties. These transformations reveal the fundamental principles of material structural changes, paving the way for creating novel materials with unique properties. Layered materials readily undergo structural or compositional changes due to their stacked atomic layers and bonding features. MAX phases, as nonvan der Waals (non-vdW) layered compounds, exhibit distinctive elemental compositions and bonding characters that make them suitable for topotactic transformations. A notable example is the typical transformation from MAX phases to MXenes, a new addition to two-dimensional (2D) materials, through A-site etching within MAX phases. In turn, the 2D structure of MXenes further promoted versatile topotactic transformations utilizing the interlayer space and tunable surfaces. This Account comprehensively reviews the topotactic transformation in MXenes and MAX phases, covering aspects from chemical etching to versatile chemical editing. We commence with an analysis of MAX phase degradation, examining the corrosion resistance of MAX phases in liquid metals and molten salts, which is crucial for their application as nuclear materials. This leads us to introduce the novel concept of precise A-site etching in MAX phases, which has paved the way for the groundbreaking discovery of 2D MXene. Given the important effect of etching methods on MXenes, we then delve into the various etching methods employed in preparing MXene and explore the detailed processes and mechanisms behind each method. Additionally, we highlight the recent advancements made by our research group regarding the Lewis acidic molten salt (LAMS) method. This method utilizes LAMSs as etching agents to selectively etch the A-site atomic layer, creating opportunities for the subsequent intercalation of atoms or anions to achieve isomorphous replacement of A-site atoms and surface modification with novel terminations. The strong oxidation ability of LAMSs also offers versatility in selectively etching A-site atomic species, particularly confined to the Al element. The LAMS method shows potential for synthesizing and controlling the structure of MXene and MAX phases, albeit with limitations. Its success depends on the properties of LAMSs, which must facilitate both etching and intercalation. However, some LAMSs are unsuitable due to their low redox potential, low boiling points, and instability at high temperatures. Therefore, we propose a versatile chemical scissor-mediated structural editing strategy. This strategy decouples etching from intercalation, using Lewis acidic cations or reduced metal atoms as chemical scissors to create space between MX sublayers, allowing atoms or anions to diffuse and enable topotactic transitions. This approach has facilitated the intercalation of various A-site atoms, expanded ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"28–39 28–39"},"PeriodicalIF":14.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1021/accountsmr.4c0014810.1021/accountsmr.4c00148
Xiaofeng Huang, Binghui Wu* and Nanfeng Zheng*,
<p >Over the past decade, solution-processed organic–inorganic hybrid perovskite solar cells (PSCs) have emerged as a viable alternative to traditional crystalline silicon photovoltaics, with power conversion efficiency (PCE) increasing notably from 3.8% to over 26%. This remarkable advancement is attributed to the unique band structures and exceptional defect tolerance of the hybrid perovskites. The bandgaps in perovskites derive from their antibonding orbitals at both the valence band maximum and conduction band minimum. Consequently, bond breaking creates states away from the bandgap, resulting in either shallow defects or states within the valence band. Despite defect densities up to 10<sup>6</sup> times higher than single-crystal silicon, polycrystalline perovskite films (<1 μm thick) can still achieve comparable device performance due to their high defect tolerance. Superior photovoltaic performance in perovskite films depends on an efficient wet-chemical process, offering a notable advantage over silicon-based photovoltaic technology. Evidently, solvent characteristics and their potential interaction with perovskites significantly impact crystal growth from precursor inks, subsequent polycrystalline film quality, and the ultimate performance of devices. Understanding solvent properties in relation to film formation processes is essential for informing solvent selection in the emerging perovskite photovoltaics and its future commercialization. In this Account, we present a thorough analysis of solution-processed perovskite films, encompassing the crystallization process and phase transition of perovskite-related solvated complexes, and structure passivation of perovskite phase. We systematically categorize the prevalent solvents utilized in film preparation and outline a solvent roadmap for producing high-quality perovskite films from a chemical perspective, considering their interaction with the perovskite structure. We also address often-overlooked factors in solvent selection in current research. First, middle-polarity dispersion solvents fundamentally govern nucleation and growth kinetics of perovskite solvated films in the solution phase, thereby significantly shaping film morphology. However, control over the solvation interaction between dispersion solvent and perovskite structure for morphology regulation remains insufficient. Second, high-polarity binding solvents interact with the perovskite structure via solvent-involved intermediates, optimizing crystallization kinetics in the solution phase (sol–gel state) and controlling phase-transition kinetics of the intermediate phase. This interaction influences the crystal and structural properties of the resultant perovskite phase though managing the intermediate phase remains challenging. Third, low-polarity modification solvents, combined with functional passivation molecules, are employed to modulate interface energetics of perovskite films by enabling both chemical defect passiva
{"title":"Optimizing Solvent Chemistry for High-Quality Halide Perovskite Films","authors":"Xiaofeng Huang, Binghui Wu* and Nanfeng Zheng*, ","doi":"10.1021/accountsmr.4c0014810.1021/accountsmr.4c00148","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00148https://doi.org/10.1021/accountsmr.4c00148","url":null,"abstract":"<p >Over the past decade, solution-processed organic–inorganic hybrid perovskite solar cells (PSCs) have emerged as a viable alternative to traditional crystalline silicon photovoltaics, with power conversion efficiency (PCE) increasing notably from 3.8% to over 26%. This remarkable advancement is attributed to the unique band structures and exceptional defect tolerance of the hybrid perovskites. The bandgaps in perovskites derive from their antibonding orbitals at both the valence band maximum and conduction band minimum. Consequently, bond breaking creates states away from the bandgap, resulting in either shallow defects or states within the valence band. Despite defect densities up to 10<sup>6</sup> times higher than single-crystal silicon, polycrystalline perovskite films (<1 μm thick) can still achieve comparable device performance due to their high defect tolerance. Superior photovoltaic performance in perovskite films depends on an efficient wet-chemical process, offering a notable advantage over silicon-based photovoltaic technology. Evidently, solvent characteristics and their potential interaction with perovskites significantly impact crystal growth from precursor inks, subsequent polycrystalline film quality, and the ultimate performance of devices. Understanding solvent properties in relation to film formation processes is essential for informing solvent selection in the emerging perovskite photovoltaics and its future commercialization. In this Account, we present a thorough analysis of solution-processed perovskite films, encompassing the crystallization process and phase transition of perovskite-related solvated complexes, and structure passivation of perovskite phase. We systematically categorize the prevalent solvents utilized in film preparation and outline a solvent roadmap for producing high-quality perovskite films from a chemical perspective, considering their interaction with the perovskite structure. We also address often-overlooked factors in solvent selection in current research. First, middle-polarity dispersion solvents fundamentally govern nucleation and growth kinetics of perovskite solvated films in the solution phase, thereby significantly shaping film morphology. However, control over the solvation interaction between dispersion solvent and perovskite structure for morphology regulation remains insufficient. Second, high-polarity binding solvents interact with the perovskite structure via solvent-involved intermediates, optimizing crystallization kinetics in the solution phase (sol–gel state) and controlling phase-transition kinetics of the intermediate phase. This interaction influences the crystal and structural properties of the resultant perovskite phase though managing the intermediate phase remains challenging. Third, low-polarity modification solvents, combined with functional passivation molecules, are employed to modulate interface energetics of perovskite films by enabling both chemical defect passiva","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"40–51 40–51"},"PeriodicalIF":14.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}