Pub Date : 2024-12-26DOI: 10.1021/accountsmr.4c00310
Zhongbin Wang, Jiaqing He
Figure 1. Illustrations of the mechanisms of spin-enhanced charge-based thermopower. (a) Spin entropy: a spin entropy flux is created by differences in spin–orbital degeneracies (<i>g</i>), flowing from high-degeneracy to low-degeneracy states, typically in transition metals (M), contributing to the total thermopower. Additionally, spin entropy arises from disordered spin orientations caused by the breakdown of long-range order at high temperatures, referred to as spin thermodynamic entropy. (b) Spin fluctuation: thermal fluctuations of the local spin density of itinerant electrons are most significant near <i>T</i><sub>C</sub>. These fluctuations are suppressed as the net magnetic moment stabilizes under a strong magnetic field. Reproduced with permission from ref (3). Copyright 2019 The Authors. (c) Magnon drag: magnons propagate in a magnetic material from the hot to the cold end, coupling with both electrons and phonons, contributing to thermopower through momentum transfer. Reproduced with permission from ref (4). Copyright 2021 The Authors. Figure 2. (a) Schematic illustration of spin entropy contributed by the localized electrons on Co ions transfer entropy via hopping transport due to the different degeneracy. Reproduced with permission from ref (6). Copyright 2020 The Authors. (b) The relative change in thermopower of Ca<sub>3</sub>Co<sub>4</sub>O<sub>9+δ</sub> single crystal versus magnetic field for two directions (<i>B</i> along <i>c</i> axis and <i>ab</i> plane). Reproduced with permission from ref (8), Copyright 2013 John Wiley and Sons. (c) Calculated thermopower for different spin states as a function of cobalt valence in the CoO<sub>2</sub> layers. Reproduced with permission from ref (9), Copyright 2012 American Physical Society. (d) Schematic representation of spin orientation and thermodynamic entropy. Reproduced with permission from ref (10). Copyright 2021 The Authors. Figure 3. (a) Temperature dependent on thermopower with and without magnetic field in Fe<sub>2</sub>V<sub>0.9</sub>Cr<sub>0.1</sub>Al<sub>0.9</sub>Si<sub>0.1</sub>. Reproduced with permission from ref (3). Copyright 2019 The Authors.. The inset displays the spin fluctuation contribution peaks at <i>T</i><sub>C</sub>. (b) −<i>S</i>/<i>T</i> of Fe<sub>2</sub>V<sub>0.9</sub>Cr<sub>0.1</sub>Al<sub>0.9</sub>Si<sub>0.1</sub>, plotted as functions of magnetic field and temperature. −<i>S</i>/<i>T</i> has a sharp peak at <i>T</i><sub>C</sub> under zero magnetic field and is significantly suppressed with increasing <i>H</i>. Reproduced with permission from ref (3). Copyright 2019 The Authors. (c) Measured thermopower <i>S</i><sub>total</sub> and magnon drag induced thermopower <i>S</i><sub>M</sub> for Co<sub>2</sub>TiAl. The area between the <i>S</i><sub>total</sub> and <i>S</i><sub>M</sub> lines represents the sum of <i>S</i><sub>sf</sub> and <i>S</i><sub>d</sub>. The inset displays the temperature-dependent thermopower of <i>S</i><sub>sf</sub> + <i>S</i><sub>d</sub> a
图1所示。自旋增强电荷基热电的机理说明。(a)自旋熵：自旋熵通量是由自旋轨道简并态(g)的差异产生的，从高简并态流向低简并态，通常在过渡金属(M)中，对总热能有贡献。另外，自旋熵是由高温下长程有序的破坏引起的自旋方向的无序产生的，称为自旋热力学熵。(b)自旋涨落：在TC附近，流动电子的局部自旋密度的热涨落最为显著。当净磁矩在强磁场下稳定时，这些波动被抑制。经ref(3)许可转载。版权所有2019作者。(c)磁振子阻力：磁振子在磁性材料中从热端向冷端传播，与电子和声子耦合，通过动量传递产生热能。经ref(4)许可转载。版权归作者所有。图2。(a)由于不同简并度，局域电子对Co离子的自旋熵贡献通过跳变输运传递熵的示意图。经ref(6)许可转载。版权所有2020作者。(b) Ca3Co4O9+δ单晶热功率随磁场在两个方向（b沿c轴和ab平面）的相对变化。经ref(8)许可转载，版权所有2013 John Wiley and Sons。(c)计算出的不同自旋态的热能与CoO2层中钴价的函数关系。转载许可来自ref(9)，版权所有2012年美国物理学会。(d)自旋取向和热力学熵示意图。经ref（10）许可转载。版权所有2021作者。图3。(a) Fe2V0.9Cr0.1Al0.9Si0.1中有磁场和无磁场时热功率的温度依赖关系。经ref(3)许可转载。版权所有2019作者…插图显示了自旋涨落在TC处的贡献峰。(b) Fe2V0.9Cr0.1Al0.9Si0.1的−S/T随磁场和温度的变化曲线。−S/T在零磁场下在TC处有一个尖峰，随着h的增加而显著抑制，转载经ref(3)许可。(c) Co2TiAl的实测总热功率和磁振子阻力诱导的热功率SM。Stotal和SM线之间的面积表示Ssf和Sd的总和。插图显示了Ssf + Sd随温度变化的热功率以及它们各自的值。经参考文献（14）许可转载。版权所有2023作者。(d)自旋涨落与电子和声子相互作用的示意图。经ref(4)许可转载。版权归作者所有。图4。(a)两种对磁振子阻力贡献的示意图：流体动力输运（无磁振子衰变，α→0）和几何Berry相位阻力（受磁振子衰变控制）。经参考文献（20）许可转载。EPLA版权所有(b) Li1-xMnxTe的热功率测定。磁振子-阻力热功率在TN以下显著增加，顺磁振子-阻力热功率在TN以上仍然升高。b中的数据取自参考文献(4)。(c) MnTe的总比热容和部分比热容，显示了磁振子比热容Cm的贡献，在TN处呈现λ形状。经参考文献(4)许可，转载。(d)调频和AFM系统中的自旋相关散射及其相应的色散关系。经ref（21）许可转载。RSC版权所有z.b.w和j.q.h讨论了这个话题并提出了大纲。zb.w.组织并撰写了草稿。j.q.h修改了手稿。王仲斌，现任南方科技大学博士研究生。他于2021年获得哈尔滨工业大学学士学位。他的研究重点是磁性热电材料中的异常输运行为。何嘉庆，南方科技大学讲座教授。2004年获于于利希研究中心和武汉大学物理学联合博士学位。曾任美国布鲁克海文国家实验室博士后（2004-2008）、西北大学研究员（2008-2010）、研究助理教授（2010-2012）、西安交通大学教授（2012-2013）、南科大教授（2013 -至今）。主要研究方向为透射电子显微镜、热电材料、结构与性质关系。感谢国家自然科学基金（批准号：12434001,11934007,52461160258）和深圳市杰出人才培养基金（202108）的资助。本文引用了其他27篇出版物。这篇文章尚未被其他出版物引用。
{"title":"Unlocking Spin to Boost Thermopower","authors":"Zhongbin Wang, Jiaqing He","doi":"10.1021/accountsmr.4c00310","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00310","url":null,"abstract":"Figure 1. Illustrations of the mechanisms of spin-enhanced charge-based thermopower. (a) Spin entropy: a spin entropy flux is created by differences in spin–orbital degeneracies (<i>g</i>), flowing from high-degeneracy to low-degeneracy states, typically in transition metals (M), contributing to the total thermopower. Additionally, spin entropy arises from disordered spin orientations caused by the breakdown of long-range order at high temperatures, referred to as spin thermodynamic entropy. (b) Spin fluctuation: thermal fluctuations of the local spin density of itinerant electrons are most significant near <i>T</i><sub>C</sub>. These fluctuations are suppressed as the net magnetic moment stabilizes under a strong magnetic field. Reproduced with permission from ref (3). Copyright 2019 The Authors. (c) Magnon drag: magnons propagate in a magnetic material from the hot to the cold end, coupling with both electrons and phonons, contributing to thermopower through momentum transfer. Reproduced with permission from ref (4). Copyright 2021 The Authors. Figure 2. (a) Schematic illustration of spin entropy contributed by the localized electrons on Co ions transfer entropy via hopping transport due to the different degeneracy. Reproduced with permission from ref (6). Copyright 2020 The Authors. (b) The relative change in thermopower of Ca<sub>3</sub>Co<sub>4</sub>O<sub>9+δ</sub> single crystal versus magnetic field for two directions (<i>B</i> along <i>c</i> axis and <i>ab</i> plane). Reproduced with permission from ref (8), Copyright 2013 John Wiley and Sons. (c) Calculated thermopower for different spin states as a function of cobalt valence in the CoO<sub>2</sub> layers. Reproduced with permission from ref (9), Copyright 2012 American Physical Society. (d) Schematic representation of spin orientation and thermodynamic entropy. Reproduced with permission from ref (10). Copyright 2021 The Authors. Figure 3. (a) Temperature dependent on thermopower with and without magnetic field in Fe<sub>2</sub>V<sub>0.9</sub>Cr<sub>0.1</sub>Al<sub>0.9</sub>Si<sub>0.1</sub>. Reproduced with permission from ref (3). Copyright 2019 The Authors.. The inset displays the spin fluctuation contribution peaks at <i>T</i><sub>C</sub>. (b) −<i>S</i>/<i>T</i> of Fe<sub>2</sub>V<sub>0.9</sub>Cr<sub>0.1</sub>Al<sub>0.9</sub>Si<sub>0.1</sub>, plotted as functions of magnetic field and temperature. −<i>S</i>/<i>T</i> has a sharp peak at <i>T</i><sub>C</sub> under zero magnetic field and is significantly suppressed with increasing <i>H</i>. Reproduced with permission from ref (3). Copyright 2019 The Authors. (c) Measured thermopower <i>S</i><sub>total</sub> and magnon drag induced thermopower <i>S</i><sub>M</sub> for Co<sub>2</sub>TiAl. The area between the <i>S</i><sub>total</sub> and <i>S</i><sub>M</sub> lines represents the sum of <i>S</i><sub>sf</sub> and <i>S</i><sub>d</sub>. The inset displays the temperature-dependent thermopower of <i>S</i><sub>sf</sub> + <i>S</i><sub>d</sub> a","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887164","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 : 2024-12-19DOI: 10.1021/accountsmr.4c00207
Laura L. Becerra, Nicholas B. Root, Robert S. Ramji, Romke Rouw, Darren J. Lipomi
The haptic sense captures information arising from the somatosensory system─the sensor system of the body excluding the eyes, ears, nose, and tongue. That is, it captures stimuli arising from the skin (i.e., touch) and from internal structures (i.e., the musculoskeletal system and internal organs). The field of research called haptics is concerned with understanding and manipulating this sense, often using engineered technology, and usually for creating novel or realistic touch sensations. Fundamental to every tactile interaction is an interface between the skin and a material. Given that essentially all material objects are composed of or covered in organic media, we reasoned that we, as organic materials scientists, might be able to contribute to the understanding of the sense of touch by manipulating material properties on the molecular scale. Over time, our research group acquired additional skills in electrical engineering and developed strong collaborations with cognitive and behavioral scientists. With a shared curiosity about the sense of touch, we made what we believe are original contributions to the field of haptics.
{"title":"Use of Materials Science to Understand Haptic Perception","authors":"Laura L. Becerra, Nicholas B. Root, Robert S. Ramji, Romke Rouw, Darren J. Lipomi","doi":"10.1021/accountsmr.4c00207","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00207","url":null,"abstract":"The haptic sense captures information arising from the somatosensory system─the sensor system of the body excluding the eyes, ears, nose, and tongue. That is, it captures stimuli arising from the skin (i.e., touch) and from internal structures (i.e., the musculoskeletal system and internal organs). The field of research called <i>haptics</i> is concerned with understanding and manipulating this sense, often using engineered technology, and usually for creating novel or realistic touch sensations. Fundamental to every tactile interaction is an interface between the skin and a material. Given that essentially all material objects are composed of or covered in organic media, we reasoned that we, as organic materials scientists, might be able to contribute to the understanding of the sense of touch by manipulating material properties on the molecular scale. Over time, our research group acquired additional skills in electrical engineering and developed strong collaborations with cognitive and behavioral scientists. With a shared curiosity about the sense of touch, we made what we believe are original contributions to the field of haptics.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"12 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849739","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 : 2024-12-19DOI: 10.1021/accountsmr.4c00305
Phillip M. Greißel, Anna-Sophie Wollny, Yifan Bo, Dominik Thiel, René Weiß, Dirk M. Guldi
Efficient photovoltaics (PV) require capturing and converting solar energy across a broad range of energy. Losses due to thermalization and sub-bandgap photons place, however, significant boundaries on the performance of solar cells. For conventional single-junction cells, the theoretical maximum power conversion efficiency is capped at 33%, a constraint known as the detailed balance limit. Realizing the full potential of PVs requires developing novel strategies to overcome this fundamental obstacle. This Account describes the photon-management capabilities of acenes and addresses these fundamental losses en-route toward enhancing PV performances.
{"title":"Molecular Acenes for Light Capture, Conversion, and Storage","authors":"Phillip M. Greißel, Anna-Sophie Wollny, Yifan Bo, Dominik Thiel, René Weiß, Dirk M. Guldi","doi":"10.1021/accountsmr.4c00305","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00305","url":null,"abstract":"Efficient photovoltaics (PV) require capturing and converting solar energy across a broad range of energy. Losses due to thermalization and sub-bandgap photons place, however, significant boundaries on the performance of solar cells. For conventional single-junction cells, the theoretical maximum power conversion efficiency is capped at 33%, a constraint known as the detailed balance limit. Realizing the full potential of PVs requires developing novel strategies to overcome this fundamental obstacle. This Account describes the photon-management capabilities of acenes and addresses these fundamental losses en-route toward enhancing PV performances.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"52 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849738","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 : 2024-12-12DOI: 10.1021/accountsmr.4c00201
João Marreiros, Yuxiang Wang, MinGyu Song, William J. Koros, Matthew J. Realff, Christopher W. Jones, Ryan P. Lively
Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs.
{"title":"Fiber Sorbents – A Versatile Platform for Sorption-Based Gas Separations","authors":"João Marreiros, Yuxiang Wang, MinGyu Song, William J. Koros, Matthew J. Realff, Christopher W. Jones, Ryan P. Lively","doi":"10.1021/accountsmr.4c00201","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00201","url":null,"abstract":"Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816121","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 : 2024-12-12DOI: 10.1021/accountsmr.4c0020110.1021/accountsmr.4c00201
João Marreiros, Yuxiang Wang, MinGyu Song, William J. Koros, Matthew J. Realff, Christopher W. Jones and Ryan P. Lively*,
<p >Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs.</p><p >These processability limitations have been historically addressed through powder shaping methods aimed at the fabrication of structured sorbent contactors based on pellets, beads or monoliths, commonly obtained as extrudates. These structures overcome limitations such as elevated pressure drops commonly recorded across powder adsorption beds but often accrue thermal limitations arising from elevated particle density and aggregation, which ultimately cap their maximum separation performance. Furthermore, the harsh mechanical strain to which powder particles are subjected during contactor fabrication, in the form of extrusion/compression forces, can result in partial pore occlusion and framework degradation, further limiting their performance.</p><p >Here, we present the development of porous fiber sorbents as an alternative sorbent contactor design capable of addressing sorbent processability limitations while enabling an array of performance-maximizing heat integration capabilities. This new sorbent form factor leverages pre-existing know-how from hollow fiber spinning to produce fiber-shaped sorbent contactors through the phase inversion of known polymers in a process known as dry-jet/wet quenching. The process of phase inversion allows microporous sorbent particles to be latched onto a macroporous polymer matrix under mild processing conditions, thus making it compatible with soft porous materials prone to amorphization under traditional pelletization conditions.</p><p >Sorbent fibers can be created with different geometries through control of the spinning apparatus and process, offering the possibility to produce monolithic and hollow fibers alike, the latter of which can be integrated with thermalization fluid flows. In this Account, we summarize our progress in the field of fiber sorbents from both design and application standpoints. We further guide the reader through the evolution of this field from the early inceptive work on zeolite hollow fibers to recent developments on MOF fibers. We highlight the versatile nature of fiber sorbents, both from the composition, fabrication and structure points of view, and further demonstrate how fiber sorbents offer alternative paths in tackling new and challenging chemical separation challenges like direct air capture (DAC), with a final perspective on the future of the fiel
{"title":"Fiber Sorbents – A Versatile Platform for Sorption-Based Gas Separations","authors":"João Marreiros, Yuxiang Wang, MinGyu Song, William J. Koros, Matthew J. Realff, Christopher W. Jones and Ryan P. Lively*, ","doi":"10.1021/accountsmr.4c0020110.1021/accountsmr.4c00201","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00201https://doi.org/10.1021/accountsmr.4c00201","url":null,"abstract":"<p >Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs.</p><p >These processability limitations have been historically addressed through powder shaping methods aimed at the fabrication of structured sorbent contactors based on pellets, beads or monoliths, commonly obtained as extrudates. These structures overcome limitations such as elevated pressure drops commonly recorded across powder adsorption beds but often accrue thermal limitations arising from elevated particle density and aggregation, which ultimately cap their maximum separation performance. Furthermore, the harsh mechanical strain to which powder particles are subjected during contactor fabrication, in the form of extrusion/compression forces, can result in partial pore occlusion and framework degradation, further limiting their performance.</p><p >Here, we present the development of porous fiber sorbents as an alternative sorbent contactor design capable of addressing sorbent processability limitations while enabling an array of performance-maximizing heat integration capabilities. This new sorbent form factor leverages pre-existing know-how from hollow fiber spinning to produce fiber-shaped sorbent contactors through the phase inversion of known polymers in a process known as dry-jet/wet quenching. The process of phase inversion allows microporous sorbent particles to be latched onto a macroporous polymer matrix under mild processing conditions, thus making it compatible with soft porous materials prone to amorphization under traditional pelletization conditions.</p><p >Sorbent fibers can be created with different geometries through control of the spinning apparatus and process, offering the possibility to produce monolithic and hollow fibers alike, the latter of which can be integrated with thermalization fluid flows. In this Account, we summarize our progress in the field of fiber sorbents from both design and application standpoints. We further guide the reader through the evolution of this field from the early inceptive work on zeolite hollow fibers to recent developments on MOF fibers. We highlight the versatile nature of fiber sorbents, both from the composition, fabrication and structure points of view, and further demonstrate how fiber sorbents offer alternative paths in tackling new and challenging chemical separation challenges like direct air capture (DAC), with a final perspective on the future of the fiel","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"6–16 6–16"},"PeriodicalIF":14.0,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.4c00201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-10DOI: 10.1021/accountsmr.4c0030210.1021/accountsmr.4c00302
Woo Je Chang, Allison M. Green, Zarko Sakotic, Daniel Wasserman*, Thomas M. Truskett* and Delia J. Milliron*,
<p >Metamaterials operating at infrared (IR) frequencies have garnered significant attention due to the opportunities for resonant interactions with vibrational modes of molecules and materials and manipulation of thermal emission. These metamaterials usually consist of periodic arrangements of subwavelength scale metallic or dielectric elements, patterned either top-down by nanolithographic methods or bottom-up by nanocrystal (NC) assembly. However, conventional metals are inherently constrained by their fixed electron concentrations, which limits the degrees of freedom in the design of the meta-atom unit cells to achieve the desired optical response. In this context, doped metal oxide NCs, with the prototypical case being tin-doped indium oxide (ITO) NCs, are exceptional candidates for self-assembled IR metamaterials, owing to their relatively low and synthetically tunable electron concentrations that govern the frequencies of their IR plasmon resonances. Focusing on ITO NCs as building blocks, this Account describes recent progress in the synthetic tuning of NC optical properties, NC superlattice monolayer preparation methods for fabricating IR resonant metamaterials, and the emerging understanding of the optical response, facilitated by recently developed simulation methods.</p><p >Based on experimental and simulation methods we helped develop, we are advancing a mechanistic understanding of how self-assembled NC metamaterials can produce distinctive near- and far-field optical properties not readily achievable in lithographically patterned structures. First, the impacts of the inevitable defects and disorder associated with self-assembly can be rationalized and, in some cases, recognized as advantageous. Second, self-assembly enables intimate nanoscale intermixing of different NC and molecular components. By incorporating probe molecules within the gaps between NCs where the electric field enhancement is the strongest, we show enhanced detection of molecular vibrations that can be optimized by tuning the size and resonance frequency of the NCs. We show how metasurfaces incorporating mixtures of NCs with different doping concentrations can achieve an epsilon-near-zero dielectric response over a broad frequency range. Finally, considering the NC metasurface itself as a building block, we show how photonic structures incorporating these assemblies can harness and amplify their distinctive properties. Through modeling the NC monolayer as a slab with an effective permittivity response, we designed a frequency-tunable IR perfect absorber by layering the NCs on a simple open cavity structure. Since the perfect absorption architecture further enhances the IR electric field localization strength, we expect that this integration strategy can enhance molecular vibration coupling or nonlinear optical response. The versatility of the NC assembly and integration approach suggests opportunities for various metal oxide NC superstructures, including mixing a
{"title":"Plasmonic Metal Oxide Nanocrystals as Building Blocks for Infrared Metasurfaces","authors":"Woo Je Chang, Allison M. Green, Zarko Sakotic, Daniel Wasserman*, Thomas M. Truskett* and Delia J. Milliron*, ","doi":"10.1021/accountsmr.4c0030210.1021/accountsmr.4c00302","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00302https://doi.org/10.1021/accountsmr.4c00302","url":null,"abstract":"<p >Metamaterials operating at infrared (IR) frequencies have garnered significant attention due to the opportunities for resonant interactions with vibrational modes of molecules and materials and manipulation of thermal emission. These metamaterials usually consist of periodic arrangements of subwavelength scale metallic or dielectric elements, patterned either top-down by nanolithographic methods or bottom-up by nanocrystal (NC) assembly. However, conventional metals are inherently constrained by their fixed electron concentrations, which limits the degrees of freedom in the design of the meta-atom unit cells to achieve the desired optical response. In this context, doped metal oxide NCs, with the prototypical case being tin-doped indium oxide (ITO) NCs, are exceptional candidates for self-assembled IR metamaterials, owing to their relatively low and synthetically tunable electron concentrations that govern the frequencies of their IR plasmon resonances. Focusing on ITO NCs as building blocks, this Account describes recent progress in the synthetic tuning of NC optical properties, NC superlattice monolayer preparation methods for fabricating IR resonant metamaterials, and the emerging understanding of the optical response, facilitated by recently developed simulation methods.</p><p >Based on experimental and simulation methods we helped develop, we are advancing a mechanistic understanding of how self-assembled NC metamaterials can produce distinctive near- and far-field optical properties not readily achievable in lithographically patterned structures. First, the impacts of the inevitable defects and disorder associated with self-assembly can be rationalized and, in some cases, recognized as advantageous. Second, self-assembly enables intimate nanoscale intermixing of different NC and molecular components. By incorporating probe molecules within the gaps between NCs where the electric field enhancement is the strongest, we show enhanced detection of molecular vibrations that can be optimized by tuning the size and resonance frequency of the NCs. We show how metasurfaces incorporating mixtures of NCs with different doping concentrations can achieve an epsilon-near-zero dielectric response over a broad frequency range. Finally, considering the NC metasurface itself as a building block, we show how photonic structures incorporating these assemblies can harness and amplify their distinctive properties. Through modeling the NC monolayer as a slab with an effective permittivity response, we designed a frequency-tunable IR perfect absorber by layering the NCs on a simple open cavity structure. Since the perfect absorption architecture further enhances the IR electric field localization strength, we expect that this integration strategy can enhance molecular vibration coupling or nonlinear optical response. The versatility of the NC assembly and integration approach suggests opportunities for various metal oxide NC superstructures, including mixing a","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"104–113 104–113"},"PeriodicalIF":14.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084648","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 : 2024-12-10DOI: 10.1021/accountsmr.4c00302
Woo Je Chang, Allison M. Green, Zarko Sakotic, Daniel Wasserman, Thomas M. Truskett, Delia J. Milliron
Metamaterials operating at infrared (IR) frequencies have garnered significant attention due to the opportunities for resonant interactions with vibrational modes of molecules and materials and manipulation of thermal emission. These metamaterials usually consist of periodic arrangements of subwavelength scale metallic or dielectric elements, patterned either top-down by nanolithographic methods or bottom-up by nanocrystal (NC) assembly. However, conventional metals are inherently constrained by their fixed electron concentrations, which limits the degrees of freedom in the design of the meta-atom unit cells to achieve the desired optical response. In this context, doped metal oxide NCs, with the prototypical case being tin-doped indium oxide (ITO) NCs, are exceptional candidates for self-assembled IR metamaterials, owing to their relatively low and synthetically tunable electron concentrations that govern the frequencies of their IR plasmon resonances. Focusing on ITO NCs as building blocks, this Account describes recent progress in the synthetic tuning of NC optical properties, NC superlattice monolayer preparation methods for fabricating IR resonant metamaterials, and the emerging understanding of the optical response, facilitated by recently developed simulation methods.
{"title":"Plasmonic Metal Oxide Nanocrystals as Building Blocks for Infrared Metasurfaces","authors":"Woo Je Chang, Allison M. Green, Zarko Sakotic, Daniel Wasserman, Thomas M. Truskett, Delia J. Milliron","doi":"10.1021/accountsmr.4c00302","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00302","url":null,"abstract":"Metamaterials operating at infrared (IR) frequencies have garnered significant attention due to the opportunities for resonant interactions with vibrational modes of molecules and materials and manipulation of thermal emission. These metamaterials usually consist of periodic arrangements of subwavelength scale metallic or dielectric elements, patterned either top-down by nanolithographic methods or bottom-up by nanocrystal (NC) assembly. However, conventional metals are inherently constrained by their fixed electron concentrations, which limits the degrees of freedom in the design of the meta-atom unit cells to achieve the desired optical response. In this context, doped metal oxide NCs, with the prototypical case being tin-doped indium oxide (ITO) NCs, are exceptional candidates for self-assembled IR metamaterials, owing to their relatively low and synthetically tunable electron concentrations that govern the frequencies of their IR plasmon resonances. Focusing on ITO NCs as building blocks, this Account describes recent progress in the synthetic tuning of NC optical properties, NC superlattice monolayer preparation methods for fabricating IR resonant metamaterials, and the emerging understanding of the optical response, facilitated by recently developed simulation methods.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"49 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805092","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 : 2024-12-09DOI: 10.1021/accountsmr.4c0031510.1021/accountsmr.4c00315
Chao Lu*, Xiaohong Zhang and Xi Chen,
<p >Piezoionic skin sensors are one kind of artificial electrical skin that can output sensing signals in response to external strain or stress stimulus with merits of flexibility, lightness, scalability, and high sensitivity. They have been emerging as an important platform in artificial intelligence, such as in smart healthcare, bionic robotics, and microelectromechanical systems. Piezoionic sensors are typically composed of an electrolyte laminated with symmetric electrodes and are based on ion migration and redistribution under a gradient strain or stress field. However, existing challenges significantly impede the sensing performance of piezoionic sensors, including the low electromechanical coupling efficiency of the electrode materials, instability of electrolyte materials, and strain-induced interface separation of sensor interfaces. In recent years, our group and collaborators have made attempts addressing the as-mentioned critical challenges in order to achieve flexible piezoionic sensors with satisfying performance for wearable smart applications. First, for the electromechanical coupling efficiency of electrode materials, we have developed various electrode materials with highly efficient ion storage and transfer, such as graphdiyne, quinone composites, and graphitic carbon nitride. These materials present superior electrical and mechanical properties with enhanced electromechanical coupling efficiency. Second, in order to improve the stability of electrolytes, especially in an air environment, we have developed ionogel electrolytes instead of conventional hydrogel electrolytes. Ionogels contain highly stable ionic liquids, which effectively improve the air stability of sensor electrolytes, and the sensing properties of devices are preserved even after several months. Third, with regard to sensor interface separation, we have engineered stable material interfaces for piezoionic sensors with elaborate structures. The as-designed tree-root-inspired interfaces show high mechanical stability under various flexible conditions, and the piezoionic sensors display negligible performance deterioration under thousands of bending cycles in an ambient environment. Finally, we have obtained flexible piezoionic sensors and studied their practical applications, such as wearable electronics, health monitoring, and smart detections. For example, we have realized the accurate detection of blood pressure based on an out-of-plane piezoionic mechanism. This innovative technique completely avoids the cuff issue that commercial sphygmomanometers have. Moreover, we have developed multifinger-touch piezoionic sensor arrays for effective braille recognition, which have the potential to eliminate communication barriers with sight-impaired people. Human voices can be easily differentiated by detecting vocal-cord vibrations based on captured sensing signals with obviously different patterns. This smart technique is promising for extended and applied use in virtua
{"title":"Piezoionic Skin Sensors for Wearable Applications","authors":"Chao Lu*, Xiaohong Zhang and Xi Chen, ","doi":"10.1021/accountsmr.4c0031510.1021/accountsmr.4c00315","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00315https://doi.org/10.1021/accountsmr.4c00315","url":null,"abstract":"<p >Piezoionic skin sensors are one kind of artificial electrical skin that can output sensing signals in response to external strain or stress stimulus with merits of flexibility, lightness, scalability, and high sensitivity. They have been emerging as an important platform in artificial intelligence, such as in smart healthcare, bionic robotics, and microelectromechanical systems. Piezoionic sensors are typically composed of an electrolyte laminated with symmetric electrodes and are based on ion migration and redistribution under a gradient strain or stress field. However, existing challenges significantly impede the sensing performance of piezoionic sensors, including the low electromechanical coupling efficiency of the electrode materials, instability of electrolyte materials, and strain-induced interface separation of sensor interfaces. In recent years, our group and collaborators have made attempts addressing the as-mentioned critical challenges in order to achieve flexible piezoionic sensors with satisfying performance for wearable smart applications. First, for the electromechanical coupling efficiency of electrode materials, we have developed various electrode materials with highly efficient ion storage and transfer, such as graphdiyne, quinone composites, and graphitic carbon nitride. These materials present superior electrical and mechanical properties with enhanced electromechanical coupling efficiency. Second, in order to improve the stability of electrolytes, especially in an air environment, we have developed ionogel electrolytes instead of conventional hydrogel electrolytes. Ionogels contain highly stable ionic liquids, which effectively improve the air stability of sensor electrolytes, and the sensing properties of devices are preserved even after several months. Third, with regard to sensor interface separation, we have engineered stable material interfaces for piezoionic sensors with elaborate structures. The as-designed tree-root-inspired interfaces show high mechanical stability under various flexible conditions, and the piezoionic sensors display negligible performance deterioration under thousands of bending cycles in an ambient environment. Finally, we have obtained flexible piezoionic sensors and studied their practical applications, such as wearable electronics, health monitoring, and smart detections. For example, we have realized the accurate detection of blood pressure based on an out-of-plane piezoionic mechanism. This innovative technique completely avoids the cuff issue that commercial sphygmomanometers have. Moreover, we have developed multifinger-touch piezoionic sensor arrays for effective braille recognition, which have the potential to eliminate communication barriers with sight-impaired people. Human voices can be easily differentiated by detecting vocal-cord vibrations based on captured sensing signals with obviously different patterns. This smart technique is promising for extended and applied use in virtua","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":"114–123 114–123"},"PeriodicalIF":14.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143086911","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 : 2024-12-09DOI: 10.1021/accountsmr.4c00315
Chao Lu, Xiaohong Zhang, Xi Chen
Piezoionic skin sensors are one kind of artificial electrical skin that can output sensing signals in response to external strain or stress stimulus with merits of flexibility, lightness, scalability, and high sensitivity. They have been emerging as an important platform in artificial intelligence, such as in smart healthcare, bionic robotics, and microelectromechanical systems. Piezoionic sensors are typically composed of an electrolyte laminated with symmetric electrodes and are based on ion migration and redistribution under a gradient strain or stress field. However, existing challenges significantly impede the sensing performance of piezoionic sensors, including the low electromechanical coupling efficiency of the electrode materials, instability of electrolyte materials, and strain-induced interface separation of sensor interfaces. In recent years, our group and collaborators have made attempts addressing the as-mentioned critical challenges in order to achieve flexible piezoionic sensors with satisfying performance for wearable smart applications. First, for the electromechanical coupling efficiency of electrode materials, we have developed various electrode materials with highly efficient ion storage and transfer, such as graphdiyne, quinone composites, and graphitic carbon nitride. These materials present superior electrical and mechanical properties with enhanced electromechanical coupling efficiency. Second, in order to improve the stability of electrolytes, especially in an air environment, we have developed ionogel electrolytes instead of conventional hydrogel electrolytes. Ionogels contain highly stable ionic liquids, which effectively improve the air stability of sensor electrolytes, and the sensing properties of devices are preserved even after several months. Third, with regard to sensor interface separation, we have engineered stable material interfaces for piezoionic sensors with elaborate structures. The as-designed tree-root-inspired interfaces show high mechanical stability under various flexible conditions, and the piezoionic sensors display negligible performance deterioration under thousands of bending cycles in an ambient environment. Finally, we have obtained flexible piezoionic sensors and studied their practical applications, such as wearable electronics, health monitoring, and smart detections. For example, we have realized the accurate detection of blood pressure based on an out-of-plane piezoionic mechanism. This innovative technique completely avoids the cuff issue that commercial sphygmomanometers have. Moreover, we have developed multifinger-touch piezoionic sensor arrays for effective braille recognition, which have the potential to eliminate communication barriers with sight-impaired people. Human voices can be easily differentiated by detecting vocal-cord vibrations based on captured sensing signals with obviously different patterns. This smart technique is promising for extended and applied use in virtual re
{"title":"Piezoionic Skin Sensors for Wearable Applications","authors":"Chao Lu, Xiaohong Zhang, Xi Chen","doi":"10.1021/accountsmr.4c00315","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00315","url":null,"abstract":"Piezoionic skin sensors are one kind of artificial electrical skin that can output sensing signals in response to external strain or stress stimulus with merits of flexibility, lightness, scalability, and high sensitivity. They have been emerging as an important platform in artificial intelligence, such as in smart healthcare, bionic robotics, and microelectromechanical systems. Piezoionic sensors are typically composed of an electrolyte laminated with symmetric electrodes and are based on ion migration and redistribution under a gradient strain or stress field. However, existing challenges significantly impede the sensing performance of piezoionic sensors, including the low electromechanical coupling efficiency of the electrode materials, instability of electrolyte materials, and strain-induced interface separation of sensor interfaces. In recent years, our group and collaborators have made attempts addressing the as-mentioned critical challenges in order to achieve flexible piezoionic sensors with satisfying performance for wearable smart applications. First, for the electromechanical coupling efficiency of electrode materials, we have developed various electrode materials with highly efficient ion storage and transfer, such as graphdiyne, quinone composites, and graphitic carbon nitride. These materials present superior electrical and mechanical properties with enhanced electromechanical coupling efficiency. Second, in order to improve the stability of electrolytes, especially in an air environment, we have developed ionogel electrolytes instead of conventional hydrogel electrolytes. Ionogels contain highly stable ionic liquids, which effectively improve the air stability of sensor electrolytes, and the sensing properties of devices are preserved even after several months. Third, with regard to sensor interface separation, we have engineered stable material interfaces for piezoionic sensors with elaborate structures. The as-designed tree-root-inspired interfaces show high mechanical stability under various flexible conditions, and the piezoionic sensors display negligible performance deterioration under thousands of bending cycles in an ambient environment. Finally, we have obtained flexible piezoionic sensors and studied their practical applications, such as wearable electronics, health monitoring, and smart detections. For example, we have realized the accurate detection of blood pressure based on an out-of-plane piezoionic mechanism. This innovative technique completely avoids the cuff issue that commercial sphygmomanometers have. Moreover, we have developed multifinger-touch piezoionic sensor arrays for effective braille recognition, which have the potential to eliminate communication barriers with sight-impaired people. Human voices can be easily differentiated by detecting vocal-cord vibrations based on captured sensing signals with obviously different patterns. This smart technique is promising for extended and applied use in virtual re","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"69 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793621","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 : 2024-12-03DOI: 10.1021/accountsmr.4c00303
Priyam Ghosh, 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.
{"title":"Multifunctional Fluorescent Probes Unveiling Complex Pathways in Alzheimer’s Disease Pathogenesis","authors":"Priyam Ghosh, Parameswar Krishnan Iyer","doi":"10.1021/accountsmr.4c00303","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00303","url":null,"abstract":"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.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"214 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763572","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}
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