Interface and matrix effects on light-switchable solid-state spin transitions

光可切换固态自旋跃迁的界面和基体效应

• 批准号: 1904596
• 负责人: Daniel Talham
• 金额: $ 49.66万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-15 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904596&HistoricalAwards=false
• 关键词: Interface; matrix; effects; light; switchable

Part 1: Non-Technical Summary.Using light to induce motion on a macroscopic scale is sometimes referred to as the direct conversion of light to work and is expected to lead to new technologies in areas ranging from artificial muscles to light energy harvesting to wireless machines. Spin transition solids are a class of materials known to change volume when exposed to certain stimuli, including light. This volume change alone can be used to cause motion, but the effects are greatly amplified by combining the spin transition solid in a composite with other materials. This project, supported by the Solid State and Materials Chemistry program at NSF, explores the fundamental materials chemistry questions associated with light induced volume changes when spin transition solids are combined in a matrix with other materials to form a composite. Theoretical models predict how the spin transition should change in a matrix, but experiments to verify these predictions are currently lacking, and the magnitude of matrix effects have not been quantified. Researchers at the University of Florida develop new synthetic methods to place well-defined particles of the spin transition solid in matrices of different materials enabling quantitative measurements of how the volume change associated with the spin transition is transmitted to and amplified by the supporting matrix. The project utilizes national scientific user facilities including the Advanced Photon Source at Argonne National Labs and the NSLS II at Brookhaven National Labs, and provides students training in these advanced technologies. Results of the project will enable better design of the next generation of materials used for directly converting light to work. The relationship of this project to these developing technologies is highlighted in a planned exhibit themed Creating Motion with Light, to be displayed at local education and public outreach forums.Part 2: Technical SummaryThe significant volume change accompanying alterations in metal-ligand bonding during a solid-state spin transition opens the prospect of harvesting these effects for mechanical actuator technology. These emerging applications require the spin transition material to physically couple to other material components, yet the material interface can influence the characteristics of a spin transition, especially at high surface to volume ratios characteristic of the nanoscale or mesoscale. This project, supported by the Solid State and Materials Chemistry program at NSF, quantifies matrix or interface attributes and their influence on spin transitions in mesoscale particles. Experimentally, the charge transfer induced spin transition (CTIST) of rubidium cobalthexacyanoferrate as the light-switchable core with isostructural but chemically distinct cyanometallate shells as surrounding matrix are studied. Theoretical models predict the elastic properties of the core are the key determinants of the order and kinetics of the phase transition. These properties can be affected by the stiffness of the shell, the relative lattice constants of the core and shell, and the shell thickness; all are parameters that can be synthetically altered. Light-induced and temperature-dependent phase behavior is monitored with X-ray diffraction and magnetometry to provide activation energies and information about the order and cooperativity of the transition as components are changed. The elastic properties are measured using nuclear inelastic scattering (NIS) and X-ray diffraction under pressure, and they are correlated with the phase change behavior to quantify the matrix effects. In parallel, the scope extends to chemically dissimilar matrices. These studies inform the subject area of light-induced mechanical actuation, potential applications of which are the use of light to directly perform work and new light energy harvesting schemes. The relationship of this project to these developing technologies is highlighted in a planned exhibit themed Creating Motion with Light, to be displayed at local education and public outreach forums. The research tasks are designed to be platforms for graduate and undergraduate student education, providing technical expertise and knowledge along with general skills needed to be competitive in materials chemistry related high-technology professions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

第1部分：非技术总结。利用光在宏观尺度上诱导运动有时被称为光到工作的直接转换，并有望在从人造肌肉到光能收集到无线机器等领域带来新技术。自旋转变固体是一类已知的材料，当暴露在某些刺激下，包括光，体积会发生变化。这种体积变化本身可以用来引起运动，但如果将复合材料中的自旋转变固体与其他材料结合起来，效果就会大大增强。该项目由美国国家科学基金会固态和材料化学项目支持，探索了当自旋转变固体与其他材料在基质中结合形成复合材料时，与光诱导体积变化相关的基本材料化学问题。理论模型预测了自旋跃迁在矩阵中应该如何变化，但目前缺乏验证这些预测的实验，并且矩阵效应的大小尚未被量化。佛罗里达大学的研究人员开发了一种新的合成方法，将定义良好的自旋转变固体颗粒放置在不同材料的基质中，从而可以定量测量与自旋转变相关的体积变化是如何传递给支撑基质并被支撑基质放大的。该项目利用国家科学用户设施，包括阿贡国家实验室的先进光子源和布鲁克海文国家实验室的NSLS II，并为学生提供这些先进技术的培训。该项目的结果将有助于更好地设计用于直接将光转换为工作的下一代材料。这个项目与这些发展中的技术的关系在一个以“用光创造运动”为主题的计划展览中得到强调，该展览将在当地教育和公共宣传论坛上展出。在固态自旋转变过程中，金属-配体键的显著体积变化为机械致动器技术带来了收获这些效应的前景。这些新兴的应用需要自旋过渡材料与其他材料组件物理耦合，然而材料界面可以影响自旋过渡的特性，特别是在纳米尺度或中尺度的高表面体积比特征下。该项目由美国国家科学基金会固态与材料化学项目资助，旨在量化基质或界面属性及其对中尺度粒子自旋跃迁的影响。实验研究了以同种结构但化学性质不同的氰金属酸盐壳层为周围基体的光可切换核的电荷转移诱导自旋跃迁。理论模型预测，核的弹性性质是相变顺序和动力学的关键决定因素。这些性能受壳刚度、核壳相对晶格常数和壳厚的影响；所有这些参数都可以被人工改变。利用x射线衍射和磁强计监测光诱导和温度相关的相行为，以提供活化能以及随组分改变而转变的顺序和协同性的信息。利用核非弹性散射（NIS）和压力下的x射线衍射测量了材料的弹性性能，并将其与相变行为相关联，量化了基体效应。同时，范围扩展到化学上不同的矩阵。这些研究为光致机械驱动的主题领域提供了信息，其潜在的应用是利用光直接进行工作和新的光能收集方案。这个项目与这些发展中的技术的关系在一个以“用光创造运动”为主题的计划展览中得到强调，该展览将在当地教育和公共宣传论坛上展出。研究任务旨在成为研究生和本科生教育的平台，提供技术专长和知识以及在材料化学相关高科技专业中具有竞争力所需的一般技能。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Sub-micrometer particle size effects on metastable phases for a photoswitchable Co–Fe Prussian blue analog

• DOI: 10.1063/5.0074165
• 发表时间: 2022-02
• 期刊: Journal of Applied Physics
• 影响因子: 3.2
• 作者: M. Itoi;I. Maurin;K. Boukheddaden;M. J. Andrus;D. Talham;E. Elkaim;Y. Uwatoko

Crafting Spin-State Switchable Strain Profiles within Rb x Co[Fe(CN) 6 ] y @K j Ni[Cr(CN) 6 ] k Heterostructures

在 Rb x Co[Fe(CN) 6 ] y @K j Ni[Cr(CN) 6 ] k 异质结构内制作自旋态可切换应变分布

• DOI: 10.1021/acs.chemmater.0c03608
• 发表时间: 2021
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Cain, John M.;Felts, Ashley C.;Meisel, Mark W.;Talham, Daniel R.
• 通讯作者: Talham, Daniel R.

Light-Switchable Exchange-Coupled Magnet

• DOI: 10.1021/acsaelm.9b00520
• 发表时间: 2019-11
• 作者: D. Rajan;J. M. Cain;T. Brinzari;C. F. Ferreira;N. Rudawski;Ashley C Felts;M. Meisel;D. Talham

Interplay between core and shell in a RbCoFe@RbNiCo Prussian blue analogue spin transition heterostructure

RbCoFe@RbNiCo 普鲁士蓝类似自旋跃迁异质结构中核与壳之间的相互作用

• DOI: 10.1039/d1tc01514a
• 发表时间: 2021
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: He, Wanhong;Cain, John M.;Meisel, Mark W.;Talham, Daniel R.
• 通讯作者: Talham, Daniel R.

Design and Synthesis of Concentration Gradient Prussian Blue Analogues

• DOI: 10.1021/acs.cgd.0c01271
• 发表时间: 2021-01-20
• 期刊: CRYSTAL GROWTH & DESIGN
• 影响因子: 3.8
• 作者: Jeon, SuKyung;Li, Carissa H.;Talham, Daniel R.
• 通讯作者: Talham, Daniel R.