Structure and Function of Heteroanionic Materials

杂阴离子材料的结构与功能

• 批准号: 2011208
• 负责人: James Rondinelli
• 金额: $ 46万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2011208&HistoricalAwards=false
• 关键词: Structure; Function; Heteroanionic; Materials

NONTECHNICAL SUMMARYTwenty-first century microelectronic and battery technologies rely on components consisting of transition metal oxides that can accommodate reversible changes in the distribution of their electrons. This award supports theoretical and computational research on the fundamental science of heteroanionic materials, which are compounds consisting of more than one anion beyond oxygen such as oxynitrides, oxyfluorides, and oxysulfides. These compounds benefit from the stability of oxide materials, but have the added advantage of tunable electronic, magnetic, and topological properties owing to the additional secondary anion, which allows for greater control over the electron distribution.The project goals are to design, discover, and control the properties of heteroanionic materials displaying ferroelectricity, metal-insulator transitions, and topological band structures by establishing links between crystal structure and anion chemistry, profiting from a coupling of theory, simulation, and comprehensive experimentation. The project utilizes quantum-mechanical based calculations to establish model frameworks and knowledge that are both descriptive and predictive. These models and approaches may be expanded to materials beyond heteroanionic materials, enabling an unprecedented expansion of compounds with varying electronic functions for future technologies.The teaching and training of students and the discovery capabilities of the project are also interwoven and aimed at broadening participation of underrepresented students in Science Technology Engineering and Mathematics disciplines through public outreach events, through undergraduate and graduate curriculum development, and by involving students with experiential and interdisciplinary training. The educational impact extends to high-school students by developing materials physics/engineering modules that meet Next Generation Science Standards in concert with high school teachers.TECHNICAL SUMMARYComplex transition metal oxides are utilized in a variety of technologies owing to their properties ranging from ferroelectricity to high-temperature superconductivity supported by polarizable oxide anions. The design, discovery, and control of new transition metal compounds, particularly those with multiple anions (heteroanionic materials) rather than multiple cations (homoanionic oxides with a single anion), with novel properties and superior performance are crucial to the continued development of present and future technologies. This award supports theoretical and computational research on the fundamental science of heteroanionic materials such as oxynitrides, oxyfluorides, and oxysulfides.The project goals are to implement and extend a heteroanionic materials design scheme for understanding the complex interplay among atomic structure, anion order, and band structure on novel electronic and quantum states and to advance new heteroanionic materials exhibiting superior functionalities and/or responses not found in homoanionic materials. The project utilizes a computational strategy, which integrates group theoretical techniques, derivative-structure tools, and density functional theory, to understand the electronic and optical properties of oxynitrides, oxyfluorides, and oxysulfides within three thrusts focused on (i) geometric and chemical control of noncentrosymmetry for acentric function; (ii) probing metal-insulator transition mechanisms for materials discovery; and (iii) novel routes to anion-ordered topological semimetals. The project will deliver new knowledge to facilitate the selection and design of materials with tunable electronic states derived from multiple anions. It benefits society by advancing the repertoire of structure-based design strategies to control electronic properties, which could lead to discovery of reconfigurable materials for low-power and brain-inspired microelectronics, transparent optoelectronics, and quantum information systems. In addition, educational goals of the project include the teaching and training of students at multiple levels and broadening STEM participation by underrepresented students. These goals extend to high-school students by developing materials physics/engineering modules in concert with high school teachers that meet Next Generation Science Standards. These efforts will impact the next-generation workforce by endowing students and teachers problem-solving skills to be success in globally competitive careers.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.

21世纪的微电子和电池技术依赖于由过渡金属氧化物组成的组件，这些组件可以适应其电子分布的可逆变化。该奖项支持对异阴离子材料基础科学的理论和计算研究，异阴离子材料是由除氧以外的一个以上阴离子组成的化合物，如氮氧化物、氟氧化物和硫化物。这些化合物受益于氧化物材料的稳定性，但由于额外的仲阴离子，这些化合物具有可调谐的电子、磁性和拓扑性质的额外优势，从而可以更好地控制电子分布。该项目的目标是通过建立晶体结构和阴离子化学之间的联系，从理论，模拟和综合实验的耦合中获益，设计，发现和控制具有铁电性，金属-绝缘体转变和拓扑带结构的异阴离子材料的特性。该项目利用基于量子力学的计算来建立既具有描述性又具有预测性的模型框架和知识。这些模型和方法可以扩展到异阴离子材料以外的材料，为未来技术提供具有不同电子功能的化合物的前所未有的扩展。学生的教学和培训与项目的发现能力也相互交织，旨在通过公共宣传活动，通过本科和研究生课程开发，以及通过让学生参与体验和跨学科培训，扩大代表性不足的学生在科学技术工程和数学学科的参与。通过与高中教师合作开发符合下一代科学标准的材料物理/工程模块，教育影响扩展到高中生。技术概述复杂的过渡金属氧化物由于其从铁电性到由可极化的氧化阴离子支持的高温超导性的性质，被应用于各种技术中。设计、发现和控制新的过渡金属化合物，特别是那些具有多个阴离子（异阴离子材料）而不是多个阳离子（具有一个阴离子的同阴离子氧化物）的化合物，具有新颖的性质和优越的性能，对当前和未来技术的持续发展至关重要。该奖项支持异质阴离子材料（如氮氧化物、氟氧化物和硫化物）基础科学的理论和计算研究。该项目的目标是实现和扩展异质阴离子材料的设计方案，以了解原子结构，阴离子顺序和新型电子和量子态的能带结构之间的复杂相互作用，并推进新的异质阴离子材料，表现出在同质阴离子材料中没有的优越功能和/或响应。该项目采用了一种计算策略，整合了群论技术、衍生结构工具和密度泛函理论，以了解氮氧化物、氟氧化物和硫化物在三个推力中的电子和光学性质，重点关注(i)非中心对称函数的几何和化学控制；（ii）探索材料发现的金属-绝缘体过渡机制；(3)制造阴离子有序拓扑半金属的新途径。该项目将提供新的知识，以促进选择和设计具有可调谐电子状态的材料，这些材料来源于多个阴离子。它通过推进基于结构的设计策略来控制电子特性，从而使社会受益，这可能导致发现用于低功耗和脑启发微电子，透明光电子和量子信息系统的可重构材料。此外，该项目的教育目标还包括对不同层次的学生进行教学和培训，以及扩大代表性不足的学生对STEM的参与。通过与高中教师合作开发符合下一代科学标准的材料物理/工程模块，这些目标扩展到高中生。这些努力将通过赋予学生和教师解决问题的能力，在全球竞争激烈的职业生涯中取得成功，从而影响下一代劳动力。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

From Heterostructures to Solid‐Solutions: Structural Tunability in Mixed Halide Perovskites

从异质结构到固体解决方案：混合卤化物钙钛矿的结构可调性

• DOI: 10.1002/adma.202205923
• 发表时间: 2023
• 期刊: Advanced Materials
• 影响因子: 29.4
• 作者: Shin, Donghoon;Lai, Minliang;Shin, Yongjin;Du, Jingshan S.;Jibril, Liban;Rondinelli, James M.;Mirkin, Chad A.
• 通讯作者: Mirkin, Chad A.

Pressure effects on magnetism in Ca2Mn2O5 -type ferrites and manganites

• DOI: 10.1103/physrevb.102.104426
• 发表时间: 2020-09
• 期刊: Physical Review B
• 影响因子: 3.7
• 作者: Yongjin Shin;J. Rondinelli

Strain-Induced Anion-Site Occupancy in Perovskite Oxyfluoride Films

• DOI: 10.1021/acs.chemmater.0c04793
• 发表时间: 2021-02
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Jiayi Wang;Yongjin Shin;J. Paudel;J. Grassi;R. Sah;Weibing Yang;E. Karapetrova;A. Zaidan;V. Strocov;C. Klewe;P. Shafer;A. Gray;J. Rondinelli;S. May

Low-energy electronic structure of perovskite and Ruddlesden-Popper semiconductors in the Ba-Zr-S system probed by bond-selective polarized x-ray absorption spectroscopy, infrared reflectivity, and Raman scattering

• DOI: 10.1103/physrevb.105.195203
• 发表时间: 2022-05
• 期刊: Physical Review B
• 影响因子: 3.7
• 作者: Kevin Ye;Nathan Z. Koocher;Stephen Filippone;Shanyuan Niu;Boyang Zhao;M. Yeung;S. Bone;Adam J. Robinson;P. Vora;A. Schleife;Long Ju;A. Boubnov;J. Rondinelli;J. Ravichandran;R. Jaramillo

Hybrid improper antiferroelectricity—New insights for novel device concepts

混合不当反铁电——新颖器件概念的新见解

• DOI: 10.1557/adv.2020.450
• 发表时间: 2020
• 期刊: MRS Advances
• 影响因子: 0.8
• 作者: Lu, Xue-Zeng;Rondinelli, James M.
• 通讯作者: Rondinelli, James M.