Solid-State Oxides and Oxide-Fluorides

固态氧化物和氧化物-氟化物

• 批准号: 1307698
• 负责人: Kenneth Poeppelmeier
• 金额: $ 45万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1307698&HistoricalAwards=false
• 关键词: Solid; State; Oxides; Oxide; Fluorides

TECHNICAL SUMMARYEmerging technologies require high-performance nonlinear optical (NLO) materials that exhibit enhanced optical properties at the microscopic and macroscopic level. The rational design of crystal structures, in particular noncentrosymmetric (NCS) materials, and how to target polar, polar-chiral, and chiral structures, is an ongoing theme in crystal engineering. A new class of potentially high performance NLO inorganic materials, solid-state oxide-fluorides, has been identified with the synthesis of new compounds containing [MOxF6-x]2- units in inorganic, solid-state environments. In the process it has been discovered that i) the use of fluoride ligands with early-transition metals (ETMs) enhances the second-order Jahn-Teller distortion in comparison to pure oxide ETM compounds, ii) the synthesis of NCS materials can be achieved with the use of polar basic-building units (BBUs), iii) design of NCS BBUs can predictably lead to NCS structures, iv) the synthesis of compounds that contain two, separate anionic BBUs is likely to result in an NCS compound, and v) the synthesis of ETM oxide-fluoride compounds can produce energy-storage materials such as high-potential primary batteries. Drawing from these learned principles, a program of discovery-based research on NCS structures based on acentric ETM oxide-fluorides (ETMOFs) is planned. These materials comprise a large and new class of solids with properties associated with piezoelectricity, pyroelectricity, ferroelectricity and second harmonic generation (SHG). The structural-property relationships that give rise to high, low, or null nonlinearities of the NLO material are examined. Finally, the growth of large crystals (on the order of 1 cm3) allows detailed analysis with measurements of the NLO tensor and phase-matchability properties, and other properties of interest such as piezoelectricity. The materials synthesized will have potential use in relaxor ferroelectrics and non-linear optics. These materials will have a high damage threshold and the potential for bulk growth to create large, single crystals suitable for optical use and examination. This work is supported by the Solid State and Materials Chemistry Program.NON TECHNICAL SUMMARYAs recently described in a Nature News Feature, the highly-efficient non-linear optical (NLO) oxide-fluoride material KBe2BO3F4 and other NLO materials are essential to act as wave guides for the modification of the amplitude, phase, and/or frequency of an optical signal. Such materials are used in femtosecond laser spectroscopy and-more recently-to generate UV laser light for nanolithography. Such NLO materials are increasingly needed to upconvert laser light to higher energies by second-harmonic generation (SHG). Current research and engineering activities in the field of NLO materials typically concern synthesis of NLO crystals; however, research is lacking in understanding how to design NLO materials and why materials exhibit a particular NLO response. While exploring the fundamental driving factors that create NLO materials, research will be performed to grow large (on the order of cm3) single crystals with a floating zone image furnace to allow a quantitative understanding of the interaction of light with the NLO material. This project concerns such analyses and progress made towards rational synthesis of solid-state inorganic materials and analysis of their structure-property relationships. These analyses of basic principles of the chemistry by graduate students and postdoctoral associates - who are engaged in local education, teaching, mentoring, and leadership - will facilitate broad understanding of stable solid-state compounds.

技术摘要技术需要高性能的非线性光学（NLO）材料，这些材料在显微镜和宏观水平上表现出增强的光学特性。晶体结构的合理设计，尤其是非中心对称（NCS）材料，以及如何靶向极性，极性手续和手性结构，是晶体工程中的一个持续主题。已经确定了一种新的潜在高性能无机材料，即固态氧化氟化物，并通过合成无机固态环境中含有[MOXF6-X] 2-单元的新化合物的合成。在此过程中，已经发现i）使用早期过渡金属（ETM）使用氟化物配体可以增强二阶Jahn-Teller扭曲，而与纯氧化物ETM化合物相比，II）可以通过使用NC的合成来实现NCS材料的合成。包含两个，单独的阴离子BBU的化合物的合成可能会导致NCS化合物，V）ETM氧化物氧化物氟化物化合物的合成可以产生能量储存材料，例如高电位的一电池。从这些学到的原理中借鉴了基于发现基于Acentric ETM氧化物氟化物（ETMOF）的基于发现的NCS结构的计划。这些材料包括一类新的固体类别，具有与压电性，高电度，铁电性和第二次谐波生成（SHG）相关的特性。检查了NLO材料的高，低或无线性的结构性关系关系。 最后，大晶体的生长（在1 cm3的阶段）可以通过测量NLO张量和相匹配性能的测量以及其他感兴趣的特性（例如压电性）进行详细分析。合成的材料将有潜在地用于放松器铁电和非线性光学元件。这些材料将具有高伤害阈值，并且有可能产生适合光学使用和检查的大型单晶的潜力。这项工作得到了固态和材料化学计划的支持。最近在自然新闻特征，高效的非线性光学（NLO）氧化氟化物材料KBE2BO3F4和其他NLO材料的NON技术摘要中，对于振幅，相位和/或频率修饰的波浪指南至关重要。此类材料用于飞秒激光光谱法中，并且最近生成的紫外线光线用于纳米光刻。 越来越需要使用这种NLO材料将激光光转化为第二次谐波生成（SHG）的更高能量。 NLO材料领域的当前研究和工程活动通常涉及NLO晶体的合成；但是，缺乏了解如何设计NLO材料以及材料表现出特定NLO响应的原因。在探索创建NLO材料的基本驱动因子时，将进行研究，以增强具有浮动区图像炉的大型（在CM3）的单晶体中，以允许对光的相互作用与NLO材料的相互作用进行定量理解。该项目涉及对固态无机材料合理综合的分析和进展，并分析了其结构 - 核关系关系。从事当地教育，教学，指导和领导力的研究生和博士后同事对化学基本原理的这些分析将有助于对稳定的固态化合物的广泛理解。