CAREER: New Models for Controlling InP Nucleation, Growth, and Luminescence using Magic-Sized Clusters and Targeted Surface Chemistry

职业生涯：使用神奇大小的簇和目标表面化学来控制 InP 成核、生长和发光的新模型

• 批准号: 1552164
• 负责人: Brandi Cossairt
• 金额: $ 67.5万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-02-01 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1552164&HistoricalAwards=false
• 关键词: CAREER; New; Models; Controlling; InP

One of the hallmarks of modern society has been efficiently and effectively transforming energy from one form to another, which has enabled increased human productivity and aided economic development. As technologies mature, continued progress on this front requires developing new materials with new and improved function. As a result of their emergent, size-dependent properties, nanomaterials are forecasted to significantly shape the future of next generation energy technologies. Nanomaterial function relies on the ability of scientists to access these materials with uniform and precise atomic structures. This is an enormous challenge since nanomaterials contain hundreds to thousands of atoms and even a few atoms out of place can significantly alter their function. Research conducted under this CAREER award aims to address the fundamental challenges in controlling the composition and interfaces of nanomaterials with atom-level precision. The globally-relevant nature of this research is leveraged to advance the major educational goals of this project, namely to: 1) create an undergraduate specialization in Chemistry for Energy at the University of Washington (UW), 2) develop hands-on demonstration materials and workshops on the topic of colloidal nanoscience targeted to middle and high school students in collaboration with the UW Phi Lambda Upsilon (National Chemistry Honor Society) chapter, and 3) broaden participation in chemistry at the undergraduate, graduate and professional level through work with the Chemistry Women Mentorship Network, the UW Women in Chemical Sciences, and the NSF-supported Louis Stokes Alliance for Minority Participation program.The scientific goal of this award is to understand how indium phosphide (InP) and related colloidal quantum dots (QDs) nucleate and grow in solution and how to rationally modify that mechanism and the properties of the resulting nanocrystals using surface chemistry. As a step toward this goal, several themes are initiated to provide the experimental context in which nucleation, growth, and photoluminescence modulation in these materials can be studied. These include: 1) testing new models of InP nucleation using isolable, structurally characterized and atomically precise magic-sized cluster intermediates; 2) understanding how surface chemistry impacts the structure and function of InP magic-sized clusters to gain access to general strategies for anisotropic shape control and doping; and 3) discovering new post-synthetic surface chemistry to turn-on and color-tune the luminescence of InP and related QDs using Lewis acid coordination chemistry. The research approach focuses primarily on the development of new hypothesis-driven synthetic methods as well as spectroscopic and theoretical characterization of the properties and electronic structure of these materials. Ongoing collaborations with experts in time-dependent electronic structure theory, X-ray crystallography, and X-ray photoelectron spectroscopy are leveraged to help answer fundamental structural and mechanistic questions. The educational component addresses the need to train the next generation of scientists and engineers to solve scientific grand challenges through the development of relevant and applicable lecture materials, learning tools and demonstrations.

现代社会的标志之一是高效和有效地将能源从一种形式转化为另一种形式，从而提高了人类生产力并有助于经济发展。随着技术的成熟，这方面的持续进步需要开发具有新功能和改进功能的新材料。由于其新兴的，尺寸依赖的属性，纳米材料被预测将显着塑造下一代能源技术的未来。纳米材料的功能依赖于科学家获得这些具有均匀和精确原子结构的材料的能力。这是一个巨大的挑战，因为纳米材料包含数百到数千个原子，甚至几个原子的位置可以显着改变它们的功能。该职业奖下进行的研究旨在解决以原子级精度控制纳米材料成分和界面的根本挑战。这项研究的全球相关性被用来推进该项目的主要教育目标，即：1）在华盛顿大学（UW）开设能源化学本科专业，2）与UW Phi Lambda Upgrades合作，针对初中和高中学生开发关于胶体纳米科学主题的实践演示材料和研讨会（国家化学荣誉学会）章，和3）扩大参与化学在本科生，研究生和专业水平，通过与化学妇女导师网络，华盛顿大学妇女在化学科学，以及NSF支持的路易斯·斯托克斯少数民族参与联盟计划。该奖项的科学目标是了解磷化铟（InP）以及相关的胶体量子点（QD）在溶液中成核和生长，以及如何使用表面化学合理地修改该机制和所得纳米晶体的性质。作为实现这一目标的一步，几个主题发起提供的实验背景下，在这些材料的成核，生长和光致发光调制可以进行研究。其中包括：1）使用可分离的、结构表征的和原子精确的魔尺寸团簇中间体测试InP成核的新模型; 2）理解表面化学如何影响InP魔尺寸团簇的结构和功能，以获得各向异性形状控制和掺杂的一般策略;以及3）发现新的合成后表面化学以使用刘易斯酸配位化学来开启和颜色调节InP和相关QD的发光。研究方法主要集中在新的假设驱动的合成方法的发展，以及这些材料的性质和电子结构的光谱和理论表征。与时间相关电子结构理论，X射线晶体学和X射线光电子能谱专家的持续合作被用来帮助回答基本的结构和机制问题。 教育部分通过开发相关和适用的讲座材料、学习工具和演示，满足了培训下一代科学家和工程师解决科学重大挑战的需要。

项目成果

Quantifying Ligand Exchange on InP Using an Atomically Precise Cluster Platform

• DOI: 10.1021/acs.inorgchem.8b03524
• 发表时间: 2019-02-18
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Ritchhart, Andrew;Cossairt, Brandi M.
• 通讯作者: Cossairt, Brandi M.

Purification and In Situ Ligand Exchange of Metal-Carboxylate-Treated Fluorescent InP Quantum Dots via Gel Permeation Chromatography

• DOI: 10.1021/acs.jpclett.7b01772
• 发表时间: 2017-09-07
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY LETTERS
• 影响因子: 5.7
• 作者: Roberge, Adam;Stein, Jennifer L.;Greytak, Andrew B.
• 通讯作者: Greytak, Andrew B.

Investigating the role of amine in InP nanocrystal synthesis: destabilizing cluster intermediates by Z-type ligand displacement

• DOI: 10.1039/c6cc07952k
• 发表时间: 2017-01-04
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Gary, Dylan C.;Petrone, Alessio;Cossairt, Brandi M.
• 通讯作者: Cossairt, Brandi M.

Conversion of InP Clusters to Quantum Dots

• DOI: 10.1021/acs.inorgchem.8b02945
• 发表时间: 2019-01-07
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Friedfeld, Max R.;Johnson, Dane A.;Cossairt, Brandi M.
• 通讯作者: Cossairt, Brandi M.

Cation Exchange Induced Transformation of InP Magic-Sized Clusters

• DOI: 10.1021/acs.chemmater.7b03075
• 发表时间: 2017-09
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: J. L. Stein;M. Steimle;M. Terban;A. Petrone;S. Billinge;Xiaosong Li;B. Cossairt