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Synthesis of New Chalcogenide-Containing Perovskite Semiconductor Nanomaterials: Towards Earth-Abundant and Non-Toxic Solar Absorbers

新型含硫族化物钙钛矿半导体纳米材料的合成：走向地球丰富且无毒的太阳能吸收器

基本信息

批准号：
2004421
负责人：
Sidney Creutz
金额：
$ 25.88万
依托单位：
Mississippi State 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：
2020-06-01 至 2023-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2004421&HistoricalAwards=false
关键词：
Synthesis New Chalcogenide Containing Perovskite

项目摘要

PART 1: NON-TECHNICAL SUMMARYThe discovery and refinement of new materials for renewable energy production and storage is one of the most impactful challenges for materials chemistry in the 21st century. Recently, there has been considerable focus on a class of materials known as lead halide perovskites for applications in solar cells, but they may be limited by concerns about the toxicity of lead. Therefore, there is an ongoing need for the development of emerging classes of semiconductor materials which could show similarly promising properties, but without the corresponding drawbacks; they should be non-toxic, highly stable, solution-processible, and ideally composed of earth-abundant elements. Many materials with potentially promising properties have been proposed computationally, but only a small subset have been realized experimentally. This research project, supported by the Solid State and Materials Chemistry program within the Division of Materials Research, involves the development of new synthetic methods to access emerging and proposed inorganic semiconductors using solution synthesis. The project focuses on two classes of lead-free perovskite materials containing sulfur or selenium whose synthesis is currently either unknown or very limited. The development of facile synthetic routes to these materials in solution allows for experimental validation of their properties and lays the groundwork for their potential application in solar cells or other devices. Through their involvement in this project, graduate and undergraduate students are trained in materials chemistry and in renewable energy science, preparing them for future careers in energy research and green technology. Concepts related to this work, and materials chemistry in general, are also being developed into coursework to reach a broader audience of students at Mississippi State University. PART 2: TECHNICAL SUMMARYThis research project focuses on the development of two classes of chalcogenide-containing inorganic materials based on a perovskite lattice, which have been proposed as promising non-toxic and earth-abundant replacements for the hybrid lead halide perovskites, but whose synthesis is either unknown or underdeveloped. First, the research team is targeting the synthesis of chalcogenide perovskites including BaZrS3 and SrHfS3 as colloidal nanocrystals using solution synthesis approaches. Synthetic methods include the use of reactive sulfide and metal precursors (e.g., trimethysilyl sulfide and metal alkoxides and amides), the use of single-source precursors such as metal dithiocarbamates and heterobimetallic metal thiolate clusters, and the sulfurization of oxide nanocrystals. Synthesis as nanocrystals allows for the potential use of these materials as colloidal inks for solution-processing. Additionally, the research team is investigating the preparation of mixed-anion halide-chalcogenide perovskites such as CsBiSI2, CsSbSI2, and CsSnS2Cl, through approaches such as anion exchange on colloidal nanocrystals of chalcogenide or halide precursors. Through this approach, it is possible to access compositions, structures, and morphologies that may be metastable and difficult or impossible to access through direct synthesis under thermal equilibrium conditions. The materials prepared are characterized in terms of their compositional, structural, and optical properties and compared to computational predictions. This project is supported by the Solid State and Materials Chemistry program within the Division of Materials Research.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.

第一部分：非技术总结发现和改进用于可再生能源生产和储存的新材料是材料化学在21世纪世纪最具影响力的挑战之一。最近，人们相当关注一类被称为卤化铅钙钛矿的材料在太阳能电池中的应用，但它们可能受到铅毒性问题的限制。因此，持续需要开发新兴类别的半导体材料，其可以显示类似的有希望的性质，但没有相应的缺点;它们应该是无毒的，高度稳定的，溶液可加工的，并且理想地由地球丰富的元素组成。许多具有潜在前景的材料已被提出计算，但只有一小部分已实现实验。该研究项目由材料研究部内的固态和材料化学计划支持，涉及开发新的合成方法，以使用溶液合成来访问新兴和拟议的无机半导体。该项目的重点是两类含有硫或硒的无铅钙钛矿材料，其合成目前未知或非常有限。这些材料在溶液中的简易合成路线的开发允许对其性质进行实验验证，并为其在太阳能电池或其他设备中的潜在应用奠定了基础。通过他们在这个项目的参与，研究生和本科生在材料化学和可再生能源科学的培训，为他们在能源研究和绿色技术未来的职业生涯做好准备。与这项工作有关的概念，以及一般的材料化学，也正在发展成为课程，以达到更广泛的观众在密西西比州立大学的学生。第二部分：该研究项目集中于开发基于钙钛矿晶格的两类含硫族化物的无机材料，其已被提出作为混合卤化铅钙钛矿的有前景的无毒和地球丰富的替代品，但其合成是未知的或不发达的。首先，研究小组的目标是使用溶液合成方法合成硫属钙钛矿，包括BaZrS 3和SrHfS 3作为胶体纳米晶体。合成方法包括使用反应性硫化物和金属前体（例如，三甲基甲硅烷基硫化物和金属醇盐和酰胺），使用单源前体如金属二硫代氨基甲酸盐和杂环金属硫醇盐簇，以及氧化物纳米晶体的硫化。作为纳米晶体的合成允许这些材料作为用于溶液处理的胶体油墨的潜在用途。此外，研究小组正在研究混合阴离子卤化物-硫族化物钙钛矿的制备，如CsBiSI 2，CsSbSI 2和CsSnS 2Cl，通过硫族化物或卤化物前体的胶体纳米晶体上的阴离子交换等方法。通过这种方法，可以获得可能是亚稳态的并且难以或不可能通过在热平衡条件下直接合成获得的组合物、结构和形态。所制备的材料的特征在于其组成，结构和光学性质，并与计算预测。该项目由材料研究部的固态和材料化学项目支持。该奖项反映了NSF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。