CAREER: Coordination Polymer Superlattices with Tailored Properties through Chemical Vapor Deposition Synthesis

非技术摘要配位聚合物是一种用途广泛的材料，目前用于过滤污染物、储存能量和将原材料转化为有用的化学品。最近，利用这些材料广泛的结构和化学可调性来制造新一代电子设备，如开关、传感器和智能储能系统，引起了人们的极大兴趣。然而，这些材料糟糕的电性能，以及缺乏能够创造所需材料性能的合成方法，减缓了进展。这个职业项目由材料研究部的固态和材料化学项目支持，通过开发从气相中生长高质量晶体配位聚合物的新方法来应对这些挑战。此外，这项提议解决了通过创建一种名为超晶格的新材料结构来提高这些材料的电性能的需要，这种材料结构由各种配位聚合物的单晶片相互堆叠组成。可以控制各个片材的组成、结构和分层。由于结构和功能在超晶格中是如此可定制，它有可能支持增强和新颖的性能，使其超过传统聚合物和固态材料的性能限制。这项研究可以推动能量存储和转换方面的技术进步，并催生新一代过滤器、执行器、传感器和光学/电子设备。其中许多技术可以用来确保社会的可持续性和改善社会福利。本研究所采用的研究创新和方法为学生在材料的合成、结构-性质测定和应用方面提供了大量的培训机会。除了本提案中描述的研究目标外，首席调查员还将介绍两项教育和外联活动：一个侧重于材料科学主题的播客频道，以及一个管理材料合成方案的在线众包数据库。这些活动的目的是让人数不足的少数群体更多地参与科学、技术和经济管理领域，并建立研究基础设施，以加快研究方案的传播和核查。技术摘要配位聚合物(CP)可以被设计成表达一系列不同的结构、孔隙率和化学成分，从而使它们在能量存储、分离和催化方面具有应用价值。然而，如果要成功地将CP集成到电子设备中，则需要具有更复杂的功能和响应特性的CP。这个项目的主要假设是，Cp超晶格可以支持复杂的、多变量的和响应性的性质，这一假设得到了材料研究部固态和材料化学项目职业奖的支持。由层状二维CP晶格组成的超晶格是一种很有吸引力的结构，因为它固有的结构和组成层次可以被定制来促进所需的或紧急的物理性质。这一职业项目致力于化学气相沉积方法的开发，用于定制合成Cp超晶格，并研究这些材料的动态和响应特性。化学气相沉积(CVD)是制备高质量Cp晶体超晶格的一种方法。该项目侧重于三个核心目标。首先，确定了化学气相沉积合成Cp超晶格的范围和机理。其次，在Cp超晶格单晶上制作的器件上进行的输运研究正在被用来阐明它们的电子性质。第三，具有多变量和响应特性的异质结构Cp超晶格正在开发中，并正在确定其超越传统块体3D材料性能极限的潜力。除了该项目的研究目标外，首席调查员还介绍了两项教育和外联活动：一个侧重于材料科学主题的播客频道，以及一个管理CVD合成方案的在线众包数据库。这些活动旨在增加代表不足的少数群体在STEM领域的参与，并建立研究基础设施，以加快研究方案的传播和验证。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Non-Technical AbstractCoordination polymers are versatile materials that are currently used to filter pollutants, store energy, and convert raw materials into useful chemicals. Recently, there has been great interest in using the extensive structural and chemical tunability of these materials to make a new generation of electronic devices, such as switches, sensors, and smart energy storage systems. However, the poor electrical performance of these materials, and a lack of synthetic methods capable of creating desired material properties has slowed progress. This CAREER project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, addresses these challenges by developing new methods to grow high quality crystalline coordination polymers from the gas phase. Furthermore, this proposal addresses the need to improve the electrical performance of these materials by creating a new material architecture called a superlattice, which is composed of single crystal sheets of various coordination polymers stacked on top of one another. The composition, structure, and layering of the individual sheets can be controlled. Because structure and function are so tailorable in the superlattice, it has the potential to support enhanced and novel properties, allowing it to exceed the performance limits of conventional polymers and solid-state materials. This research can enable technological advances in energy storage and conversion, and spawn a new generation of filters, actuators, sensors, and optical/electronic devices. Many of these technologies can be used to assure the sustainability and improved welfare of society. The research innovations and methods used in this research provide a multitude of student training opportunities in the synthesis, structure-property determination, and application of materials. In addition to the research objectives described in this proposal, the principal investigator is introducing two education and outreach activities: a podcast channel focused on materials science topics, and an online crowd-sourced database that curates materials synthesis protocols. These activities aim to increase the participation of under-represented minorities in STEM fields and to build a research infrastructure to accelerate the dissemination and verification of research protocols. Technical AbstractCoordination polymers (CPs) can be designed to express a diverse array of structures, porosities, and chemistries rendering them useful for applications in energy storage, separations, and catalysis. However, CPs with more complex functionalities and responsive properties are desired if they are to be successfully integrated into electronic devices. The principal hypothesis of this project, supported by a CAREER award through the Solid State and Materials Chemistry program in the Division of Materials Research, is that a CP superlattice can support complex, multivariate, and responsive properties. A superlattice comprising layered two-dimensional CP crystal lattices is an attractive architecture, because its inherent hierarchies of structure and composition can be tailored to promote desired or emergent physical properties. This CAREER project addresses the development of chemical vapor deposition methods for the tailored synthesis of CP superlattices and the study of these materials' dynamic and responsive properties. Chemical vapor deposition (CVD) is introduced as a strategy for the preparation of high-quality crystalline CP superlattices. The project focuses on three core objectives. First, the scope and mechanism of chemical vapor deposition synthesis of CP superlattices are being established. Second, transport studies conducted on devices fabricated on single crystals of CP superlattices are being used to elucidate their electronic properties. Third, heterostructured CP superlattices with multivariate and responsive properties are being developed and their potential to surpass the performance limits of conventional bulk 3D materials is being determined. In addition to the research objectives of this project, the principal investigator has introduced two education and outreach activities: a podcast channel focused on materials science topics, and an online crowd-sourced database that curates CVD synthesis protocols. These activities aim to increase the participation of under-represented minorities in STEM fields and to build a research infrastructure to accelerate the dissemination and verification of research protocols.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.