RUI: Enabling Rational Design of Smart Interfaces Incorporating Metal-Organic Coordinated Assemblies

RUI：结合金属-有机协同组装的智能界面的合理设计(CHE-1508244)玛丽·E·安德森，霍普学院公共摘要金属-有机骨架(MOF)是具有极高比表面积的结晶、多孔材料，在化学传感、反应催化和气体存储方面显示出巨大的潜力。对于许多这样的应用，需要将直接生长在支撑材料上的MOF薄膜结合在一起。为了有效地制造具有智能接口的器件，利用这些MOF材料的特性，了解薄膜形成的基本原理是至关重要的。这项研究系统地研究了薄膜MOF的生长，并制定了各种与技术相关的衬底上的低能量处理技术的设计规则。这些用于定制薄膜结构和成分的设计规则被用于1)调整薄膜的光学、电学和机械性能，以及2)开发将MOF薄膜集成到化学传感和太阳能获取的尖端技术中的制造技术。本科生积极参与研究的各个方面，为他们提供了材料化学、表面科学和现代分析仪器等跨学科领域的经验。NSF化学部的大分子、超分子和纳米化学项目获得该奖项，支持霍普学院的Anderson博士研究表面锚定金属-有机骨架(SurMOF)的形成，以便直接集成到化学传感和光子应用的设备架构中。对具有递增复杂性的不同系统(即HKUST-1、MOF-14、MOF-5、IRMOF-3)的成膜进行了研究。研究了温度、时间和沉积方法(即逐层沉积、共沉积、种子沉积)等沉积参数对薄膜性能的影响。研究范围扩大到理解在不同技术相关的衬底上的沉积，例如氧化物材料(即二氧化硅、氧化铟、三氧化二铝)和柔性聚合物材料。确定了合理的生长启动和生长抑制设计规则。扫描探针显微镜(SPM)和表面特定光谱仪(即椭圆偏振光谱仪，FT-IR)被用来表征SurMOF薄膜的生长，以确定沉积条件的影响，特别是对在衬底-薄膜界面形成的基础层的影响。使用先进的扫描电子显微镜模式(即定量纳米机械作图、导电探针)、电化学(即循环伏安法、计时库仑法)和光谱电化学表征来评估薄膜的机械、电学和光学性能。通过遵循先进的设计规则，了解材料特性，并采用膜模板技术，本研究将SurMOF薄膜作为智能接口集成到用于化学传感和太阳能收集的试验台结构中。

RUI: Enabling Rational Design of Smart Interfaces Incorporating Metal-Organic Coordinated Assemblies (CHE-1508244)Mary E. Anderson, Hope CollegePublic AbstractMetal-organic frameworks (MOFs) are crystalline, porous materials with extremely high surface areas that exhibit great potential for chemical sensing, reaction catalysis, and gas storage. For many of these applications, the incorporation of MOF thin films grown directly on supporting materials is required. To effectively fabricate devices with smart interfaces that harness the properties of these MOF materials, it is crucial to understand the fundamentals of film formation. This research systematically investigates thin film MOF growth and develops design rules for low-energy processing techniques on a variety of technologically-relevant substrates. These design rules, for tailoring film structure and composition, are utilized 1) to tune the optical, electrical, and mechanical properties of the film and 2) to develop fabrication techniques that integrate MOF thin films into cutting-edge technologies for chemical sensing and harvesting solar energy. Undergraduate students are actively engaged in all aspects of the research, providing them with experience in the interdisciplinary areas of materials chemistry, surface science, and modern analytical instrumentation. Technical AbstractWith this award the Macromolecular, Supramolecular and Nanchemistry Program of the NSF Chemistry Division supports the research of Dr. Anderson at Hope College to investigate the formation of surface-anchored metal-organic frameworks (SurMOF) for integration directly into device architectures for chemical sensing and photonic applications. Film formation is studied for different systems with incrementally increasing complexity (i.e. HKUST-1, MOF-14, MOF-5, IRMOF-3). Effects of deposition variables such as temperature, time, and deposition methods (i.e. layer-by-layer, co-deposition, seeded deposition) are investigated. Studies are extended to understand deposition on different substrates of technological relevance, such as oxide materials (i.e. SiO2, ITO, Al2O3) and flexible polymeric materials. Rational design rules for growth initiation as well as inhibition are determined. Scanning probe microscopy (SPM) and surface-specific spectroscopies (i.e. ellipsometry, FT-IR) are used to characterize SurMOF film growth to determine the effect of deposition conditions with particular focus on foundational layers forming at the substrate-film interface. Mechanical, electrical, and optical properties of films are evaluated using advanced SPM modes (i.e. quantitative nanomechanical mapping, conductive probe), electrochemistry (i.e. cyclic voltammetry, chronocoulometry), and spectroelectrochemical characterization. By following developed design rules, understanding material properties, and employing membrane-templating techniques, this research integrates SurMOF films as smart interfaces into test-bed structures fabricated for chemical sensing and solar energy harvesting.