Area-Selective Atomic Layer Deposition Using Chemisorbed Carboxylate Inhibitors

计算机芯片制造是移动计算、云计算、第五代（5G）蜂窝网络技术、人工智能等应用的基础。制造计算芯片现在要求能够以前所未有的精度在成分、空间位置和尺寸上将材料放置在基板上。然而，这种制造能力的发展仍处于早期阶段，需要新的使能知识。该奖项支持基础研究，为原子级增材制造的发展提供知识。这种新工艺使制造具有原子精确控制的材料系统的可扩展方法成为可能。这种材料系统也可能带来新的机会，如环保制造和污染控制的新催化剂。这项研究的结果导致了有用的高性能材料和新知识的生产，加速了新型芯片制造工艺的发展，从而促进了科学的进步，帮助美国在先进制造业中保持领先地位。这项研究是跨学科的，培养学生在制造、真空技术、表面化学、材料科学和分析化学方面的技能。该项目涉及让学生，特别是妇女和代表性不足的少数民族参与研究，从而改善工程教育。区域选择性原子层沉积（ALD）是减小功能器件尺寸、降低集成电路制造复杂性和成本、降低计算芯片能耗的关键使能技术。然而，该技术的潜力受到选择性生长化学选择的限制，以及对ALD中成核选择性表面化学异质性的了解不足。本研究旨在建立选择性化学吸附羧酸自组装单层膜（SAMs）作为ALD过程中阻断或抑制成核的抑制剂。本研究填补了ALD抑制机制的知识空白和抑制剂阻断成核能力的逐渐丧失，并最终导致了改善抑制剂阻断成核能力的新策略。该合作团队通过研究羧酸盐的形成和ALD化学成核的选择性来实现这些目标，通过原位表征底物的质量和化学，以及气态副产物，并使用非原位原子力显微镜-红外（AFM-IR）光谱来检查表面化学的非均质性，并建立化学-过程参数-成核抑制的关系。该奖项反映了美国国家科学基金会的法定使命，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。

Computer chip manufacturing is the foundation for mobile computing, cloud computing, fifth generation (5G) cellular network technology, artificial intelligence and other applications. Manufacturing computing chips now demands the capability that can place materials on substrates with unprecedented precision in composition, spatial location and dimensions. However, development of such manufacturing capability is still in early stages and demands new enabling knowledge. This award supports fundamental research to generate knowledge for the development of atomic-scale additive manufacturing. This new process enables a scalable method of manufacturing material systems with atomic precise control. Such material systems could also lead to new opportunities such as new catalysts for environmentally-friendly manufacturing and pollution control. The results from this research lead to production of useful, high performance materials and new knowledge to accelerate the development of a novel chip manufacturing process, thus promoting the progress of science and helping the U.S. sustain its leading role in advanced manufacturing. This research is cross-disciplinary and trains students in skills in manufacturing, vacuum technology, surface chemistry, materials science and analytical chemistry. The project involves engaging students, especially, women and underrepresented minorities in research, thus improving engineering education. Area-selective atomic layer deposition (ALD) is a key enabling technology to reduce functional device dimensions, reduce manufacturing complexity and cost for integrated circuits and reduce the energy consumption by computing chips. However, the potential of this technology is severely limited by the narrow choices of selective growth chemistries, as well as poor understanding of the heterogeneity of surface chemistry on the selectivity of nucleation in ALD. This research aims at establishing selectively-chemisorbed carboxylate self-assembled monolayers (SAMs) as inhibitors to block or inhibit nucleation during ALD. This research fills the knowledge gap of the inhibition mechanisms and the gradual loss of the inhibitor's ability in blocking nucleation during ALD, and eventually leads to new strategies to improve the inhibitor in blocking nucleation. The collaborative team achieves these goals by studying the formation of carboxylates and selectivity of the nucleation of ALD chemistries with in situ characterizations of the substrate's mass and chemistry, and gaseous byproducts, and with ex situ atomic force microscope-infrared (AFM-IR) spectroscopy to exam the heterogeneity of surface chemistries and establish the relationship of chemistry-process parameter-nucleation inhibition.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.