Chemical Vapor Deposition of Metallic Films at Low Temperatures: Precursor Synthesis and Hydrogen-Assisted Reaction Chemistry

低温金属薄膜化学气相沉积：前驱体合成和氢辅助反应化学

• 批准号: 0420768
• 负责人: Gregory Girolami
• 金额: $ 60.53万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-07-01 至 2007-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0420768&HistoricalAwards=false
• 关键词: Chemical; Vapor; Deposition; Metallic; Films

This project aims for greater understanding of thin film growth/deposition, achievement of new routes to chemical vapor deposition of metal diboride thin films, and atomic layer deposition (ALD) of copper, tantalum, and other metallic films, all at low substrate temperatures. The scientific goal is to understand the chemistry of film formation using in situ optical, mass, and electron spectroscopies. The approach involves four parallel efforts: 1) New precursor molecules will be synthesized that are designed for the growth of Cu, Ta, and other metals using hydrogen plasma enhanced atomic layer deposition, and for the growth of ZrB2, MgB2, and other diboride alloys using hydrogen plasma enhanced CVD. 2) Film growth strategies using the new precursors will be developed: deposition of Cu and Ta by hydrogen plasma enhanced ALD, CrB2 by thermal CVD (chemical vapor deposition), and MgB2 by hydrogen plasma enhanced CVD. CrB2 and MgB2 growth will be investigated using precursors Cr(B3H8) 2 and Mg(B3H8) 2 recently discovered by the PIs. Heteroepitaxial growth of single crystal films of ZrB2 and CrB2 on Si(111) and MgB2 films on ZrB2 or CrB2 will be explored, as well as the synthesis of ZrB2 or CrB2 nanotubes using multi-walled C nanotubes as a template. 3) Film formation pathways will be analyzed using in situ spectroscopies to determine the mechanisms that govern ALD and CVD processes. Surface reactions will be analyzed using downstream mass spectroscopy, reflection IR absorption, quartz crystal microbalance, temperature programmed desorption, and Auger electron spectroscopy. Where applicable, isotopic labeling (D for H) will be utilized. Both static (post-growth) and dynamic (during growth) surfaces will be studied, including the use of time-modulated fluxes. Conformal coverage experiments on trench substrates will be used to extract the surface reaction probability of precursors, as a function of temperature and the concurrent flux of atomic hydrogen. Nucleation, composition, and surface roughness will be studied using real time spectroscopic ellipsometry. 4) Film structure and properties will be evaluated, including crystal structure, electrical conductivity, and performance as impurity diffusion barriers. Deposition, annealing, and analysis of structures consisting of Cu/Ta/Si or Cu/CrB2/Si will be carried out to determine Cu in-diffusion into Si. %%% The project addresses fundamental materials science and chemistry research issues associated with electronic/photonic materials having technological relevance, and emphasizes the integration of research and education. The project will support four graduate students, and 1-2 undergraduates per year conducting summer projects or senior theses. The UIUC SURGE (Support of Under-represented Groups in Engineering) and WISE (Women in Science and Engineering) programs will be utilized to assist with broadening participation by under-represented groups. Research results will be broadly disseminated by presentations at international conferences and by publication in scientific journals. Industrial microelectronics organizations, e.g., IBM, Intel, Novellus, or Applied Materials, will be visited to present and discuss project results to enhance university/industry interactions. The project is co-supported by the MPS/DMR and MPS/CHE Divisions.***

该项目旨在更好地了解薄膜生长/沉积，实现金属二硼化物薄膜的化学气相沉积新途径，以及铜，钽和其他金属薄膜的原子层沉积（ALD），所有这些都在低衬底温度下进行。科学的目标是利用原位光学、质谱和电子光谱来了解薄膜形成的化学过程。 该方法涉及四个平行的努力：1）将合成新的前体分子，其设计用于使用氢等离子体增强原子层沉积生长Cu、Ta和其他金属，以及使用氢等离子体增强CVD生长ZrB 2、MgB 2和其他二硼化物合金。 2)将开发使用新前体的薄膜生长策略：通过氢等离子体增强ALD沉积Cu和Ta，通过热CVD（化学气相沉积）沉积CrB 2，通过氢等离子体增强CVD沉积MgB 2。 CrB 2和MgB 2的生长将使用PI最近发现的前体Cr（B3 H8）2和Mg（B3 H8）2进行研究。将探索在Si（111）上异质外延生长ZrB 2和CrB 2单晶薄膜和在ZrB 2或CrB 2上异质外延生长MgB 2薄膜，以及使用多壁C纳米管作为模板合成ZrB 2或CrB 2纳米管。 3)薄膜形成途径将使用原位光谱分析，以确定机制，管理ALD和CVD工艺。将使用下游质谱、反射红外吸收、石英晶体微量天平、程序升温脱附和俄歇电子能谱分析表面反应。如适用，将使用同位素标记（D代表H）。将研究静态（生长后）和动态（生长期间）表面，包括使用时间调制通量。 沟槽衬底上的保形覆盖实验将用于提取前体的表面反应概率，作为温度和原子氢的并发通量的函数。 成核，成分和表面粗糙度将使用真实的时间光谱椭圆偏振法进行研究。 4)薄膜的结构和性能将进行评估，包括晶体结构，导电性和性能作为杂质扩散障碍。 将进行由Cu/Ta/Si或Cu/CrB 2/Si组成的结构的沉积、退火和分析，以确定Cu向Si中的内扩散。 该项目解决了与具有技术相关性的电子/光子材料相关的基础材料科学和化学研究问题，并强调研究和教育的整合。该项目将支持四名研究生，每年1-2名本科生进行暑期项目或高级论文。将利用UIUC SURGE（支持工程学中代表性不足的群体）和WISE（科学和工程学中的妇女）方案，协助扩大代表性不足的群体的参与。 研究结果将通过在国际会议上的介绍和在科学杂志上发表而广泛传播。工业微电子组织，例如，IBM，英特尔，Novellus或应用材料公司将被访问，以介绍和讨论项目结果，以加强大学/行业的互动。该项目由MPS/DMR和MPS/CHE司共同支助。