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.***

该项目旨在更深入地了解薄膜的生长/沉积，实现金属二吡啶薄膜化学蒸气沉积的新途径，以及铜，坦塔木和其他金属膜的原子层沉积（ALD），均在低底物温度下。科学的目标是使用原位光学，质量和电子光谱了解膜形成的化学。 该方法涉及四个平行的努力：1）将合成新的前体分子，这些分子是为铜，TA和其他金属而设计的，使用氢等离子体增强原子层沉积，以及Zrb2，MGB2和其他DIBORIDE合金的生长，以及其他二苯乙烯合金使用氢等离子体增强CVD。 2）将开发使用新前体的膜生长策略：通过氢等离子体增强ALD，通过热CVD（化学蒸气沉积）和MGB2通过氢等离子体增强CVD对CU和TA的沉积。 CRB2和MGB2生长将使用PIS最近发现的前体CR（B3H8）2和Mg（B3H8）2研究。将探索ZRB2和CRB2在SI（111）和Zrb2或CRB2上的MGB2膜上的单晶膜的异质增长，以及使用多壁C纳米管作为模板作为模板的多壁C纳米管的ZRB2或CRB2纳米管的合成。 3）将使用原位光谱法对膜形成途径进行分析，以确定控制ALD和CVD过程的机制。将使用下游质谱，反射IR吸收，石英晶体微平衡，温度编程的解吸和螺旋钻电子光谱来分析表面反应。如果适用，将使用同位素标记（H）。将研究静态（后生长）和动态（在生长期间）表面，包括使用时间调节通量。 沟渠底物上的共形覆盖范围实验将用于提取前体的表面反应概率，这是温度和原子氢的并发通量的函数。 将使用实时光谱椭圆法研究成核，组成和表面粗糙度。 4）将评估膜结构和性能，包括晶体结构，电导率和作为杂质扩散屏障的性能。 将进行由CU/TA/SI或CU/CRB2/SI组成的结构的沉积，退火和分析，以确定Cu向Si中的切除。 %%％该项目解决了与具有技术相关性的电子/光子材料相关的基本材料科学和化学研究问题，并强调了研究和教育的整合。该项目将为四名研究生提供支持，每年有1-2名本科生进行夏季项目或高级论文。 UIUC激增（在工程领域代表性不足的群体的支持）和WISE（科学和工程领域的女性）计划将用于协助扩大代表性不足的群体的参与。 在国际会议上的演讲和科学期刊上的出版物将广泛传播研究结果。将访问工业微电子组织，例如IBM，Intel，Novellus或应用材料，以呈现和讨论项目结果，以增强大学/行业的互动。该项目由国会议员/DMR和MPS/CHE部门共同支持***