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本文基于第一性原理方法研究了非晶态二氧化硅中性氧空位缺陷及其与氢原子的反应机理. 结果显示, 非晶态二氧化硅中存在5种稳定中性氧空位缺陷构型, 相应的缺陷形成能与缺陷硅原子间距呈现显著正相关关系. 其中, $ {\mathrm{V}}_{\mathrm{D}} $构型因形成能最低可能是辐照或制备过程中的主要缺陷, $ {\mathrm{V}}_{\mathrm{F}} $和$ {\mathrm{V}}_{\mathrm{B}} $构型的费米接触与$ {\mathrm{E}}_{\gamma }'$中心相近, 而$ {\mathrm{V}}_{\mathrm{D}} $, $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $和$ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $构型因电子成对存在导致费米接触为零. 氢原子与中性氧空位缺陷通过形成Si—H键或硅羟基两种钝化方式可产生两类共7种中性氢化氧空位缺陷. 电子定域化函数与EPR模拟分析发现, $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{H}}\mathrm{和}{\mathrm{V}}_{\mathrm{B}\mathrm{M}}^{\mathrm{H}}\mathrm{构}\mathrm{型} $与$ {\mathrm{E}}_{\gamma }' $中心的EPR参数高度接近, 表明氢钝化过程可能干扰$ {E}' $中心的识别. $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{O}\mathrm{H}} $构型中硅羟基的生成可为氧化层和界面处水分子的形成提供理论依据. 研究获得了氢诱导缺陷跨网格迁移以及生成硅羟基的路径, 并揭示了氢原子具有钝化原始缺陷和诱发次生缺陷的双重作用. 这些发现可为双极型器件低剂量率辐射损伤增强效应提供微观机理解释.Amorphous silica (a-SiO2) with excellent insulating properties, uniform disordered structure, and good thermal stability, is the preferred material for field oxide layers, gate insulation layers and passivation layers in many semiconductor devices. However, in space environments, the oxygen vacancies generated by high-energy particle radiation and their interaction with hydrogen atoms in a-SiO2 can lead to enhanced low-dose-rate sensitivity, potentially causing threshold voltage to shift and leakage current to increase in semiconductor devices. These seriously threaten the operation safety of spacecraft, and the exploration of related reaction mechanisms is crucial. The neutral oxygen vacancies in amorphous silica and their reaction mechanism with hydrogen atoms are investigated using first-principles calculations. Five types of neutral oxygen vacancies are identified, namely $ {\mathrm{V}}_{\mathrm{D}} $, $ {\mathrm{V}}_{\mathrm{B}} $, $ {\mathrm{V}}_{\mathrm{F}} $, $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $ and $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $ configurations. A significant positive correlation is observed between the defect formation energy and the distance between two defective silicon atoms. Due to the lowest defect formation energy, the $ {\mathrm{V}}_{\mathrm{D}} $ configuration may become the main type of defect in irradiation or fabrication.$ {\mathrm{V}}_{\mathrm{F}} $ and $ {\mathrm{V}}_{\mathrm{B}} $ configurations show that Fermi contacts are comparable to those of $ {\mathrm{E}}_{\mathrm{\gamma }}' $ centers. The presence of electron pairs leads to zero fermi contacts in $ {\mathrm{V}}_{\mathrm{D}} $, $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $ and $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $ configurations. Previous studies have often focused more on the reaction between oxygen vacancies and hydrogen atoms at the middle-sites of oxygen vacancies. And, a key characteristic of the disordered a-SiO2 structure is that this method ignores the structure: the reaction may extend to the neighboring networks and occur at the side-sites of oxygen defects. For a full understanding of actual reactions, both the middle-sites and side-sites are considered for hydrogen atoms in present investigations. The research shows that hydrogen atoms passivate neutral oxygen vacancies through two different mechanisms: the formation of Si-H bonds and the generation of silanol groups. These processes generate two types of neutral hydrogenated oxygen vacancies, $ {\mathrm{V}}^{\mathrm{H}} $ and $ {\mathrm{V}}^{\mathrm{O}\mathrm{H}} $ configurations, which can be further divided into seven different configurations based on the orientation of dangling bonds and Si-H bonds. By combining the analyses of ELF maps and EPR simulations, it is demonstrated that $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{H}} $ and $ {\mathrm{V}}_{\mathrm{B}\mathrm{M}}^{\mathrm{H}} $ configurations have EPR parameters comparable to those of $ {\mathrm{E}}_{\mathrm{\gamma }}' $ center, indicating that hydrogen passivation processes may interfere with the identification of $ {\mathrm{E}}' $ center. The formation of silanol group in $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{O}\mathrm{H}} $ configuration provides theoretical bases for explaining water molecules formation within oxide layers and at interfaces. This study elucidates the pathways of hydrogen-induced cross-network migration and silanol group formation, jointly revealing the dual role of hydrogen in passivating defects and inducing secondary defects. A microscopic explanation for the increased sensitivity to low dose rates in bipolar devices is derived from these findings.
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Keywords:
- neutral oxygen vacancy /
- hydrogen atom /
- passivation /
- first-principles
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图 2 a-SiO2中5种中性氧空位缺陷的典型结构(红色为氧原子、黄色硅原子)和ELF图
Fig. 2. Typical configurations and ELF maps of five types of neutral oxygen vacancies in a-SiO2 (red spheres, oxygen atoms; yellow spheres, silicon atoms).
图 4 a-SiO2中7种中性氢化氧空位缺陷的典型结构(红色为氧原子、黄色硅原子、白色为氢原子)
Fig. 4. Seven typical configurations of neutral hydrogen-passivated oxygen vacancies in a-SiO2 (red spheres, oxygen atoms; yellow spheres, silicon atoms; white spheres, hydrogen atoms).
图 5 a-SiO2中7种中性氢化氧空位缺陷的ELF图
Fig. 5. ELF maps of seven neutral hydrogen-passivated oxygen vacancies in a-SiO2.
图 6 (a) $ {\mathrm{V}}_{\mathrm{D}} $和(b) $ {\mathrm{V}}_{\mathrm{B}} $构型与氢原子的反应路径和能量曲线
Fig. 6. Reaction pathways and energy curves of (a) $ {\mathrm{V}}_{\mathrm{D}} $ and (b) $ {\mathrm{V}}_{\mathrm{B}} $ configurations with hydrogen atoms.
图 7 (a) $ {\mathrm{V}}_{\mathrm{F}} $和(b) $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $构型与氢原子的反应路径和能量曲线
Fig. 7. Reaction pathways and energy curves of (a) $ {\mathrm{V}}_{\mathrm{F}} $ and (b) $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $ configurations with hydrogen atoms.
图 8 $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $构型与氢原子的反应路径和能量曲线
Fig. 8. Reaction pathway and energy curve of $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $ configuration with a hydrogen atom.
表 1 五种中性氧空位缺陷的结构参数
Table 1. Structural parameters of five types of neutral oxygen vacancies.
种类 数量 平均$ {D}_{\mathrm{S}\mathrm{i}1-\mathrm{S}\mathrm{i}2} $
/Å平均Si—O
键长/Å平均O—Si—O
键角/(°)Si1 Si2 Si1 Si2 $ {\mathrm{V}}_{\mathrm{D}} $ 24 2.42 1.66 1.66 106.95 107.34 $ {\mathrm{V}}_{\mathrm{F}} $ 7 4.19 1.66 1.66 108.52 108.91 $ {\mathrm{V}}_{\mathrm{B}} $ 14 4.81 1.66 1.66 109.31 108.19 $ {\mathrm{V}}_{\mathrm{B}\mathrm{P}4} $ 2 5.32 1.80 1.60 96.27 114.07 $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}} $ 1 3.53 1.71 1.66 99.67 111.63 
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表 2 中性氧空位缺陷和中性氢化氧空位缺陷的平均费米接触和g因子
Table 2. Average Fermi contacts and g values of neutral oxygen vacancies and neutral hydrogen-passivated oxygen vacancies.
缺陷构型 费米接触/mT g1 g2 g3 Si1 Si2 $ {\mathrm{V}}_{\mathrm{B}} $ –38.10 –40.69 2.0006 1.9988 1.9981 $ {\mathrm{V}}_{\mathrm{F}} $ –41.79 –42.95 2.0005 1.9986 1.9979 $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{H}} $ –39.29 –0.00 2.0017 2.0006 2.0002 $ {\mathrm{V}}_{\mathrm{B}\mathrm{F}}^{\mathrm{H}} $ –0.03 –45.07 2.0017 2.0002 1.9998 $ {\mathrm{V}}_{\mathrm{F}\mathrm{B}}^{\mathrm{H}} $ –44.27 –0.12 2.0017 2.0003 2.0000 $ {\mathrm{V}}_{\mathrm{F}\mathrm{F}}^{\mathrm{H}} $ –16.55 –41.14 2.0014 2.0002 1.9997 $ {\mathrm{V}}_{\mathrm{B}\mathrm{M}}^{\mathrm{H}} $ –0.01 –0.27 (–41.72 a) 2.0016 2.0004 2.0001 $ {\mathrm{V}}_{\mathrm{D}\mathrm{S}\mathrm{i}}^{\mathrm{H}} $ –22.89 –0.02 2.0021 2.0020 2.0005 $ {\mathrm{V}}_{\mathrm{B}\mathrm{B}}^{\mathrm{O}\mathrm{H}} $ –43.75 –0.60 2.0016 2.0005 1.9998 注: a 表示Si4费米接触.
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