高阻隔主动包装SiOx/Polymer复合薄膜的磁控共溅射制备及反应路径研究

High barrier packaging materials are widely used as food, medicine packaging to extend the shelf-life and prevent harmful material migration and to improve the service life of precision machinery parts, electronic parts and solar module encapsulation. In this project, composite barrier SiOx/Polymer film is deposited by RF co-sputtering from the two magnetrons equipped with SiO2 and DCPD/MA targets, which can solve the brittle cracks and defects existence in the SiOx layers prepared by the traditional PVD methods. The DCPD/MA are depolymerized into flexible contains free radicals of unsaturated polymer chain segment under Ar+ bombardment, and incorporated into the silicon oxide films. Unsaturated bonds are retained as active sites to scavenge oxygen, which gives active packaging function for the SiOx/Polymer film. The structures and properties of SiOx/polymer composite films are investigated. The relationship between the structure and property of the films are explored. The improvement mechanism for film barrier material are studied. The real-time and in situ technologies including mass spectrometry, spectrum and probe are used to diagnosis plasma discharge atmosphere and disclose particles energy transfer, material transmission and chemical reaction, and other important plasma physics and chemical process. The implementation of the project will expand the application field of magnetron sputtering, promote the research related plasma chemical reaction, provide a new way for organic-inorganic composite, and provides a new idea for the design of active packaging materials.

高阻隔性包装材料应用极为广泛，如：食品、药品等包装延长保质期并防止有害物质迁移；精密机械零配件、电子零件与太阳能组件的封装提高其使用寿命。项目创新的设计磁控溅射高分子环氧树脂（DCPD/MA）靶材，并与SiO2靶共溅射，制备高阻隔SiOx/Polymer薄膜。通过Ar+轰击DCPD/MA将其解聚成柔性的包含自由基的不饱和高分子链片段，与Ar+轰击SiO2形成的Si悬挂键键合成复合薄膜，解决PVD法制备陶瓷透明阻隔薄膜的易脆裂问题。薄膜包含不饱和键吸氧活性位点，具备主动包装功能。项目将表征薄膜结构，测试阻隔性能，探求沉积工艺、结构及性能之间的关系，探求薄膜提高基材阻隔性机理。通过原位、实时监测技术实施等离子放电氛围诊断，明确氛围中物质成分及成分之间的化学组装行为、反应路径。项目实施将拓展磁控溅射应用领域，促进相关等离子化学反应研究，为有机无机复合提供新途径，为主动包装材料设计提供新思路。

SiOx薄膜类高阻隔性包装材料有较好的前景，其制备主要手段为物理气相沉积（PVD）。该法制备的SiOx薄膜存在大量裂纹、针孔等固有缺陷并在使用过程中易脆裂，严重影响该类薄膜的应用。本课题创新的设计高分子靶材，并将之与SiO2靶共置磁场中进行反应共溅射，通过Ar+轰击高分子靶材获得柔性不饱和高分子链片段自由基，与Ar+轰击SiO2形成的Si悬挂键键合成复合薄膜，解决PVD法制备隔薄膜的固有缺陷，且复合薄膜包含不饱和碳碳双键与碳氧双键，成为包装薄膜中的吸氧活性位点，实现主动包装。课题执行过程中完成了适用于磁控溅射的高分子靶材的开发，掌握了可调控SiOx/Polymer复合薄膜阻隔性能的关键参数，并对薄膜的制备工艺、结构、组分、形貌以及性能进行研究；利用质谱对磁控反应溅射过程中的真空氛围的反应路径进行了探索，得到了等离子状态下复合薄膜的反应路径并构建了薄膜的结构模型；最后对薄膜的阻隔机制进行了研究。.本课题开发的复合薄膜以Si―O―Si键结构为主体，形成阻氧阻水的关键结构，存在明显的C=C、C=O双键结构的吸氧活性位点实现主动包装。薄膜生长初始阶段的高分子片段优势生长的倾向大大降低了基材PET与SiOx之间的热胀系数差异，解决了传统PVD方法易裂的固有缺陷。利用原位质谱探测了等离子氛围，掌握了单靶溅射SiO2与高分子靶材的解聚规律、解离路径以及粒子结构形式；探索出了活性位点的来源以及等离子状态下复合薄膜SiO、SiO2是主要的与高分子链段结合的硅氧化物粒子形式的组装行为。本课题复合薄膜的成功制备拓宽了磁控溅射技术的应用领域，为有机无机复合材料制备提供了新途径，为同类材料制备进行了有意义的探索。本课题明确了复合薄膜对惰性气体阻隔的渗透激活能与纳米缺陷结构机制；对O2、H2O蒸汽阻隔的化学阻隔机制，该机制为阻隔类材料提供设计基础。