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等离子体技术在现代材料制备和表面处理过程中起着重要的作用. 本文聚焦于非热等离子体(NTP)材料表面处理及功能化应用, 重点综述NTP在材料表面处理及功能化过程中的最新研究进展, 包括激励产生等离子体的等离子体源、NTP材料表面处理及功能化工艺以及具体应用. 其中, 激励产生等离子体的等离子体源包括感应耦合等离子体/容性耦合等离子体、电子回旋共振/表面波等离子体、螺旋波等离子体、大气压射流等离子体和介质阻挡放电等; NTP材料表面处理及功能化工艺包括等离子体表面接枝和聚合、等离子体增强化学气相沉积和等离子体辅助原子层沉积、等离子体增强反应刻蚀和等离子体辅助原子层刻蚀工艺等; 等离子体表面处理及功能化的具体应用领域包括亲水/疏水表面改性、表面微纳加工、生物组织表面处理、催化剂表面处理等. 最后提出了NTP技术材料表面处理及功能化的应用前景与发展趋势.Plasma technology plays an important role in preparing and processing materials nowadays. This review focuses on the applications of non-thermal plasma (NTP) in the surface treatment and functionalization of materials, including the plasma sources for generating plasmas, NTP techniques and specific application fields. The plasma sources include inductively coupled plasma, capacitively coupled plasma, electron cyclotron resonance plasma, surface wave plasma, helicon wave plasma, atmospheric pressure plasma jet, and dielectric barrier discharge plasma. The NTP techniques for material surface treatment and functionalization include plasma surface grafting and polymerization, plasma enhanced chemical vapor deposition, plasma assisted atomic layer deposition, plasma enhanced reactive ion etching, and plasma assisted atomic layer etching. Specific applications of plasma surface treatment and functionalization cover hydrophilic/hydrophobic surface modification, surface micro-nano processing, biological tissue surface treatment, and catalyst surfaces treatment. Finally, the application prospects and development trends of NTP technology for material surface treatment and functionalization are proposed.
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Keywords:
- plasma/
- surface treatment/
- grafting/
- polymerization/
- deposition/
- etching
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NTP源 频率/MHz 气压/Pa 电子温度/eV 电子密度/cm–3 磁场强度/G 参考文献 CCP 0.05—13.56 1—102 1—5 109—1011 0 蒲以康等[45] ICP 1—100 (常用13.56) 10–1—1 1—10 1011—1012 0 戴忠玲等[46] ECR 300—2450 (常用2450, 915) 10–2—10–1 2—20 1011—1013 0—1000 (与频率有关) Weng等[47] SWP 1—10000 (常用2450) 10–1—102 1—10 1011—1012 0 Moisan等[48] HWP 1—50 (常用13.56) 10–2—10 2—20 1011—1014 100—2000 Boivin等[49] APPJ 0—10000 105 1—5 1011—1014 0 吴淑群等[36] DBD 0.05—10 105 1—10 1014—1015 0 Wang等[39] 
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NTP源 改性气氛 改性基材 主要结论 参考文献 RF-CCP (13.56 MHz) Ar 棉、麻织物 超疏水性(↑)、穿着舒适度(↑) Xu等[74] RF-CCP (13.56 MHz, 20 W) C2H2 聚乳酸、聚已酸内酯 涂层附着性(↑)、氧气阻隔性(↑) Bélard等[75] RF-ICP (27.12 MHz, 200 W) O2, CO2 PET 亲水性(↑)、含氧基团数量(↑) Tkavc等[76] RF-ICP (13.56 MHz, 400 W) O2 PET 表面粗糙度(↑)、水接触角(↓)、
含氧基团数量(↑)Han等[77] MW-ECR (2.45 GHz, 300 W) Ar, AAc PP 表面张力(↑)、Cu涂层附着性(↑) Dayss等[78] MW-SWP (2.45 GHz, 250 W) CO2 聚四氟乙烯(PTFE) 水接触角(↓)、含氧基团数量(↑) Vasilets等[60] MW-SWP (2.45 GHz, 1600 W) Ar 氟基三聚物(THV) 含氧基团数量(↑) Sasai等[21] APPJ (50 kHz, 0—20 kV) TEOS/O2/Ar 聚全氟乙丙烯(FEP) 含硅基团数量(↑)、沿面闪络电压(↑) 胡多等[38] DBD (1 kHz, 25 kV) 空气 PET 表面粗糙度(↑)、水接触角(↓)、
含氧基团数量(↑)Fang等[79] DBD (RTR, 40 kHz) AAc, C2H6O, C3H7N PE 水接触角(↓)、Al 涂层附着性(↑) Zhang等[44] 下载:
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无机薄膜 NTP源 工作气氛 衬底 主要结论 参考文献 SiOx PECVD (DBD, 200 kHz, 3 kV) TEOS/O2/N2 PEN 附着性能(↑)、阻隔性能(↑) Starostin等[83] SiOx PECVD (CPP, 40 kHz, 50 W) HMDSO/O2 PVC 抗迁移性能(↑) Fei等[86,87] AlOx PECVD (1 Hz, 30 W) TMA/O2 硅片 沉积速率(↑)、薄膜纯度(↑) Seman等[88] DLC PECVD (RF, 13.56 MHz, 250 W) CH4 PTFE 薄膜质量(↑)、阻隔性能(↑) Ozeki等[89] a-C:H PECVD (RF, 13.56 MHz) C2H2/Ar PC, PET 薄膜硬度(↓)、阻隔性能(↑) Abbas等[90] a-C:H PECVD (RF, 13.56 MHz, 0-90 W) n-C6H14/Ar PET, 硅片 致密性(↑)、阻隔性能(↑) Polonsky等[80] SiOxCyHz PECVD (APPJ, 20 kHz, 350 V) 空气/HMDSO PP 阻隔性能(↑) Scopece等[84] SiOxCyH PECVD (MW-APPJ, 2.45 GHz, 2000 W) Ar/HMDSO 玻璃 抗雾性能(↑) Durocher-Jean等[85] AlxOy PAALD (CCP, 60 Hz, 500 W) TMA/O2 PEN WVTR: 8.85 × 10–4g·m–2·d–1 Lee等[94] Al2O3 PAALD (RF-ICP) TMA/O2 PEN WVTR: 5.0 × 10–3g·m–2·d–1 Langereis等[95] Al2O3/TiO2 PAALD (APPJ, 20 kHz, 350 V) TMA/TDMAT OTFT 防腐性能(↑)、阻隔性能(↑) Kim等[96] 下载:
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衬底 NTP源 刻蚀气体 主要结果 参考文献 Si PERIE (RF-APPJ, 13.56 MHz) He/N2/CF4 刻蚀速率: 0.068 mm3·min–1;RRMS: 0.2—2.44 nm Paetzelt等[98] SiC PERIE (RF-ICP, 6.78 MHz, 1000 W) SF6/O2 刻蚀速率: 1.28 µm·min–1;RRMS: 0.7 nm Osipov等[99] SiO2 PERIE (RF-ICP, 13.56 MHz, 500 W) Cl2 刻蚀速率: 2.2 nm·min-1 Petit-Etienne等[100] GaN PERIE (MW-ECR, 2.45 GHz, 850 W) Cl2 刻蚀速率: 0.28 μm·min–1; 刻蚀选择性: 39∶1 Harrison等[101] HfO2 PERIE (MW-ECR, 2.45 GHz, 600 W) CF4/Ar/O2 刻蚀速率: 0.36 nm·min–1;RRMS: 0.17 nm 罗童等[102] SiO2 PAALE (RF-ICP, 13.56 MHz) Ar/C4F8 刻蚀速率: 0.2—0.3 Å·s–1 Metzler等[105] GaN PAALE (RF-ICP) Cl2/Ar EPC: 0.4 nm·cycle–1;RRMS: 0.6 nm Ohba等[107] GaN PAALE (RF-ICP, 50 W) Cl2/Ar 刻蚀速率: 2.87 Å·cycle–1 Kauppinen等[108] ZnO PAALE (RF-ICP, 13.56 MHz, 200 W) Hacac/O2 EPC: 0.5—1.3 Å·cycle–1; 刻蚀选择性: 80∶1 Mameli等[110] SiO2 PAALE (RF-ICP, 13.56 MHz) Ar/C4F8 EPC: 0.4 nm·cycle–1;RRMS: 1.2 nm Antoun等[111] 下载:
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