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非热等离子体材料表面处理及功能化研究进展

张海宝 陈强

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非热等离子体材料表面处理及功能化研究进展

张海宝, 陈强

Recent progress of non-thermal plasma material surface treatment and functionalization

Zhang Hai-Bao, Chen Qiang
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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.
      通信作者: 陈强, chenqiang@bigc.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 11505013, 11875090)、北京市自然科学基金(批准号: 1192008)、北京市委组织部优秀人才青年拔尖项目(批准号: 2016000026833ZK12)和北京市教委科技项目(批准号: KM202010015003)资助的课题
      Corresponding author: Chen Qiang, chenqiang@bigc.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11505013, 11875090), the Natural Science Foundation of Beijing, China (Grant No. 1192008), the Outstanding Talent Youth Top-notch Project of Beijing Municipal Party Committee Organization Department, China (Grant No. 2016000026833ZK12), and the Science and Technology Project of Beijing Municipal Education Commission, China (Grant No. KM202010015003)
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  • 图 1  非热等离子体材料表面处理及功能化过程中的等离子体源、等离子体工艺以及具体应用

    Fig. 1.  Non-thermal plasma for material surface treatment and functionalization: Plasma sources, plasma techniques and specific applications.

    图 2  DBD等离子体设备示意图 (a)—(c)平板型放电电极结构; (d), (e)填充床型放电电极结构[1]

    Fig. 2.  Schematical configurations of several DBD: (a)–(c) DBD with planar type discharge electrode structure; (d), (e) DBD with packed bed type discharge electrode structure[1].

    图 3  等离子体表面接枝处理两种工艺模式—“接枝自”模式和“接枝到”模式[1]

    Fig. 3.  Two kinds of different strategies of plasma grafting for modification: “plasma grafting from” and “plasma grafting onto”[1].

    图 4  ALE过程示意图 (a) ALE工艺; (b) Si ALE工艺; (c) SiO2 ALD工艺. ALE工艺与ALD工艺类似, 区别在于反应B中发生钝化层的移除而不是吸附[103]

    Fig. 4.  Schematic of ALE (a) generic concept, (b) for the Si case study, and (c) in comparison to SiO2 ALD. ALE is similar to ALD except that removal takes place instead of adsorption in reaction B[103].

    图 5  H2等离子体表面处理石墨烯 (a)处理700 s时石墨烯的水接触角从原始样品的93°下降至16°; (b)改性石墨烯表面亲水性区域对癌细胞的吸附定位[114]

    Fig. 5.  Modification of graphene by H2 plasma: (a) Control of the graphene wettability via hydrogenation. The as-grown graphene is hydrophobic, with a large wetting angle of 93°. As hydrogenation proceeds, leading to a very small wetting angle of 16° at 700 s. (b) Optical microscopic image of cancer cells positioned on the hydrophilic surface of patterned graphene[114].

    表 1  几种非热等离子体源放电参数

    Table 1.  Discharge parameters of several NTP sources.

    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
    CCP0.05—13.561—1021—5109—10110蒲以康等[45]
    ICP1—100 (常用13.56)10–1—11—101011—10120戴忠玲等[46]
    ECR300—2450 (常用2450, 915)10–2—10–12—201011—10130—1000 (与频率有关)Weng等[47]
    SWP1—10000 (常用2450)10–1—1021—101011—10120Moisan等[48]
    HWP1—50 (常用13.56)10–2—102—201011—1014100—2000Boivin等[49]
    APPJ0—100001051—51011—10140吴淑群等[36]
    DBD0.05—101051—101014—10150Wang等[39]
    下载: 导出CSV

    表 2  非热等离子体聚合物基材表面接枝和聚合

    Table 2.  Polymer substrate surface grafting and polymerization by NTP.

    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, CO2PET亲水性(↑)、含氧基团数量(↑)Tkavc等[76]
    RF-ICP (13.56 MHz, 400 W)O2PET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, AAcPP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, C3H7NPE水接触角(↓)、Al 涂层附着性(↑)Zhang等[44]
    下载: 导出CSV

    表 3  非热等离子体沉积无机功能涂层

    Table 3.  Inorganic functional coatings deposited by NTP.

    无机薄膜NTP源工作气氛衬底主要结论参考文献
    SiOxPECVD (DBD, 200 kHz, 3 kV)TEOS/O2/N2PEN附着性能(↑)、阻隔性能(↑)Starostin等[83]
    SiOxPECVD (CPP, 40 kHz, 50 W)HMDSO/O2PVC抗迁移性能(↑)Fei等[86,87]
    AlOxPECVD (1 Hz, 30 W)TMA/O2硅片沉积速率(↑)、薄膜纯度(↑)Seman等[88]
    DLCPECVD (RF, 13.56 MHz, 250 W)CH4PTFE薄膜质量(↑)、阻隔性能(↑)Ozeki等[89]
    a-C:HPECVD (RF, 13.56 MHz)C2H2/ArPC, PET薄膜硬度(↓)、阻隔性能(↑)Abbas等[90]
    a-C:HPECVD (RF, 13.56 MHz, 0-90 W)n-C6H14/ArPET, 硅片致密性(↑)、阻隔性能(↑)Polonsky等[80]
    SiOxCyHzPECVD (APPJ, 20 kHz, 350 V)空气/HMDSOPP阻隔性能(↑)Scopece等[84]
    SiOxCyHPECVD (MW-APPJ, 2.45 GHz, 2000 W)Ar/HMDSO玻璃抗雾性能(↑)Durocher-Jean等[85]
    AlxOyPAALD (CCP, 60 Hz, 500 W)TMA/O2PENWVTR: 8.85 × 10–4 g·m–2·d–1Lee等[94]
    Al2O3PAALD (RF-ICP)TMA/O2PENWVTR: 5.0 × 10–3 g·m–2·d–1Langereis等[95]
    Al2O3/TiO2PAALD (APPJ, 20 kHz, 350 V)TMA/TDMATOTFT防腐性能(↑)、阻隔性能(↑)Kim等[96]
    下载: 导出CSV

    表 4  非热等离子体辅助材料表面刻蚀

    Table 4.  Material surface etching assisted by NTP.

    衬底NTP源刻蚀气体主要结果参考文献
    SiPERIE (RF-APPJ, 13.56 MHz)He/N2/CF4刻蚀速率: 0.068 mm3·min–1; RRMS: 0.2—2.44 nmPaetzelt等[98]
    SiCPERIE (RF-ICP, 6.78 MHz, 1000 W)SF6/O2刻蚀速率: 1.28 µm·min–1; RRMS: 0.7 nmOsipov等[99]
    SiO2PERIE (RF-ICP, 13.56 MHz, 500 W)Cl2刻蚀速率: 2.2 nm·min-1Petit-Etienne等[100]
    GaNPERIE (MW-ECR, 2.45 GHz, 850 W)Cl2刻蚀速率: 0.28 μm·min–1; 刻蚀选择性: 39∶1Harrison等[101]
    HfO2PERIE (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]
    SiO2PAALE (RF-ICP, 13.56 MHz)Ar/C4F8刻蚀速率: 0.2—0.3 Å·s–1Metzler等[105]
    GaNPAALE (RF-ICP)Cl2/ArEPC: 0.4 nm·cycle–1; RRMS: 0.6 nmOhba等[107]
    GaNPAALE (RF-ICP, 50 W)Cl2/Ar刻蚀速率: 2.87 Å·cycle–1Kauppinen等[108]
    ZnOPAALE (RF-ICP, 13.56 MHz, 200 W)Hacac/O2EPC: 0.5—1.3 Å·cycle–1; 刻蚀选择性: 80∶1Mameli等[110]
    SiO2PAALE (RF-ICP, 13.56 MHz)Ar/C4F8EPC: 0.4 nm·cycle–1; RRMS: 1.2 nmAntoun等[111]
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-12-30
  • 修回日期:  2021-02-03
  • 上网日期:  2021-04-27
  • 刊出日期:  2021-05-05

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