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

Zhang Hai-Bao; Chen Qiang

doi:10.7498/aps.70.20202233

Abstract

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.

Keywords:

Authors and contacts

Laboratory of Plasma Physics and Materials, Beijing Institute of Graphic Communication, Beijing 102600, China

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

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

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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]

Figure 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].

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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]

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

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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]

Figure 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].

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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]

Figure 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].

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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
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]

DownLoad: 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, 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]

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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
SiO_x	PECVD (DBD, 200 kHz, 3 kV)	TEOS/O₂/N₂	PEN	附着性能(↑)、阻隔性能(↑)	Starostin等^[83]
SiO_x	PECVD (CPP, 40 kHz, 50 W)	HMDSO/O₂	PVC	抗迁移性能(↑)	Fei等^[86,87]
AlO_x	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]
SiO_xC_yH_z	PECVD (APPJ, 20 kHz, 350 V)	空气/HMDSO	PP	阻隔性能(↑)	Scopece等^[84]
SiO_xC_yH	PECVD (MW-APPJ, 2.45 GHz, 2000 W)	Ar/HMDSO	玻璃	抗雾性能(↑)	Durocher-Jean等^[85]
Al_xO_y	PAALD (CCP, 60 Hz, 500 W)	TMA/O₂	PEN	WVTR: 8.85 × 10^–4 g·m^–2·d^–1	Lee等^[94]
Al₂O₃	PAALD (RF-ICP)	TMA/O₂	PEN	WVTR: 5.0 × 10^–3 g·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]

DownLoad: 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
Si	PERIE (RF-APPJ, 13.56 MHz)	He/N₂/CF₄	刻蚀速率: 0.068 mm³·min^–1; R_RMS: 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; R_RMS: 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; R_RMS: 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; R_RMS: 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; R_RMS: 1.2 nm	Antoun等^[111]

DownLoad: CSV

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Vol. 70, Issue 9 - 2021-05-05

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