目的 采用磁过滤电弧离子镀技术在氰酸酯复材表面沉积Cu膜,并探究沉积气压对氰酸酯复材表面Cu膜结构与性能的影响规律与作用机理,优选出最佳沉积气压。方法 采用磁过滤电弧离子镀技术分别在0.10、0.30、0.50、0.70和0.90 Pa沉积气压下制备Cu膜,通过检测Cu膜的表面形貌、微观结构、成分及元素含量,探究沉积气压对薄膜晶粒尺寸、择优取向、化学元素成分等薄膜微观状态的影响规律,并结合Cu膜的电阻率及结合力,分析讨论Cu膜的微观状态对其宏观电学性能与结合强度的影响。结果 随着沉积气压由0.10 Pa升高至0.90 Pa,Cu膜晶粒尺寸呈先增大后减小的趋势,薄膜纯度下降、织构由(200)转化为(111)。薄膜电阻率在低沉积气压下变化较小,基本维持在1.7×10-8 Ω·m左右,超过0.50 Pa时受氧化物生成、晶界散射增加、取向转变等因素影响,电阻率明显升高,沉积气压为0.90 Pa时,电阻率升至7.7×10-8 Ω·m。Cu膜/氰酸酯复材界面处化学键对结合强度影响显著,界面处C—O、C==O等含氧化学键的增加及CuO的生成有助于提升界面结合强度,沉积气压为0.50~0.70 Pa时,结合性能最佳,约为3 MPa。结论 沉积气压对Cu膜微观状态及宏观性能调控作用显著,沉积气压为0.50 Pa时,薄膜具有高导电性、高结合强度等最佳的综合性能。
Abstract
Cyanate ester resin composites reinforced with quartz fibers (cyanate ester composites) exhibit high heat resistance, low water absorption, high strength, and superior dielectric properties, making them an ideal aerospace material. Surface metallization of cyanate ester composites can provide them with good electrical and magnetic conductivity without altering their excellent properties, better meeting functional applications in the aerospace field such as electromagnetic shielding of aircraft fuselages. Magnetic-filtered cathodic arc ion plating technology has the advantages of high ionization rate, high particle impact energy, strong adhesion strength, and precise controllability of film thickness, making it an effective method for the surface metallization of cyanate ester composites. Film deposition is a kinetic process where deposition pressure effectively modulates the kinetic impact of particles during the deposition. This alters the growth behavior of deposition, enabling precise control over the microstructure of Cu films, including grain size, crystallographic texture, and defects, thereby affecting their macroscopic properties. The work aims to adopt the magnetic-filtered cathodic arc ion plating technology to prepare Cu films on the surface of cyanate ester composites under deposition pressures of 0.10, 0.30, 0.50, 0.70 and 0.90 Pa, in order to investigate the effect of deposition pressure on the structure and properties of the Cu films. Micromorphology and microstructure, including grain size, crystallographic texture, and chemical composition. were characterized through scanning electron microscope (SEM), atomic force microscope (AFM), X-ray Diffraction (XRD), and energy dispersive X-ray Spectroscopy (EDS). Furthermore, electrical resistivity and adhesion strength were evaluated via four-probe resistance measurements and tensile testing to analyze the correlation between structure and properties. To better analyze the interfacial bonding mechanism, SEM and X-ray photoelectron spectroscopy (XPS) were also used to examine the morphology and chemical bonds at the Cu film/cyanate ester composite interface. As the deposition pressure increased from 0.10 to 0.90 Pa, the grain size initially increased and then decreased, reaching a maximum of 67 nm at 0.50 Pa. while the smallest grain size of 11 nm was observed at 0.90 Pa, accompanied by numerous intergranular voids. Residual impurity gases inside the composite and vacuum chamber distributed along film defects, leading to lower purity. Additionally, at low pressures, the Cu film exhibited (200) texture. As deposition pressure increased to 0.90 Pa, the increase collision resulted in reduced particle energy and restricted diffusion, driving force for the growth of (111) oriented grains with the lowest surface free energy. The resistivity exhibited minimal variation at low deposition pressures, remaining around 1.7×10-8 Ω·m. When the pressure exceeded 0.50 Pa, resistivity increased significantly due to oxide formation, enhancing grain boundary scattering, and crystallographic texture transformations. At a deposition gas pressure of 0.90 Pa, the resistivity increased to 7.7×10-8 Ω·m. Chemical bonds at the Cu film/cyanate ester composite interface significantly affected bonding strength. Increased oxygen-containing bonds (such as C—O, C==O) and CuO formation at the interface enhanced adhesion strength. Optimal adhesion performance (approximately 3 MPa) was achieved at a deposition pressure of 0.50 Pa and 0.70 Pa. Deposition pressure significantly regulates the microstructure and properties of the Cu film. At a deposition pressure of 0.50 Pa, the film exhibits the optimal comprehensive performance.
关键词
磁过滤电弧离子镀 /
沉积气压 /
氰酸酯 /
微观结构 /
电学性能 /
结合强度
Key words
magnetic-filtered cathodic arc ion plating /
deposition pressure /
cyanate ester /
microstructure /
electrical resistivity /
adhesion strength
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] HAMERTON I.Chemistry and Technology of Cyanate Ester Resins[M]. Dordrecht: Springer Netherlands, 1994.
[2] INAMDAR A, CHERUKATTU J, ANAND A, et al.Thermoplastic-Toughened High-Temperature Cyanate Esters and Their Application in Advanced Composites[J]. Industrial & Engineering Chemistry Research, 2018, 57(13): 4479-4504.
[3] 王飞, 石佩洛. 树脂基复合材料在雷达天线罩领域的应用及发展[J]. 宇航材料工艺, 2017, 47(2): 10-13.
WANG F, SHI P L.Application and Development of Resin Matrix Composites for Radomes[J]. Aerospace Materials & Technology, 2017, 47(2): 10-13.
[4] KANGISHWAR S, RADHIKA N, SHEIK A A, et al.A Comprehensive Review on Polymer Matrix Composites: Material Selection, Fabrication, and Application[J]. Polymer Bulletin, 2023, 80(1): 47-87.
[5] ZEGAOUI A, WANG A R, QADEER DAYO A, et al.Effects of Gamma Irradiation on the Mechanical and Thermal Properties of Cyanate Ester/Benzoxazine Resin[J]. Radiation Physics and Chemistry, 2017, 141: 110-117.
[6] CZERWINSKI F.Aluminum Alloys for Electrical Engineering: A Review[J]. Journal of Materials Science, 2024, 59(32): 14847-14892.
[7] PARK J Y, JUNG Y S, CHO J, et al.Chemical Reaction of Sputtered Cu Film with PI Modified by Low Energy Reactive Atomic Beam[J]. Applied Surface Science, 2006, 252(16): 5877-5891.
[8] JIANG T, HU H Y.Review of Evolution and Rising Significance of Wafer-Level Electroplating Equipment in Semiconductor Manufacturing[J]. Electronics, 2025, 14(5): 894.
[9] CHOI M R, KIM H G, LEE T W, et al.Microstructural Evaluation and Failure Analysis of Ag Wire Bonded to Al Pads[J]. Microelectronics Reliability, 2015, 55(11): 2306-2315.
[10] 邱家稳, 赵栋才. 电弧离子镀技术及其在硬质薄膜方面的应用[J]. 表面技术, 2012, 41(2): 93-100.
QIU J W, ZHAO D C.A Review of Vacuum Arc Deposition and its Application in Hardness Films[J]. Surface Technology, 2012, 41(2): 93-100.
[11] 王福贞, 武俊伟. 现代离子镀膜技术[M]. 北京: 机械工业出版社: 2021.
WANG F Z, WU J W.Modern Ion Plating Technology[M]. Beijing: China Machine Press, 2021.
[12] SONG Y J, LÜ W M, ZHANG D Y, et al.The Impact of Various Arc Ion Plating Parameters on the Deposition Speed of Copper Thin Films[J]. Journal of Physics: Conference Series, 2025, 3080(1): 012133.
[13] 刘星, 岳守晶, 李帅,等. 复合材料表面电弧离子镀金属化工艺研究[J]. 真空与低温, 2020, 26(5): 417-423.
LIU X, YUE S J, LI S, et al.Study on Metallization Process of Composite Surface by Arc Ion Plating[J]. Vacuum and Cryogenics, 2020, 26(5): 417-423.
[14] JIANG M Q, LI Y, ZHANG H Y.Corrosion Resistance and Plasma Surface Treatment on Titanium and Titanium Alloys: A Review[J]. Coatings, 2025, 15(10): 1180.
[15] 张泽, 张远涛, 张林, 等. 电弧离子镀涂层大颗粒缺陷控制与抑制技术研究进展[J]. 表面技术, 2025, 54(1): 1-16.
ZHANG Z, ZHANG Y T, ZHANG L, et al.Research Progress of Large Particle Defect Removal in Arc Ion Plating Coatings[J]. Surface Technology, 2025, 54(1): 1-16.
[16] 孟超, 岳守晶, 轩立新, 等. 等离子体处理对氰酸酯基复合材料表面性能影响研究[J]. 真空, 2022, 59(2): 6-10.
MENG C, YUE S J, XUAN L X, et al.Influence of Surface Plasma Activation on Cyanate Ester Composites[J]. Vacuum, 2022, 59(2): 6-10.
[17] 王新超, 但敏, 张帆, 等. 米级范围内不同距离的等离子体活化对玻璃纤维/氰酸酯基复合材料表面沉积Al涂层性能研究[J]. 真空科学与技术学报, 2021, 41(8): 732-738.
WANG X C, DAN M, ZHANG F, et al.Study on the Performance of Al Coating Deposited on the Surface of Glass Fiber/Cyanate Composites by Plasma Activation at Different Distances in the Meter Range[J]. Chinese Journal of Vacuum Science and Technology, 2021, 41(8): 732-738.
[18] 王恩哥. 薄膜生长中的表面动力学(Ⅰ)[J]. 物理学进展, 2003, 23(1): 1-61.
WANG E G.Atomic-scale Study of Kinetics in Film Growth(Ⅰ)[J]. Progress in Physics, 2003, 23(1): 1-61.
[19] MES-ADI H, SAADOUNI K, BADAWI M, et al.Growth and Annealing Effect on the Cu Thin Film Deposited on Si (001) Surface[J]. Journal of Crystal Growth, 2022, 586: 126631.
[20] KARWAL S, VERHEIJEN M A, ARTS K, et al.Plasma- Assisted ALD of Highly Conductive HFNX: On the Effect of Energetic Ions on Film Microstructure[J]. Plasma Chemistry and Plasma Processing, 2020, 40(3): 697-712.
[21] WEI H L, LIU Z L, YAO K L.The Influence of the Incidence Energy of Deposited Particles on the Growth Morphology of Thin Films[J]. Vacuum, 2000, 57(1): 87-97.
[22] ZHU G, SUN J P, ZHANG L B, et al.Molecular Dynamics Simulation of Temperature Effects on Deposition of Cu Film on Si by Magnetron Sputtering[J]. Journal of Crystal Growth, 2018, 492: 60-66.
[23] 王宇, 黄美东, 李云珂, 等. 沉积气压对杂化离子镀TiCN薄膜结构和性能的影响[J]. 中国表面工程, 2015, 28(5): 24-29.
WANG Y, HUANG M D, LI Y K, et al.Effects of Deposition Pressure on Structure and Properties of TiCN Films by Hybrid Ion Plating[J]. China Surface Engineering, 2015, 28(5): 24-29.
[24] ZHANG J, LIU C, FAN J.Comparison of Cu Thin Films Deposited on Si Substrates with Different Surfaces and Temperatures[J]. Applied Surface Science, 2013, 276: 417-423.
[25] PEETERS S A, LENNON C T, MERKX M J M, et al. Ultrathin Superconducting TaCxN1-x Films Prepared by Plasma-Enhanced Atomic Layer Deposition with Ion- Energy Control[J]. Applied Physics Letters, 2023, 123(13): 132603.
[26] MUSIL J.Low-Pressure Magnetron Sputtering[J]. Vacuum, 1998, 50(3/4): 363-372.
[27] BUNSHAH R F.Handbook of Hard Coatings[M]. Park Ridge, NJ: Noyes Publications, 2001.
[28] BILEK M M M, MARTIN P J, MCKENZIE D R. Influence of Gas Pressure and Cathode Composition on Ion Energy Distributions in Filtered Cathodic Vacuum Arcs[J]. Journal of Applied Physics, 1998, 83(6): 2965-2970.
[29] 方应翠. 真空镀膜原理与技术[M]. 北京: 科学出版社, 2014.
FANG Y C.The Theory and Technology of Vacuum Coating[M]. Beijing: Science Press, 2014.
[30] 赵彦辉, 史文博, 刘忠海, 等. 沉积工艺参数对电弧离子镀薄膜沉积速率影响的研究进展[J]. 真空与低温, 2020, 26(5): 385-391.
ZHAO Y H,SHI W B,LIU Z H,et al.Progress on Effects of Deposition Processing Parameters on Coatings Deposition Rate for Arc Ion Plating[J]. Vacuum and Cryogenics, 2020, 26(5): 385-391.
[31] 李海凤, 牛玉超, 苏超, 等. 工艺参数对直流磁控溅射膜沉积的影响[J]. 表面技术, 2009, 38(5): 67-70.
LI H F, NIU Y C, SU C, et al.Effect of Process Parameters on the Deposition of DC Magnetron Sputtered Films[J]. Surface Technology, 2009, 38(5): 67-70.
[32] 杨杭生, 邱发敏, 聂安民. 立方氮化硼薄膜中的氧杂质[J]. 无机材料学报, 2010, 25(7): 748-752.
YANG H S, QIU F M, NIE A M.Oxygen Impurity in Cubic Boron Nitride Thin Films Prepared by Plasma- enhanced Chemical Vapor Deposition[J]. Journal of inorganic materials, 2010, 25(7): 748-752.
[33] ZHANG Y, JING P P, MA D L, et al.Tribological Properties of Mn-TiN Films and Formation of Graphite- Like Layers in Physiological Solution[J]. Vacuum, 2022, 200: 111021.
[34] CHEN T S.Dependence of Stress and Resistivity of Sputtered Copper Films on Deposition Conditions[J]. Rochester: Rochester Institute of Technology, 1989: 44-60.
[35] YANG C Y, WANG J X, SANG C C, et al.In situ Engineering of a Multifunctional Cathode-Electrolyte Interphase for Advanced Sodium-Ion Batteries[J]. ACS Energy Letters, 2025, 10(7): 3544-3553.
[36] 周耐根, 周浪, 宋固全, 等. 等轴应变作用下Cu,Al薄膜的取向择优生长[J]. 金属学报, 2005, 41(8): 809-813.
ZHOU N G, ZHOU L, SONG G Q, et al.Preferential Growth of Copper and Aluminum Films Under Biaxial Strain[J]. Acta Metallurgica Sinica, 2005, 41(8): 809-813.
[37] VOLKENSHTEIN N V, DYAKINA V P, STARTSEV V E.Scattering Mechanisms of Conduction Electrons in Transition Metals at Low Temperatures[J]. Physica Status Solidi (b), 1973, 57(1): 9-42.
[38] LIM J W, ISSHIKI M.Electrical Resistivity of Cu Films Deposited by Ion Beam Deposition: Effects of Grain Size, Impurities, and Morphological Defect[J]. Journal of Applied Physics, 2006, 99(9): 094909.
[39] BISHARA H, LEE S, BRINK T, et al.Understanding Grain Boundary Electrical Resistivity in Cu: The Effect of Boundary Structure[J]. ACS Nano, 2021, 15(10): 16607-16615.
[40] KOIKE J, WADA M, SANADA M, et al.Effects of Crystallographic Texture on Stress-Migration Resistance in Copper Thin Films[J]. Applied Physics Letters, 2002, 81(6): 1017-1019.
[41] SEKIGUCHI A, KOIKE J, KAMIYA S, et al.Void Formation by Thermal Stress Concentration at Twin Interfaces in Cu Thin Films[J]. Applied Physics Letters, 2001, 79(9): 1264-1266.
[42] PARK I S, AHN E C, YU J, et al.Cohesive Failure of the Cu/Polyimide System[J]. Materials Science and Engineering: A, 2000, 282(1/2): 137-144.
[43] HSU P C, CHANG S C, LU W X, et al.Enhanced Adhesion Strength between Electroplated Cu and ABF Substrate with Isothermal Annealing Treatment[J]. Surface and Coatings Technology, 2024, 479: 130576.
[44] TSAI Y N, CHEN H Y, TSENG I H, et al.Adhesive Properties of Deposited Cu Films on Colorless Polyimide Using High Power Impulse Magnetron Sputtering System[J]. Surface and Coatings Technology, 2024, 484: 130710.
[45] ZHANG Z H, WANG P.Highly Stable Copper Oxide Composite as an Effective Photocathode for Water Splitting via a Facile Electrochemical Synthesis Strategy[J]. Journal of Materials Chemistry, 2012, 22(6): 2456-2464.
[46] KOO S B, LEE C M, KWON S J, et al.Study on Aging Effect of Adhesion Strength between Polyimide Film and Copper Layer[J]. Metals and Materials International, 2019, 25(1): 117-126.
基金
西物创新行动项目（202301XWCX003）;中核集团青年英才项目（2023JZYF-01）
PDF(11875 KB)
渝公网安备 50010702501715号 渝ICP备15012534号-3
