CN116905056A - 一种铜箔表面耐热阻挡层处理液及应用 - Google Patents
一种铜箔表面耐热阻挡层处理液及应用 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000011889 copper foil Substances 0.000 title claims abstract description 74
- 230000004888 barrier function Effects 0.000 title claims abstract description 70
- 239000012530 fluid Substances 0.000 title claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 9
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940081974 saccharin Drugs 0.000 claims abstract description 9
- 235000019204 saccharin Nutrition 0.000 claims abstract description 9
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims abstract description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 8
- -1 sodium propiolate propane sulfonate Chemical compound 0.000 claims abstract description 7
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 25
- 230000005389 magnetism Effects 0.000 abstract description 5
- 230000008054 signal transmission Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 50
- 239000010410 layer Substances 0.000 description 49
- 229910052759 nickel Inorganic materials 0.000 description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 18
- 239000011574 phosphorus Substances 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- 238000000151 deposition Methods 0.000 description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 17
- 229910052721 tungsten Inorganic materials 0.000 description 17
- 239000010937 tungsten Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008021 deposition Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- MSYSXACBDVOYRR-UHFFFAOYSA-N [Na].OCC#C Chemical compound [Na].OCC#C MSYSXACBDVOYRR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
本发明属于铜箔表面处理技术领域,涉及一种铜箔表面耐热阻挡层处理液及应用,每升处理液中包含以下组分原料:硫酸镍17‑25g,氯化镍5‑8g,钨酸钠4‑5g,硼酸30‑40g,次亚磷酸钠3‑7g,硫脲0.1‑0.3g,丙炔醇醚丙烷磺酸钠0.05‑0.08g,糖精0.8‑1.3g,余量为水。本发明的铜箔表面耐热阻挡层处理液,材料简单易得,安全环保;采用本发明的铜箔表面耐热阻挡层处理液制备的表面耐热阻挡层镀层致密、光滑性好、孔隙率低;磁性弱,对高频信号传输影响小;用于制备的高速板用HVLP铜箔具有优良的耐热性,尤其可提高铜箔压制后的耐热性及高温剥离强度。
Description
技术领域
本发明属于铜箔表面处理技术领域,尤其涉及一种铜箔表面耐热阻挡层处理液及应用。
背景技术
随着通信技术的突飞猛进,数字电路逐渐步入信息处理高速化、信息传输高频化阶段。在高频化的印制电路板(PCB)和覆铜箔层压板(CCL)中,信号传输是沿着铜箔的轮廓曲线进行的,其传送距离与表面粗糙度的大小密切相关。当铜箔轮廓大时,信号传输距离增长,造成信号传送速度减慢,并传送损失也增加。因此减小传输路径和减小表面粗化铜瘤是缓解趋肤效应的有效手段。高频超低轮廓铜箔(HVLP铜箔)因其平滑的表面轮廓及极低的表面粗糙度,是高速板使用的主流产品。
另外,为保证高速板的使用可靠性,对铜箔表面的耐热性也提出了更高要求。高速板的加工使用温度较常规产品高,线路板在整机元器件装配焊接时,由于受到高温影响,树脂易裂解产生小分子化合物,如与裸铜表面相接触,将发生反应释放水分,水分高温汽化引起鼓泡,会使铜箔与基板分离。耐热处理层可以阻挡该裂解产物对铜箔表面的攻击,有助于增加铜箔基材与树脂的化学亲和力,进而提高剥离强度。
耐热阻挡层处理一般采用在铜箔粗化层表面再沉积一层其他金属的办法,主要是为了提高铜箔压制后的耐热性及高温剥离强度。一般企业在对电解铜箔进行表面处理时,其阻挡层主要采用锌沉积层或镍沉积层。随着印制电路朝着高频、高速、高密度和高多层化方向发展,印制电路的线宽和线间距越来越窄,在对沉积纯锌铜箔进行电路蚀刻时,会发生侧蚀现象,同时在对印制线路板进行酸洗过程中,也会对镀锌铜箔进行腐蚀,因而会造成铜箔与绝缘基体的结合力下降,严重时铜箔甚至会从绝缘基体上脱落。传统镀镍工艺,镍镀层孔隙率较高,高孔隙率的镍镀层无法保证铜箔受到很好的保护,孔隙部位的裸铜易受到攻击,而影响结合力。增加镍镀层厚度或镍含量,可一定程度减小孔隙率,如果要使镀层达到无孔状态需要超过一定的厚度,而该厚度对于铜箔行业是无法实现的;如果增加镍镀层镍含量,而镍属于磁性元素,过高的镍含量又会严重影响高速板材高频信号的传输性能。
发明内容
本发明针对上述现有技术存在的不足,提供一种铜箔表面耐热阻挡层处理液及应用,具体的技术方案如下:
本发明的第一个目的在于提供一种铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍17-25g,氯化镍5-8g,钨酸钠4-5g,硼酸30-40g,次亚磷酸钠3-7g,硫脲0.1-0.3g,丙炔醇醚丙烷磺酸钠0.05-0.08g,糖精0.8-1.3g,余量为水。
采用本发明铜箔表面耐热阻挡层处理液可形成镍共沉积钨及磷形成三元合金的镍基合金镀层的铜箔表面耐热阻挡层。与常规镀镍工艺相比,相同镍含量的镀层,本发明的合金镀层因钨、磷的存在,可使铜箔表面耐热阻挡层结构更加致密、耐热性、耐腐蚀性及覆盖率更高、磁性更弱。在镍磷合金镀层中,含磷3%晶粒显著细化,磁性随含磷量升高而减弱,耐腐蚀性随含磷量升高而增强。
钨是自然界中熔点最高的金属,同时具有较高的硬度和化学稳定性,镍钨合金镀层结构致密,具有高耐腐蚀性和耐热性,钨可改善镀层的性能。磷可以改变镍镀层的相组成,可提高镀层耐腐蚀性,又能减弱镀层磁性。镀层中的磷来自于次亚磷酸钠,而次亚磷酸钠作为一种强还原剂,在镍合金沉积过程中,会提供电子用于还原镍离子,形成部分镍镀层。因此,镍沉积是电镀和化学镀反应的共同作用。因电沉积过程受阴极表面状态影响,电场作用无法均匀发生,导致合金的均镀性、致密性较差。而化学镀受表面状态影响低,而化学镀具备深度能力和均镀能力好的特点,可均匀地发生在材料表面,填补电镀沉积层的孔隙及缺陷,进而改善镀层的均匀性、降低镀层孔隙率。硫脲作为一种稳定剂,可防止镀液自行分解,有助于控制还原。
钨的标准电极电位为负,且氢在金属钨上的过电位又很小,所以在水溶液中单独电沉积钨是不可能的,本发明采用硼酸为络合剂,通过镍-钨诱导共沉积的方式,共析形成镍钨合金。糖精为一种镀镍光亮剂,能使镀镍层晶粒尺寸减小,还能减小镀层的张应力,增加镀层的延展性。丙炔醇醚丙烷磺酸钠起到整平和光亮的作用,镀液覆盖能力好,镀层应力低。丙炔醇醚丙烷磺酸钠和糖精这两种添加剂协同作用,使镀层达到平滑细晶的效果,增加镀层均匀覆盖性。在这两种添加剂的作用下,阴极极化作用会强,对金属沉积有一定抑制作用,导致金属镀层总量下降;也使金属析出电位适当负移,钨的标准电极电位较镍正,共沉积的钨含量占比会适当降低。
进一步地,所述铜箔表面耐热阻挡层处理液的pH值为1.5-2.5,温度为50-70℃。
进一步地,所述铜箔表面耐热阻挡层处理液的pH值采用酸液或碱液进行调节,酸液为硫酸,碱液为氢氧化钠。
本发明的第二个目的在于提供上述铜箔表面耐热阻挡层处理液在制备高速板用HVLP铜箔中的应用。
进一步地,所述高速板用HVLP铜箔的制备方法包括耐热阻挡层处理,所述耐热阻挡层处理的处理液为上述铜箔表面耐热阻挡层处理液。
进一步地,所述耐热阻挡层处理的阴极电流密度为2-5A/dm2。
进一步地,所述耐热阻挡层处理的电沉积量为50-70mg/m2。
所述高速板用HVLP铜箔的粗化处理面的耐热阻挡层中钨含量占比6-10%,磷含量占比3-6%。
本发明的有益效果为:
1)本发明的铜箔表面耐热阻挡层处理液,材料简单易得,安全环保。
2)采用本发明的铜箔表面耐热阻挡层处理液制备的表面耐热阻挡层镀层致密、光滑性好、孔隙率低;磁性弱,对高频信号传输影响小。
3)本发明的铜箔表面耐热阻挡层处理液可应用于高速板用HVLP铜箔的制备,工艺流程简单,制备的高速板用HVLP铜箔具有优良的耐热性,尤其可提高铜箔压制后的耐热性及高温剥离强度。
附图说明
图1为本发明实施例1所得高速板用HVLP铜箔的表面粗化层的扫描电子显微镜图(5000×)。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
本发明实施例的高速板用HVLP铜箔的制备方法,其步骤包括:
(1)酸洗:硫酸200g/L,温度30℃,浸泡时间6s。
(2)粗化处理:硫酸铜60g/L,硫酸220g/L,微细粗化处理添加剂12g/L,温度30℃,电流密度35A/dm2,时间6s。粗化处理的表面粗糙度Rz值为1.20-1.30μm,该粗糙度值由3D测量激光显微镜测得。
(3)固化处理:硫酸铜320g/L,硫酸160g/L,温度45℃,电流密度26A/dm2,时间8s。
(4)耐热阻挡层处理:形成高速板用HVLP铜箔的表面耐热阻挡层;其中,具体的铜箔表面耐热阻挡处理液及阴极电流密度和电沉积量详见各实施例与对比例;
(5)防氧化处理:重铬酸钾9.5g/L,硫酸锌6g/L,pH 9.0,温度46℃,电流密度3.4A/dm2,时间3s。
(6)硅烷处理:将浓度为0.5wt%的硅烷偶联剂水溶液,在18-28℃条件下喷涂于铜箔粗化处理表面。
(7)烘干。
其中,使用的铜箔为电解法制备的18μm双光毛箔,毛面光泽度Gs(60°)在500以上。
实施例1:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍20g,氯化镍7g,钨酸钠5g,硼酸40g,次亚磷酸钠6g,硫脲0.3g,丙炔醇醚丙烷磺酸钠0.06g,糖精1.1g,余量为水;溶液pH值为2.1,溶液温度为65℃;
耐热阻挡层处理的阴极电流密度为4A/dm2。
实施例2:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍25g,氯化镍5g,钨酸钠4g,硼酸30g,次亚磷酸钠3g,硫脲0.1g,丙炔醇醚丙烷磺酸钠0.08g,糖精1.3g,余量为水;溶液pH值为1.5,溶液温度为50℃;
耐热阻挡层处理的阴极电流密度为2A/dm2。
实施例3:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍20g,氯化镍8g,钨酸钠5g,硼酸35g,次亚磷酸钠7g,硫脲0.3g,丙炔醇醚丙烷磺酸钠0.05g,糖精0.8g,余量为水;溶液pH值为2.5,溶液温度为70℃;
耐热阻挡层处理的阴极电流密度为5A/dm2。
对比例1:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍20g/L,氯化镍7g/L,钨酸钠5g/L,硼酸40g/L,丙炔醇醚丙烷磺酸钠0.06g/L,糖精1.1g/L,余量为水;溶液pH值为2.1,溶液温度为65℃;
耐热阻挡层处理的阴极电流密度为4A/dm2。
对比例2:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍20g/L,氯化镍7g/L,钨酸钠5g/L,硼酸40g/L,次亚磷酸钠6g/L,硫脲0.3g/L,余量为水;溶液pH值为2.1,溶液温度为65℃;
耐热阻挡层处理的阴极电流密度为4A/dm2。
对比例3:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍20g/L,氯化镍7g/L,钨酸钠5g/L,硼酸40g/L,余量为水;溶液pH值为2.1,溶液温度为65℃;
耐热阻挡层处理的阴极电流密度为4A/dm2。
对比例4:
一种高速板用HVLP铜箔的制备:
步骤(4)耐热阻挡层处理中,铜箔表面耐热阻挡层处理液,每升处理液中包含以下组分原料:硫酸镍30g/L,硼酸40g/L,余量为水;溶液pH值为3.5,溶液温度为46℃;
耐热阻挡层处理的阴极电流密度为3A/dm2。
对上述实施例和对比例制备的高速板用HVLP铜箔进行表面耐热阻挡层元素分析,测试结果如表1所示。其中,总沉积量为镍、钨、磷的沉积量加和。
表1实施例和对比例中的表面耐热阻挡层元素分析测试结果表
由表1可知,实施例1-3的耐热阻挡层合金总沉积量均在50-70mg/m2范围内,具有较低的镍沉积量在45-57mg/m2范围内,钨含量占比6%-10%,磷含量占比4%-6%,可使耐热阻挡层具有致密性、表面平滑性;高耐腐蚀性和耐热性,又能减弱磁性。对比例1的耐热阻挡层中的磷含量为0,因其处理液中无含磷盐使用,无化学镀反应发生,且电镀也无法发生磷共沉积。对比例2的耐热阻挡层处理液中未使用起光亮镀镍作用的添加剂,阴极极化作用减弱,所以镀层金属总含量提升。另外,不含添加剂的镍-钨沉积电位相对正移,钨含量有所升高,占比近14%。对比例3为诱导共沉积镍钨合金,不使用添加剂及含磷盐,镀层钨含量占比12.35%,磷含量0。对比例4为常规镀纯镍,钨含量及磷含量均为0。
取实施例1-3及对比例1-4的高速板用HVLP铜箔,搭配ULL级别聚苯醚体系树脂压制高速基板,进行初始及耐高温抗剥离强度测试,测试结果如表2所示。其中,耐高温抗剥离强度为288℃浸锡处理后测得,衰减率=(初始抗剥-浸锡后抗剥)÷初始抗剥×100%。
表2初始及耐高温抗剥离强度测试结果表
由表2可知,实施例1-3在288℃浸锡3min、5min后的抗剥离强度与初始值相近,无明显衰减,浸锡10min后的衰减率也在10%以内。因为实施例1-3的镍合金耐热阻挡层在添加剂的作用下晶粒细致,而化学镀具备深度能力和均镀能力好的特点,可填补电镀沉积层的孔隙,铜、树脂间的阻挡效果较好,所以表现出更高的可靠性。且实施例1-3采用较低的镍沉积量(45-57mg/m2),即可达到对比例无法实现的效果。对比例1-3在浸锡5min后,抗剥离强度呈现衰减现象,浸锡10min后的抗剥衰减达到20%左右,说明阻挡效果出现一定程度下降。对比例4在浸锡5min后,抗剥离强度出现明显衰减,10min后衰减率高达近40%,说明该耐热阻挡层致密性差、孔隙率大,已无法很好的保护铜层。在基板受热后,铜表面受到分解物的强烈攻击,导致粘结力大幅下降,存在起泡、分层的使用风险。虽然共沉积钨、磷对镀层有益,但钨、磷含量不宜过高。过量沉积钨、磷,会导致析氢反应加剧,降低耐热阻挡层的致密性及表面平滑性,会对镀层性能产生不利影响。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种铜箔表面耐热阻挡层处理液,其特征在于,每升处理液中包含以下组分原料:硫酸镍17-25g,氯化镍5-8g,钨酸钠4-5g,硼酸30-40g,次亚磷酸钠3-7g,硫脲0.1-0.3g,丙炔醇醚丙烷磺酸钠0.05-0.08g,糖精0.8-1.3g,余量为水。
2.根据权利要求1所述的铜箔表面耐热阻挡层处理液,其特征在于,所述铜箔表面耐热阻挡层处理液的pH值为1.5-2.5,温度为50-70℃。
3.如权利要求1或2所述的铜箔表面耐热阻挡层处理液在制备高速板用HVLP铜箔中的应用。
4.根据权利要求3所述的应用,其特征在于,所述高速板用HVLP铜箔的制备方法包括耐热阻挡层处理,所述耐热阻挡层处理的处理液为权利要求1或2所述的铜箔表面耐热阻挡层处理液。
5.根据权利要求4所述的应用,其特征在于,所述耐热阻挡层处理的阴极电流密度为2-5A/dm2。
6.根据权利要求4所述的应用,其特征在于,所述耐热阻挡层处理的电沉积量为50-70mg/m2。
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