CN114908340B - 一种附载体超薄铜箔及其制备方法 - Google Patents
一种附载体超薄铜箔及其制备方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011889 copper foil Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 claims abstract description 22
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 17
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 17
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 239000004519 grease Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 102000008186 Collagen Human genes 0.000 claims description 6
- 108010035532 Collagen Proteins 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 229920001436 collagen Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002085 enols Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 22
- 230000008021 deposition Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1657—Electroless forming, i.e. substrate removed or destroyed at the end of the process
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1667—Radiant energy, e.g. laser
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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Abstract
本发明公开了一种附载体超薄铜箔，包括金属箔载体层、合金层与超薄铜箔层；超薄铜箔层的厚度为1‑4μm，通过光催化沉积法沉积于合金层上；合金层通过电镀沉积于金属箔载体层上，电解液为含有稀土元素Ce的Ni‑Co合金溶液。本发明还提供了上述附载体超薄铜箔的制备方法，包括步骤：(1)对金属箔载体层进行预处理；(2)在金属箔载体层表面电沉积合金层；(3)在合金层表面沉积超薄铜箔层：在含有光催化剂的硫酸铜混合溶液中通过光催化沉积法在金属箔载体层上形成超薄铜箔层。本发明能够得到可与载体稳定分离的超薄铜箔，剥离后的超薄铜箔致密性、均匀性好，具有优异的抗拉性能，在减小铜箔厚度的同时提高超薄铜箔性能。
Description
技术领域
本发明涉及附载体超薄铜箔制备技术领域，特别涉及一种附载体超薄铜箔及其制备方法。
背景技术
近年来，随着手机、电脑、数码相机等电子产品的高集成化和轻薄化，用于电子产品的印制线路板(Printed Circuit Board，简称PCB)和锂电池也要求更轻薄、更轻巧。电解铜箔是PCB和锂离子电池负极集流体的基础材料，在这样的一个趋势之下电解铜箔的开发研究趋于更薄、性能更高的方向发展。铜箔厚度越小，越不易于长途运输、长期保存，且在使用过程中也越容易发生折皱和撕裂。将超薄铜箔电沉积在载体上制成附载体超薄铜箔，有了载体的支撑，可以很好的解决超薄铜箔运输和保存困难的问题。
目前国内厂家生产的超薄铜箔厚度主要为6-9μm，现有的电解铜箔工艺制备6μm以下超薄铜箔工艺难度较大，针对更轻、更薄、降本增效的需求，铜箔的进一步轻薄化是当前铜箔产业发展的重要方向，减小超薄铜箔厚度，同时实现更大的性能突破，以满足多样化生产的需求，是实现超薄铜箔发展的重点、难点问题。
发明内容
本发明的目的在于解决现有技术中存在的上述技术问题。本发明提供了一种附载体超薄铜箔及其制备方法，可得到可与载体稳定分离的超薄铜箔，剥离后的超薄铜箔致密性、均匀性好，具有优异的抗拉性能，在减小铜箔厚度的同时提高超薄铜箔性能。
为解决上述技术问题，本发明的实施方式公开了一种附载体超薄铜箔，包括金属箔载体层、合金层与超薄铜箔层；
所述超薄铜箔层的厚度为1-4μm，所述超薄铜箔层通过光催化沉积法沉积于所述合金层上；
所述合金层通过电镀沉积于所述金属箔载体层上，电解液为含有稀土元素Ce的Ni-Co合金溶液。
进一步，所述光催化沉积法中采用功率为140-160W的紫外灯，特征波长为254.6nm，紫外灯距离石英反应器50mm，紫外灯照射0.2-1h。
进一步，所述金属箔载体层为35μm铝箔。
进一步，所述超薄铜箔层与所述金属箔载体层之间的剥离强度为0.14-0.20N/mm。
本发明的实施方式还公开了上述附载体超薄铜箔的制备方法，包括以下步骤：
(1)对金属箔载体层进行预处理，去除金属箔载体层表面的油脂和氧化层；
(2)在金属箔载体层表面电沉积合金层：电沉积所用电解液为含有稀土元素Ce的Ni-Co合金溶液；
(3)在合金层表面沉积超薄铜箔层：在含有光催化剂的硫酸铜混合溶液中通过光催化沉积法在所述金属箔载体层上形成厚度为1-4μm的超薄铜箔层。
进一步，步骤(2)中，电沉积条件为：电解液温度为45℃，pH为4，电流密度为15-20A/dm2。
进一步，步骤(2)中含有稀土元素Ce的Ni-Co合金溶液中，硫酸镍10-25g/L，硫酸钴20-50g/L，硫酸铈0.1-0.5g/L，硼酸20g/L，氯化钠5-10g/L，十二烷基硫酸钠0.5-2.5g/L。
进一步，步骤(3)中，所述硫酸铜混合溶液的组成为：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白、40ppm盐酸、2-5g/L三硬脂酸甘油酯和光催化剂。
进一步，步骤(3)中，所述光催化剂通过以下方法制备得到：在15-30g/L无水乙醇中边搅拌边滴加5g/L钛酸四丁酯、7g/L烯醇硅醚和5g/L二丁基锡二月桂酸酯中的一种，滴加完成后加入超纯水，继续搅拌1-3h，将得到的混合溶液置于60-75℃烘箱中烘干，对烘干后得到的样品进行研磨，最后在400-550℃下煅烧0.5-1.5h，即可得到所述光催化剂。
进一步，步骤(1)中，所述油脂通过使用丙酮溶液清洗去除；
所述氧化层通过使用体积浓度为50％的硝酸(65-68wt％浓度级)、5％的硫酸(98wt％浓度级)与5％的氢氟酸(40wt％浓度级)混合水溶液去除。
与现有技术相比，本发明具有如下有益技术效果：
本发明以35μm铝箔为载体，对其表面预处理后，在铝箔表面沉积含有稀土元素Ce的Ni-Co合金剥离层，最后通过光催化沉积法制备附载体超薄铜箔层；
在Ni-Co合金中引入稀土元素Ce可以改善镀液的稳定性，增加镀液阴极极化，降低氢气在阴极析出，细化镀层晶粒，提高镀层的耐蚀性，改善镀层的抗剥离能力，提高镀层性能；此外，与合金层复合时，稀土元素Ce只需要微小的添加量即可实现优异的剥离效果；
光催化沉积法可以对超薄铜箔的厚度进行严格控制，得到的超薄铜箔可与载体稳定分离，剥离后的超薄铜箔致密性、均匀性好，具有优异的抗拉性能，在减小铜箔厚度的同时提高超薄铜箔性能；
本发明提供的制备方法简单，易于操作。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。虽然本发明的描述将结合较佳实施例一起介绍，但这并不代表此发明的特征仅限于该实施方式。恰恰相反，结合实施方式作发明介绍的目的是为了覆盖基于本发明的权利要求而有可能延伸出的其它选择或改造。为了提供对本发明的深度了解，以下描述中将包含许多具体的细节。本发明也可以不使用这些细节实施。此外，为了避免混乱或模糊本发明的重点，有些具体细节将在描述中被省略。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
实施例1
(1)对金属箔载体层进行预处理
取35μm铝箔为载体，用丙酮溶液清洗表面，去除表面油脂等杂质，再通过硝酸、硫酸与氢氟酸混合水溶液去除铝箔表面的氧化层；
(2)在金属箔载体层表面沉积合金层
以步骤(1)中的铝箔为载体层，在Ni-Co镀液进行合金层的沉积，Ni-Co镀液中含有硫酸镍20g/L，硫酸钴30g/L，硫酸铈0.1g/L，硼酸20g/L，氯化钠6g/L，十二烷基硫酸钠0.6g/L，镀液温度为45℃，PH值为4，电流密度为15A/dm2，电沉积时间为8s；
(3)在合金层表面沉积超薄铜箔层
将步骤(2)经过镀合金层后的铝箔置于含有光催化剂的硫酸铜混合溶液中进行光催化沉积，制得厚度为4μm的超薄铜箔；
硫酸铜电解液的组成：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白、40ppm盐酸、2g/L三硬脂酸甘油酯和光催化剂；
光催化剂制备：在25g/L无水乙醇中边搅拌边滴加5g/L钛酸四丁酯，滴加完成后加入超纯水，继续搅拌1h，将得到的混合溶液置于60℃烘箱中烘干，对烘干后得到的样品进行研磨，最后在400℃下煅烧1.5h，得到光催化剂；
光催化沉积的工艺参数：功率为150W的紫外灯，特征波长为254.6nm，紫外灯距离石英反应器50mm，紫外灯照射0.5h。
实施例2
(1)对金属箔载体层进行预处理
取35μm铝箔为载体层，用丙酮溶液清洗表面，去除表面油脂等杂质，再通过硝酸、硫酸与氢氟酸混合水溶液去除铝箔表面的氧化层；
(2)在金属箔载体表面沉积合金层
以步骤(1)中的铝箔为载体层，在Ni-Co镀液进行合金层的沉积，Ni-Co镀液中含有硫酸镍25g/L，硫酸钴27g/L，硫酸铈0.5g/L，硼酸20g/L，氯化钠5g/L，十二烷基硫酸钠1g/L，镀液温度为45℃，PH值为4，电流密度为18A/dm2，电沉积时间为10s；
(3)在合金层表面沉积超薄铜箔层
将步骤(2)经过镀合金层后的铝箔置于含有光催化剂的硫酸铜混合溶液中进行光催化沉积，制得厚度为3μm的超薄铜箔；
硫酸铜电解液的组成：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白、40ppm盐酸、5g/L三硬脂酸甘油酯和光催化剂；
光催化剂制备：在30g/L无水乙醇中边搅拌边滴加7g/L烯醇硅醚，滴加完成后加入超纯水，继续搅拌1.5h，将得到的混合溶液置于66℃烘箱中烘干，对烘干后得到的样品进行研磨，最后在435℃下煅烧1h，即可得到光催化剂；
光催化沉积工艺参数：功率为150W的紫外灯，特征波长为254.6nm，紫外灯距离石英反应器50mm，紫外灯照射0.5h。
实施例3
(1)对金属箔载体层进行预处理
取35μm铝箔为载体，用丙酮溶液清洗表面，去除表面油脂等杂质，再通过硝酸、硫酸与氢氟酸混合水溶液去除铝箔表面的氧化层；
(2)在金属箔载体表面沉积合金层
以步骤(1)中的铝箔为载体，在Ni-Co镀液进行合金层的沉积，Ni-Co镀液中含有硫酸镍18g/L，硫酸钴35g/L，硫酸铈0.2g/L，硼酸20g/L，氯化钠8g/L，十二烷基硫酸钠2g/L，镀液温度为45℃，PH值为4，电流密度为20A/dm2，电沉积时间为10s；
(3)在合金层表面沉积超薄铜箔层
将步骤(2)经过镀合金层后的铝箔置于含有光催化剂的硫酸铜混合溶液中进行光催化沉积，制得厚度为3.5μm的超薄铜箔；
硫酸铜电解液的组成：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白、40ppm盐酸、3g/L三硬脂酸甘油酯和光催化剂；
光催化剂制备：在15g/L无水乙醇中边搅拌边滴加5g/L二丁基锡二月桂酸酯，滴加完成后加入超纯水，继续搅拌2h，将得到的混合溶液置于75℃烘箱中烘干，对烘干后得到的样品进行研磨，最后在550℃下煅烧0.5h，即可得到光催化剂；
光催化沉积工艺参数：功率为150W的紫外灯，特征波长为254.6nm，紫外灯距离石英反应器50mm，紫外灯照射0.5h。
实施例4
用实施例2相同的方法得到厚度为3μm的超薄铜箔层，不同的是将步骤(3)中光催化沉积工艺参数替换成功率为140W的紫外灯，紫外灯照射1h。
实施例5
用实施例2相同的方法得到厚度为2.5μm的超薄铜箔层，不同的是将步骤(3)中光催化沉积工艺参数替换成功率为150W的紫外灯，紫外灯照射0.2h。
实施例6
用实施例2相同的方法得到厚度为1μm的超薄铜箔层，不同的是将步骤(3)中光催化沉积工艺参数替换成功率为160W的紫外灯，紫外灯照射0.2h。
对照例1
(1)对金属箔载体层进行预处理
取35μm铝箔为载体，用丙酮溶液清洗表面，去除表面油脂等杂质，再通过硝酸、硫酸与氢氟酸混合水溶液去除铝箔表面的氧化层；
(2)在金属箔载体表面沉积合金层
以步骤(1)中的铝箔为载体层，在Ni-Co镀液进行合金层的沉积，Ni-Co镀液中含有硫酸镍25g/L，硫酸钴27g/L，硫酸铈0.5g/L，硼酸20g/L，氯化钠5g/L，十二烷基硫酸钠1g/L，镀液温度为45℃，PH值为4，电流密度为18A/dm2，电沉积时间为10s；
(3)在合金层表面沉积超薄铜箔层
将步骤(2)经过镀合金层后的铝箔置于硫酸铜电解液中进行电镀铜，制得厚度为6μm的超薄铜箔；
硫酸铜电解液的组成：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白和40ppm盐酸；电流密度为30A/dm2，电解液温度为55℃，沉积时间为35s；
对照例2
用对照例1相同的方法得到厚度为4μm的超薄铜箔层，不同的是将步骤(3)中电解工艺参数替换成电流密度为20A/dm2，沉积时间为20s。
对照例3
用对照例1相同的方法得到厚度为3μm的超薄铜箔层，不同的是将步骤(3)中电解工艺参数替换成电流密度为20A/dm2，沉积时间为15s。
性能测试
取实施例1-6和对照例1-3制备的样品，在180℃条件下与FR-4半固化片进行压合，通过机械方法对载体箔进行剥离强度测试。此外，对剥离后的超薄铜箔进行性能测试，结果如表1所示。
表1
测试结果表明，本发明实施例1-6的超薄铜箔层与铝箔载体之间的剥离效果优异，剥离强度为0.14-0.20N/mm，剥离后的超薄铜箔表面光亮整洁，无撕裂、褶皱情况出现。实施例样品的剥离强度比对照例样品的剥离强度更小，这是由于光催化沉积法利用光催化铜盐，在铝箔表面直接沉积铜，得到的超薄铜箔致密性和均匀性好，更易于从载体上完整剥离。此外，实施例样品与对照例样品相较而言具有更薄的厚度和更高的抗拉强度。
虽然通过参照本发明的某些优选实施方式，已经对本发明进行了描述，但本领域的普通技术人员应该明白，以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。本领域技术人员可以在形式上和细节上对其作各种改变，包括做出若干简单推演或替换，而不偏离本发明的精神和范围。
Claims (5)
1.一种附载体超薄铜箔，其特征在于，包括金属箔载体层、合金层与超薄铜箔层；
所述超薄铜箔层的厚度为1-4μm，所述超薄铜箔层通过光催化沉积法沉积于所述合金层上，所述光催化沉积法中采用功率为140-160W的紫外灯，特征波长为 254.6nm，紫外灯距离石英反应器50mm，紫外灯照射0.2-0.5h；
所述合金层通过电镀沉积于所述金属箔载体层上，电解液为含有稀土元素Ce的Ni-Co合金溶液；
所述附载体超薄铜箔的制备方法，包括以下步骤：
（1）对金属箔载体层进行预处理，去除金属箔载体层表面的油脂和氧化层；
（2）在金属箔载体层表面电沉积合金层：电沉积所用电解液为含有稀土元素Ce的Ni-Co合金溶液；
（3）在合金层表面沉积超薄铜箔层：在含有光催化剂的硫酸铜混合溶液中通过光催化沉积法在所述金属箔载体层上形成厚度为1-4μm的超薄铜箔层；
其中，步骤（3）中，所述硫酸铜混合溶液的组成为：90g/L硫酸铜、100g/L硫酸、30ppm水解胶原蛋白、40ppm盐酸、2-5g/L三硬脂酸甘油酯和光催化剂；
所述光催化剂通过以下方法制备得到：在15-30g/L无水乙醇中边搅拌边滴加5g/L钛酸四丁酯、7g/L烯醇硅醚和5g/L二丁基锡二月桂酸酯中的一种，滴加完成后加入超纯水，继续搅拌1-3h，将得到的混合溶液置于60-75℃烘箱中烘干，对烘干后得到的样品进行研磨，最后在400-550℃下煅烧0.5-1.5h，即可得到所述光催化剂；
步骤（2）中，电沉积条件为：电解液温度为45℃，pH为4，电流密度为15-20A/dm2；
含有稀土元素Ce的Ni-Co合金溶液中，硫酸镍10-25g/L，硫酸钴20-50g/L，硫酸铈0.1-0.5g/L，硼酸20g/L，氯化钠5-10g/L，十二烷基硫酸钠0.5-2.5g/L。
2.如权利要求1所述的附载体超薄铜箔，其特征在于，所述金属箔载体层为35μm铝箔。
3.如权利要求1所述的附载体超薄铜箔，其特征在于，所述超薄铜箔层与所述金属箔载体层之间的剥离强度为0.14-0.20N/mm。
4.一种权利要求1至3任一项所述的附载体超薄铜箔的制备方法，其特征在于，包括以下步骤：
（1）对金属箔载体层进行预处理，去除金属箔载体层表面的油脂和氧化层；
（2）在金属箔载体层表面电沉积合金层：电沉积所用电解液为含有稀土元素Ce的Ni-Co合金溶液；
（3）在合金层表面沉积超薄铜箔层：在含有光催化剂的硫酸铜混合溶液中通过光催化沉积法在所述金属箔载体层上形成厚度为1-4μm的超薄铜箔层。
5.如权利要求4所述的附载体超薄铜箔的制备方法，其特征在于，步骤（1）中，所述油脂通过使用丙酮溶液清洗去除；
所述氧化层通过使用体积浓度为50％的65-68wt％浓度级硝酸、5％的98wt％浓度级硫酸与5％的40wt％浓度级氢氟酸混合水溶液去除。
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