CN113789513A - 一种基于正负脉冲的陶瓷基板表面镀铜方法 - Google Patents
一种基于正负脉冲的陶瓷基板表面镀铜方法 Download PDFInfo
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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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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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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Abstract
本发明公开了一种基于正负脉冲的陶瓷基板表面镀铜方法，具体步骤如下：步骤一、瓷片清洗，去除陶瓷表面污渍；步骤二、磁控溅射；步骤三、图形转移，利用黄光微影制程完成图形转移；步骤四、正反脉冲电镀，使金属层增厚；其中：正向脉冲电流密度为1—5ASD，正向脉冲持续时间10—100ms，反向脉冲电流密度为2—20ASD，反向脉冲持续时间0.5—8ms；步骤五、去膜蚀刻，蚀刻出所需的图形；步骤六、表面处理。该方法镀出来的铜层晶粒细小、均匀、致密，镀层纯度高，可用于制作精细线路。
Description
技术领域
本发明属于陶瓷金属化领域，涉及一种基于正负脉冲的陶瓷基板表面镀铜方法。
背景技术
陶瓷镀铜基板，是一种高机械强度、化学稳定性好、高导热和具有电绝缘性的电路基板，主要应用于大功率半导体模块、半导体致冷器及LED散热基板及太阳能电池组件等。目前市场上陶瓷镀铜基板的制程主要包括：采用磁控溅射的方法在陶瓷基板上溅射种子层、表面图形化、电镀铜增厚、表面处理等。
关于脉冲电镀铜的研究主要集中在冶金级电镀和印刷电路板(PCB)布线方面，现有技术中未见脉冲电镀有效应用于陶瓷基板上的报道。
现有技术中陶瓷基板电镀铜工艺镀得的铜层晶粒尺寸较大，不利于制作精细线路。
发明内容
本发明的目的主要在于提供一种基于正负脉冲的陶瓷基板表面镀铜方法，该方法镀出来的铜层晶粒细小、均匀、致密，镀层纯度高，可用于制作精细线路。
本发明的技术方案是：一种基于正负脉冲的陶瓷基板表面镀铜方法，具体步骤如下：
步骤一、瓷片清洗，去除陶瓷表面污渍；
步骤二、磁控溅射；
步骤三、图形转移，利用黄光微影制程完成图形转移；
步骤四、正反脉冲电镀，使金属层增厚；
其中：正向脉冲电流密度为1—5ASD，正向脉冲持续时间10—100ms，反向脉冲电流密度为2—20ASD，反向脉冲持续时间0.5—8ms；
步骤五、去膜蚀刻，蚀刻出所需的图形；
步骤六、表面处理。
进一步的，步骤四中正反脉冲电镀采用的电镀液为酸性镀铜溶液，CuSO4·5H2O浓度为 40—140g/L，H2SO4浓度为180—240g/L，HCl浓度为40—80ppm，光亮剂浓度1—3ml/L，整平剂浓度10—20ml/L，余量为水。
进一步的，所述光亮剂聚二硫二丙烷磺酸钠、甲苯基聚二硫丙烷磺酸钠、醇硫基丙烷磺酸钠中的一种或几种混合；所述整平剂为乙基硫脲、氨基硫脲、酰基硫脲中的一种或几种混合。
进一步的，步骤二中所述磁控溅射是利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。
进一步的，步骤二中所述磁控溅射为在陶瓷基板表面溅射一层TiW层和一层Cu层，使陶瓷表面导电。
进一步的，TiW层厚度为50—300nm，Cu层厚度为100—1000nm。
进一步的，步骤一中所述清洗为通过除油剂和酸洗去除陶瓷表面的油污和杂质。
进一步的，所述清洗具体方式为在无水乙醇、异丙醇、丙酮中的一种溶剂或几种混合液中常温超声5min-30min，随后在HF溶液中进行微蚀1-3min、超声水洗1-3min、溢流水洗、吸水滚轮、80℃-100℃的热风烘干3-5min。
进一步的，步骤六中，所述表面处理方式为防氧化、化学镍金、化学镀银或电镀镍金。其中，OSP是印刷电路板(PCB)铜箔表面处理的符合RoHS指令要求的一种工艺。
本发明的有益效果是：1)提供了一种用于制作陶瓷基板的新型的正负脉冲电镀铜方法； 2)该方法电镀铜一小时以上仍能够获得细小、均匀、致密的铜晶粒，从而可以制备精细的铜线路；3)本发明提供的方法经济有效，适配性强，操作简单，能够应用于工业量产。
附图说明
图1为不采用脉冲电镀铜层的SEM图片(晶粒大、均匀性差)。
图2为实施例1中脉冲电镀铜层的SEM图片。
图3为实施例2中脉冲电镀铜层的SEM图片。
图4为实施例3中脉冲电镀铜层的SEM图片。
具体实施方式
下面结合附图对本发明做进一步的说明。
实施例1
一种基于正负脉冲的陶瓷基板表面镀铜方法，具体步骤如下：
步骤一、瓷片清洗，去除陶瓷表面污渍。所述清洗为通过除油剂和酸洗去除陶瓷表面的油污和杂质。清洗具体方式为在无水乙醇、异丙醇、丙酮中的一种溶剂或几种混合液中常温超声5min-30min，随后在HF溶液中进行微蚀1-3min、超声水洗1-3min、溢流水洗、吸水滚轮、80℃-100℃的热风烘干3-5min。
步骤二、磁控溅射，利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。具体的，所述磁控溅射是利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。 TiW层厚度为100nm，Cu层厚度为500nm。
步骤三、图形转移，利用黄光微影制程完成图形转移。
步骤四、正反脉冲电镀，使金属层增厚。
其中：正向脉冲电流密度为2ASD，正向脉冲持续时间20ms，反向脉冲电流密度为6ASD，反向脉冲持续时间1ms，电镀时间1小时。
正反脉冲电镀采用的电镀液为酸性镀铜溶液，CuSO4·5H2O浓度为80g/L，H2SO4浓度为 220g/L，HCl浓度为60ppm，聚二硫二丙烷磺酸钠浓度2ml/L，乙基硫脲浓度18ml/L。余量为水。
步骤五、去膜蚀刻，蚀刻出所需的图形。
步骤六、表面处理，表面处理方式为OSP、化学镍金、化学镀银或电镀镍金均可。
图2为实施例1中脉冲电镀铜层的SEM图片。
实施例2
一种基于正负脉冲的陶瓷基板表面镀铜方法，具体步骤如下：
步骤一、瓷片清洗，去除陶瓷表面污渍。所述清洗为通过除油剂和酸洗去除陶瓷表面的油污和杂质。清洗具体方式为在无水乙醇、异丙醇、丙酮中的一种溶剂或几种混合液中常温超声5min-30min，随后在HF溶液中进行微蚀1-3min、超声水洗1-3min、溢流水洗、吸水滚轮、80℃-100℃的热风烘干3-5min。
步骤二、磁控溅射，利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。具体的，所述磁控溅射是利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。 TiW层厚度为100nm，Cu层厚度为500nm。
步骤三、图形转移，利用黄光微影制程完成图形转移。
步骤四、正反脉冲电镀，使金属层增厚。
其中：正向脉冲电流密度为3ASD，正向脉冲持续时间20ms，反向脉冲电流密度为9ASD，反向脉冲持续时间1ms，电镀时间1小时。
正反脉冲电镀采用的电镀液为酸性镀铜溶液，CuSO4·5H2O浓度为80g/L，H2SO4浓度为 220g/L，HCl浓度为60ppm，甲苯基聚二硫丙烷磺酸钠浓度2ml/L，氨基硫脲浓度18ml/L。
步骤五、去膜蚀刻，蚀刻出所需的图形。
步骤六、表面处理，表面处理方式为OSP、化学镍金、化学镀银或电镀镍金均可。
图3为实施例2中脉冲电镀铜层的SEM图片。
实施例3
一种基于正负脉冲的陶瓷基板表面镀铜方法，具体步骤如下：
步骤一、瓷片清洗，去除陶瓷表面污渍。所述清洗为通过除油剂和酸洗去除陶瓷表面的油污和杂质。清洗具体方式为在无水乙醇、异丙醇、丙酮中的一种溶剂或几种混合液中常温超声5min-30min，随后在HF溶液中进行微蚀1-3min、超声水洗1-3min、溢流水洗、吸水滚轮、80℃-100℃的热风烘干3-5min。
步骤二、磁控溅射，利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。具体的，所述磁控溅射是利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。 TiW层厚度为150nm，Cu层厚度为800nm。
步骤三、图形转移，利用黄光微影制程完成图形转移。
步骤四、正反脉冲电镀，使金属层增厚。
其中：正向脉冲电流密度为3ASD，正向脉冲持续时间10ms，反向脉冲电流密度为9ASD，反向脉冲持续时间0.7ms，电镀时间1小时。
正反脉冲电镀采用的电镀液为酸性镀铜溶液，CuSO4·5H2O浓度为80g/L，H2SO4浓度为 220g/L，HCl浓度为60ppm，醇硫基丙烷磺酸钠2ml/L，酰基硫脲18ml/L。
步骤五、去膜蚀刻，蚀刻出所需的图形。
步骤六、表面处理，表面处理方式为OSP、化学镍金、化学镀银或电镀镍金均可。
图4为实施例3中脉冲电镀铜层的SEM图片。
表1
由表1可知，该方法能够获得细小、均匀、致密的铜晶粒，从而可以制备精细的铜线路。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：具体步骤如下：
步骤一、瓷片清洗，去除陶瓷表面污渍；
步骤二、磁控溅射；
步骤三、图形转移，利用黄光微影制程完成图形转移；
步骤四、正反脉冲电镀，使金属层增厚；
其中：正向脉冲电流密度为1—5ASD，正向脉冲持续时间10—100ms，反向脉冲电流密度为2—20ASD，反向脉冲持续时间0.5—8ms；
步骤五、去膜蚀刻，蚀刻出所需的图形；
步骤六、表面处理。
2.根据权利要求1所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：步骤四中正反脉冲电镀采用的电镀液为酸性镀铜溶液，CuSO4·5H2O浓度为40—140g/L，H2SO4浓度为180—240g/L，HCl浓度为40—80ppm，光亮剂浓度1—3ml/L，整平剂浓度10—20ml/L，余量为水。
3.根据权利要求2所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：所述光亮剂聚二硫二丙烷磺酸钠、甲苯基聚二硫丙烷磺酸钠、醇硫基丙烷磺酸钠中的一种或几种混合；所述整平剂为乙基硫脲、氨基硫脲、酰基硫脲中的一种或几种混合。
4.根据权利要求1所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：步骤二中所述磁控溅射是利用辉光放电产生的Ar离子轰击靶材来实现金属薄膜在瓷片上沉积。
5.根据权利要求1所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：步骤二中所述磁控溅射为在陶瓷基板表面溅射一层TiW层和一层Cu层，使陶瓷表面导电。
6.根据权利要求5所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：TiW层厚度为50—300nm，Cu层厚度为100—1000nm。
7.根据权利要求1所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：步骤一中所述清洗为通过除油剂和酸洗去除陶瓷表面的油污和杂质。
8.根据权利要求7所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：所述清洗具体方式为在无水乙醇、异丙醇、丙酮中的一种溶剂或几种混合液中常温超声5min-30min，随后在HF溶液中进行微蚀1-3min、超声水洗1-3min、溢流水洗、吸水滚轮、80℃-100℃的热风烘干3-5min。
9.根据权利要求1所述的一种基于正负脉冲的陶瓷基板表面镀铜方法，其特征在于：步骤六中，所述表面处理方式为防氧化、化学镍金、化学镀银或电镀镍金。
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