CN116377429A - 一种高速且稳定的化学镀铜液用添加剂 - Google Patents
一种高速且稳定的化学镀铜液用添加剂 Download PDFInfo
- Publication number
- CN116377429A CN116377429A CN202310151208.2A CN202310151208A CN116377429A CN 116377429 A CN116377429 A CN 116377429A CN 202310151208 A CN202310151208 A CN 202310151208A CN 116377429 A CN116377429 A CN 116377429A
- Authority
- CN
- China
- Prior art keywords
- plating solution
- copper plating
- additive
- electroless copper
- speed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- 239000010949 copper Substances 0.000 title claims abstract description 62
- 239000000654 additive Substances 0.000 title claims abstract description 18
- 230000000996 additive effect Effects 0.000 title claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 20
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- UTYXJYFJPBYDKY-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UTYXJYFJPBYDKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 230000002035 prolonged effect Effects 0.000 claims abstract description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229940095064 tartrate Drugs 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical group [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052763 palladium Inorganic materials 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009713 electroplating Methods 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemically Coating (AREA)
Abstract
本发明提供一种高速且稳定的化学镀铜液用添加剂，包括2‑氨基‑5‑巯基‑1,3,4‑噻二唑和三水合亚铁氰化钾，其中，2‑氨基‑5‑巯基‑1,3,4‑噻二唑的用量为1‑30ppm；三水合亚铁氰化钾为0.5‑50ppm。本发明的2‑氨基‑5‑巯基‑1,3,4‑噻二唑能够提高镀液对浸出钯的耐受能力，加入一定量三水合亚铁氰化钾后，两者有较好的协同作用，镀液对浸出钯的耐受能力进一步增强，有利于提高镀液使用寿命，延长镀液分解时间；即使在高浸出钯浓度下，也不会影响电镀铜液的起镀活性以及均镀能力，可以获0.5‑0.6μm/12min的沉积速率；稳定性良好，镀液分解时间延长2‑6小时，提高使用寿命，降低生产成本。
Description
技术领域
本发明涉及镀铜液技术领域，尤其是一种高速且稳定的化学镀铜液用添加剂。
背景技术
PCB化学镀铜是孔金属化而设计的工艺，在基材上沉积铜层是PCB化学镀铜的关键工艺，化学沉铜占据沉铜工艺流程成本的35-50％。
PCB化学沉铜的工艺流程为：溶胀-除胶-中和-除油-微蚀-预浸-活化-加速-沉铜，其中，化学镀铜作为线路板化学沉铜的最后一步流程，是PCB制造过程中孔金属化品质保证的关键所在。
PCB板经过活化槽吸附胶态钯-加速槽中解胶后孔内壁吸附的钯核暴露，每一批板材进入镀铜槽后，钯核作为催化剂，催化铜沉积于基材板上，但孔内暴露的钯均有不同程度的浸出、剥离并扩散向镀铜液，随着做板批次(数量)的增加，化学镀液中钯含量累积到一定浓度，将在镀液中形成多个铜离子析出活性位点，化学镀液稳定性下降，最终导致镀液在沉铜过程中析出铜粉，槽壁上铜，严重影响化学镀铜液使用寿命。
另外当前的沉铜程序耗时长，平均在垂直沉铜缸中的反应时间达到15-25min，沉积速率在0.5um/20min，生产效率低，产能影响较大。
发明内容
针对现有技术的不足，本发明提供一种高速且稳定的化学镀铜液用添加剂，确保在高沉积速率的同时，具备稳定的性能，在获得良好沉铜层品质的同时，减少维护的频率，促进生产效率。
本发明的技术方案为：一种高速且稳定的化学镀铜液用添加剂，包括2-氨基-5-巯基-1,3,4-噻二唑和三水合亚铁氰化钾，其中，所述的2-氨基-5-巯基-1,3,4-噻二唑的用量为1-30ppm；所述的三水合亚铁氰化钾为0.5-50ppm。
作为优选的，所述的2-氨基-5-巯基-1,3,4-噻二唑和三水合亚铁氰化钾的质量比为0.1～1:1。
作为优选的，所述的添加剂还包括配位剂。
作为优选的，所述的配位剂的浓度为20-50g/L。
作为优选的，所述的配位剂为酒石酸或者酒石酸盐。
作为优选的，所述的酒石酸盐为酒石酸钾钠。
作为优选的，在所述的添加剂的作用下，镀铜液分解时间延长2-6小时，沉积速率为0.5-0.6μm/12min。
本发明的有益效果为：
1、本发明的2-氨基-5-巯基-1,3,4-噻二唑能够提高镀液对浸出钯的耐受能力，加入一定量三水合亚铁氰化钾后，两者有较好的协同作用，镀液对浸出钯的耐受能力进一步增强，有利于提高镀液使用寿命，延长镀液分解时间；
2、本发明的化学镀铜液即使在高浸出(钯)浓度下，也不会影响电镀铜液的起镀活性以及均镀能力，在正常生产的负载下，可以获0.5-0.6μm/12min的沉积速率；
3、本发明镀铜液稳定性良好，镀液分解时间延长2-6小时，提高使用寿命，降低生产成本。
具体实施方式
下面对本发明的具体实施方式作进一步说明：
实施例1
为了便于理解，本实施例简单介绍化学沉铜的工艺：
化学沉铜的工艺流程为：溶胀-除胶渣-中和-除油-微蚀-预浸-活化-加速-化学镀铜，其中溶胀剂、中和剂、除油剂、预浸、活化、加速剂分别选自硕成集团广东利尔化学有限公司的EC-7Y、EC-18S、EC-31F、EC-33D、EC-34、EC-35L。
以下实施例和对比例以五水合硫酸铜、酒石酸钾钠、氢氧化钠、甲醛、聚乙二醇1000、2,2-联吡啶作为化学镀铜液的基础成分，在此基础上通过是否加入本发明的添加剂形成实施例和对比例。
起镀前30s通过向化学镀液中添加活化钯，检验镀液对钯的耐受能力，分解时间越长则镀液对钯耐受能力越强，即化学镀铜液的稳定性越好。
通过沉积速率片来测定沉积速率，确认化学镀铜液的沉积活性，镀铜速度。
实施例1-4和对比例1，电镀铜液组成如表1下所示，起镀前30s向镀液中添加活化钯。以板材放入镀液起开始计时，当板材板面全部附着沉铜层的那一刻为计时终点，记录为镀铜启镀时间；化学镀铜12min取出板材，磨切片，用金相显微镜观察背光情况并评级，并通过测试片测定化学镀铜的沉积速率；沉铜后的镀液静置，观察镀液分解情况，记录出现分解时间，评判化学镀液的稳定性，实验结果如表2下所示。
表1实施例1-4和对比例1电镀铜液组成
表2实施例1-4和对比例1实验结果
根据对比例1的实验结果可知，当镀铜液中钯含量达到1mg/L，没有添加稳定剂2-氨基-5-巯基-1,3,4-噻二唑、三水合亚铁氰化钾的化学镀液会迅速分解，无法上铜，可知浸出钯会破坏镀液的稳定性。
根据实施例1-4的结果显示，2-氨基-5-巯基-1,3,4-噻二唑、三水合亚铁氰化钾在较宽的浓度范围内都能获得良好的沉积速率和稳定性。
实施例5-10
实施例5-10，电镀铜液组成如表3下所示，主要对比单独加入2-氨基-5-巯基-1,3,4-噻二唑或三水合亚铁氰化钾对镀液的稳定与沉积速率的影响。起镀前30s向镀液中添加活化钯。以板材放入镀液起开始计时，当板材板面全部附着沉铜层的那一刻为计时终点，记录为镀铜启镀时间；化学镀铜12min取出板材，磨切片，用金相显微镜观察背光情况并评级，并通过测试片测定化学镀铜的沉积速率；沉铜后的镀液在通风橱中放置，观察镀液分解情况，记录出现分解时间，评判镀液的稳定性，实验结果如表4下所示。
表3实施例5-10镀铜液组成
表4实施例5-10实验结果
根据实施例5-10的实验结果可知。当基础化学镀液中单独加入2-氨基-5-巯基-1,3,4-噻二唑或者三水合亚铁氰化钾时，沉积速率高，但化学镀液分解较快，稳定性不如实施例1-4；实施例5-10的起镀时间差异不大，说明单独加入2-氨基-5-巯基-1,3,4-噻二唑或者三水合亚铁氰化钾并不明显影响起镀时间。
上述实施例和说明书中描述的只是说明本发明的原理和最佳实施例，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。
Claims (7)
1.一种高速且稳定的化学镀铜液用添加剂，其特征在于：包括2-氨基-5-巯基-1,3,4-噻二唑和三水合亚铁氰化钾，其中，所述的2-氨基-5-巯基-1,3,4-噻二唑的用量为1-30ppm；所述的三水合亚铁氰化钾为0.5-50ppm。
2.根据权利要求1所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：所述的2-氨基-5-巯基-1,3,4-噻二唑和三水合亚铁氰化钾的质量比为0.1～1:1。
3.根据权利要求2所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：所述的添加剂还包括配位剂。
4.根据权利要求3所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：所述的配位剂为酒石酸或者酒石酸盐。
5.根据权利要求4所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：所述的酒石酸盐为酒石酸钾钠。
6.根据权利要求4所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：所述的配位剂的浓度为20-50g/L。
7.根据权利要求1所述的一种高速且稳定的化学镀铜液用添加剂，其特征在于：在所述的添加剂的作用下，镀铜液分解时间延长2-6小时，沉积速率为0.5-0.6μm/12min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310151208.2A CN116377429A (zh) | 2023-02-22 | 2023-02-22 | 一种高速且稳定的化学镀铜液用添加剂 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310151208.2A CN116377429A (zh) | 2023-02-22 | 2023-02-22 | 一种高速且稳定的化学镀铜液用添加剂 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116377429A true CN116377429A (zh) | 2023-07-04 |
Family
ID=86968275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310151208.2A Pending CN116377429A (zh) | 2023-02-22 | 2023-02-22 | 一种高速且稳定的化学镀铜液用添加剂 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116377429A (zh) |
-
2023
- 2023-02-22 CN CN202310151208.2A patent/CN116377429A/zh active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110724943A (zh) | 铜表面化学镀镍前无钯活化液及制备方法和镀镍方法 | |
| US9228262B2 (en) | Plating catalyst and method | |
| CN113388829A (zh) | 化学镀铜液以及利用化学镀铜液镀铜基板的方法 | |
| CN109852952B (zh) | 一种水合肼化学镀镍镀液及其制备方法和镀镍方法 | |
| CN112501598B (zh) | 一种铝基材pcb线路板上用化学镀镍液及其制备方法 | |
| CN1063395A (zh) | 无化学镀孔金属化工艺——黑孔化方法 | |
| CN113005437B (zh) | 一种用于印制线路板的化学沉金液 | |
| RU2398049C2 (ru) | Усовершенствованные стабилизация и рабочие характеристики автокаталитических способов нанесения покрытия методом химического восстановления | |
| CN116377429A (zh) | 一种高速且稳定的化学镀铜液用添加剂 | |
| US9227182B2 (en) | Plating catalyst and method | |
| CN113046733B (zh) | 一种用于pcb电路板化学镍金的钯活化方法 | |
| CN117385348A (zh) | 一种沉铜液以及稳定剂 | |
| CN102877044A (zh) | 一种环保型无铅化学镍金的生产方法 | |
| CN117904612A (zh) | 一种高稳定的添加剂及化学铜液 | |
| CN113897600A (zh) | 一种双络合体系低应力化学镀铜液及其制备方法和应用 | |
| CN117448800A (zh) | 一种镀铜液以及稳定剂 | |
| CN113005438B (zh) | 一种银离子促进剂作为提高化学镀钯液中镀钯速率的添加剂的方法 | |
| CN111118482A (zh) | 一种化学镀银液及应用 | |
| CN115505977A (zh) | 一种提高电镀铜液稳定性的复合添加剂 | |
| CN114411130A (zh) | 一种延展性良好的厚化学镀铜溶液 | |
| CN113026004B (zh) | 一种用于化学镍金印制线路板的高磷化学镍溶液 | |
| CN118028793A (zh) | 一种pcb化学镀铜用镀铜液及pcb板沉厚铜工艺 | |
| CN117551992A (zh) | 一种化学镀金溶液及其镀金工艺 | |
| CN114059053A (zh) | 化学镀Ni-W-P镀液及其制备方法、Ni-W-P镀层及其制备方法 | |
| CN117966140A (zh) | 一种化学镀钯溶液及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |