CN118028814B - Ceramic copper clad laminate surface treatment agent and ceramic copper clad laminate surface treatment working fluid - Google Patents
Ceramic copper clad laminate surface treatment agent and ceramic copper clad laminate surface treatment working fluid Download PDFInfo
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- CN118028814B CN118028814B CN202311654426.4A CN202311654426A CN118028814B CN 118028814 B CN118028814 B CN 118028814B CN 202311654426 A CN202311654426 A CN 202311654426A CN 118028814 B CN118028814 B CN 118028814B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 17
- 238000004381 surface treatment Methods 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 60
- 229910052802 copper Inorganic materials 0.000 title abstract description 58
- 239000010949 copper Substances 0.000 title abstract description 58
- 239000012530 fluid Substances 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims abstract description 14
- -1 heterocyclic amine Chemical class 0.000 claims abstract description 11
- 239000012224 working solution Substances 0.000 claims description 35
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 12
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 12
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 11
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 11
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 10
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 10
- 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 10
- 229960003767 alanine Drugs 0.000 claims description 10
- 229950010030 dl-alanine Drugs 0.000 claims description 10
- 235000004279 alanine Nutrition 0.000 claims description 7
- 229960001367 tartaric acid Drugs 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- QNAYBMKLOCPYGJ-UWTATZPHSA-N D-alanine Chemical compound C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims description 3
- 229940048879 dl tartaric acid Drugs 0.000 claims description 3
- 229960001270 d- tartaric acid Drugs 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000536 complexating effect Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000008139 complexing agent Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 238000006557 surface reaction Methods 0.000 abstract description 4
- 238000009736 wetting Methods 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 34
- 229910052709 silver Inorganic materials 0.000 description 34
- 239000004332 silver Substances 0.000 description 34
- 238000001556 precipitation Methods 0.000 description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005219 brazing Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000000080 wetting agent 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本申请提供一种陶瓷覆铜板表面处理剂及陶瓷覆铜板表面处理工作液，陶瓷覆铜板表面处理剂包括α位取代的有机酸、杂环胺、PEG‑600及去离子水；处理剂中α位取代的有机酸起到络合剂的作用，其一方面通过对三价铁的弱络合作用抑制三价铁的水解，促进三价铁对铜的氧化反应，另一方面，通过α位取代的有机酸对生成的二价铁的络合作用，进一步促进三价铁对铜的氧化反应，进而提高工作液对铜面微蚀的速率；杂环胺通过其氨基与铜离子的络合作用，增大了反应后的铜面粗糙度；通过PEG‑600的湿润作用，降低了铜表面的张力，使得铜表面各个位置能够均匀地进行反应，以此提高铜面反应的均匀性。The present application provides a surface treatment agent for a ceramic copper-clad laminate and a surface treatment working liquid for a ceramic copper-clad laminate. The surface treatment agent for a ceramic copper-clad laminate comprises an α-substituted organic acid, a heterocyclic amine, PEG-600 and deionized water. The α-substituted organic acid in the treatment agent acts as a complexing agent. On the one hand, it inhibits the hydrolysis of ferric iron by weakly complexing it with ferric iron, thereby promoting the oxidation reaction of ferric iron on copper. On the other hand, the α-substituted organic acid further promotes the oxidation reaction of ferric iron on copper by complexing the generated divalent iron, thereby increasing the rate of micro-etching of the copper surface by the working liquid. The heterocyclic amine increases the roughness of the copper surface after the reaction by complexing its amino group with copper ions. The wetting effect of PEG-600 reduces the tension of the copper surface, so that each position on the copper surface can react evenly, thereby improving the uniformity of the copper surface reaction.
Description
Technical Field
The invention relates to the technical field of ceramic plate manufacturing processes, in particular to a ceramic copper-clad plate surface treating agent and a ceramic copper-clad plate surface treating working solution.
Background
The ceramic plate (also called ceramic substrate circuit board) is formed by taking a ceramic copper-clad plate as a substrate to make a circuit, and the ceramic copper-clad plate can be generally divided into DBC (Direct bonded copper, direct copper-clad ceramic substrate), DPC (DIRECT PLATED copper, direct electroplating ceramic substrate), AMB (ACTIVE METAL brazing, active metal brazing ceramic substrate) and the like according to the process, wherein the AMB ceramic copper-clad plate is formed by tightly welding copper foil and a ceramic substrate under the conditions of high temperature and high pressure by utilizing a metal brazing material containing a small amount of active elements.
Unlike DPC or DBC technology, AMB ceramic copper-clad plate is affected by high temperature and high pressure, and the metal crystal structure of copper is greatly different from that of common electrolytic copper foil, so that the copper surface is difficult to be treated by common microetching liquid medicine.
The final surface treatment of the ceramic plate usually uses nickel-plated gold or silver-plated, the copper surface of the ceramic copper-clad plate needs microetching treatment before depositing a plating layer, in the prior art, the microetching agent of a potassium hydrogen persulfate system, a ferric sulfate system or a hydrogen peroxide system is generally used for microetching the copper surface, and the following problems exist when the microetching agent is used for surface treatment of the ceramic copper-clad plate, in particular to an AMB ceramic copper-clad plate: 1. the treatment efficiency is low, and the copper surface is often required to be microetched by prolonging the treatment time by more than four times; 2. the roughness of the copper surface after microetching is poor, and even if the copper surface is prolonged for a plurality of times of treatment time, the problem that a certain proportion of silver deposition layers fall off exists; 3. the micro-etching is uneven on the surface of the ceramic copper-clad plate.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a ceramic copper-clad plate surface treating agent.
The application discloses a ceramic copper-clad plate surface treating agent, which comprises the following components: 1.0 to 5.5 parts of alpha-substituted organic acid, 0.05 to 0.5 part of heterocyclic amine, 0.1 to 1.0 part of PEG-600 and 3.5 to 7.0 parts of deionized water.
Preferably, the alpha-substituted organic acid comprises at least one of tartaric acid and alanine.
Preferably, the heterocyclic amine is at least one of 2-aminothiazole and 5-aminotetrazole.
Preferably, the tartaric acid is at least one of DL-tartaric acid, D-tartaric acid, L-tartaric acid.
Preferably, the alanine is at least one of DL-alanine, D-alanine, L-alanine.
Preferably, the alpha-substituted organic acid comprises 0.8-4.0 parts tartaric acid and 0.2-1.5 parts alanine.
Preferably, the tartaric acid is 1.5-3.0 parts and the alanine is 0.6-1.2 parts.
Preferably, the heterocyclic amine comprises 0.03-0.3 parts of 2-aminothiazole and 0.02-0.2 parts of 5-aminotetrazole.
Preferably, the 2-aminothiazole is 0.08-0.15 part and the 5-aminotetrazole is 0.07-0.14 part.
According to a second aspect of the application, the application provides a ceramic copper-clad plate surface treatment working solution.
The application discloses a ceramic copper-clad plate surface treatment working solution which comprises 85.5-94.5g/l sulfuric acid, 57-63g/l ferric sulfate, 95-105ml/l ceramic copper-clad plate surface treatment agent and the balance deionized water.
The application has the beneficial effects that: in the microetching process, the alpha-substituted organic acid in the working solution plays a role of a complexing agent, so that on one hand, the hydrolysis of ferric iron is inhibited through the weak complexing effect on the ferric iron, the oxidation reaction of the ferric iron on copper is promoted, and on the other hand, the oxidation reaction of the ferric iron on copper is further promoted through the complexing effect of the alpha-substituted organic acid on generated divalent iron, and the microetching rate of the working solution on copper surface is further improved; the heterocyclic amine can be paired with copper ions through the complexation of amino groups and the copper ions to generate an organic film, and the organic film is easier to form at the crest of the copper rough surface because the copper surface is the rough surface, and the organic film plays a role in protecting the copper surface, so that the reaction rate at the trough of the copper rough surface is faster than the reaction rate at the crest, thereby increasing the roughness of the reacted copper surface, and moreover, the organic film can be easily removed by pickling in the subsequent process without affecting the quality of subsequent silver precipitation; by the wetting action of PEG-600, the tension of the copper surface is reduced, so that each position of the copper surface can uniformly react, and the uniformity of copper surface reaction is improved.
Detailed Description
In order to further understand the contents, features and effects of the present application, the following embodiments are exemplified, and the technical solutions of the embodiments may be combined with each other, but it is necessary that the technical solutions should be based on that the technical solutions can be implemented by those skilled in the art, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered to be absent, and not fall within the scope of protection claimed by the present application.
Example 1
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 2.5 parts of DL-alanine: 1.0 part of 2-aminothiazole: 0.13 part of 5-aminotetrazole: 0.1 part of PEG-600:0.4 part and 5.88 parts of deionized water, wherein the parts are mass ratios, for example, the mass ratio of DL-tartaric acid to DL-alanine is 2.5:1.
The surface treating agent for the ceramic copper-clad plate is a treating agent for carrying out copper surface microetching on the ceramic copper-clad plate, especially an AMB ceramic copper-clad plate under an acidic condition based on compounds with oxidability such as ferric sulfate, potassium hydrogen persulfate or hydrogen peroxide, and the like, and is used before a silver precipitation or nickel-gold plating process is carried out in the production process of the ceramic copper-clad plate, and aims to improve the silver precipitation quality of the ceramic copper-clad plate.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Before the silver precipitation process of the AMB ceramic copper-clad plate, the ceramic copper-clad plate surface treatment working solution prepared by the ceramic copper-clad plate surface treatment agent is used for carrying out surface treatment on a copper surface, wherein alpha-substituted organic acid is used as a complexing agent, the weak complexing effect of carboxyl on ferric ions is adopted to inhibit the hydrolysis of ferric ions, heterocyclic amine is used as an inhibitor, and amino is used for complexing copper, so that the working solution can selectively react with the copper surface, PEG is used as a wetting agent, the tension of the copper surface is reduced, all positions on the copper surface can be uniformly reacted, and deionized water is used as a solvent.
In the microetching process, the alpha-substituted organic acid in the working solution plays a role of a complexing agent, so that on one hand, the hydrolysis of ferric iron is inhibited through the weak complexing effect on the ferric iron, the oxidation reaction of the ferric iron on copper is promoted, and on the other hand, the oxidation reaction of the ferric iron on copper is further promoted through the complexing effect of the alpha-substituted organic acid on generated divalent iron, and the microetching rate of the working solution on copper surface is further improved; the heterocyclic amine can be paired with copper ions through the complexation of amino groups and the copper ions to generate an organic film, and the organic film is easier to form at the crest of the copper rough surface because the copper surface is the rough surface, and the organic film plays a role in protecting the copper surface, so that the reaction rate at the trough of the copper rough surface is faster than the reaction rate at the crest, thereby increasing the roughness of the reacted copper surface, and moreover, the organic film can be easily removed by pickling in the subsequent process without affecting the quality of subsequent silver precipitation; by the wetting action of PEG-600, the tension of the copper surface is reduced, so that each position of the copper surface can uniformly react, and the uniformity of copper surface reaction is improved.
Example two
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 3.0 parts of DL-alanine: 0.8 part of 2-aminothiazole: 0.08 part of 5-aminotetrazole: 0.1 part of PEG-600:0.4 part and 5.55 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Example III
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 1.5 parts of DL-alanine: 1.5 parts of 2-aminothiazole: 0.12 part of 5-aminotetrazole: 0.08 parts of PEG-600:0.4 part and 6.36 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
Example IV
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 0.8 part of DL-alanine and/or D-alanine and/or L-alanine: 0.2 parts of 2-aminothiazole: 0.03 part of 5-aminotetrazole: 0.02 parts of PEG-600:0.1 part and 3.5 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Example five
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 4.0 parts of DL-alanine: 1.5 parts of 2-aminothiazole: 0.3 part of 5-aminotetrazole: 0.2 parts of PEG-600:1.0 part and 7.0 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Example six
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 1.3 parts of DL-alanine: 0.5 part of 2-aminothiazole: 0.08 part of 5-aminotetrazole: 0.01 part of PEG-600:0.4 part and 5.55 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Example seven
The ceramic copper-clad plate surface treating agent in the example is prepared from the following raw materials in parts by weight: 1.5 parts of DL-alanine: 0.5 part of 2-aminothiazole: 0.05 part of 5-aminotetrazole: 0.05 parts of PEG-600:0.4 part and 6.36 parts of deionized water, wherein the parts are mass ratios.
The surface treatment working solution for the ceramic copper-clad plate is prepared by the surface treatment agent for the ceramic copper-clad plate as follows:
Sulfuric acid: 90g/l, ferric sulfate: 60g/l, ceramic copper-clad plate surface treating agent: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Comparative example one
The silver precipitation pretreatment working solution is prepared by a potassium hydrogen persulfate system in the market as follows:
sulfuric acid: 70g/l, potassium hydrogen persulfate: 90g/l, citric acid: 5g/l potassium hydrogen persulfate stabilizing additive: 100ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Comparative example two
The silver precipitation pretreatment working solution is prepared by a hydrogen peroxide system in the market as follows:
the traditional microetching agent working solution is prepared as follows:
Sulfuric acid: 70g/l, hydrogen peroxide: 40ml/l, hydrogen peroxide stabilizing additive: 40ml/l, deionized water: the balance.
And carrying out silver precipitation pretreatment and silver precipitation performance test by using the prepared working solution.
Data of silver deposit performance test
1. Copper surface roughness test:
The AMB ceramic plate after line etching was subjected to silver precipitation pretreatment using the working solution prepared in the above examples, and the resultant plate was subjected to surface roughness test, with the results shown in table 1 below:
TABLE 1
2. And (3) silver deposition binding force test:
Carrying out silver precipitation pretreatment on the AMB ceramic plate subjected to circuit etching by using the working solution prepared in each embodiment, controlling the working solution prepared in each embodiment to have the same treatment time, carrying out chemical silver precipitation on the ceramic plate, carrying out silver precipitation binding force test on the obtained plate, and carrying out test on the binding force by pulling with a 3M adhesive tape, wherein the results are shown in the following table 2:
TABLE 2
3. Thickness uniformity test:
The line etched AMB ceramic plate was subjected to silver precipitation pretreatment with the working solution prepared in each of the above examples, and the ceramic plate was subjected to chemical silver precipitation, and the thickness uniformity test was performed on the resulting plate, and the silver precipitation thickness was tested with an XRF thickness tester, with the following table 3:
TABLE 3 Table 3
In summary, in the microetching process, the alpha-substituted organic acid in the working solution plays a role of a complexing agent, so that on one hand, the hydrolysis of ferric iron is inhibited through the weak complexing effect on the ferric iron, the oxidation reaction of the ferric iron on copper is promoted, and on the other hand, the oxidation reaction of the ferric iron on copper is further promoted through the complexing effect of the alpha-substituted organic acid on generated ferrous iron, and the microetching rate of the working solution on copper surfaces is further improved; the heterocyclic amine can be paired with copper ions through the complexation of amino groups and the copper ions to generate an organic film, and the organic film is easier to form at the crest of the copper rough surface because the copper surface is the rough surface, and the organic film plays a role in protecting the copper surface, so that the reaction rate at the trough of the copper rough surface is faster than the reaction rate at the crest, thereby increasing the roughness of the reacted copper surface, and moreover, the organic film can be easily removed by pickling in the subsequent process without affecting the quality of subsequent silver precipitation; by the wetting action of PEG-600, the tension of the copper surface is reduced, so that each position of the copper surface can uniformly react, and the uniformity of copper surface reaction is improved.
The above is merely an embodiment of the present application, and is not intended to limit the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, or the like, which is within the spirit and principles of the present application, should be included in the scope of the claims of the present application.
Claims (6)
1. The ceramic copper-clad plate surface treating agent is characterized by comprising the following components: 1.0 to 5.5 parts of alpha-substituted organic acid, 0.05 to 0.5 part of heterocyclic amine, 0.1 to 1.0 part of PEG-600 and 3.5 to 7.0 parts of deionized water; the alpha-substituted organic acid comprises 0.8-4.0 parts of tartaric acid and 0.2-1.5 parts of alanine; the heterocyclic amine comprises 0.03-0.3 part of 2-aminothiazole and 0.02-0.2 part of 5-aminotetrazole.
2. The ceramic copper-clad plate surface treatment agent according to claim 1, wherein the tartaric acid is at least one of DL-tartaric acid, D-tartaric acid and L-tartaric acid.
3. The ceramic copper-clad plate surface treatment agent according to claim 1, wherein the alanine is at least one of DL-alanine, D-alanine, and L-alanine.
4. The ceramic copper-clad plate surface treatment agent according to claim 1, wherein the tartaric acid is 1.5-3.0 parts and the alanine is 0.6-1.2 parts.
5. The ceramic copper-clad plate surface treatment agent according to claim 1, wherein the 2-aminothiazole is 0.08-0.15 part and the 5-aminotetrazole is 0.07-0.14 part.
6. A ceramic copper-clad plate surface treatment working solution, which is characterized by comprising 85.5-94.5g/l sulfuric acid, 57-63g/l ferric sulfate, 95-105ml/l ceramic copper-clad plate surface treatment agent according to any one of claims 1-5 and the balance deionized water.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4118764A1 (en) * | 1991-06-07 | 1992-12-10 | Chema Technologien Gmbh | Organic additives for ferric chloride-contg. copper@ etch solns. - comprising complex-forming organic acids which prevent sludge formation |
| CN115354327A (en) * | 2022-08-22 | 2022-11-18 | 上海天承化学有限公司 | Micro-etching roughening solution suitable for SAP (super absorbent Polymer) manufacturing process and application thereof |
| CN115786916A (en) * | 2022-12-21 | 2023-03-14 | 肇庆微纳芯材料科技有限公司 | Copper etching solution and preparation method thereof, and etching method of glass substrate copper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000328268A (en) * | 1999-05-13 | 2000-11-28 | Shikoku Chem Corp | Etching treating agent for copper and copper alloy |
| DE602005023739D1 (en) * | 2005-10-25 | 2010-11-04 | Atotech Deutschland Gmbh | Composition and method of improving the adhesion of the polymeric materials to copper or copper alloy surfaces |
| JP5576525B1 (en) * | 2013-03-29 | 2014-08-20 | メルテックス株式会社 | Copper etchant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4118764A1 (en) * | 1991-06-07 | 1992-12-10 | Chema Technologien Gmbh | Organic additives for ferric chloride-contg. copper@ etch solns. - comprising complex-forming organic acids which prevent sludge formation |
| CN115354327A (en) * | 2022-08-22 | 2022-11-18 | 上海天承化学有限公司 | Micro-etching roughening solution suitable for SAP (super absorbent Polymer) manufacturing process and application thereof |
| CN115786916A (en) * | 2022-12-21 | 2023-03-14 | 肇庆微纳芯材料科技有限公司 | Copper etching solution and preparation method thereof, and etching method of glass substrate copper |
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