CN115478266A - Activated immersion liquid used for carrier plate and method for chemically plating nickel and gold on carrier plate - Google Patents
Activated immersion liquid used for carrier plate and method for chemically plating nickel and gold on carrier plate Download PDFInfo
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- CN115478266A CN115478266A CN202210989906.5A CN202210989906A CN115478266A CN 115478266 A CN115478266 A CN 115478266A CN 202210989906 A CN202210989906 A CN 202210989906A CN 115478266 A CN115478266 A CN 115478266A
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- 238000007654 immersion Methods 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 238000007747 plating Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 71
- 229910052759 nickel Inorganic materials 0.000 title abstract description 34
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910052737 gold Inorganic materials 0.000 title abstract description 18
- 239000010931 gold Substances 0.000 title abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 25
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical group [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 claims description 8
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical group O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 62
- 229910052763 palladium Inorganic materials 0.000 abstract description 33
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- -1 palladium ions Chemical group 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 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 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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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
- C23C18/18—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
- C23C18/1837—Multistep pretreatment
-
- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/42—Coating with noble metals
Abstract
The invention belongs to the field of printed circuit board preparation, and particularly relates to an activated immersion liquid used for a carrier plate and a method for chemically plating nickel and gold on the carrier plate. The immersion liquid used by the carrier plate after activation comprises the following components: passivating agent, complexing agent, dispersing agent, inorganic salt and water; the passivating agent is thiourea and sodium sulfide, and the concentration of the passivating agent in the immersion liquid after activation is 3-5g/L and 0.5-2g/L respectively. The activated immersion liquid can be used for cleaning ink of high-precision circuits (such as carrier plates) and ionic palladium adsorbed on pp sheet areas, can realize a better post-immersion effect by implementing the method, has a good effect of removing the ionic palladium, and can realize no phenomena of diffusion plating and leakage plating after nickel and gold plating.
Description
Technical Field
The invention belongs to the field of printed circuit board preparation, and particularly relates to an activated immersion liquid used for a carrier plate, and a method for chemically plating nickel and gold on the carrier plate by using the activated immersion liquid.
Background
A Printed Circuit Board (PCB) is a functional substrate for connecting components by forming a pre-designed Circuit on the surface of an insulating substrate using electronic printing. In order to ensure the weldability, corrosion resistance, oxidation resistance and the like of the printed circuit board during later assembly and use, the surface treatment process is finally carried out on the surface of the line. Electroless nickel/displacement gold (ENIG) plating is widely used as one of the surface treatment processes for its good conductivity and compatibility with high density packaging. In the chemical nickel plating process in the process, sodium hypophosphite is mostly used as a reducing agent, a nickel-phosphorus layer is continuously deposited on the surface with catalytic activity, the copper-based surface of the printed circuit board does not have autocatalysis activity, and metal with catalytic activity is deposited on the surface of the copper-based surface of the printed circuit board to further initiate chemical nickel plating, so that the plating leakage and the plating overflow are easily caused in the production of the current process, and the production cost is increased.
For example, a palladium activation method for electroless nickel/gold plating of a PCB disclosed in chinese patent CN202110238810.0 and a double-layer nickel/gold plating process for surface treatment of PCBs disclosed in chinese patent CN201611270127.0, the pretreatment of electroless nickel/displacement gold plating (ENIG) process surface treatment generally includes a series of treatment processes such as degreasing, microetching, pickling, presoaking, activation, and post-immersion, wherein the purpose of activation is to form a layer of palladium on copper by displacement to catalyze electroless nickel plating. However, the microetched plate surface not only roughens the copper surface, but also roughens the pp sheet and the ink, so that a layer of ionic palladium is adsorbed on the pp sheet and the ink. Both the substitutional palladium and the ionic palladium have the function of catalyzing nickel, and if the palladium is not treated, the phenomenon of diffusion plating can be caused. At present, the post-dip is generally used for removing palladium in the post-dip treatment in the PCB process production, and the current post-dip generally adopts a sulfuric acid solution to dissociate ionic palladium adsorbed on the ink or the pp sheet, but cannot corrode and replace the palladium. Along with the narrowing of the line width and the line distance of the carrier plate, the rough area formed by the micro-etched printing ink or the pp sheet is increased, so that the adsorption quantity of the ionic palladium is greatly increased, and along with the generation of firmer palladium ions and chemical bond coordination compounds on the printing ink, the pp sheet and other high polymer materials in the adsorption process, the ionic palladium is difficult to separate. Therefore, the technical problem that the sulfuric acid solution cannot completely clean the ionic palladium adsorbed by the ink, the pp sheet and the like of a high-precision circuit (such as a carrier plate) is of great significance to the field by providing the activated immersion liquid for the carrier plate stably and efficiently.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the activated immersion liquid used for the carrier plate can remove ionic palladium adsorbed on a pp sheet and ink after palladium plating activation in a carrier plate preparation process by using the activated immersion liquid.
The second technical problem to be solved by the invention is to provide a method for plating nickel and gold on the carrier plate by post-immersion using the activated immersion liquid, and the method can be better applied to the activated immersion liquid, so that the prepared carrier plate has no phenomena of plating leakage and plating penetration after being plated with nickel and gold.
The technical scheme of the invention for solving the technical problems is as follows:
the invention provides an activated immersion liquid used for a carrier plate, which comprises the following components: passivating agent, complexing agent, dispersing agent, inorganic salt and water; the passivator is thiourea and sodium sulfide, and the concentration of the passivator in the immersion liquid after activation is 3-5g/L and 0.5-2g/L respectively.
Further, the complexing agents are N-nitrosophenylhydroxylamine and 3, 5-dinitrosalicylic acid, and the concentrations in the immersion liquid after the activation are 0.1-0.5g/L and 0.5-2.5g/L, respectively. The weight ratio of N-nitrosophenylhydroxylamine to 3, 5-dinitrosalicylic acid is 1. The proportion and the substance combination can improve the stability of palladium ions under acidic conditions, can well solve the problems caused by acidity, and simultaneously has good resistance to impurity metal ions such as iron, copper, zinc and the like.
Further, the dispersant is sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, and the concentration in the post-activation dip is 0.01 to 0.05g/L. Sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate acts as a dispersant to disperse and encapsulate ionic palladium complexed with N-nitrosophenylhydroxylamine and 3, 5-dinitrosalicylic acid, thereby preventing aggregation and re-adsorption on the substrate.
Further, the inorganic salt is sodium chloride, and the concentration in the immersion liquid after activation is 0.2 to 0.8g/L, preferably 0.5g/L. The sodium chloride is helpful for accelerating dissociation of the adsorbed palladium ions and plays a role in assistance.
The invention also provides a method for chemically plating nickel and gold on the carrier plate, which comprises the step of carrying out post-dipping treatment by using the activated immersion liquid. The remaining steps other than the post-dip step may be any known electroless nickel-gold plating process and include a palladium activation step, the details of which are also known. For example, including, but not limited to, steps that may include printed circuit board copper surfaces, degreasing, microetching, pickling, presoaking, palladium activation, electroless nickel gold plating, and the like. The palladium activation refers to a process step of forming a palladium layer on the surface of the carrier plate by using a physical or chemical means, and aims to play a role in catalyzing chemical nickel plating.
Further, the post-dip comprises the steps of:
s1, adding water into a passivating agent and inorganic salt to prepare an aqueous solution according to X times of an expected concentration, adjusting the pH value to 3-4 to obtain a first solution, adding water into a dispersing agent and a complexing agent to prepare an aqueous solution according to X times of the expected concentration to obtain a second solution, wherein X is more than or equal to 5 and less than or equal to 25;
the first solution and the second solution are prepared respectively, and the dissociation of thiourea can be prevented by combining the operation of adjusting the pH value, so that the shelf life is prolonged. The concentrated solution is prepared, which is beneficial to storage, transportation and use.
S2, recording the volume of the first solution as 1 part by volume, injecting 1/X part by volume of the first solution into a container, adding (2-5)/X part by volume of pure water, adjusting the pH to 5-5.6, mixing with 1/X part by volume of the second solution, and supplementing the mixture with pure water until the concentration of each component reaches the expected concentration to obtain the activated immersion liquid;
s3, immersing the carrier plate needing post-immersion into the activated immersion liquid at the temperature of 25-30 ℃ for 1-2 minutes.
Further, the above-mentioned pH adjusting step may use general pH adjusting agents, and in some embodiments, the pH adjusting agent is selected from sulfuric acid and sodium hydroxide.
Further, step S3 further includes: titrating by using a zinc sulfate precipitation method, testing the concentration of the sodium sulfide, opening the cylinder again if the concentration of the sodium sulfide is more than 2g/L, and supplementing the sodium sulfide to 0.5-2g/L if the concentration of the sodium sulfide is less than 0.5g/L. On one hand, the sodium sulfide has high concentration, can generate precipitates with palladium to be adsorbed on the surface of a base material to cause poor board surface quality, and on the other hand, the palladium is incompletely dissociated due to too low concentration, and is easy to separate out a tank. The sulfur ions may be consumed by plate surface entrainment, and the adsorption capacity of the sulfur ions and palladium to form colloidal clusters is enhanced, so that analysis and control are required.
Further, step S3 further includes: after the carrier plate is immersed, the complex is promoted to be separated from the surface of the base material in a micro-vibration mode under the nitrogen atmosphere, and the nitrogen pressure is 1.5-2.5kg/cm 3 . This approach can prevent the sulfur in the activated bath from adsorbing and complexing the palladium ions with thiourea, and it needs to be performed under nitrogen-filled condition to promote the complex to be separated from the substrate surface in a slight shock manner.
Further, step S3 further includes: the pH value is controlled to be 3-6. In some embodiments, the higher the concentration is adjusted with 10% sulfuric acid and the lower the concentration is adjusted with 10% sodium hydroxide solution.
The invention has the following beneficial effects:
the thiourea and the sodium sulfide disclosed by the invention are used as passivators, and have a strong pulling effect on ionic palladium; the sodium chloride improves the dissociation effect of the ionic palladium; n-nitrosophenylhydroxylamine and 3, 5-dinitrosalicylic acid play a role in complexing palladium, prevent the formation of precipitates which accumulate too much sulfur-containing palladium and prolong the service life of the immersion liquid after activation; sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate is used as a dispersant to dispersedly wrap ionic palladium complexed with N-nitrosophenylhydroxylamine and 3, 5-dinitrosalicylic acid, thereby preventing aggregation and re-adsorption on the substrate.
Drawings
Fig. 1 is a SEM image of carrier ring (left) and PAD (right) nickel corrosion prepared in example 1 of the present invention.
Fig. 2 shows SEM images of carrier ring holes (left) and PAD holes (right) prepared in example 2 of the present invention.
Fig. 3 is SEM images of carrier ring holes (left) and PAD holes (right) prepared in example 3 of the present invention.
FIG. 4 is SEM images of Ni-etched carrier ring (left) and PAD (right) prepared by using a common post-activation solution in the market of comparative example 1.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
A certain carrier plate with the same size and size is taken as a test base material, and the condition of plating leakage and diffusion is observed by comparing the common post-activation immersion liquid in the market with the complete post-activation immersion liquid in the scheme, plating nickel for 25min, plating gold for 10min, comparing the thickness difference of nickel and gold, the color difference of a gold surface and the nickel corrosion comparison difference.
The following examples and comparative examples were all carried out using the following electroless nickel-gold pretreatment method:
the pretreatment method of electroless nickel and gold plating comprises the steps of removing oil by using acid for 3-5min, 50-60 ℃, micro-etching for 2-3min,25-30 ℃, pickling for 1min to 25-30 ℃, presoaking for 1-2min, 25-30 ℃, activating for 30s to 2min, 25-30 ℃ and then soaking for 1-2min to 25-30 ℃.
The post-leaching comprises the following steps:
s1, adding water into a passivating agent and inorganic salt to prepare an aqueous solution according to 10 times of an expected concentration, adjusting the pH value to 3-4 to obtain a first solution, and adding water into a dispersing agent and a complexing agent to prepare an aqueous solution according to 10 times of the expected concentration;
s2, recording the volume of the first solution as 1 part, injecting 1/10 part of the first solution into a container, adding 1/10 part of pure water, adjusting the pH to 5-5.6 by using sodium hydroxide, mixing with 1/10 part of the second solution by volume, and supplementing the mixture with pure water until the concentration of each component is equal to that of the components of the activated immersion liquid, so as to obtain the activated immersion liquid;
s3, immersing the carrier plate needing post-immersion into the activated immersion liquid at the temperature of 25-30 ℃ for 1-2 minutes.
Step S3 further includes: titrating by using a zinc sulfate precipitation method, testing the concentration of the sodium sulfide, discarding the current immersion liquid after activation if the concentration of the sodium sulfide is more than 2g/L, returning to the step S2 to prepare the immersion liquid after activation again, and supplementing the sodium sulfide to 0.5-2g/L if the concentration of the sodium sulfide is less than 0.5g/L.
Step S3 further includes: the carrier plate is immersed and then the complex is promoted to be separated from the surface of the base material in a micro-vibration mode under the nitrogen atmosphere, and the nitrogen pressure is 1.5-2.5kg/cm 3 。
Step S3 further includes: the pH value is controlled to be 3-6, the higher part is adjusted by 10 percent sulfuric acid, and the lower part is adjusted by 10 percent sodium hydroxide solution.
Example 1 consists of the following components: 4g/L of thiourea, 1g/L of sodium sulfide, 0.5g/L of sodium chloride, 0.3/L of N-nitrosophenylhydroxylamine amine, 0.03g/L of sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, and 1.8g/L of 3, 5-dinitrosalicylic acid.
Example 2 consists of the following components: 3g/L of thiourea, 0.5g/L of sodium sulfide, 0.5g/L of sodium chloride, 0.1g/L of N-nitrosophenylhydroxylamine, 0.01g/L of sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, and 0.4g/L of 3, 5-dinitrosalicylic acid.
Example 3 consists of the following components: 5g/L of thiourea, 2g/L of sodium sulfide, 0.5g/L of sodium chloride, 0.5g/L of N-nitrosophenylhydroxylamine amine, 0.05g/L of sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, and 2.5g/L of 3, 5-dinitrosalicylic acid.
Comparative example 1 is a commercial common post-activation dip.
Comparative example 2 contains no dispersant sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, and the other components are constituted in the same manner as in example 1.
Comparative example 3 contains no sodium sulfide and the other components are the same as in example 1.
Comparative example 4 contains no thiourea, and the other components are constituted in the same manner as in example 1.
Comparative example 5 contains no thiourea and sodium sulfide and the other component constitution is the same as example 1.
And (3) taking support plates with the same model size as a test substrate, comparing the activated immersion liquids of the examples 1-3 and the comparative examples 1-5, plating nickel for 25min, plating gold for 10min, comparing the nickel-gold thickness difference, the gold surface color difference and the nickel corrosion difference, and observing the condition of plating leakage and diffusion.
From the carrier boards treated by the following examples using the immersion liquid after activation, 10 carrier boards in each group were observed for the number of the carrier boards in which the plating occurred, and the plating rate = (number of carrier boards in which the plating occurred/number of carrier boards in each group) = 100%, and the results are shown in the following table.
| Immersion liquid after activation | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Rate of diffusion coating | 0% | 0% | 0% | 40% | 50% | 60% | 40% | 80% |
As can be seen from the data in the table, the immersion liquid after common activation in the market of the comparative example 1 can cause the diffusion plating, and the absence of the dispersant in the comparative example 2 can cause the diffusion plating rate to reach 50 percent; comparative examples 3-5 have no sodium sulfide, no thiourea and sodium sulfide, respectively, and the plating rates are all higher than the post-activation dip claimed in this application, indicating that thiourea and sodium sulfide have a synergistic effect.
Immersion liquid after activation according to the scheme, after treatment in example 1, in Ni 2+ The concentration was 4.9g/L, the temperature was 81 ℃ and the pH was 4.6, the P contents were 8.64 and 8.35, and the deposition rate was 7.4 u'/min. The SEM image of the Ni-corrodes taken at the position of the annular ring is shown in FIG. 1 (left), and the SEM image of the Ni-corrodes taken at the position of the annular ring is shown in FIG. 1 (right).
Immersion liquid after activation according to the scheme, after treatment in example 2, in Ni 2+ The concentration was 4.9g/L, the temperature was 81 ℃ and the pH was 4.6, the P content was 8.31 and 8.34, and the deposition rate was 7.4 u'/min. The SEM of the Ni-etch taken at the position of the annular ring is shown in FIG. 2 (left), and the SEM taken at the position of the PAD is shown in FIG. 2 (right).
Immersion liquid after activation according to the scheme, after treatment in example 3, in Ni 2+ The concentration was 4.9g/L, the temperature was 81 ℃ and the pH was 4.6, the P content was 8.42 and 8.21, and the deposition rate was 7.4 u'/min. The SEM image of the ring nickel is shown in FIG. 3 (left), and the SEM image of the PAD nickel is shown in FIG. 3 right.
After the immersion liquid treatment after the common activation in the market of the comparative example 1, ni 2+ The concentration was 4.9g/L, the temperature was 81 ℃ and the pH was 4.6, the P contents were 7.7 and 8.24, and the deposition rate was 7.2u "/min. The SEM image of the nickel corrosion at the position of the annular ring is shown on the left of FIG. 4, and the SEM image of the nickel corrosion at the position of the PAD is shown on the right of FIG. 4.
From the above experimental results and SEM images, it can be seen that the post-activation immersion liquid claimed in the present invention does not affect the nickel deposition rate and nickel corrosion in the normal nickel plating process without the occurrence of the diffusion plating, and can form a nickel layer similar to the nickel layer after the common post-activation immersion liquid treatment in the market on the orifice ring and PAD.
The carrier plate which is subjected to post-dipping by using the common post-activation dipping liquid in the market has no phenomena of plating leakage and plating penetration, and the carrier plate which is subjected to post-dipping by using the dipping liquid after activation in the embodiment 1-3 has no phenomena of plating leakage and plating penetration. It can also be seen that the nickel corrosion of the carrier plate after-immersed with the common post-activation immersion liquid in the market is severe.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (9)
1. An activated immersion liquid used for a carrier plate is characterized by comprising the following components: passivating agent, complexing agent, dispersing agent, inorganic salt and water; the passivator is thiourea and sodium sulfide, and the concentration of the passivator in the immersion liquid after activation is 3-5g/L and 0.5-2g/L respectively.
2. The activated dip according to claim 1, wherein the complexing agent is N-nitrosophenylhydroxylamine and 3, 5-dinitrosalicylic acid, the concentrations in the activated dip being 0.1 to 0.5g/L and 0.5 to 2.5g/L, respectively, and the weight ratio of N-nitrosophenylhydroxylamine to 3, 5-dinitrosalicylic acid being 1.
3. The post-activation dip according to claim 1, wherein the dispersant is sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, and the concentration in the post-activation dip is 0.01 to 0.05g/L.
4. The post-activation dip according to claim 1, wherein the inorganic salt is sodium chloride, and the concentration in the post-activation dip is 0.2 to 0.8g/L.
5. A method for electroless nickel-gold plating of a carrier plate, characterized by comprising a post-dipping step of post-dipping using the post-activation dipping solution according to any one of claims 1 to 4.
6. The method according to claim 5, characterized in that the post-leaching comprises the steps of:
s1, adding water into a passivating agent and inorganic salt to prepare an aqueous solution according to X times of an expected concentration, adjusting the pH value to 3-4 to obtain a first solution, adding water into a dispersing agent and a complexing agent to prepare an aqueous solution according to X times of the expected concentration to obtain a second solution, wherein X is more than or equal to 5 and less than or equal to 25;
s2, recording the volume of the first solution as 1 part by volume, injecting 1/X part by volume of the first solution into a container, adding (2-5)/X part by volume of pure water, adjusting the pH value to 5-5.6, mixing with 1/X part by volume of the second solution, and supplementing the mixture with pure water until the concentration of each component reaches the expected concentration to obtain the activated immersion liquid;
s3, immersing the carrier plate needing post-immersion into the activated immersion liquid at the temperature of 25-30 ℃ for 1-2 minutes.
7. The method of claim 6, wherein step S3 further comprises: titrating by using a zinc sulfate precipitation method, testing the concentration of the sodium sulfide, discarding the current immersion liquid after activation if the concentration of the sodium sulfide is more than 2g/L, returning to the step S2 to prepare the immersion liquid after activation again, and supplementing the sodium sulfide to 0.5-2g/L if the concentration of the sodium sulfide is less than 0.5g/L.
8. The method of claim 6, wherein step S3 further comprises: the carrier plate is immersed and then the complex is promoted to be separated from the surface of the base material in a micro-vibration mode under the nitrogen atmosphere, and the nitrogen pressure is 1.5-2.5kg/cm 3 。
9. The method of claim 6, wherein step S3 further comprises: controlling the pH value to be 3-6 after the carrier plate is immersed.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287583A (en) * | 1992-04-07 | 1993-11-02 | Okuno Chem Ind Co Ltd | Method for directly forming electroplating layer on non-electroconductive material surface |
| CN104294044A (en) * | 2014-10-20 | 2015-01-21 | 贵研铂业股份有限公司 | Preparation method of activated carbon capable of selectively adsorbing palladium |
| KR101660520B1 (en) * | 2015-04-08 | 2016-09-29 | 한국생산기술연구원 | Method of performing continuous electroless plating of copper and nickel and plating layer using the same |
| CN112867275A (en) * | 2021-01-06 | 2021-05-28 | 深圳市迅捷兴科技股份有限公司 | Method for plating nickel and gold on part without lead |
| CN113151812A (en) * | 2021-04-20 | 2021-07-23 | 广东工业大学 | Tin activating solution, preparation method thereof and chemical nickel plating method |
-
2022
- 2022-08-18 CN CN202210989906.5A patent/CN115478266B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287583A (en) * | 1992-04-07 | 1993-11-02 | Okuno Chem Ind Co Ltd | Method for directly forming electroplating layer on non-electroconductive material surface |
| CN104294044A (en) * | 2014-10-20 | 2015-01-21 | 贵研铂业股份有限公司 | Preparation method of activated carbon capable of selectively adsorbing palladium |
| KR101660520B1 (en) * | 2015-04-08 | 2016-09-29 | 한국생산기술연구원 | Method of performing continuous electroless plating of copper and nickel and plating layer using the same |
| CN112867275A (en) * | 2021-01-06 | 2021-05-28 | 深圳市迅捷兴科技股份有限公司 | Method for plating nickel and gold on part without lead |
| CN113151812A (en) * | 2021-04-20 | 2021-07-23 | 广东工业大学 | Tin activating solution, preparation method thereof and chemical nickel plating method |
Non-Patent Citations (1)
| Title |
|---|
| 姚俊合;何湘柱;陈云毅;唐旭东;彭胜隆;: "印刷电路板铜电路表面化学镀镍前预镀镍替代无钯活化", 电镀与涂饰, no. 04 * |
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