CN111954378A - Reduction repairing agent for copper oxide layer on surface of copper bonding pad and normal-temperature in-situ reduction repairing method - Google Patents
Reduction repairing agent for copper oxide layer on surface of copper bonding pad and normal-temperature in-situ reduction repairing method Download PDFInfo
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- CN111954378A CN111954378A CN202010699427.0A CN202010699427A CN111954378A CN 111954378 A CN111954378 A CN 111954378A CN 202010699427 A CN202010699427 A CN 202010699427A CN 111954378 A CN111954378 A CN 111954378A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 72
- 230000009467 reduction Effects 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 28
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 48
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003466 welding Methods 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 230000008439 repair process Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011975 tartaric acid Substances 0.000 claims abstract description 19
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- FINXTJFVUXNTOQ-UHFFFAOYSA-N 2-hexyl-1h-benzimidazole Chemical compound C1=CC=C2NC(CCCCCC)=NC2=C1 FINXTJFVUXNTOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 claims abstract description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 18
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012964 benzotriazole Substances 0.000 claims abstract description 18
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims abstract description 4
- 230000002829 reductive effect Effects 0.000 claims description 13
- 239000004745 nonwoven fabric Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- YFDKVXNMRLLVSL-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O YFDKVXNMRLLVSL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims 10
- 238000002845 discoloration Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 52
- 239000010410 layer Substances 0.000 description 33
- 238000002791 soaking Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CQVPPLWYIDMWDA-UHFFFAOYSA-N OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] Chemical compound OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] CQVPPLWYIDMWDA-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- H05K3/0085—Apparatus for treatments of printed circuits with liquids not provided for in groups H05K3/02 - H05K3/46; conveyors and holding means therefor
-
- 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
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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a reduction repairing agent for a copper oxide layer on the surface of a copper bonding pad and a normal-temperature in-situ reduction repairing method, wherein the reduction repairing agent comprises the following raw materials in parts by mass: 1-20 parts of tartaric acid, 1-20 parts of acetic acid, 1-20 parts of thiourea, 1-20 parts of sodium hypophosphite, 0.1-1 part of n-dodecyl phosphoric acid, 0.1-1 part of sodium n-dodecyl benzene sulfonate, 0.1-1 part of 2-hexyl benzimidazole, 0.1-1 part of benzotriazole, 0.01-0.1 part of copper acetate, 0.01-0.1 part of hexadecyl trimethyl ammonium bromide and 60-95 parts of deionized water. During repair, dipping the reduction repair liquid by using the fabric, and lightly wiping the surface of the copper pad with the oxidation layer until the natural color of copper is recovered on the surface of the copper pad; and (4) removing the reduction repair liquid on the surface of the copper bonding pad before welding. By adopting the reduction repairing agent, the product can be directly repaired in situ at normal temperature without reworking the printed circuit board, and the reduction repairing agent is particularly suitable for products with larger size (>10m), saves cost, is simple, convenient and quick to operate, has good treatment effect on the problem of oxidative discoloration of a copper pad of the printed circuit board, and can effectively improve the welding quality.
Description
Technical Field
The invention belongs to the technical field of surface treatment, and particularly relates to a reduction repairing agent for a copper oxide layer on the surface of a copper bonding pad and a normal-temperature in-situ reduction repairing method.
Background
With the development of the electronic industry, the yield of the printed circuit board is increased year by year, and the state of the copper bonding pad directly influences the welding quality of the subsequent electronic assembly of the printed circuit board. At present, in the printed circuit industry, an OSP organic protective agent is mainly adopted to carry out anti-oxidation treatment on a copper bonding pad of a printed circuit board.
When the OSP preparation process fluctuates or the storage environment and the storage time of the printed circuit board exceed the specified requirements due to reasons, the protective layer on the surface of the copper bonding pad has the characteristic of gradual failure, the copper bonding pad of the printed circuit board has a local oxidation discoloration phenomenon, the welding reliability of the product is greatly reduced, and the product generally needs to be reworked or directly scrapped. At present, some large-size products have the characteristic of long assembly working period, part of interfaces are assembled and solidified, and the rest parts cannot be treated in situ if oxidized, so that the whole products need to be disassembled and reworked or directly scrapped.
The center of gravity of the current industry work is mainly to improve the environmental tolerance and the preparation process stability of the OSP, the in-situ treatment means of the copper surface oxidation layer is limited to physical polishing, the method is difficult to quantitatively control, and the deformation and damage of the ultrathin copper layer can be caused to influence the reliability of subsequent welding. The ex-situ method, such as plate grinding or chemical acid washing, requires disassembly and rework, and also causes the copper layer to be thinned and damaged, thereby affecting the reliability of subsequent welding. At present, the copper reducing agent and the nondestructive reduction technology which are limited and can be checked need to repair the oxidation layer on the surface of the copper by adopting a soaking element mode, and the soaking usually needs heating or high temperature, so that the method cannot be directly implemented on products. Particularly, the length of a continuous flexible printed circuit board such as a flat type inter-board cable used for solar cell wing power transmission in the aerospace field is about 30m, and due to the fact that other space environment protection coatings exist on the surface of the cable, in-situ reduction repair cannot be carried out by the existing known technical method when an exposed welding disc is oxidized.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor of the invention makes a keen study, and provides a copper oxide layer reduction repairing agent on the surface of a copper pad and a normal-temperature in-situ reduction repairing method, the problem of oxidative discoloration on the surface of the copper pad of a printed circuit board can be simply and economically treated by adopting the reduction repairing agent and the normal-temperature in-situ reduction repairing method, the welding quality is effectively improved, the copper layer is not damaged by thinning the copper layer, and the method is particularly suitable for products with larger size (more than 10m), so that the invention is completed.
The technical scheme provided by the invention is as follows:
in a first aspect, a copper oxide layer reduction repairing agent for a copper pad surface comprises the following raw materials in parts by mass: 1-20 parts of tartaric acid, 1-20 parts of acetic acid, 1-20 parts of thiourea, 1-20 parts of sodium hypophosphite, 0.1-1 part of n-dodecyl phosphoric acid, 0.1-1 part of sodium n-dodecyl benzene sulfonate, 0.1-1 part of 2-hexyl benzimidazole, 0.1-1 part of benzotriazole, 0.01-0.1 part of copper acetate, 0.01-0.1 part of hexadecyl trimethyl ammonium bromide and 60-95 parts of deionized water.
In a second aspect, a method for normal-temperature in-situ reduction repairing of a copper oxide layer on a surface of a copper pad is implemented by the reduction repairing agent of the first aspect, and includes the following steps:
step 1, preparing a copper oxide layer reduction repair liquid according to a set mass part;
step 2, dipping the reduction repair liquid by using the fabric, and lightly wiping the surface of the copper pad with the oxidation layer until the natural color of copper is recovered on the surface of the copper pad;
and 3, removing the reduction repair liquid on the surface of the copper bonding pad before welding.
According to the copper pad surface copper oxide layer reduction repairing agent and the normal-temperature in-situ reduction repairing method provided by the invention, the following beneficial effects are achieved:
the reduction repairing agent is prepared from specific components with specific proportions, so that the repairing method integrates copper in-situ reduction and protection after reduction, is suitable for rapidly performing in-situ repair on a copper pad of a product at normal temperature, does not need heating or soaking treatment, and is particularly suitable for products with larger sizes (>10 m). When the surface of the copper pad of the printed circuit board is subjected to partial oxidation discoloration due to OSP failure, rework operation of plate grinding or acid pickling is not required, the method can simply and economically wipe the discolored area on the surface of the pad in the in-situ position of a product to reduce copper oxide, the main body of the reaction is reduction reaction without damaging the surface of the copper pad, the oxidation discoloration phenomenon of the copper pad after the treatment by the method is eliminated, and the weldability is greatly improved.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
According to the first aspect of the invention, the reduction repairing agent for the copper oxide layer on the surface of the copper bonding pad is provided, and comprises the following raw materials in parts by mass: 1-20 parts of tartaric acid, 1-20 parts of acetic acid, 1-20 parts of thiourea, 1-20 parts of sodium hypophosphite, 0.1-1 part of n-dodecyl phosphoric acid, 0.1-1 part of sodium n-dodecyl benzene sulfonate, 0.1-1 part of 2-hexyl benzimidazole, 0.1-1 part of benzotriazole, 0.01-0.1 part of copper acetate, 0.01-0.1 part of hexadecyl trimethyl ammonium bromide and 60-95 parts of deionized water.
Preferably, the reduction repairing agent comprises the following raw materials in parts by mass: 3-12 parts of tartaric acid, 3-12 parts of acetic acid, 3-12 parts of thiourea, 4-12 parts of sodium hypophosphite, 0.2-0.8 part of n-dodecyl phosphoric acid, 0.2-0.8 part of n-dodecyl benzene sulfonic acid sodium, 0.3-0.8 part of 2-hexyl benzimidazole, 0.3-0.8 part of benzotriazole, 0.05-0.1 part of copper acetate, 0.05-0.1 part of hexadecyl trimethyl ammonium bromide and 60-80 parts of deionized water.
Preferably, the reduction repairing agent comprises the following raw materials in parts by mass: 3-5 parts of tartaric acid, 3-6 parts of acetic acid, 3-8 parts of thiourea, 4-6 parts of sodium hypophosphite, 0.2-0.8 part of n-dodecyl phosphoric acid, 0.5-0.8 part of n-dodecyl benzene sulfonate, 0.3-0.4 part of 2-hexyl benzimidazole, 0.3-0.4 part of benzotriazole, 0.05-0.1 part of copper acetate, 0.05-0.1 part of hexadecyl trimethyl ammonium bromide and 60-80 parts of deionized water.
Preferably, the reduction repairing agent comprises the following raw materials in parts by mass: 5 parts of tartaric acid, 5 parts of acetic acid, 4 parts of thiourea, 4 parts of sodium hypophosphite, 0.5 part of n-dodecyl phosphoric acid, 0.5 part of sodium n-dodecyl benzene sulfonate, 0.4 part of 2-hexyl benzimidazole, 0.4 part of benzotriazole, 0.1 part of copper acetate, 0.1 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
Preferably, the reduction repairing agent comprises the following raw materials in parts by mass: 3 parts of tartaric acid, 6 parts of acetic acid, 3 parts of thiourea, 6 parts of sodium hypophosphite, 0.8 part of n-dodecyl phosphoric acid, 0.5 part of sodium n-dodecyl benzene sulfonate, 0.3 part of 2-hexyl benzimidazole, 0.3 part of benzotriazole, 0.05 part of copper acetate, 0.05 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
Preferably, the reduction repairing agent comprises the following raw materials in parts by mass: 3 parts of tartaric acid, 3 parts of acetic acid, 8 parts of thiourea, 4 parts of sodium hypophosphite, 0.2 part of n-dodecyl phosphoric acid, 0.8 part of sodium n-dodecyl benzene sulfonate, 0.4 part of 2-hexyl benzimidazole, 0.4 part of benzotriazole, 0.1 part of copper acetate, 0.1 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
In the components of the reduction repairing agent, tartaric acid and acetic acid mainly provide an acidic environment, and the reduction reaction of a copper oxide layer on the surface of a copper pad can be realized in an acid-base environment, but the acidic environment is adopted in consideration of the fact that polyimide is usually adopted as an insulating layer in a flexible printed circuit and the insulating effect of the polyimide is reduced in an alkaline environment; and tartaric acid and acetic acid are matched, so that rapid repair can be realized on the premise of not damaging the copper plating layer. Thiourea in the components can form a complex with copper ions to capture the copper ions in the oxide layer, and the thiourea is slightly soluble in alcohol to be convenient for removal, so that subsequent welding cannot be influenced, and welding tension is reduced. Sodium hypophosphite is a mild reducing agent, can react with copper oxide at normal temperature, does not need heating to promote the reaction, and ensures wide applicability of the reduction repairing agent and the repairing method. The n-dodecyl phosphoric acid provides the acidity of the composition and improves the temperature resistance of an OSP system, the n-dodecyl sodium benzenesulfonate mainly performs an additional cleaning effect on the surface of a bonding pad, the 2-hexyl benzimidazole and benzotriazole mainly repair the OSP system, copper acetate is used for activating copper ions in an oxide layer, cetyl trimethyl ammonium bromide is used as a surface dispersant, and a small amount of the surface dispersant can improve the reduction repair efficiency considering the use in a non-soaking environment.
According to a second aspect of the present invention, there is provided a normal temperature in-situ reduction repairing method for a copper oxide layer on a surface of a copper pad, the method is implemented by the reduction repairing agent of the first aspect, and includes:
step 1, preparing a copper oxide layer reduction repair liquid according to a set mass part;
step 2, dipping the reduction repair liquid by using the fabric, and lightly wiping the surface of the copper pad with the oxidation layer until the natural color of copper is recovered on the surface of the copper pad;
and 3, removing the reduction repair liquid on the surface of the copper bonding pad before welding.
In step 1, the raw material ratio in the reduction repair liquid is the same as that described in the first aspect, and is not described herein again.
In the step 2, the prepared reduction repair liquid is dipped by using non-woven fabric, and the part of the surface of the copper pad with the oxide layer is lightly wiped in one direction until the surface of the copper pad recovers the natural color of copper.
In step 3, the specific implementation method for removing the reduction repair liquid on the surface of the copper bonding pad before welding comprises the following steps: and (3) dipping the non-woven fabric in an alcohol solution, wiping the surface of the copper pad for about 3-5 times, performing an acid-base test (such as a pH test paper test wetted by deionized water) on the surface of the copper pad, and repeating the alcohol wiping operation until the pH value is greater than or equal to 7.0 if the detection result shows that the pH value is less than 7.0.
Examples
Example 1
A copper oxide layer reduction repairing agent and a normal-temperature in-situ reduction repairing method for the surface of a copper bonding pad are disclosed, and comprise the following steps:
step 1, preparing a copper oxide layer reduction repairing agent according to the mass parts, wherein 5g of tartaric acid, 5g of acetic acid, 4g of thiourea, 4g of sodium hypophosphite, 0.5g of n-dodecyl phosphoric acid, 0.5g of n-dodecyl benzene sulfonic acid sodium, 0.4g of 2-hexyl benzimidazole, 0.4g of benzotriazole, 0.1g of copper acetate, 0.1g of hexadecyl trimethyl ammonium bromide and 80g of deionized water are stirred and mixed uniformly.
And 2, dipping the prepared copper oxide layer reduction repairing agent by using non-woven fabric at room temperature, and lightly wiping the surface of the copper bonding pad with local color change in one direction until the bonding pad restores the copper natural color.
And 3, before welding, dipping the non-woven fabric into alcohol solution to wipe the surface of the copper pad until the pH value is greater than or equal to 7.0 as shown by a test result of wide pH test paper wetted by deionized water.
And (3) welding the plurality of sample pieces (15) by adopting a resistance butt welding mode, wherein the tensile force values of the single welding points (phi 2mm) are all larger than 30N.
Example 2
A copper oxide layer reduction repairing agent and a normal-temperature in-situ reduction repairing method for the surface of a copper bonding pad are disclosed, and comprise the following steps:
step 1, preparing a copper oxide layer reduction repairing agent according to the mass parts, wherein 3g of tartaric acid, 6g of acetic acid, 3g of thiourea, 6g of sodium hypophosphite, 0.8g of n-dodecyl phosphoric acid, 0.5g of n-dodecyl benzene sulfonic acid sodium, 0.3g of 2-hexyl benzimidazole, 0.3g of benzotriazole, 0.05g of copper acetate, 0.05g of hexadecyl trimethyl ammonium bromide and 80g of deionized water are stirred and mixed uniformly.
And 2, dipping the prepared copper oxide layer reduction repairing agent by using non-woven fabric at room temperature, and lightly wiping the surface of the copper bonding pad with local color change in one direction until the bonding pad restores the copper natural color.
And 3, before welding, dipping the non-woven fabric into alcohol solution to wipe the surface of the copper pad until the pH value is greater than or equal to 7.0 as shown by a test result of wide pH test paper wetted by deionized water.
And (3) welding the plurality of sample pieces (15) by adopting a resistance butt welding mode, wherein the tensile force values of the single welding points (phi 2mm) are all larger than 30N.
Example 3
A copper oxide layer reduction repairing agent and a normal-temperature in-situ reduction repairing method for the surface of a copper bonding pad are disclosed, and comprise the following steps:
step 1, preparing a copper oxide layer reduction repairing agent according to the mass parts, wherein 3g of tartaric acid, 3g of acetic acid, 8g of thiourea, 4g of sodium hypophosphite, 0.2g of n-dodecyl phosphoric acid, 0.8g of n-dodecyl benzene sulfonic acid sodium, 0.4g of 2-hexyl benzimidazole, 0.4g of benzotriazole, 0.1g of copper acetate, 0.1g of hexadecyl trimethyl ammonium bromide and 80g of deionized water are stirred and mixed uniformly.
And 2, dipping the prepared copper oxide layer reduction repairing agent by using non-woven fabric at room temperature, and lightly wiping the surface of the copper bonding pad with local color change in one direction until the bonding pad restores the copper natural color.
And 3, before welding, dipping the non-woven fabric into alcohol solution to wipe the surface of the copper pad until the pH value is greater than or equal to 7.0 as shown by a test result of wide pH test paper wetted by deionized water.
And (3) welding the plurality of sample pieces (15) by adopting a resistance butt welding mode, wherein the tensile force values of the single welding points (phi 2mm) are all larger than 30N.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (9)
1. The reduction repairing agent for the copper oxide layer on the surface of the copper bonding pad is characterized by comprising the following raw materials in parts by mass:
1-20 parts of tartaric acid, 1-20 parts of acetic acid, 1-20 parts of thiourea, 1-20 parts of sodium hypophosphite, 0.1-1 part of n-dodecyl phosphoric acid, 0.1-1 part of sodium n-dodecyl benzene sulfonate, 0.1-1 part of 2-hexyl benzimidazole, 0.1-1 part of benzotriazole, 0.01-0.1 part of copper acetate, 0.01-0.1 part of hexadecyl trimethyl ammonium bromide and 60-95 parts of deionized water.
2. The reductive remediation agent of claim 1, wherein the reductive remediation agent comprises the following raw materials in parts by mass:
3-12 parts of tartaric acid, 3-12 parts of acetic acid, 3-12 parts of thiourea, 4-12 parts of sodium hypophosphite, 0.2-0.8 part of n-dodecyl phosphoric acid, 0.2-0.8 part of n-dodecyl benzene sulfonic acid sodium, 0.3-0.8 part of 2-hexyl benzimidazole, 0.3-0.8 part of benzotriazole, 0.05-0.1 part of copper acetate, 0.05-0.1 part of hexadecyl trimethyl ammonium bromide and 60-80 parts of deionized water.
3. The reductive remediation agent of claim 1, wherein the reductive remediation agent comprises the following raw materials in parts by mass:
3-5 parts of tartaric acid, 3-6 parts of acetic acid, 3-8 parts of thiourea, 4-6 parts of sodium hypophosphite, 0.2-0.8 part of n-dodecyl phosphoric acid, 0.5-0.8 part of n-dodecyl benzene sulfonate, 0.3-0.4 part of 2-hexyl benzimidazole, 0.3-0.4 part of benzotriazole, 0.05-0.1 part of copper acetate, 0.05-0.1 part of hexadecyl trimethyl ammonium bromide and 60-80 parts of deionized water.
4. The reductive remediation agent of claim 1, wherein the reductive remediation agent comprises the following raw materials in parts by mass:
5 parts of tartaric acid, 5 parts of acetic acid, 4 parts of thiourea, 4 parts of sodium hypophosphite, 0.5 part of n-dodecyl phosphoric acid, 0.5 part of sodium n-dodecyl benzene sulfonate, 0.4 part of 2-hexyl benzimidazole, 0.4 part of benzotriazole, 0.1 part of copper acetate, 0.1 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
5. The reductive remediation agent of claim 1, wherein the reductive remediation agent comprises the following raw materials in parts by mass:
3 parts of tartaric acid, 6 parts of acetic acid, 3 parts of thiourea, 6 parts of sodium hypophosphite, 0.8 part of n-dodecyl phosphoric acid, 0.5 part of sodium n-dodecyl benzene sulfonate, 0.3 part of 2-hexyl benzimidazole, 0.3 part of benzotriazole, 0.05 part of copper acetate, 0.05 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
6. The reductive remediation agent of claim 1, wherein the reductive remediation agent comprises the following raw materials in parts by mass:
3 parts of tartaric acid, 3 parts of acetic acid, 8 parts of thiourea, 4 parts of sodium hypophosphite, 0.2 part of n-dodecyl phosphoric acid, 0.8 part of sodium n-dodecyl benzene sulfonate, 0.4 part of 2-hexyl benzimidazole, 0.4 part of benzotriazole, 0.1 part of copper acetate, 0.1 part of hexadecyl trimethyl ammonium bromide and 80 parts of deionized water.
7. A normal-temperature in-situ reduction repairing method for a copper oxide layer on the surface of a copper bonding pad is characterized in that the normal-temperature in-situ reduction repairing is carried out on the copper oxide layer by adopting the reduction repairing liquid of one of claims 1 to 6, and comprises the following steps:
step 1, preparing a copper oxide layer reduction repair liquid according to a set mass part;
step 2, dipping the reduction repair liquid by using the fabric, and lightly wiping the surface of the copper pad with the oxidation layer until the natural color of copper is recovered on the surface of the copper pad;
and 3, removing the reduction repair liquid on the surface of the copper bonding pad before welding.
8. The reduction repairing method according to claim 7, wherein in the step 2, the prepared reduction repairing liquid is dipped by using non-woven fabric, and the part of the surface of the copper pad with the oxide layer is wiped lightly in one direction until the surface of the copper pad recovers the natural color of copper.
9. The reduction repairing method according to claim 7, wherein in the step 3, the reduction repairing liquid for removing the surface of the copper pad before welding is implemented by: and dipping the non-woven fabric into an alcohol solution, wiping the surface of the copper bonding pad, performing acid-base test on the surface of the copper bonding pad, and repeating the alcohol wiping operation until the pH value is more than or equal to 7.0 if the detection result shows that the pH value is less than 7.0.
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