CN114016031B - Quick etching liquid and preparation method thereof - Google Patents
Quick etching liquid and preparation method thereof Download PDFInfo
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- CN114016031B CN114016031B CN202111235290.4A CN202111235290A CN114016031B CN 114016031 B CN114016031 B CN 114016031B CN 202111235290 A CN202111235290 A CN 202111235290A CN 114016031 B CN114016031 B CN 114016031B
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- 238000005530 etching Methods 0.000 title claims abstract description 173
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 title claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000080 wetting agent Substances 0.000 claims abstract description 30
- 239000003223 protective agent Substances 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- JNXJYDMXAJDPRV-UHFFFAOYSA-N 2-(benzotriazol-1-yl)butanedioic acid Chemical compound C1=CC=C2N(C(C(O)=O)CC(=O)O)N=NC2=C1 JNXJYDMXAJDPRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- VJEFVEHNRRGNQX-UHFFFAOYSA-N 3-(benzotriazol-1-yl)propane-1,1-diol Chemical compound C1=CC=C2N(CCC(O)O)N=NC2=C1 VJEFVEHNRRGNQX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims abstract description 6
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims abstract description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims abstract description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003628 erosive effect Effects 0.000 claims abstract description 3
- 239000011814 protection agent Substances 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 230000002265 prevention Effects 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000000669 biting effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 drilling Chemical compound 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides a rapid etching solution and a preparation method thereof. The rapid etching solution comprises the following components in percentage by weight: 30-150 g/L sulfuric acid, 10-50 g/L hydrogen peroxide, 0.1-5 g/L side erosion protection agent, 0.05-0.5 g/L wetting agent and 0.5-20 g/L stabilizer; wherein the anti-undercut protective agent comprises at least one of 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole, the wetting agent comprises at least one of fluorocarbon surfactant and acetylenic glycol polyoxyethylene ether, and the stabilizer comprises at least one of N-dimethylethanolamine, N-ethylethanolamine, sodium polycarboxylate, sulfamic acid and 5-sulfosalicylic acid.
Description
Technical Field
The invention relates to the technical field of circuit board processing, in particular to a rapid etching solution and a preparation method thereof.
Background
With the rapid development and demand of miniaturization of electronic products and high frequency of signals, the PCB must be accelerated toward high density-! The essence of the high density of the PCB is mainly the problem of refinement of the PCB wires (body): not only the wire is required to be miniaturized, but also the wire must be precise ≡! Today the line width/spacing (L/S) of high-end PCB conductors has moved to the micron-scale (e.g., 20 μm or less) era, while the dimensional accuracy (error range) is to meet + -5% (or even less).
The manufacturing technology for realizing the high-density fine wire mainly comprises a full addition method, a half addition method (SAP) and a modified half addition method (mSAP). The addition method has the defects of poor bonding force between the copper foil added and the surface of the insulating substrate, influence on reliability and service life, and the factors of high manufacturing process complexity, poor stability, difficult scale, high cost and the like, so that the addition method cannot be widely popularized and applied. The processes used for the semi-additive process (SAP) and the modified semi-additive process (mspa) are similar: firstly, coating a thin copper layer on a substrate, then carrying out negative pattern design, electroplating a copper layer with a required thickness, and then removing the seed copper layer.
When the line etching is performed by the semi-additive method (SAP) and the modified semi-additive method (mSAP), the general sulfuric acid/hydrogen peroxide etching direction is not controlled, and side etching phenomenon can occur, so that the defect and deviation of the fine pattern are caused, and the stability of signal transmission is poor.
Disclosure of Invention
The invention aims to provide a rapid etching solution capable of reducing line side etching and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides a rapid etching solution, which comprises the following components in parts by weight: 30-150 g/L sulfuric acid, 10-50 g/L hydrogen peroxide, 0.1-5 g/L side erosion protection agent, 0.05-0.5 g/L wetting agent and 0.5-20 g/L stabilizer; wherein the anti-undercut protective agent comprises at least one of 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole, the wetting agent comprises at least one of fluorocarbon surfactant and acetylenic diol polyoxyethylene ether, and the stabilizer comprises at least one of N-dimethylethanolamine, N-ethylethanolamine, sodium polycarboxylate, sulfamic acid and 5-sulfosalicylic acid.
In one embodiment, the anti-undercut protective agent comprises a ratio of 0.5:0.5: (0.1 to 0.25) 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole.
In one embodiment, the content of the undercut preventing protective agent is 0.5-2 g/L.
In one embodiment, the fluorocarbon surfactant includes fluorocarbon nonionic surfactant FS-31 and fluorocarbon nonionic surfactant Capstone FS-3100.
In one embodiment, the wetting agent comprises the components in the ratio of (1 to 5): 1:0.5 fluorocarbon nonionic surfactant FS-31, fluorocarbon nonionic surfactant Capstone FS-3100 and acetylenic diol polyoxyethylene ether.
In one embodiment, the wetting agent is present in an amount of 0.1 to 0.3g/L.
In one embodiment, the stabilizer comprises 1:1:1, sodium polycarboxylate and 5-sulfosalicylic acid.
The invention also provides a preparation method of the rapid etching liquid, which comprises the following steps:
And weighing the sulfuric acid, the hydrogen peroxide, the side-etching prevention protective agent, the wetting agent and the stabilizing agent according to the rapid etching solution, adding water with the conductivity less than or equal to 10 mu S/cm, and uniformly stirring to obtain the rapid etching solution.
The invention also provides a preparation method of the rapid etching liquid, which comprises the following steps:
measuring (1/3-1/2) V Presetting of water, wherein the conductivity of the water is less than or equal to 10 mu S/cm, and V Presetting is the volume of the rapid etching solution;
According to the rapid etching solution, adding the sulfuric acid and the hydrogen peroxide, and uniformly stirring;
Adding the side-etching prevention protective agent, the wetting agent and the stabilizing agent, and uniformly stirring to obtain concentrated rapid etching solution;
And adding water into the concentrated rapid etching solution to dilute the rapid etching solution to V Presetting , thus obtaining the rapid etching solution.
The invention also provides a preparation method of the rapid etching liquid, which comprises the following steps:
weighing the sulfuric acid and the hydrogen peroxide according to the rapid etching solution, and uniformly stirring to obtain a solution A;
Weighing the side-etching prevention protective agent, the wetting agent and the stabilizing agent, adding a small amount of water with the conductivity less than or equal to 10 mu S/cm, and uniformly stirring to obtain an additive concentrated solution;
and diluting the additive concentrated solution, and mixing with the solution A to obtain the rapid etching solution.
According to the technical scheme, the invention has the advantages and positive effects that:
The rapid etching liquid comprises sulfuric acid, hydrogen peroxide, an anti-side-etching protective agent, a wetting agent and a stabilizing agent, and when copper is etched, the anti-etching protective agent forms more adsorption films on the surface and the side surface of the electrolytic copper surface layer, and the adsorption films protect the copper layer, so that the etching rate of the rapid etching liquid on the side surface is slowed down, and the phenomenon of side etching of a circuit can be obviously reduced.
Drawings
Fig. 1 is an image of a scanning microscope after the rapid etching solution of example 1 of the present invention etches a line.
Fig. 2 is an image of a scanning microscope after the rapid etching solution of comparative example 1 etches the line.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention will be described in detail in the following description. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description and illustrations herein are intended to be by way of illustration only and not to be construed as limiting the invention.
For the purpose of further illustrating the principles and structure of the present invention, preferred embodiments of the invention will now be described in detail with reference to the accompanying drawings.
The specific processes of the semi-additive method (SAP) and the modified semi-additive method (mspa) are as follows:
Core plate, laminated thin base copper, drilling, copper deposition, flash plating, film pasting, pattern transfer, development, pattern electroplating, film stripping and flash etching.
When the system of sulfuric acid and hydrogen peroxide is adopted in the flash etching, not only the bottom copper can be etched downwards, but also two sides of a circuit can be etched, so that the defect and deviation of a fine pattern are caused, and the stability of signal transmission is poor.
Therefore, the invention provides a rapid etching solution which can remarkably reduce the phenomenon of line side etching. The rapid etching liquid is suitable for etching the plate in the manufacturing process of the printed circuit board, and the printed circuit board is obtained by etching the metal copper on the printed circuit board.
The rapid etching liquid can meet the accurate etching requirement of fine lines with the line/gap smaller than 20 mu m/20 mu m, and is particularly suitable for etching lines in a semi-additive method (SAP) and a modified semi-additive method (mSAP).
The etching principle of the rapid etching solution is specifically described in detail below.
Specifically, the rapid etching solution comprises the following components in parts by weight: 30-150 g/L sulfuric acid, 10-50 g/L hydrogen peroxide, 0.1-5 g/L side-etching preventive, 0.05-0.5 g/L wetting agent and 0.5-20 g/L stabilizer.
The application takes sulfuric acid and hydrogen peroxide as a system, and the rest are additives, so that the line side etching phenomenon is reduced while the rapid etching is realized.
From the overall point of view of the rapid etching solution, the concentration of sulfuric acid is too low, the etching reaction speed is too slow, the concentration of sulfuric acid is too high, and copper sulfate crystals are easily generated and deposited in the process of etching copper. The concentration of hydrogen peroxide is too low, the etching rate is too low, burrs and copper teeth are easy to generate in circuit etching; the concentration of the hydrogen peroxide is too high, the reaction is too severe, the balance maintenance of the liquid medicine is not good, and the etching is affected. Therefore, the sulfuric acid of the application is 30-150 g/L, and the concentration of hydrogen peroxide is 10-50g/L.
The undercut-preventing protective agent comprises at least one of 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole. The side-etching-preventing protective agent belongs to azole derivatives, is a long-chain high polymer substance, and has a main structure with a corrosion inhibition effect.
Further, the corrosion inhibitor includes a ratio of 0.5:0.5: (0.1 to 0.25) 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole. The combination can ensure a better corrosion inhibition effect.
The anti-corrosion protective agent is used for forming more adsorption films on the surface and the side surface of the electrolytic copper surface layer, and the adsorption films protect the copper layer, so that the etching rate of the rapid etching liquid on the side surface is slowed down. The copper layer of the circuit substrate is less adsorbed, so that the etching is vertically and vertically snapped, the accurate etching is realized, and the situation that the lattice directly remains in the cavity gap during the etching of electrolytic copper is avoided.
The corrosion-resistant protective agents in the application are cathode adsorption type corrosion inhibitors, the thickness of the formed adsorption film is moderate, and the adsorption film is easy to remove, so that the next procedure is not affected.
The weight portion of the corrosion-resistant protective agent is 0.1-5g/L. Below the above range, less of the corrosion-preventing protective agent can react with copper to form an adsorption film, and the remaining copper not forming the adsorption film can still be etched, resulting in relatively poor corrosion prevention. Above the above range, too much copper acts with the corrosion-preventing protective agent to form an adsorption film, preventing etching of copper, thereby affecting the morphology of the etched copper surface.
The wetting agent comprises at least one of fluorocarbon surfactant and acetylene glycol polyoxyethylene ether.
Fluorocarbon surfactants include fluorocarbon nonionic surfactant FS-31 and fluorocarbon nonionic surfactant Capstone FS-3100.
The structural formula of the fluorocarbon nonionic surfactant FS-31 is as follows:
RfCH 2CH2O(CH2CH2O)n H, where n=0 to 25, rf=f (CF 2CF2) m, m=1 to 9, molecular weight: 950.
Further, the wetting agent comprises the components in the proportion of (1-5): 1:0.5 fluorocarbon nonionic surfactant FS-31, fluorocarbon nonionic surfactant Capstone FS-3100 and acetylenic diol polyoxyethylene ether.
The wetting agent is 0.1-0.3 g/L.
The wetting agent is used for wetting copper crystals, so that etching is rapidly and uniformly performed, and a flat biting effect is obtained.
The weight portion of the wetting agent is 0.05-5g/L. Below the above range, the wetting effect of the wetting agent is poor, and the effect is not obvious. Above the above range, the excess copper is wasted on the premise that the copper is wet.
The stabilizer comprises at least one of N-dimethylethanolamine, N-ethylethanolamine, sodium polycarboxylate, sulfamic acid and 5-sulfosalicylic acid.
The stabilizer can stabilize hydrogen peroxide and accelerate the rapid corrosion of the bottom copper.
The weight portion of the stabilizer is 0.5-20g/L. When the hydrogen peroxide consumption is lower than the above range, the hydrogen peroxide consumption is too fast, and the effect of stabilizing the hydrogen peroxide is unstable. Above the above range, the effect of stabilizing hydrogen peroxide remains unchanged, and there is waste.
The corrosion-resistant protective agent, the wetting agent and the stabilizing agent of the application act together to realize the remarkable reduction of the phenomenon of line side corrosion. Wherein, the wetting agent assists in the uniformity of etching, the anticorrosive agent forms a protective layer on the side surface of the circuit to prevent the side etching of the liquid medicine, and the stabilizer is used for stabilizing the decomposition rate of hydrogen peroxide to avoid the occurrence of larger fluctuation of the etching rate and uneven etching.
The preparation method of the rapid etching liquid comprises the following steps:
And weighing sulfuric acid, hydrogen peroxide, a side-etching prevention protective agent, a wetting agent and a stabilizing agent according to the content of the rapid etching liquid, adding water with the conductivity less than or equal to 10 mu S/cm, and uniformly stirring to obtain the rapid etching liquid.
Wherein, the conductivity of the water is less than or equal to 10 mu S/cm, so as to ensure that impurities in the water can not influence the copper biting rate of the rapid etching liquid during etching.
The application also provides a preparation method of the concentrated rapid etching liquid, and the concentrated rapid etching liquid is diluted when in use. The method specifically comprises the following steps:
And (3) measuring (1/3-1/2) V Presetting of water, wherein the conductivity of the water is less than or equal to 10 mu S/cm, and V Presetting is the volume of the rapid etching solution.
According to the rapid etching solution, sulfuric acid and hydrogen peroxide are added and stirred uniformly.
And the side-etching prevention protection, the wetting agent and the stabilizing agent are uniformly stirred to obtain the concentrated rapid etching solution.
And (3) adding water into the concentrated rapid etching solution to dilute the rapid etching solution to V Presetting , thus obtaining the rapid etching solution.
In use, the concentrated rapid etching solution can be diluted by adding water. And the device is convenient to supplement and maintain, is simple and convenient to operate, and has small overflow discharge amount of the liquid medicine.
The application also provides a preparation method of the rapid etching liquid, which specifically comprises the following steps:
According to the rapid etching solution, sulfuric acid and hydrogen peroxide are weighed and stirred uniformly to obtain solution A.
Weighing the side corrosion preventing protective agent, the wetting agent and the stabilizing agent, adding a small amount of water with the conductivity less than or equal to 10 mu S/cm, and uniformly stirring to obtain the additive concentrated solution.
And diluting the additive concentrated solution, and mixing with the solution A to obtain the rapid etching solution.
When in use, the additive concentrate is diluted and mixed with the solution A to obtain the rapid etching solution, namely the rapid etching solution can be started to be used.
In the process of etching copper by using the rapid etching solution, the composition of the rapid etching solution is continuously changed due to the consumption of chemical reaction, and if the consumed part is not timely replenished, the copper etching rate is affected, so that the rapid etching solution is required to be continuously replenished. And when the liquid medicine is supplemented, concentrated solution with higher concentration is added, so that the dosage of the liquid medicine can be reduced, and the discharge amount of waste liquid can be further reduced.
The rapid etching solution of the application can be used in a dipping treatment and spraying mode.
The use temperature of the rapid etching liquid is 15-40 ℃. When the etching rate is lower than 15 ℃, the etching rate is slower, and when the etching rate is higher than 40 ℃, the consumption of the rapid etching solution is excessive.
The inventors of the present application realized the function of the rapid etching liquid that the etching rate is faster and the line side etching is remarkably reduced by strictly designing the content of each component, and the content of each component is described below by each example.
Example 1
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
The preparation method of the rapid etching solution in this embodiment is not limited, and any one of the three preparation methods of the present application may be adopted.
Example 2
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 3
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 4
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 5
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 6
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 7
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 8
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Example 9
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
the preparation method of the rapid etching solution of this example remained the same as that of example 1.
Comparative example 1
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
Comparative example 2
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
Comparative example 3
Taking the preparation of the rapid etching liquid 1L as an example, the components and the contents are as follows:
A560 mm by 650mm copper clad laminate was subjected to a laser drilling, electroless copper plating, flash plating, dry film (29 μm) sticking, electroplating of 20 μm, and film stripping process to obtain a test board. Wherein the thickness of the copper of the chemical substrate of the test board is controlled within the range of 6-8 mu m
The test board is cut into areas with the size of 50mm multiplied by 50mm to serve as a test substrate, and the prepared rapid etching liquid is used for testing the appearance of the circuit morphology and the side etching effect. The rapid etching solutions of examples 1 to 9 and comparative examples 1 to 3 were used to conduct etching at a temperature of 30℃for a suitable etching time, and the test results are shown in Table 1.
Definition of appropriate etching time: etching until the chemical copper on the test substrate is etched, and the condition of leaking out the resin surface is calibrated to be proper etching time.
Whether or not the electroless copper plating layer was removed was evaluated, and the resin surface between the wirings was observed after 500-fold magnification by a metal microscope.
Judging the side etching effect of the circuit: the image measurement of the line is performed under a scanning microscope by taking a section, grinding a section slice of the line by a grinder. The slope method is used to calculate the etching factor: ef=v/X.
Where EF is an abbreviation for Ecth Factor, representing the etching factor. X= (bottom width-top line width), V is etch layer thickness.
And (3) line appearance observation: the topographical features of the wire surface were observed through a metal microscope at 500 x magnification. The undercut effect is illustrated by the magnitude of the etch factor. By way of example, fig. 1 shows an image of example 1 under a scanning microscope, where x= (5.00-4.88) mil, V is 1.29mil, ef=1.29/(5.00-4.88) =10.75. Fig. 2 shows an image of comparative example 1 under a scanning microscope, where x= (3.91-3.58) mil, V is 1.29mil, ef=1.29/(3.91-3.58) =3.90.
TABLE 1
As can be seen from the above table, the copper surfaces of the lines etched by the rapid etching solutions of examples 1 to 9 were fine and free of holes, and the side etching factors were large, i.e., the side etching effect was small, while the copper surfaces of the lines etched by the rapid etching solutions of comparative examples were porous, and the side etching factors were small, i.e., the side etching effect was large. Therefore, the rapid etching solution in this embodiment has a good etching effect.
According to the technical scheme, the invention has the advantages and positive effects that:
The rapid etching liquid comprises sulfuric acid, hydrogen peroxide, an anti-side-etching protective agent, a wetting agent and a stabilizing agent, and when copper is etched, the anti-etching protective agent forms more adsorption films on the surface and the side surface of the electrolytic copper surface layer, and the adsorption films protect the copper layer, so that the etching rate of the rapid etching liquid on the side surface is slowed down, and the phenomenon of side etching of a circuit can be obviously reduced.
While the invention has been described with reference to several exemplary embodiments, it is to be understood that the terminology used is intended to be in the nature of words of description and of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (10)
1. The rapid etching liquid is used for etching metal copper on a printed circuit board and is characterized by comprising the following components in percentage by weight: 30-150 g/L sulfuric acid, 10-50 g/L hydrogen peroxide, 0.1-5 g/L side erosion protection agent, 0.05-0.5 g/L wetting agent and 0.5-20 g/L stabilizer; wherein the anti-undercut protective agent comprises at least one of 1- (1, 2-dicarboxyethyl) benzotriazole and 1-dihydroxypropyl benzotriazole, the wetting agent comprises at least one of fluorocarbon surfactant and acetylenic diol polyoxyethylene ether, and the stabilizer comprises at least one of N-dimethylethanolamine, N-ethylethanolamine, sodium polycarboxylate, sulfamic acid and 5-sulfosalicylic acid.
2. The rapid etching solution of claim 1, wherein the anti-undercut protective agent comprises a ratio of 0.5:0.5: (0.1 to 0.25) 1- (1, 2-dicarboxyethyl) benzotriazole, 1-dihydroxypropyl benzotriazole and 5-aminotetrazole.
3. The rapid etching solution according to claim 1, wherein the content of the undercut preventing agent is 0.5 to 2g/L.
4. The rapid etching solution of claim 1, wherein the fluorocarbon surfactant comprises fluorocarbon nonionic surfactant FS-31 and fluorocarbon nonionic surfactant Capstone FS-3100.
5. The rapid etching solution according to claim 4, wherein the wetting agent comprises a mixture of (1 to 5): 1:0.5 fluorocarbon nonionic surfactant FS-31, fluorocarbon nonionic surfactant Capstone FS-3100 and acetylenic diol polyoxyethylene ether.
6. The rapid etching solution according to claim 1, wherein the wetting agent is 0.1 to 0.3g/L.
7. The rapid etching solution of claim 1, wherein the stabilizer comprises 1:1:1, sodium polycarboxylate and 5-sulfosalicylic acid.
8. The preparation method of the rapid etching liquid is characterized by comprising the following steps:
The rapid etching solution according to any one of claims 1 to 7, wherein the sulfuric acid, the hydrogen peroxide, the side-etching prevention protective agent, the wetting agent and the stabilizing agent are weighed, water with conductivity less than or equal to 10 mu S/cm is added, and the rapid etching solution is obtained after uniform stirring.
9. The preparation method of the rapid etching liquid is characterized by comprising the following steps:
measuring (1/3-1/2) V Presetting of water, wherein the conductivity of the water is less than or equal to 10 mu S/cm, and V Presetting is the volume of the rapid etching solution;
The rapid etching solution according to any one of claims 1 to 7, wherein the sulfuric acid and the hydrogen peroxide are added and stirred uniformly;
Adding the side-etching prevention protective agent, the wetting agent and the stabilizing agent, and uniformly stirring to obtain concentrated rapid etching solution;
And adding water into the concentrated rapid etching solution to dilute the rapid etching solution to V Presetting , thus obtaining the rapid etching solution.
10. The preparation method of the rapid etching liquid is characterized by comprising the following steps:
the rapid etching solution according to any one of claims 1 to 7, wherein the sulfuric acid and the hydrogen peroxide are weighed and stirred uniformly to obtain a solution A;
Weighing the side-etching prevention protective agent, the wetting agent and the stabilizing agent, adding a small amount of water with the conductivity less than or equal to 10 mu S/cm, and uniformly stirring to obtain an additive concentrated solution;
and diluting the additive concentrated solution, and mixing with the solution A to obtain the rapid etching solution.
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