CN115928072A - Copper surface micro-etching roughening solution and application thereof - Google Patents
Copper surface micro-etching roughening solution and application thereof Download PDFInfo
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Abstract
The invention provides a copper surface microetching coarsening liquid and application thereof, wherein the solvent of the copper surface microetching coarsening liquid comprises water, and solutes comprise copper ions, chloride ions, organic acid salt and 0.00001-0.007 mol/L corrosion inhibitor. The copper surface micro-etching roughening solution provided by the invention can effectively improve the roughness of the copper surface, so that the adhesive force of dielectric materials such as a photosensitive resist layer and printing ink and the adhesive force of metals such as tin, nickel, palladium and gold on the copper surface are improved; on the other hand, the copper surface with different copper crystals has better micro-etching and coarsening effects and wider application range.
Description
Technical Field
The invention belongs to the technical field of printed circuit board manufacturing, relates to a copper surface microetching and roughening solution, and particularly relates to a copper surface microetching and roughening solution and application thereof.
Background
With the miniaturization, light weight, thinning and functional diversification of electronic consumer products, the printed circuit board industry is correspondingly pushed to develop towards the direction of high density, high integration, multilayering and thinning. This trend is more pronounced, especially with respect to the development of high-end PCBs. Due to the fact that the line width and the line distance are continuously reduced, the line distance is continuously increased in concentration degree, and the machining precision of the traditional reduction method meets the requirements satisfactorily. At present, dense fine circuit boards are mainly realized by an additive method, which mainly comprises the following procedures of drilling, glue removal, hole metallization, pattern transfer (film pasting, exposure, development), electroplating, film stripping, etching, surface treatment and solder resist. In the whole process, the microetching and roughening treatment of the copper surface is carried out all the time through the whole process, and the microetching and roughening treatment method has the functions of cleaning the copper surface, increasing the roughness of the copper surface and improving the adhesive force of other materials on the copper surface. For example, in the pattern transfer process, the copper surface needs to be subjected to microetching and roughening treatment before the dry film is coated so as to improve the adhesive force of the dry film on the copper surface, and if the adhesive force of a plurality of films is poor, the diffusion plating phenomenon is easy to occur in the subsequent electroplating process, so that the subsequent incomplete etching is caused, and the circuit board is scrapped. And if the anti-welding process is adopted, the copper surface needs to be roughened before treatment, otherwise, the phenomenon of oil throwing is easy to occur, reworking is needed, and the time and the labor are consumed.
The existing copper surface microetching and roughening solution can be mainly divided into two types, the first type is a hydrogen sulfate and hydrogen peroxide system, and the surface roughness of the treated copper surface is uniform but is easily polluted by chloride ions. For example, patent CN104342701A discloses a sulfuric acid-hydrogen peroxide roughening solution, which can effectively improve the surface roughness of sputtered copper and enhance the adhesion of a dry film on the surface of the sputtered copper by adding tetrazole compounds as corrosion inhibitors. The second type is a copper (iron) ion/organic acid system, the performance of which is slightly influenced by chloride ions and can form a concave-convex microstructure on the copper surface. For example, patent CN1629357 discloses an organic acid roughening agent containing a nonionic polymer compound, which can make the copper surface obtain a certain roughness and a high surface roughness value. Patent CN103890233A discloses an organic acid super-roughening agent containing a nonionic surfactant, which can form irregularities on the metal surface to obtain better adhesion. However, the organic acid roughening system has strong selectivity on copper crystals, so that the same microetching roughening solution has different roughening effects on different copper crystals, and the general applicability is not strong for different types of copper materials produced and manufactured by different processes.
In summary, the existing microetching roughening solution still has some defects, and a novel roughening microetching solution still needs to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a copper surface micro-etching roughening solution and application thereof, and on one hand, the copper surface micro-etching roughening solution provided by the invention can effectively improve the roughness of the copper surface, so that the adhesion force of a photosensitive resist layer, dielectric materials such as printing ink and the like, and tin, nickel, palladium, gold and other metals on the copper surface is improved; on the other hand, the copper surface with different copper crystals has better micro-etching and coarsening effects and wider application range.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a copper surface microetching coarsening liquid, wherein the solvent of the copper surface microetching coarsening liquid comprises water, and solutes comprise copper ions, chloride ions, organic acid salt and 0.00001-0.007 mol/L corrosion inhibitor.
The copper surface microetching and roughening solution provided by the invention can effectively improve the roughness of the copper surface, so that the adhesive force of dielectric materials such as a photosensitive resist layer and ink and the adhesive force of metals such as tin, nickel, palladium and gold on the copper surface are improved; on the other hand, the copper surface with different copper crystals has better micro-etching and coarsening effects and wider application range.
The solvent of the roughening solution for copper surface microetching in the invention includes 0.00001-0.007 mol/L of corrosion inhibitor, for example, 0.00001mol/L, 0.00002mol/L, 0.00005mol/L, 0.0001mol/L, 0.0002mol/L, 0.0005mol/L, 0.0007mol/L, 0.001mol/L, 0.002mol/L, 0.005mol/L or 0.007mol/L, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the invention, the copper ions are provided by any one or combination of at least two of a copper ion source, a chloride ion source or an organic acid salt, and the chloride ions are provided by the copper ion source and/or the chloride ion source.
Preferably, the concentration of the copper ions is 0.3 to 0.6mol/L, and may be, for example, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, or 0.6mol/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the copper ions are provided by a source of copper ions including any one or combination of at least two of copper chloride, copper formate, copper oxalate, copper acetate, copper citrate, copper diethylhexanoate or copper gluconate, typical but not limiting combinations include copper chloride in combination with copper formate, copper formate in combination with copper oxalate, copper oxalate in combination with copper acetate, copper acetate in combination with copper citrate, copper diethylhexanoate in combination with copper gluconate, copper chloride, copper formate in combination with copper oxalate, or copper acetate, copper citrate, copper diethylhexanoate in combination with copper gluconate, preferably copper chloride.
Preferably, the concentration of the chloride ion is 0.7 to 1.4mol/L, and may be, for example, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, or 1.4mol/L, but is not limited to the values listed, and other values not listed within the range of values are also applicable.
Preferably, the chloride ions are provided by a source of chloride ions comprising any one or a combination of at least two of sodium chloride, potassium chloride, calcium chloride, zinc chloride, copper chloride, typical but non-limiting combinations include sodium chloride and potassium chloride, potassium chloride and calcium chloride, zinc chloride and copper chloride, sodium chloride, potassium chloride and calcium chloride, or potassium chloride, calcium chloride, zinc chloride and copper chloride, preferably sodium chloride and/or copper chloride.
Preferably, the organic acid concentration is 1 to 2mol/L, and may be, for example, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, or 2mol/L, but is not limited to the values listed, and other values not listed within the range of values are also applicable.
Preferably, the organic acid comprises any one or a combination of at least two of formic acid, acetic acid, citric acid, malic acid, maleic acid, acrylic acid, gluconic acid or glycine, typical but non-limiting combinations include formic acid and acetic acid, acetic acid and citric acid, malic acid and maleic acid, acrylic acid and gluconic acid, gluconic acid and glycine, formic acid, acetic acid and citric acid, or malic acid, maleic acid, acrylic acid and gluconic acid.
Preferably, the concentration of the organic acid salt is 1 to 2.5mol/L, and may be, for example, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.4mol/L, or 2.5mol/L, but is not limited to the values listed, and other values not listed within the range of the values are also applicable.
Preferably, the organic acid salt organic acid ions include any one of formate, acetate, citrate, malate, maleate, acrylate, gluconate, or glycinate ions, or combinations of at least two thereof, and typical, but not limiting combinations include formate and acetate, acetate and citrate, malate and maleate, maleate and acrylate, gluconate and glycinate, or formate, acetate and citrate; the metal ions include any one or a combination of at least two or more of sodium ions, potassium ions, or copper ions, and typical, but non-limiting combinations include combinations of sodium ions and potassium ions, potassium ions and copper ions, sodium ions and copper ions, or sodium ions, potassium ions, and copper ions.
Preferably, the corrosion inhibitor comprises any one or a combination of at least two of diallyldimethylammonium chloride, N-3- (2-methylallylamido) -1-propylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, polydiallyldimethylammonium chloride, polyquaternium-7, polyquaternium-11, or 1-butyl-3-methylimidazolium tetrafluoroborate, typical but non-limiting combinations include the combination of diallyldimethylammonium chloride with N, N-3- (2-methylallylamido) -1-propylammonium chloride, N, a combination of N-3- (2-methallylamido) -1-propylamine chloride with methacryloyloxyethyl trimethylammonium chloride, a combination of polydiyldimethylammonium chloride with polyquaternium-7, a combination of polyquaternium-11 with 1-butyl-3-methylimidazolium tetrafluoroborate, a combination of di-allyldimethylammonium chloride, N, N, N-3- (2-methallylamido) -1-propylamine chloride with methacryloyloxyethyl trimethylammonium chloride, or a combination of N, N, N-3- (2-methallylamido) -1-propylamine chloride, methacryloyloxyethyl trimethylammonium chloride, polydiethylene dimethylammonium chloride with polyquaternium-7.
Preferably, the solute of the copper surface micro-etching roughening solution further comprises an additional corrosion inhibitor, and the molar concentration of the additional corrosion inhibitor is 0.00001mol/L to 0.0002mol/L, and for example, may be 0.00001mol/L, 0.00002mol/L, 0.00005mol/L, 0.00007mol/L, 0.0001mol/L, 0.00013mol/L, 0.00015mol/L, 0.00017mol/L, 0.00019mol/L, or 0.0002mol/L, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the additional corrosion inhibitor comprises an organic cationic compound.
The organic cation compound of the invention contains other groups, such as amino, imino, amido and the like which can react with copper or copper ions, besides quaternary ammonium bonds in molecules.
Preferably, the solute of the copper surface micro-etching roughening solution further comprises a wetting agent, and the wetting agent has a molar concentration of 0.001-0.05 mol/L, for example, 0.001mol/L, 0.003mol/L, 0.005mol/L, 0.007mol/L, 0.009mol/L, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, or 0.05mol/L, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the wetting agent comprises any one or a combination of at least two of sodium cumene sulfonate, N- (2-hydroxyethyl) -N- (2-ethylhexyl) beta-alanine monosodium salt, polyethylene glycol or isomeric tridecanol polyoxyethylene ether, typical but non-limiting combinations include sodium cumene sulfonate in combination with N- (2-hydroxyethyl) -N- (2-ethylhexyl) beta-alanine monosodium salt, N- (2-hydroxyethyl) -N- (2-ethylhexyl) beta-alanine monosodium salt in combination with polyethylene glycol, polyethylene glycol in combination with isomeric tridecanol polyoxyethylene ether, or sodium cumene sulfonate, N- (2-hydroxyethyl) -N- (2-ethylhexyl) beta-alanine monosodium salt in combination with polyethylene glycol.
Preferably, the pH of the copper surface microetching and roughening solution is 2.8 to 3.0, and may be, for example, 2.8, 2.82, 2.84, 2.86, 2.88, 2.9, 2.92, 2.94, 2.96, 2.98 or 3, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the density of the copper surface micro-etching coarsening liquid is 1.06-1.26 g/cm 3 It may be, for example, 1.06g/cm 3 、1.07g/cm 3 、1.08g/cm 3 、1.09g/cm 3 、1.10g/cm 3 、1.11g/cm 3 、1.12g/cm 3 、1.13g/cm 3 、1.14g/cm 3 、1.15g/cm 3 、1.16g/cm 3 、1.17g/cm 3 、1.18g/cm 3 、1.19g/cm 3 、1.20g/cm 3 、1.21g/cm 3 、1.22g/cm 3 、1.23g/cm 3 、1.24g/cm 3 、1.25g/cm 3 Or 1.26g/cm 3 However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
In a second aspect, the invention provides an application of the copper surface microetching and roughening solution of the first aspect, and the copper surface microetching and roughening solution is used for manufacturing a printed circuit board.
Compared with the prior art, the invention has the following beneficial effects:
the copper surface microetching and roughening solution provided by the invention can effectively improve the roughness of the copper surface, so that the adhesive force of dielectric materials such as a photosensitive resist layer and ink and the adhesive force of metals such as tin, nickel, palladium and gold on the copper surface are improved; on the other hand, the copper surface with different copper crystals has better micro-etching and coarsening effects and wider application range.
Drawings
FIG. 1 is a surface SEM of a plated plate (current density 0.5 ASD) treated with the copper surface micro-etching roughening solution in example 1.
FIG. 2 is a surface SEM of a plated board (current density 3 ASD) treated by the copper surface micro-etching roughening solution in example 1.
FIG. 3 is a surface SEM of a copper-clad plate (from Taiwan Changchun group) treated by the copper surface microetching and roughening solution in example 1.
FIG. 4 is a surface SEM of a copper clad laminate (manufactured by Mitsui copper foil (Guangdong) Co., ltd.) after the treatment of the copper surface micro-etching roughening solution in example 1.
FIG. 5 is a surface SEM of the copper clad laminate (manufactured by Taihe Circuit Board, inc., guangzhou city) treated with the copper surface micro-etching roughening solution of example 1.
FIG. 6 is a surface SEM of a copper clad laminate (produced by Taihe Circuit Board, inc. of Guangzhou city) treated by the copper surface microetching and roughening solution in example 2.
FIG. 7 is a surface SEM of the copper clad laminate (manufactured by Taihe Circuit Board, inc., guangzhou city) treated with the copper surface micro-etching roughening solution of example 3.
FIG. 8 is a surface SEM of the copper clad laminate (manufactured by Taihe Circuit Board, inc., guangzhou city) treated with the copper surface micro-etching roughening solution of example 4.
FIG. 9 is a surface SEM of a copper clad laminate (produced by Taihe Circuit Board, inc. of Guangzhou city) treated by the copper surface microetching and roughening solution of example 5.
FIG. 10 is a surface SEM of a copper clad laminate (produced by Taihe Circuit Board, inc. of Guangzhou city) treated by the copper surface microetching and roughening solution of example 6.
FIG. 11 is a surface SEM of a copper clad laminate (manufactured by Taihe Circuit Board, inc., guangzhou city) treated with the copper surface micro-etching roughening solution of example 7.
FIG. 12 is a surface SEM of a copper clad laminate (manufactured by Taihe Circuit Board, inc., guangzhou city) treated with the copper surface micro-etching roughening solution of example 8.
FIG. 13 is a surface SEM of a copper clad laminate (produced by Taihe Circuit Board, inc. of Guangzhou city) treated by the copper surface microetching and roughening solution of comparative example 1.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a copper surface microetching and roughening solution, wherein the pH value of the copper surface microetching and roughening solution is 2.8-3.0, and the density of the copper surface microetching and roughening solution is 1.06-1.26 g/cm 3 The solvent is water, and the solute comprises the following components in molar concentration:
wherein the corrosion inhibitor is trimethyl ammonium acetyl hydrazine chloride.
Example 2
The embodiment provides a copper surface microetching and roughening solution, wherein the pH value of the copper surface microetching and roughening solution is 2.8-3.0, and the density of the copper surface microetching and roughening solution is 1.06-1.26 g/cm 3 The solvent is water, and the solute comprises the following components in molar concentration:
wherein the additional corrosion inhibitor is 1- (2-hydrazino-2-oxoethyl) pyridine-1-ammonium chloride.
Example 3
The embodiment provides a copper surface microetching and roughening solution, wherein the pH value of the copper surface microetching and roughening solution is 2.8-3.0, and the density of the copper surface microetching and roughening solution is 1.06-1.26 g/cm 3 The solvent is water, and the solute comprises the following components in molar concentration:
wherein the additional corrosion inhibitor is N, N, N-triethyl 2-hydrazino-2-oxoethyl ammonium chloride.
Example 4
The embodiment provides a copper surface microetching and roughening solution, wherein the pH value of the copper surface microetching and roughening solution is 2.8-3.0, and the density of the copper surface microetching and roughening solution is 1.06-1.26 g/cm 3 The solvent is water, and the solute comprises the following components in molar concentration:
wherein the additional corrosion inhibitor is N- (3- (trimethyl ammonium) propyl) methacrylamide hydrochloride.
Example 5
This example provides a copper surface micro-etching roughening solution, wherein the copper surface micro-etching roughening solution has a pH of 2.8 to 3.0 and a density of 1.06 to 1.26g/cm 3 The solvent is water, and the solute comprises the following components in molar concentration:
wherein the additional corrosion inhibitor is 3-amino-N, N, N-trimethylpropane-1-ammonium chloride hydrochloride.
Example 6
This example provides a copper surface microetching roughening solution similar to that of example 1 except that diallyl dimethyl ammonium chloride and 1-butyl-3-methylimidazolium tetrafluoroborate were replaced with guanidine hydrochloride.
Example 7
This example provides a roughening solution for copper surface microetching, which is the same as example 1 except that a polyamine cationic compound C-1800 is replaced with polyethyleneimine.
Example 8
This example provides a roughening solution for copper surface microetching, which is the same as example 1 except that the solute does not include polyamine cationic compound C-1800.
Example 9
This example provides a roughening solution for copper surface microetching which is the same as example 1 except that the molar concentration of the polyamine-based cationic compound C-1800 is 0.0005 mol/L.
Comparative example 1
This comparative example provides a copper surface microetching roughening solution that was the same as example 1 except that the solutes included no diallyl dimethyl ammonium chloride and no 1-butyl-3-methylimidazolium tetrafluoroborate.
Comparative example 2
This comparative example provides a copper surface microetching solution which was the same as in example 1 except that the molar concentration of the diallyl dimethyl ammonium chloride was 0.005mol/L and the molar concentration of the 1-butyl-3-methylimidazolium tetrafluoroborate was 0.007 mol/L.
To evaluate the performance of the copper surface microetching roughening solution, the following tests were performed:
the flow of the spraying test is as follows: acid washing, water washing, microetching coarsening, water washing, acid washing, water washing and hot air drying; the temperature of the copper surface microetching coarsening liquid used in the spraying test process is 30 ℃, and the spraying pressure is 1kg/cm 2 The linear speed of the spraying machine is 1m/min, and the effective spraying length is 50cm; the solution used for pickling was an aqueous hydrochloric acid solution having a mass fraction of 37% by weight;
1. microetching rate test
Placing a copper-clad plate (produced by Taihe circuit board Co., ltd. In Guangzhou city) with the thickness of 5cm multiplied by 10cm in a spraying machine, spraying the copper surface microetching and roughening solution in the examples 1-9 and the comparative examples 1 and 2 for 1min, and recording the quality of the copper-clad plate before and after spraying, wherein the calculation method of the microetching rate comprises the following steps: microetching rate (mum/min) = (m 1-m 2)/(2 x s x rho) × 10000, wherein m1 and m2 are the mass of the copper-clad plate before and after spraying treatment respectively; rho is the density of copper and is 8.96g/cm 3 (ii) a S is the area of the copper-clad plate, and the calculated microetching rate result is shown in Table 1.
2. Roughness test
The copper clad laminate (manufactured by taihe circuit board limited, guangzhou city) was subjected to roughening microetching with a roughening microetching amount of 1.0 μm using the copper surface microetching roughening solution in examples 1 to 9 and comparative examples 1 and 2, and surface roughness data Ra and Rz values of the copper clad laminate after roughening microetching were obtained by an olympus 3D measurement laser microscope (OLS 5100) are shown in table 1.
3. Uniformity test
The copper-clad plate (produced in tai and circuit board limited, guangzhou city) is roughened and microetched by using the copper surface microetching roughening solution in the embodiments 1-9 and the comparative examples 1 and 2, the surface micro-morphology of the copper-clad plate after the roughening and microetching is measured by a scanning electron microscope, the surface uniformity of the copper-clad plate after the microetching is evaluated under a 2500-fold scanning electron microscope image, the evaluation result of the uniformity is shown in table 1, and the evaluation standard is as follows:
4. dry film adhesion test
Carrying out coarsening and microetching on a copper-clad plate (produced in Taihe circuit board Co., ltd. In Guangzhou city) by using the copper surface microetching coarsening solution in the examples 1-9 and the comparative examples 1 and 2, wherein the coarsening and microetching amount is 0.7 mu m; after roughening and microetching treatment, firstly laminating a dry film resist layer on the surface of the copper clad laminate after roughening and microetching treatment, after exposure and curing treatment, marking 100 cells with the size of 1mm multiplied by 1mm on a dry film through a cell cutter, then completely covering the cell area with a 3M adhesive tape, peeling the cell area in the vertical direction, and evaluating the adhesion strength of the dry film on the copper clad laminate by observing the cell pull-off condition, wherein the evaluation result is shown in table 1, and the evaluation standard is as follows:
5. solder resist ink adhesion test
Carrying out coarsening and microetching on a copper-clad plate (produced in Taihe circuit board Co., ltd. In Guangzhou city) by using the copper surface microetching coarsening solution in the examples 1-9 and the comparative examples 1 and 2, wherein the coarsening and microetching amount is 1.0 mu m; after roughening and microetching treatment, firstly coating ink with the thickness of 25 micrometers on the surface of a roughened and microetched copper-clad plate, transferring the copper-clad plate coated with the ink into an oven, baking for 3 hours at 80 ℃, then exposing, finally continuously baking for 1 hour at 150 ℃, after baking is finished, cutting two cuts with the interval of 1cm on the surface of the solder resist ink by using a scalpel, soaking for 10 minutes by using 6N hydrochloric acid, washing and drying, attaching a 3M600 series adhesive tape on the surface of the ink for stripping treatment, evaluating the adhesion strength of the solder resist ink on the copper-clad plate, wherein the evaluation result is shown in Table 1, and the evaluation standard is as follows:
6. topography testing
The copper surface microetching and roughening solution provided in example 1 was used to perform microetching and roughening on the plated board, the plated board was obtained by electroplating copper on a copper-clad plate provided by tai and circuit board ltd, guangzhou, in an electroplating solution, the thickness of a copper layer deposited after the electroplating copper was 20 μm, and the current densities used during the electroplating copper were 0.5ASD (to obtain plated board 1) and 3ASD (to obtain plated board 2), respectively, and the electroplating solution was a commercial electroplating solution SkyPlate 6257 from shanghai-shi chemical ltd. SEM images obtained by respectively testing the electroplated plates 1 and 2 subjected to the micro-etching roughening treatment through a scanning electron microscope are shown in figures 1 and 2;
the copper surface microetching and roughening solution provided in the embodiment 1 is used for respectively carrying out microetching and roughening on copper clad plates produced by the taiwan vinpock group, the mitsui copper foil (guangdong) limited company and the guangzhou taihe circuit board limited company, and a scanning electron microscope is used for respectively testing the copper clad plates subjected to the microetching and roughening so as to obtain SEM images of the copper clad plates subjected to the microetching and roughening, as shown in figures 3, 4 and 5;
the copper surface microetching and roughening solutions provided in examples 2 to 8 and comparative example 1 were used to respectively perform microetching and roughening on the copper-clad plates produced by taihe, guanzhou city and circuit board limited company, and the microetching and roughening copper-clad plates were tested by a scanning electron microscope to obtain SEM images of the copper-clad plates after the microetching and roughening, as shown in fig. 6 to 13.
TABLE 1
From the data in table 1 and fig. 1 to 13, it can be seen that:
(1) The copper surface microetching and roughening solution in the embodiments 1 to 5 has universal applicability to the microetching and roughening of copper-clad plates with different copper crystals, and the copper surface can form a concave-convex microstructure after the copper-clad plates produced by different manufacturers or electroplated plates obtained under different current densities are roughened by the microetching and roughening solution; from the aspect of roughness, the roughness Ra value of the copper-clad plate treated by the copper surface microetching and roughening solution in the embodiments 1 to 5 fluctuates within the range of 0.36 to 0.43 μm, and the Rz value fluctuates within the range of 3.02 to 3.34 μm, so that the copper surface microetching and roughening solution provided by the invention can effectively improve the roughness of the copper surface; from the uniformity point of view, no obvious large-grain crystal grains are found on the surface of the copper-clad plate treated by the copper surface micro-etching roughening solution in the embodiments 1 to 5, and the uniformity reaches level I; from the adhesion strength of the dry film and the solder resist ink, the copper-clad plate treated by the copper surface microetching roughening solution in the examples 1-5 has higher adhesion strength to the dry film and the solder resist ink, and the adhesion strength reaches the I level;
(2) It can be seen from the comparison between example 1 and example 6 that the components of the corrosion inhibitor affect the performance of the copper surface microetching roughening solution, and if the corrosion inhibitor is replaced by guanidine hydrochloride, the microetching rate is slowed down, the microetching uniformity is deteriorated, and the adhesion strength of the dry film and the solder mask ink is reduced, because the guanidine hydrochloride has a lower molecular weight and does not contain quaternary ammonium bonds in the molecule, the adsorption on the copper surface is mainly through physical adsorption, the adsorption capacity is weaker, and the desorption is easy, so that the roughening solution is difficult to effectively roughen the copper surface, and the roughened copper surface has lower roughness and poorer roughness uniformity, so that the adhesion strength of the dry film and the solder mask ink on the roughened copper surface is reduced;
(3) It is understood from the comparison between example 1 and example 7 that the component of the additional corrosion inhibitor affects the performance of the copper surface microetching roughening solution, and if the additional corrosion inhibitor is replaced by polyethyleneimine, the adhesion strength of the dry film and the solder resist ink is reduced, because a large amount of amino and imino exist in polyethyleneimine molecules, the polyethyleneimine molecules are easy to complex with copper ions, but are difficult to directly react with simple substance copper. Therefore, when the additional corrosion inhibitor is polyethyleneimine, more of the additional corrosion inhibitor is attached to the copper surface through a complex film formed by the additional corrosion inhibitor and copper ions, and in the spraying process, the film layer is easy to be impacted and broken, so that discontinuous coarsening exists on the copper surface locally in the action process of coarsening micro-etching liquid, and the coarsening effect difference of each point is increased, so that the roughness and the roughness uniformity of the through surface after coarsening are poorer than those of the through surface in example 1;
(4) It can be seen from the comparison between example 1 and examples 8 and 9 that the molar concentration of the additional corrosion inhibitor affects the performance of the roughening solution for microetching of the copper surface, and if the additional corrosion inhibitor is not contained, the roughening rate is slowed down, the uniformity of microetching is deteriorated, and the adhesion strength of the dry film and the solder resist ink is decreased, because the additional corrosion inhibitor has the function of a leveling agent, and the molecules of the additional corrosion inhibitor simultaneously have quaternary ammonium bonds and other active groups such as amino groups, so that the additional corrosion inhibitor has stronger activity, can effectively promote the progress of corrosion by physical adsorption and chemical adsorption at the grain boundary of copper grains, especially larger copper grains, so that large copper grains can also be roughened, the uniformity of corrosion is improved, and when the roughening solution does not contain the additional corrosion inhibitor, large copper grains cannot be effectively corroded and roughened, so that the microetching rate is slowed down and large copper grains cannot be effectively roughened, and the adhesion strength of the dry film and the solder resist ink on the roughened copper surface is decreased; if the molar concentration of the additional corrosion inhibitor is too high, the roughness uniformity of the roughened copper surface is also deteriorated, because the concentration of the additional corrosion inhibitor is too high, the adsorption quantity of the additional corrosion inhibitor at a crystal boundary is too large, the corrosion at the crystal boundary is seriously inhibited, the local part is not corroded or is slightly corroded, the roughness is reduced, the uniformity is deteriorated, and the adhesive force of a dry film and the solder resist ink is reduced;
(5) As can be seen from the comparison between example 1 and comparative examples 1 and 2, the molar concentration of the corrosion inhibitor affects the performance of the copper surface microetching coarsening solution, and if no corrosion inhibitor is contained, the microetching rate is slowed down, the uniformity of the microetching is sharply reduced, and the adhesion strength of the dry film and the solder resist ink is extremely low, because under the condition of no corrosion inhibitor, the corrosion condition of each point of the copper crystal grain is only affected by the additional corrosion inhibitor, the concentration of the additional corrosion inhibitor is relatively low, and the influence on the overall corrosion condition of the copper surface is limited, so that the copper surface is difficult to form coarsening with better roughness; if the molar concentration of the corrosion inhibitor is too high, the microetching rate of the microetching coarsening solution is reduced, and the coarsening effect is poor, because the corrosion inhibition on the whole copper crystal grains on the copper surface is too strong due to the too high concentration of the corrosion inhibitor, so that the local corrosion is not or slightly, the local roughness is too low, and the difference of the overall roughness is increased.
In conclusion, the copper surface microetching and roughening solution provided by the invention can effectively improve the roughness of the copper surface, so that the adhesive force of dielectric materials such as a photosensitive resist layer and printing ink and the adhesive force of metals such as tin, nickel, palladium and gold on the copper surface are improved; on the other hand, the copper surface with different copper crystals has better micro-etching and coarsening effects and wider application range.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The roughening solution for copper surface microetching is characterized in that a solvent of the roughening solution for copper surface microetching comprises water, and solutes comprise copper ions, chloride ions, organic acid salt and 0.00001-0.007 mol/L corrosion inhibitor.
2. The copper surface microetching and roughening solution according to claim 1, wherein the concentration of copper ions is 0.3 to 0.6mol/L;
preferably, the copper ions are provided by a copper ion source comprising any one or a combination of at least two of copper chloride, copper formate, copper oxalate, copper acetate, copper citrate, copper diethylhexanoate or copper gluconate, preferably copper chloride.
3. The copper surface microetching and roughening solution according to claim 1 or 2, wherein the concentration of the chloride ion is 0.7 to 1.4mol/L;
preferably, the chloride ions are provided by a chloride ion source comprising any one of sodium chloride, potassium chloride, calcium chloride, zinc chloride, copper chloride or a combination of at least two thereof, preferably sodium chloride and/or copper chloride.
4. The copper surface microetching roughening solution according to any one of claims 1 to 3, wherein the concentration of the organic acid is 1 to 2mol/L;
preferably, the organic acid comprises any one of formic acid, acetic acid, citric acid, malic acid, maleic acid, acrylic acid, gluconic acid or glycine or a combination of at least two thereof.
5. The copper surface microetching and roughening solution according to any one of claims 1 to 4, wherein the concentration of the organic acid salt is 1 to 2.5mol/L;
preferably, the organic acid radical ion of the organic acid salt includes any one or a combination of at least two of a formate ion, an acetate ion, a citrate ion, a malate ion, a maleate ion, an acrylate ion, a gluconate ion, or a glycinate ion, and the metal ion includes any one or a combination of at least two of a sodium ion, a potassium ion, or a copper ion.
6. The copper surface microetching and roughening solution according to any one of claims 1 to 5, wherein the corrosion inhibitor comprises any one of or a combination of at least two of diallyl dimethyl ammonium chloride, N, N, N-3- (2-methylallylamido) -1-propanaminium chloride, methacryloyloxyethyl trimethyl ammonium chloride, polydiallyl dimethyl ammonium chloride, polyquaternium-7, polyquaternium-11, or 1-butyl-3-methylimidazolium tetrafluoroborate.
7. The copper surface micro-etching roughening solution as recited in any one of claims 1 to 6, wherein the solute of said copper surface micro-etching roughening solution further comprises an additional corrosion inhibitor, and the molar concentration of said additional corrosion inhibitor is 0.00001-0.0002 mol/L;
preferably, the additional corrosion inhibitor comprises an organic cationic compound.
8. The copper surface microetching and roughening solution according to any one of claims 1 to 7, wherein the solute of the copper surface microetching and roughening solution further comprises a wetting agent, and the molar concentration of the wetting agent is 0.001 to 0.05mol/L;
preferably, the wetting agent comprises any one of or a combination of at least two of sodium cumene sulfonate, N- (2-hydroxyethyl) -N- (2-ethylhexyl) beta-alanine monosodium salt, polyethylene glycol or isomeric dodecyl polyoxyethylene ether.
9. The copper surface microetching roughening solution according to any one of claims 1 to 8, wherein the pH of the copper surface microetching roughening solution is 2.8 to 3.0;
preferably, the density of the copper surface micro-etching coarsening liquid is 1.06-1.26 g/cm 3 。
10. Use of the copper surface microetching and roughening solution according to any one of claims 1 to 9, wherein the copper surface microetching and roughening solution is used for manufacturing a printed wiring board.
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| CN202211719239.5A CN115928072A (en) | 2022-12-30 | 2022-12-30 | Copper surface micro-etching roughening solution and application thereof |
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