CN113463075A - Chemical copper plating solution and preparation method thereof - Google Patents
Chemical copper plating solution and preparation method thereof Download PDFInfo
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- CN113463075A CN113463075A CN202110624762.9A CN202110624762A CN113463075A CN 113463075 A CN113463075 A CN 113463075A CN 202110624762 A CN202110624762 A CN 202110624762A CN 113463075 A CN113463075 A CN 113463075A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Abstract
The invention relates to the field of electroless copper plating, in particular to an electroless copper plating solution and a preparation method thereof. The electroless copper plating solution comprises a copper ion donor, an accelerator, an N-containing heterocyclic substance, a nickel salt, a reducing agent and an amphiphilic substance containing an ether group. The chemical copper plating solution can effectively eliminate the stress on the surface of a copper layer, has proper plating speed and stability and also has excellent backlight effect.
Description
Technical Field
The invention relates to the field of electroless copper plating, in particular to an electroless copper plating solution and a preparation method thereof.
Background
Chemical copper plating is a copper plating method in printed circuit boards, and chemical plating plays an important role in the field of circuit boards at present. The PCB gradually develops towards the direction of narrow lines and high distribution density, and the bonding strength is not suitable for being improved by the coarsening method at present. In the process of electroless copper plating, the growth of copper plating crystal grains causes certain deformation or impurity doping, internal stress is generated on the copper plating surface, the adhesion strength between a copper layer and a substrate is reduced, and the development of electroless copper plating is influenced.
The stability of the electroless copper plating solution is one of the key indexes of the electroless copper plating solution, and the stability not only affects the effect of a plating layer, but also has certain influence on the service life of bath solution. At present, stabilizing agents are added to improve the stability of the electroless copper plating solution, however, even if the stabilizing agents and the like are added in small amount, the copper plating rate is rapidly reduced, and the industrial production of the electroless copper plating is influenced. The accelerator is added on the basis of containing the stabilizer to improve the copper plating rate, which can cause the reduction of the stability of the chemical plating solution. Therefore, it is desirable to provide an electroless copper plating solution having good stability without affecting the plating rate.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides an electroless copper plating solution, which comprises a copper ion donor, an accelerator, an N-containing heterocyclic substance, a nickel salt, a reducing agent, and an amphiphilic substance containing an ether group.
In a preferred embodiment of the present invention, the amphiphilic substance containing an ether group is one or more selected from the group consisting of a polyoxyethylene amphiphilic substance, a polyatomic alcohol amphiphilic substance, and a polyether amphiphilic substance.
As a preferred technical solution of the present invention, the nickel salt is a nickel sulfate salt and/or a nickel sulfonate salt.
As a preferable technical scheme of the invention, the N-containing heterocyclic substance is a nitrogen-containing five-membered ring compound and/or a nitrogen-containing six-membered ring compound.
As a preferable technical scheme of the invention, the nitrogen-containing five-membered ring compound is an imidazole substance.
In a preferred embodiment of the present invention, the nitrogen-containing six-membered ring compound is a pyridine.
In a preferred embodiment of the present invention, the accelerator includes (a) an organic or inorganic substance containing at least S, N, O and/or (b) a nickel-containing organic substance.
As a preferable technical scheme of the invention, the structure of the organic matter containing at least one of S, N, O is shown as a formula (1),
In a preferred embodiment of the present invention, the concentration of the accelerator is 0.005 to 0.5 g/L.
The second aspect of the invention provides a preparation method of the electroless copper plating solution, which comprises the following steps: mixing copper ion donor, accelerator, N-containing heterocyclic substance, nickel salt, reducing agent and amphiphilic substance containing ether group.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the chemical copper plating solution, a nitrogen-containing five-membered ring compound or a nitrogen-containing six-membered ring compound is adopted, particularly the nitrogen-containing five-membered ring compound is 1, 1-sulfonyl diimidazole, and the nitrogen-containing six-membered ring compound is 2,2 '-bipyridine-5, 5' -dimethanol, particularly 1, 1-sulfonyl diimidazole, so that the stability of the chemical copper plating solution can be improved, and a copper layer can be compact;
(2) in the application, the nickel (II) sulfamate not only plays a role of an accelerator, but also has a stress relief function;
(3) the application adopts the nickel sulfamate, so that the peeling strength of the copper layer is obviously improved;
(4) in the application, when the reducing agent is selected from one or more of formaldehyde and derivatives thereof, glyoxylic acid and derivatives thereof, boric acid, sodium hypophosphite, hydroquinone and catechol, palladium ions adsorbed on the surface of a substrate plate, particularly in blind holes and through holes, can be well reduced into palladium atoms to form an active center for catalyzing copper deposition;
(5) the application adopts polyethylene glycol with the weight-average molecular weight of 5000-7000 to improve the brightness of the copper layer and avoid hydrogen embrittlement.
Drawings
FIGS. 1-9 are diagrams of the backlight effect of copper plating using the electroless copper plating solutions of the present application 1-9, respectively;
fig. 10-18 are SEM images of copper layers using electroless copper plating solutions of examples 1-9 of the present application, respectively.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides an electroless copper plating solution in a first aspect, which comprises a copper ion donor, an accelerator, an N-containing heterocyclic substance, a nickel salt, a reducing agent and an amphiphilic substance containing an ether group.
In one embodiment, the electroless copper plating solution further comprises a pH adjuster.
In one embodiment, the electroless copper plating solution further comprises a complexing agent.
In one embodiment, the electroless copper plating solution further comprises distilled water.
The complexing agent described herein is not particularly limited and may be routinely selected by those skilled in the art.
In one embodiment, the complexing agent is potassium sodium tartrate.
Preferably, the concentration of the complexing agent is 10-50 g/L.
The copper ion donor of the present invention is not particularly limited and may be conventionally selected by those skilled in the art.
In one embodiment, the copper ion donor is selected from one or more of copper sulfate pentahydrate, copper chloride, copper oxide, copper nitrate, basic copper carbonate, and copper sulfamate.
Preferably, the copper ion donor is copper sulfate pentahydrate.
In one embodiment, the concentration of the copper ion donor is 5 to 20 g/L.
Preferably, the concentration of the copper ion donor is 10-15 g/L.
In one embodiment, the accelerator comprises (a) at least one of S, N, O containing organic or inorganic and/or (b) nickel containing organic.
Examples of the organic or inorganic substance containing S, N, O include 2-mercaptobenzimidazole carboxylic acid, 5-ethoxy-2-mercaptobenzopyridine, 2-dithiodipyridine, N-acetylthiourea, 1-thiocarbonyldiphidine, ethyl thioacetate, thiopropionamide, potassium ferrocyanide, sodium thiosulfate, S-carboxyethylisothiouronium betaine, pyridone, 2-hydrazinopyridine, sulfapyridine, 2-picolinamide, 3-picolinamide, sulfosuccinic acid, 3-pyridinethiourea, 2' -bipyridinamine, 4-methylaminopyridine, 2, 5-diaminopyridine, and 3-amino-2-pyridone.
Preferably, the structure of the organic matter containing at least one of S, N, O is shown as formula (1),
Preferably, the substituted alkyl group is selected from one or more of a carboxyl substituted alkyl group, a hydroxyl substituted alkyl group, a carboxyl group and a hydroxyl substituted alkyl group.
Preferably, the organic material containing at least one of S, N, O is any one of 2, 2-dithiodipyridine, sulfosuccinic acid, and 2-mercaptobenzimidazole carboxylic acid.
Preferably, the structure of the organic material containing at least S, N, O is potassium ferrocyanide.
Preferably, the inorganic substance containing at least one of S, N, O is sodium thiosulfate.
In one embodiment, the nickel-containing organic is selected from one or more of nickel acetylacetonate, nickel dibutyldithiocarbamate, nickelocene, nickel bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate), nickel acetylacetonate, nickel (II) sulfamate, nickel tetraphenylporphyrin, nickel (II) oxalate dihydrate, nickel ammonium sulfate, hexahydrate, nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate.
Preferably, the nickel-containing organic matter is selected from one or more of nickel dimethyldithiocarbamate, nickel (II) sulfamate, ammonium nickel sulfate and hexahydrate.
In this application nickel-containing organic matter can also play the effect of catalyst, the going on of the heavy copper reaction of chemistry of acceleration.
The applicant has surprisingly found that nickel (II) sulfamate in the present application not only acts as an accelerator, but also as a stress relief.
In one embodiment, the accelerator is present in a concentration of 0.005 to 0.5 g/L.
The concentration of the accelerator does not include 0.
In one embodiment, the N-containing heterocyclic substance is a nitrogen-containing five-membered ring compound and/or a nitrogen-containing six-membered ring compound.
Preferably, the nitrogen-containing five-membered ring compound is an imidazole substance; further preferably, the imidazole substances are selected from one or more of 1, 1-sulfonyl diimidazole, imidazo [1,2-b ] pyridazine and 2-mercaptobenzimidazole carboxylic acid; more preferably, the imidazole is 1, 1-sulfonyl diimidazole.
Preferably, the nitrogen-containing six-membered ring compound is a pyridine substance; further preferably, the pyridine substances are selected from one or more of bipyridyl, 2-benzopyridyl, 2-mercaptopyridine, 3-methylpyrido [3,4-e ] benzopyridin-2-amine and 2,2 '-bipyridyl-5, 5' -dimethanol; more preferably, the pyridine is 2,2 '-bipyridine-5, 5' -dimethanol.
CAS of the 3-methylpyrido [3,4-e ] benzopyridin-2-amine: 147293-14-9.
In one embodiment, the concentration of the N-containing heterocyclic substance is 1 to 20ppm, preferably 1 to 15 ppm.
The applicant found that the compactness of the copper layer is poor when the conventional substances such as pyridine, 2-mercaptobenzothiazole and sodium sulfite thiourea are used, and further, the applicant unexpectedly found that when a nitrogen-containing five-membered ring compound or a nitrogen-containing six-membered ring compound is used, particularly the nitrogen-containing five-membered ring compound is 1, 1-sulfonyldiimidazole and the nitrogen-containing six-membered ring compound is 2,2 '-bipyridine-5, 5' -dimethanol, particularly 1, 1-sulfonyldiimidazole, not only the stability of the electroless copper plating solution can be increased, but also the copper layer can be densified, and the applicant considered that the possible reason is that the specific 2 imidazole rings allow the 1, 1-sulfonyldiimidazole to fully contact and complex with copper ions or cuprous ions in the electroless copper plating solution without heating, thereby inhibiting the decomposition of the electroless copper plating solution, meanwhile, during heating reaction, the 2 imidazole ring structures can gradually release copper ions, so that the participating copper ions stably participate in the reaction, the relative concentration of the sizes of copper crystal grains is achieved, the difference of the sizes of the copper crystal grains is avoided, and meanwhile, the decrease of compactness caused by the unstable distribution of the copper crystal grains with different sizes is avoided.
In one embodiment, the nickel salt is a nickel sulfate salt and/or a nickel sulfonate salt.
Preferably, the nickel sulfonate salt is nickel sulfamate.
Preferably, the nickel salt is nickel sulfamate.
In one embodiment, the concentration of the nickel salt is from 0.005 to 0.5 g/L.
The nickel salt is used as the main salt for nickel plating, and the applicant finds that the specific content of nickel salt is added into the chemical copper plating solution in the application, particularly when the nickel salt is nickel sulfamate, the peeling strength of a copper layer can be remarkably increased.
The reducing agent is not particularly limited in the present application and may be conventionally selected by those skilled in the art.
The reducing agent of the present invention includes, but is not limited to, formaldehyde derivatives, hypophosphite, boric acid, sodium borohydride, borane, shin, hydrazine, sodium gluconate, glucuronolactone, sorbitol, sucrose, phenolic compounds, and the like.
Examples of the hypophosphite include sodium hypophosphite and potassium hypophosphite.
Examples of the phenolic compound include resorcinol, hydroquinone, catechol, hydroquinone, phenolsulfonic acid, cresolsulfonic acid, hydroquinone sulfonic acid and the like.
Preferably, the reducing agent is selected from one or more of formaldehyde and derivatives thereof, glyoxylic acid and derivatives thereof, boric acid, sodium hypophosphite, hydroquinone and catechol.
In the application, when the reducing agent is selected from one or more of formaldehyde and derivatives thereof, glyoxylic acid and derivatives thereof, boric acid, sodium hypophosphite, hydroquinone and catechol, palladium ions adsorbed on the surface of a substrate plate, particularly in blind holes and through holes, can be well reduced into palladium atoms to form an active center to catalyze copper deposition.
In one embodiment, the concentration of the reducing agent is 2 to 20g/L, preferably 1 to 5 g/L.
In one embodiment, the amphiphilic substance containing an ether group is selected from one or more of polyoxyethylene amphiphilic substances, polyatomic alcohol amphiphilic substances and polyether amphiphilic substances.
The polyether amphiphile is not particularly limited in this application and can be selected by those skilled in the art in a conventional manner.
The polyoxyethylene-based amphiphilic substance is not particularly limited in the present application, and may be conventionally selected by those skilled in the art.
The polyoxyethylene amphiphilic substance includes, but is not limited to, long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, and the like.
The polymeric polyol amphiphile is not particularly limited in this application and may be selected by those skilled in the art in a conventional manner.
In one embodiment, the polymeric polyol amphiphile is polyethylene glycol.
Preferably, the polyethylene glycol has a weight average molecular weight of 5000-7000; more preferably 6000.
The applicant unexpectedly finds that in the electroless copper plating solution of the present application, the polyethylene glycol with the weight average molecular weight of 6000 can improve the brightness of the copper layer and avoid the occurrence of hydrogen embrittlement, and the applicant believes that a possible reason is that the polyethylene glycol with the weight average molecular weight of 6000 in the present application has a molecular long chain which has a force with the bismaleimide resin and the cyanate resin which is inferior to the adhesive force with the copper crystal grains, so that the polyethylene glycol with the weight average molecular weight of 6000 can sufficiently wrap the copper crystal, the generated hydrogen can rapidly escape in the copper deposition process, and the phenomenon that the brightness of the copper layer is reduced or the hydrogen embrittlement is caused by the residual hydrogen in the later period is prevented.
In addition, the applicant has unexpectedly found that the combination of the 1, 1-sulfonyl diimidazole, the nickel sulfamate and the polyethylene glycol can keep the copper plating rate at a proper level and also can ensure the stability of the plating solution, probably because the three components can mutually promote during copper plating, the surface tension of the plating solution is reduced, copper ions are timely complexed, the plating speed is controlled, and the stability of the plating solution is kept.
In one embodiment, the concentration of the amphiphilic ether group-containing substance is 0.005 to 0.5 g/L.
The pH adjusting agent described herein is not particularly limited and may be routinely selected by those skilled in the art.
In one embodiment, the electroless copper plating solution has a pH of 12 to 13, preferably 12.8 to 13.
The substrate sheet described in this application is not particularly limited and may be selected conventionally by those skilled in the art.
In one embodiment, the substrate sheet is a BT substrate sheet and/or an ABF sheet.
Preferably, the substrate plate is a BT substrate plate.
The BT substrate board is prepared by synthesizing Bismaleimide (BMI) and Cyanate Ester (CE) resin, and the BT resin-based copper clad laminate (BT board for short) can be widely applied to high-density interconnection (HDI) multilayer printed boards and packaging substrates which are gradually popular at present due to the properties of high glass transition temperature (Tg), excellent dielectric property, low thermal expansion rate, good mechanical characteristics and the like. BT boards are initially used only for chip packaging, and there are a dozen varieties, such as: high-performance copper clad laminate, chip carrier, high-frequency copper clad laminate, resin coated copper foil and the like, and the application is wider.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Examples 1 to 9
Examples 1 to 9 of the present invention provide an electroless copper plating solution, the specific composition of which is shown in table 1.
TABLE 1
TABLE 1
The preparation method of the electroless copper plating solution in the embodiments 1, 6 and 7 comprises the following steps: adding nickel (II) sulfamate and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, sulfo succinic acid, 2 '-bipyridyl-5, 5' -dimethanol, copper sulfate and potassium sodium tartrate into the beaker, stirring uniformly, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in the embodiment 2 comprises the following steps: adding polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, sulfo succinic acid, 2 '-bipyridyl-5, 5' -dimethanol, copper sulfate and potassium sodium tartrate into the beaker, uniformly stirring, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in the embodiment 3 comprises the following steps: adding nickel sulfamate (II) and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, nickel dimethyldithiocarbamate, 2 '-bipyridine-5, 5' -dimethanol, copper sulfate and potassium sodium tartrate into the beaker, stirring uniformly, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in the embodiment 4 comprises the following steps: adding nickel (II) sulfamate and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, sulfo-succinic acid, 1-sulfonyl diimidazole, copper sulfate and potassium sodium tartrate into the beaker, stirring uniformly, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in the embodiment 5 comprises the following steps: adding nickel (II) sulfamate and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, sulfo-succinic acid, 2-mercaptobenzimidazole carboxylic acid, copper sulfate and potassium sodium tartrate into the beaker, uniformly stirring, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in the embodiment 8 comprises the following steps: adding nickel (II) sulfamate and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, potassium ferrocyanide, 2 '-bipyridine-5, 5' -dimethanol, copper sulfate and potassium sodium tartrate into the beaker, stirring uniformly, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
The preparation method of the electroless copper plating solution in example 9 comprises the following steps: adding nickel (II) sulfamate and polyethylene glycol into a beaker, then adding 600mL of distilled water until the solid in the beaker is dissolved, then sequentially adding formaldehyde, sodium thiosulfate, 2 '-bipyridyl-5, 5' -dimethanol, copper sulfate and potassium sodium tartrate into the beaker, stirring uniformly, then adding sodium hydroxide to adjust the pH value to 13, and finally using distilled water to fix the volume to 1L.
Performance evaluation
1. And (3) testing the copper deposition rate:
preparing 9 BT substrate plates of Mitsubishi, treating with SCC-A01H, leavening agent from Guangdong Shucheng technology company, Inc. at 80 deg.C for 6 min; then washing in tap water at 25 deg.C for 1 min; then treating the mixture in 52g/L aqueous solution of SCC-A02 at 80 ℃ for 12 min; then continuously washing in tap water at 25 ℃ for 1 min; then, the mixture was treated at 50 ℃ for 1min in a neutralization solution of 100ml/L of a mixture of SCC-A03H (available from Guangdong Shuichi Co., Ltd.) and 90ml/L of 50 wt% sulfuric acid, wherein the volume ratio of SCC-A03H to sulfuric acid was 10: 9; then washing in tap water at 25 deg.C for 1 min; treating at 50 deg.C with SCC-A04H in treating solution from Guangdong Shuichi Co., Ltd for 1min, and washing in 25 deg.C tap water for 1 min; continuing the treatment at 50 deg.C for 45s with a sufficient amount of sodium hydroxide as a pH buffer to provide a pH of 9, and an activator type SCC-A06H from Guangdong Shuichi Co., Ltd; then, copper was plated at 34 ℃ for 30min using the electroless copper plating solutions of examples 1 to 9, respectively.
Copper deposition rate:
m1 is the weight of the BT substrate board before SCC-a04H treatment in g;
m2 is BT substrate board weight after copper plating in g;
rho is copper deposition density and is 8.92g/cm3；
S is the plate surface area, 25cm2；
t is the copper plating time in h.
The results of the copper deposition rate test are shown in Table 2.
TABLE 2
2. Testing the backlight grade:
and after chemical copper plating is carried out according to the method in the copper deposition rate test, the obtained copper-plated base material plate is washed for 1min by using tap water at the temperature of 25 ℃, and then the side surface of the base material plate is cut to expose the copper-plated wall of the through hole. And selecting a plurality of side sections with the thickness of 1mm from the cut hole wall of each substrate plate, and observing under a metallographic optical microscope with the magnification of 50X. Wherein the backlight grade is assessed using a backlight grade table.
Wherein the backlight is graded as follows: level 1: light transmission, wherein the light transmission area is more than 90%; and 2, stage: transmitting light, wherein 80 percent of light transmitting area is less than or equal to 90 percent; and 3, level: light transmission, 70 percent < the light transmission area is less than or equal to 80 percent; 4, level: light transmission, 60 percent < the light transmission area is less than or equal to 70 percent; and 5, stage: light transmission, 50% and less than or equal to 60% of a light transmission area; and 6, level: dark light, 40% < the visible light area is less than or equal to 50%, and the fiber shape is clear; and 7, stage: dark light, 30% < the visible light area is less than or equal to 40%, the dark light is fibrous; and 8, stage: dark light, 20 percent < the visible light area is less than or equal to 30 percent, and part of the dark light is in a fiber shape initially; stage 8.5: dark light, 10% < visible light area less than or equal to 20%, initial light <10 point scattered dark light distribution; and 9, stage: dark light, 5% < visible light area less than or equal to 10%, and initial light <5 scattered dark light distribution; 9.5 level: 1% of dark light, wherein the visible light area is less than or equal to 5%, and the initial light is less than 2 points and distributes the dark light in a scattered manner; 10 level: all black.
The results are shown in Table 3.
TABLE 3
The backlight effect diagrams of examples 1-9 are shown in fig. 1-9, respectively.
SEM topography scanning test
And (3) after copper plating is finished according to a copper plating method in the copper deposition rate test, cleaning the copper plate by using clear water, drying the copper plate by using an oven, and then carrying out a shape scanning test on the plate surface by using SEM equipment. The test is to observe the appearance structure of the plate surface under a 3K-time lens.
SEM of the copper layers obtained in examples 1 to 9 are shown in 10 to 18, respectively.
4. And (3) stress testing:
the electroless copper plating solution in example 1 was used for copper plating by a copper plating method in a copper deposition rate test, the surface of the copper layer was scanned at an angle of 2 θ of 40 to 100 ° by an X-ray diffraction method, and then the stress was measured for each diffraction peak appearing in the spectrum, and the copper layer stress calculation formula was as follows:
in the formula, σ: testing the stress of the surface of the copper film, E: young's modulus of copper, 127.2GPa, v: a Poisson's ratio, of 0.364,
different angles of incidence when XRD was tested, 2 θ: diffraction angle. In the measurement adopt
The method takes 2 theta as a vertical coordinate,
for the abscissa, the slope of the straight line is measured and plotted, and the stress value σ is calculated.
Irradiation was performed using a CuKa radiation source, with the copper (311) crystal plane as the diffraction plane, at angles of incidence of 0 °,5 °, 10 °, 15 °, 20 °, 25 °, 30 °, 35 °, and 40 °, respectively.
The copper (311) crystal plane was chosen as the diffraction plane and irradiated with CuKa radiation source at incidence angles Ψ of 0 °,5 °, 10 °, 15 °, 20 °, 25 °, 30 °, 35 °, and 40 °, respectively, as shown in table 4 below.
TABLE 4
And (4) stress test results:
5. palladium catalyzed decomposition stability test
The electroless copper plating solutions obtained in examples 1 to 9 were placed in a beaker, 20mL of a palladium chloride solution having a concentration of 0.18g/L was added to 100mL of the electroless copper plating solution to perform catalytic decomposition reaction, and the time to start decomposition was recorded, and the test results are shown in Table 5.
TABLE 5
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The electroless copper plating solution is characterized by comprising a copper ion donor, an accelerator, an N-containing heterocyclic substance, a nickel salt, a reducing agent and an amphiphilic substance containing an ether group.
2. The electroless copper plating solution according to claim 1, wherein the amphiphilic substance containing an ether group is one or more selected from the group consisting of a polyoxyethylene amphiphilic substance, a polyatomic alcohol amphiphilic substance, and a polyether amphiphilic substance.
3. The electroless copper plating solution according to claim 2, wherein the nickel salt is a nickel sulfate salt and/or a nickel sulfonate salt.
4. The electroless copper plating solution according to claim 1, wherein the N-containing heterocyclic substance is a nitrogen-containing five-membered ring compound and/or a nitrogen-containing six-membered ring compound.
5. The electroless copper plating solution according to claim 4, wherein the nitrogen-containing five-membered ring compound is an imidazole-based substance.
6. The electroless copper plating solution according to claim 4, wherein the nitrogen-containing six-membered ring compound is a pyridine-based substance.
7. The electroless copper plating solution according to any of claims 1 to 6, wherein the accelerator comprises (a) at least one of S, N, O-containing organic or inorganic substance and/or (b) nickel-containing organic substance.
8. The electroless copper plating solution according to claim 7, wherein the structure of the organic compound containing at least one of S, N, O is represented by formula (1),
9. The electroless copper plating solution according to claim 8, wherein the concentration of the accelerator is 0.005 to 0.5 g/L.
10. A method for preparing an electroless copper plating solution according to any one of claims 1 to 9, comprising: mixing copper ion donor, accelerator, N-containing heterocyclic substance, nickel salt, reducing agent and amphiphilic substance containing ether group.
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| CN113463074A (en) * | 2021-06-03 | 2021-10-01 | 广东硕成科技有限公司 | Copper deposition composition and copper deposition method |
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