CN115418686B - Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof - Google Patents
Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof Download PDFInfo
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- CN115418686B CN115418686B CN202211386859.1A CN202211386859A CN115418686B CN 115418686 B CN115418686 B CN 115418686B CN 202211386859 A CN202211386859 A CN 202211386859A CN 115418686 B CN115418686 B CN 115418686B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
Abstract
The invention discloses a through hole high-depth electro-coppering solution of a glass substrate and an electro-coppering process thereof, wherein the electro-coppering solution comprises the following components in mass concentration: 60-100g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 40-80mg/L of chloride ions, 30-90mg/L of composite brightener, 20-90mg/L of composite leveler, 15-45mg/L of surfactant, 20-60mg/L of bridging agent and 30-90mg/L of stabilizer. The solution can quickly realize the filling of the electroplated copper in the through hole of the glass substrate with the depth of 20:1 without folding plating and cavity phenomenon, the filling degree is up to more than 95%, the application range of large current density is borne, and the production efficiency is improved.
Description
Technical Field
The invention relates to the technical field of copper electroplating, in particular to a through hole high-depth copper electroplating solution for a glass substrate and a copper electroplating process thereof.
Background
In recent years, with the explosion of new fields such as 5G, wearable devices, smart phones, automotive electronics, artificial intelligence, and the like, the application of integrated circuits is developing towards diversified applications, and the advanced three-dimensional packaging technology is becoming an important means for realizing miniaturization, weight reduction, and multi-functionalization of electronic products. The glass through hole (TGV) interconnection technology has the application advantages of excellent high-frequency electrical characteristics, low cost, simple process flow, strong mechanical stability and the like, and has wide application prospects in the fields of radio frequency devices, micro Electro Mechanical Systems (MEMS) packaging, optoelectronic system integration and the like.
The through-glass via (TGV) technology is derived from the through-silicon via (tsv) technology, and the via metallization filling generally includes four methods, i.e., chemical vapor deposition, physical vapor deposition, electroless plating and electroplating, which are currently used more frequently. The invention aims to provide a solution for a series of problems in the market in the aspect of a glass through hole electroplating technology, for example, a glass through hole double-sided copper plating technology is disclosed in patent CN111441071A, and the technology has the defects of a leveling agent and a brightener system, so that the current density range is narrow and the high-speed production efficiency is not suitable. In order to solve the drawbacks of levelers and brighteners, many efforts have been made by commercial manufacturers, such as the patent CN103924268A, which discloses the use of an acid copper levellerThe leveling agent is quaternary ammonium salt compound with anion X = Cl - Or Br - The electroplating solution contains one of S or N, alkyl, alkenyl, aralkyl, heteroaralkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaralkyl, and is mainly applied to wafer electroplating with adjustable surface morphology. However, the above leveling agents still do not give satisfactory results.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides a through hole high-depth copper electroplating solution for a glass substrate and a copper electroplating process thereof. The solution can quickly realize the filling of the through hole of the glass substrate with the depth of 20 < 1 > substrate with the electro-coppering, has no folding plating and no cavity phenomenon, has the filling degree of more than 95 percent, bears the application range of large current density, and improves the production efficiency.
In order to achieve the purpose, the invention provides a through hole high-depth electro-coppering solution for a glass substrate, which comprises the following components in mass concentration:
60-100g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 40-80mg/L of chloride ions, 30-90mg/L of composite brightener, 20-90mg/L of composite leveler, 15-45mg/L of surfactant, 20-60mg/L of bridging agent, 30-90mg/L of stabilizer and the balance of pure water
The operation temperature is 25-35 DEG C
The current density is 0.2-7.5A/dm 2
The composite brightener is a compound formed by combining 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide and 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide, the mass concentration ratio of the two compounds in use is 1, the mass concentration ratio of the 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide is 10-30mg/L, and the mass concentration ratio of the 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide is 20-60mg/L, so that the composite brightener can improve the deposition rate, can resist large current, and has a good improvement effect on the problem of the folding of high and deep through holes in the market.
The composite leveling agent is a triethylammonium phosphate quaternary ammonium salt, and is formed by compounding 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate and 2-methylthioadenosine 5 '-triethylammonium monophosphate, the mass concentration ratio of the 8- (4-chlorophenylthio) guanosine 3',5 '-cyclic triethylammonium monophosphate to the 2,8- (4-chlorophenylthio) guanosine 3',5 '-cyclic triethylammonium monophosphate is 10-30mg/L, and the 2-methylthioadenosine 5' -triethylammonium monophosphate is 10-60mg/L when the composite leveling agent is used, so that the deposition effect at the deep part of a through hole can be improved, and the deposition rate of the middle part of the deep hole is slightly larger than that of the opening of the through hole.
The bridging agent is one or more of imidazo [2,1-b ] thiazole carboxylic acid structural compounds, imidazo [2,1-b ] thiazole-5-carboxylic acid, imidazo [2,1-b ] thiazole-6-formic acid and imidazo [2,1-b ] thiazole-2-carboxylic acid, preferably imidazo [2,1-b ] thiazole-6-formic acid, can assist copper ions to deposit in a base material hole at a leveling agent non-inhibition position, the deeper the hole is, the lower the adsorption amount of the leveling agent is, the bridging agent can coordinate with copper ions to enter the deep hole, and the higher the amount of the deep hole internal bridging agent is, the more favorable the acceleration of deep hole internal deposition is, and the filling effect is realized.
Wherein the stabilizer is 3-indolylmethanol, and the chloride ions are provided by hydrochloric acid.
Wherein the surfactant is lauryl alcohol phosphate.
The invention also provides an electro-coppering process of the through hole high-depth electro-coppering liquid containing the glass substrate, which comprises the following specific steps:
step 1, sequentially carrying out hydrofluoric acid micro-etching on a plated part for 1-2min, cleaning with pure water, removing oil for 1-2min, cleaning and ultrasonically cleaning;
step 2, applying a dry film on a clamp, and applying a layer of dry film on the clamp for clamping the plated part to play an isolation role;
step 3, exposing and curing the clamp after film pasting;
step 4, clamping the ultrasonically cleaned plated part by using a clamp, then enabling the plated part to enter an activation tank to adsorb a layer of activated palladium, enabling the activation time to be 1-2min, and then enabling the plated part to enter a pure water washing tank;
step 5, independently introducing the clamp into an alkaline washing tank to remove a dry film, soaking the clamp in 10% nitric acid with volume concentration for 2min after water washing, washing the clamp with pure water, and returning the clamped plated part to carry out chemical copper precipitation;
and 6, formally electroplating copper, wherein the plated part subjected to chemical copper deposition enters an electroplating copper tank, and the used electroplating copper solution is any one of the electroplating copper solutions.
In the activation process of the seed layer, palladium ion adsorption can cause the clamp to generate activity, so that the copper precipitation tank liquor can be polluted. In addition, the chemical copper deposition solution provided by the invention can realize rapid copper deposition, can realize the seed layer thickness of 2-3 μm within 1h, and has excellent binding force, while the copper deposition solution on the market can only reach 0.5 μm.
Wherein, the specific conditions of the step 2 are as follows: preheating at 80-100 deg.C, pre-filming plate surface temperature of 40-60 deg.C, rolling set temperature of 110-120 deg.C, and filming pressure of 3-5kgf/cm 2 The film sticking speed is 1.5-2.5m/min, and the standing time after film sticking is 15min-24H.
Wherein, the specific conditions of the step 3 are as follows: the uniformity of exposure energy is more than 90%, the environmental humidity is more than 90%, and the exposure energy level is 17.
Wherein, the specific conditions of the dry film removing in the step 5 are as follows: sodium hydroxide concentration of 2-3%, temperature of 45-55 deg.C, 2-3kgf/cm 2 。
Wherein, the specific conditions of the electroless copper plating in the step 5 are as follows: the temperature is 65-75 ℃, the time is 30-60min, and the chemical copper deposition plating solution comprises 1.5-2.5g/L of copper sulfate, 5-10mL/L of formaldehyde with the mass fraction of 37%, 0.1g/L of sodium hydroxide, 2.5-45g/L of EDTA-4Na, 0.1-0.5g/L of 2-hydrazinopyridine and 0.1-0.5g/L of pyridine-3, 5-dicarboxylic acid.
The invention has the beneficial effects that: compared with the prior art, the through hole high-depth electro-coppering solution for the glass substrate and the electro-coppering process thereof have the following advantages:
1) The compound leveling agent is a triethylammonium phosphate quaternary ammonium salt, the compound leveling agent is compounded by 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate and 2-methylthioadenosine 5 '-triethylammonium monophosphate, the mass concentration ratio of the 8- (4-chlorophenylthio) guanosine 3',5 '-cyclic triethylammonium monophosphate to the 2,8- (4-chlorophenylthio) guanosine 3',5 '-cyclic triethylammonium monophosphate is 10-30mg/L, and the 2-methylthioadenosine 5' -triethylammonium monophosphate to the 10-60mg/L when the compound leveling agent is used, so that the deposition effect at the deep part of a through hole can be improved, and the deposition rate of the middle part of the deep hole is slightly larger than that of the opening of the through hole.
2) The composite brightener is a compound formed by combining 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide and 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide, the mass concentration ratio of the 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide to the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide is 10-30mg/L, and the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide is 20-60mg/L, so that the composite brightener can improve the deposition rate, can resist high current and has a good improvement effect on the problem of the fracture plating of high and deep through holes in the market.
3) The bridging agent is an imidazo [2,1-b ] thiazole carboxylic acid structure compound, is one or more of imidazo [2,1-b ] thiazole-5-carboxylic acid, imidazo [2,1-b ] thiazole-6-formic acid and imidazo [2,1-b ] thiazole-2-carboxylic acid, preferably imidazo [2,1-b ] thiazole-6-formic acid, can assist copper ions to deposit in a base material hole at a non-inhibited position of the leveling agent, the deeper the hole, the lower the adsorption amount of the leveling agent, the bridging agent can cooperate with copper ions to enter the deep hole, and the higher the dosage of the bridging agent in the deep hole is, the more beneficial to accelerating the deep hole deposition and realizing the effect of filling without holes.
4) The process of the invention forms a barrier layer in a form of an upper dry film to prevent the clamp from being activated, thereby prolonging the service life of the copper deposition bath solution, solving the problems that the clamp also generates activity due to palladium ion adsorption in the activation process of the seed layer, thereby polluting the copper deposition bath solution and the like, and in addition, the invention provides the chemical copper deposition solution which can realize rapid thick copper deposition, can realize the thickness of the seed layer of 2-3 mu m within 1h, has excellent binding force, and can only reach 0.5 mu m in the copper deposition solution on the market.
Drawings
FIG. 1 is a graph showing the judgment criteria of the test results of examples and comparative examples of the present invention;
FIG. 2 is a graph showing the results of the throwing power tests of the examples and comparative examples of the present invention;
FIG. 3 is a graph showing the results of the vent cracking, voiding and uniformity in the examples and comparative examples of the present invention.
Detailed Description
In order to make the invention more clear, the invention is further described below with reference to the text and the figures.
In order to achieve the purpose, the invention provides a through hole high-depth electro-coppering solution for a glass substrate, which comprises the following components in mass concentration:
60-100g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 40-80mg/L of chloride ions, 30-90mg/L of composite brightener, 20-90mg/L of composite leveler, 15-45mg/L of surfactant, 20-60mg/L of bridging agent, 30-90mg/L of stabilizer and the balance of pure water
The operation temperature is 25-35 DEG C
The current density is 0.2-7.5A/dm 2
The composite brightener is a compound formed by combining 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide and 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide, the mass concentration ratio of the compound brightener to the 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide in use is 1.
In this embodiment, the compound leveling agent is a triethylammonium phosphate quaternary ammonium salt, the compound leveling agent is compounded by 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate and 2-methylthioadenosine 5' -triethylammonium monophosphate, and the mass concentration ratio of the two is 1.
In this embodiment, the bridging agent is an imidazo [2,1-b ] thiazole carboxylic acid structure compound, which is one or more of imidazo [2,1-b ] thiazole-5-carboxylic acid, imidazo [2,1-b ] thiazole-6-carboxylic acid, imidazo [2,1-b ] thiazole-2-carboxylic acid, and preferably imidazo [2,1-b ] thiazole-6-carboxylic acid.
In this example, the stabilizer was 3-indolylmethanol and the chloride ion was provided by hydrochloric acid.
In this embodiment, the surfactant is lauryl alcohol phosphate.
A through hole high-depth copper electroplating process of a glass substrate comprises the following specific steps:
step 1, sequentially carrying out hydrofluoric acid micro-etching on a plated part for 1-2min, cleaning with pure water, removing oil for 1-2min, cleaning and ultrasonically cleaning;
step 2, applying a dry film on a clamp, and applying a layer of dry film on the clamp for clamping the plated part to play an isolation role;
step 3, exposing and curing the jig after film pasting, wherein the curing is to form a layer of curing film with inconsistent chemical properties with the original one by the chemical change of the dry film under the irradiation of ultraviolet light, and can prevent the jig from adsorbing palladium ions;
step 4, clamping the ultrasonically cleaned plated part by using a clamp, then feeding the clamped plated part into an activation tank to enable the plated part to adsorb a layer of activated palladium, activating for 1-2min, and then feeding the activated palladium into a pure water washing tank;
step 5, independently placing the clamp into an alkaline washing tank for dry film removing treatment, soaking the clamp in 10% nitric acid by volume concentration for 2min after water washing, washing the clamp with pure water, returning the clamp to the activation tank, clamping the plated part, and performing chemical copper deposition;
and 6, formally electroplating copper, wherein the plated part subjected to chemical copper deposition enters an electroplating copper tank, and the used electroplating copper solution is any one of the electroplating copper solutions.
In this embodiment, the specific conditions of step 2 are: preheating at 80-100 deg.C, pre-filming plate surface temperature of 40-60 deg.C, rolling set temperature of 110-120 deg.C, and filming pressure of 3-5kgf/cm 2 The film sticking speed is 1.5-2.5m/min, and the standing time is 15min-24H after film sticking.
In this embodiment, the specific conditions of step 3 are: the uniformity of exposure energy is more than 90%, the environmental humidity is more than 90%, and the exposure energy level is 17.
In this embodiment, the specific conditions of step 5 dry film stripping are as follows:sodium hydroxide concentration 2-3%, temperature 45-55 deg.C, 2-3kgf/cm 2 。
In this embodiment, the specific conditions of electroless copper plating in step 5 are: the temperature is 65-75 ℃, the time is 30-60min, and the plating solution components of the electroless copper plating comprise 1.5-2.5g/L of copper sulfate, 5-10mL/L of formaldehyde with the mass fraction of 37%, 0.1g/L of sodium hydroxide, 2.5-45g/L of EDTA-4Na, 0.1-0.5g/L of 2-hydrazinopyridine and 0.1-0.5g/L of pyridine-3, 5-dicarboxylic acid.
The beneficial effects of the invention are: compared with the prior art, the through hole high-depth electro-coppering solution for the glass substrate and the electro-coppering process thereof have the following advantages:
1) The invention adopts a composite leveling agent which is a triethylammonium phosphate quaternary ammonium salt, the composite leveling agent is a composite consisting of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate and 2-methylthioadenosine 5' -triethylammonium monophosphate, the mass concentration ratio of the two is 1.
2) The composite brightener used in the invention is a compound formed by combining alkyl imidazole trifluoromethanesulfonimide compounds, preferably 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide and 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide salt, the mass concentration ratio of the two compounds in use is 1.
3) The bridging agent is an imidazo [2,1-b ] thiazole carboxylic acid structure compound, such as one or more of imidazo [2,1-b ] thiazole-5-carboxylic acid, imidazo [2,1-b ] thiazole-6-formic acid and imidazo [2,1-b ] thiazole-2-carboxylic acid, preferably imidazo [2,1-b ] thiazole-6-formic acid, and can assist copper ions to deposit in a base material hole at a non-inhibited position of the leveling agent, the deeper the hole, the lower the adsorption amount of the leveling agent, the bridging agent can coordinate with copper ions to enter the deep hole, and the higher the dosage of the bridging agent in the deep hole is, the more beneficial to accelerating the deposition in the deep hole is, and the effect of filling without a hole is realized.
4) The process of the invention forms the barrier layer in the form of the upper dry film to prevent the clamp from being activated, so that the service life of the copper deposition bath solution is prolonged, the problems that the clamp also generates activity due to palladium ion adsorption in the activation process of the seed layer, the copper deposition bath solution is polluted and the like are solved, in addition, the chemical copper deposition solution provided by the invention can realize rapid thick copper deposition, the thickness of the seed layer of 2-3 mu m within 1h is realized, the binding force is excellent, and the copper deposition solution on the market can only reach 0.5 mu m.
The following are several specific examples of the invention
The judgment standards of examples and comparative examples are shown in FIG. 1.
The deep plating capability test data show that: each group of experiment has five base materials, the measured result of each group of experiment base materials has five groups, and finally the average value is obtained to show the real effectiveness of the deep plating capability.
Example 1
A through hole high-depth electro-coppering solution for glass substrates comprises the following steps:
70g/L copper sulfate, 200g/L concentrated sulfuric acid, 70mg/L chloride ion, 20 mg/L1-methyl-3-n-octylimidazole bis (trifluoromethanesulfonyl) imide, 40 mg/L1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 20 mg/L8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate, 40 mg/L2-methylthioadenosine 5' -triethylammonium monophosphate, 30mg/L lauryl alcohol phosphate, 30mg/L imidazo [2,1-b ] thiazole-6-carboxylic acid, 60 mg/L3-indolylmethanol, and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Example 2
A through hole high-depth electro-coppering solution for a glass substrate comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 60mg/L of chloride ion, 10mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide, 20mg/L of 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 10mg/L of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic-triethylammonium monophosphate, 20mg/L of 2-methylthioadenosine 5' -triethylammonium monophosphate, 15mg/L of lauryl alcohol phosphate, 20mg/L of imidazo [2,1-b ] thiazole-6-carboxylic acid, 30mg/L of 3-indolylmethanol, and the balance of pure water
The operation temperature is 25 DEG C
The current density is 4.5A/dm 2
The time is 45min.
Example 3
A through hole high-depth electro-coppering solution for a glass substrate comprises the following steps:
80g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 50mg/L of chloride ion, 30mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide, 60mg/L of 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 30mg/L of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic-guanosine monophosphate, 60mg/L of 2-methylthioadenosine 5' -monophosphate, 45mg/L of lauryl alcohol phosphate, 60mg/L of imidazo [2,1-b ] thiazole-6-carboxylic acid, 90mg/L of 3-indolylmethanol, and the balance of pure water
The operation temperature is 25 DEG C
The current density is 2.5A/dm 2
The time is 60min.
Comparative example 1
A through hole high-depth electro-coppering solution for a glass substrate comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ions, 20mg/L of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic-triethylammonium monophosphate, 40mg/L of 2-methylthioadenosine 5' -triethylammonium monophosphate, 30mg/L of lauryl alcohol phosphate, 30mg/L of imidazo [2,1-b ] thiazole-6-carboxylic acid, 60mg/L of 3-indolylmethanol and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Comparative example 2
A through hole high-depth electro-coppering solution for glass substrates comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ions, 20mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imine, 40mg/L of 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imine salt, 30mg/L of lauryl alcohol phosphate, 30mg/L of imidazo [2,1-b ] thiazole-6-carboxylic acid, 60mg/L of 3-indolylmethanol and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Comparative example 3
A through hole high-depth electro-coppering solution for a glass substrate comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ions, 20mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imine, 40mg/L of 1-butyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imine salt, 40mg/L of triethylammonium 2-methylthioadenosine 5' -monophosphate, 30mg/L of lauryl alcohol phosphate, 60mg/L of 3-indolylmethanol and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Comparative example 4
A through hole high-depth electro-coppering solution for glass substrates comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ion, 20mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide, 40mg/L of 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 20mg/L of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic-triethylammonium monophosphate, 30mg/L of lauryl alcohol phosphate, 30mg/L of imidazo [2,1-b ] thiazole-6-carboxylic acid, 60mg/L of 3-indolylmethanol, and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Comparative example 5
A through hole high-depth electro-coppering solution for a glass substrate comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ion, 20mg/L of 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide, 40mg/L of 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 20mg/L of 8- (4-chlorophenylthio) guanosine 3',5' -cyclic-guanosine monophosphate, 40mg/L of 2-methylthioadenosine 5' -monophosphate triethyl ammonium salt, 30mg/L of lauryl alcohol phosphate, 60mg/L of 3-indolylmethanol, and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
Comparative example 6
A through hole high-depth electro-coppering solution for glass substrates comprises the following steps:
70g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 70mg/L of chloride ions, 30mg/L of lauryl phosphate, 60mg/L of 3-indolylmethanol and the balance of pure water
The operation temperature is 25 DEG C
The current density is 6.5A/dm 2
The time is 30min.
The experimental results of the examples and comparative examples are shown in fig. 2 and 3. The test results of the embodiment on the orifice crack, uniformity, cavity phenomenon and deep plating capability are all excellent; compared with the example, the comparative example 1 lacks 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide in the composite brightener, the orifice fracture is good, the uniformity is good, the void phenomenon is good, and the deep plating capacity is good; comparative example 2 in comparison with the examples, the absence of 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide salt in the composite brightener results in good orifice fracture, poor uniformity, good voiding, and good throwing power; comparative example 3 in comparison with the examples, the absence of triethylammonium 8- (4-chlorophenylthio) guanosine 3',5' -cyclic monophosphate in the leveler gave the results of poorer orifice breakage, poorer uniformity, poorer void formation and poorer throwing power; comparative example 4 lacks triethylammonium 2-methylthioadenosine 5' -monophosphate compared to the examples, and results were poor in orifice breakage, poor in uniformity, poor in cavitation, and poor in throwing power; comparative example 5 lacks imidazo [2,1-b ] thiazole-6-carboxylic acid as compared with the examples, and results were obtained in which the orifice breakage was good, the uniformity was good, the cavitation phenomenon was poor, and the throwing power was good; comparative example 6 comparison with examples lacking 1-methyl-3-n-octylimidazole bis (trifluoromethanesulfonyl) imide at 10mg/L, 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt at 20mg/L, 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethylammonium monophosphate at 10mg/L, 2-methylthioadenosine 5' -triethylammonium monophosphate at 20mg/L, and imidazo [2,1-b ] thiazole-6-carboxylic acid at 20mg/L gave experimental results in good orifice breakage, good uniformity, poor voiding, and poor throwing power.
The above disclosure is only an example of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (6)
1. The through hole high-depth electro-coppering solution for the glass substrate is characterized by comprising the following components in mass concentration: 60-100g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 40-80mg/L of chloride ions, 30-90mg/L of composite brightener, 20-90mg/L of composite leveler, 15-45mg/L of surfactant, 20-60mg/L of bridging agent, 30-90mg/L of stabilizer and the balance of pure water;
the operation temperature is 25-35 DEG C
The current density is 0.2-7.5A/dm 2
The composite brightener is a composition formed by combining 1-methyl-3-n-octyl imidazole bis (trifluoromethanesulfonyl) imide and 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide, the mass concentration ratio of the two is 1;
the composite leveling agent is formed by combining 8- (4-chlorophenylthio) guanosine 3',5' -cyclic triethyl ammonium monophosphate and 2-methylthioadenosine 5 '-triethyl ammonium monophosphate, wherein the mass concentration ratio of the 8- (4-chlorophenylthio) guanosine 3',5 '-cyclic triethyl ammonium monophosphate to the 2-methylthioadenosine 5' -cyclic triethyl ammonium monophosphate in use is 1-1;
the bridging agent is one or more of imidazo [2,1-b ] thiazole-5-carboxylic acid, imidazo [2,1-b ] thiazole-6-formic acid and imidazo [2,1-b ] thiazole-2-carboxylic acid; the surfactant is lauryl alcohol phosphate;
the stabilizer is 3-indolylmethanol, and the chloride ions are provided by hydrochloric acid.
2. The copper electroplating process for the through hole of the glass substrate with high depth is characterized by comprising the following specific steps of:
step 1, sequentially carrying out hydrofluoric acid micro-etching on a plated part for 1-2min, cleaning with pure water, removing oil for 1-2min, cleaning and ultrasonically cleaning;
step 2, a dry film is coated on the clamp, and a layer of dry film is coated on the clamp of the clamping piece to play an isolation role;
step 3, exposing and curing the clamp after film pasting;
step 4, clamping the ultrasonically cleaned plated part by using a clamp, then enabling the plated part to enter an activation tank to adsorb a layer of activated palladium, enabling the activation time to be 1-2min, and then enabling the plated part to enter a pure water washing tank;
step 5, independently placing the clamp into an alkaline washing tank for dry film removing treatment, soaking the clamp in 10% volume concentration nitric acid for 2min after washing, washing the clamp with pure water, and returning the clamped plated part to chemical copper deposition;
and 6, performing formal copper electroplating, namely, enabling the plated part subjected to chemical copper deposition to enter an electroplating copper tank for electroplating copper, wherein the electroplating copper solution used for electroplating copper is the electroplating copper solution according to claim 1.
3. The copper electroplating process for the through hole with high depth of the glass substrate as claimed in claim 2, wherein the specific conditions of the step 2 are as follows: preheating at 80-100 deg.C, pre-filming plate surface temperature of 40-60 deg.C, rolling set temperature of 110-120 deg.C, and filming pressure of 3-5kgf/cm 2 The film sticking speed is 1.5-2.5m/min, and the standing time after film sticking is 15min-24H.
4. The copper electroplating process for the through hole with high depth of the glass substrate as claimed in claim 2, wherein the specific conditions of the step 3 are as follows: the uniformity of exposure energy is more than 90%, the environmental humidity is more than 90%, and the exposure energy level is 17.
5. The copper electroplating process for the through hole with high depth of the glass substrate as claimed in claim 2, wherein the specific conditions of the step 5 dry film stripping are as follows: the mass concentration of sodium hydroxide is 2-3%, the temperature is 45-55 deg.C, and the film sticking pressure is 2-3kgf/cm 2 。
6. The copper electroplating process for the through hole with high depth of the glass substrate as claimed in claim 2, wherein the specific conditions of the electroless copper deposition in the step 5 are as follows: the temperature is 65-75 ℃, the time is 30-60min, and the plating solution components of the chemical copper deposition comprise 1.5-2.5g/L of copper sulfate, 5-10mL/L of formaldehyde with the mass fraction of 37%, 0.1g/L of sodium hydroxide, 2.5-45g/L of EDTA-4Na, 0.1-0.5g/L of 2-hydrazinopyridine and 0.1-0.5g/L of pyridine-3, 5-dicarboxylic acid.
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