CN114990533B - Method for improving binding force of electroplated copper on surface of ceramic substrate - Google Patents
Method for improving binding force of electroplated copper on surface of ceramic substrate Download PDFInfo
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- CN114990533B CN114990533B CN202210382094.8A CN202210382094A CN114990533B CN 114990533 B CN114990533 B CN 114990533B CN 202210382094 A CN202210382094 A CN 202210382094A CN 114990533 B CN114990533 B CN 114990533B
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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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
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
The invention provides a method for improving the copper binding force of electroplated copper on the surface of a ceramic substrate, which combines an ALN ceramic substrate with an electroplating method through chemical plating, so that the metallization of the ceramic surface replaces a magnetron sputtering film method, the prepared ceramic substrate obtains a copper layer with uniform thickness and good performance, the copper binding force of electroplated copper on the surface of the ceramic substrate is greatly improved, and the service life of the ceramic substrate is prolonged; the ceramic surface is roughened by etching before plating, relevant technological parameters are optimized, the binding force between a ceramic substrate and a copper coating is solved, and the coating is baked for 5-10min at the high temperature of 300-350 ℃ without foaming and peeling; the 2,2', 6' -tetracarboxyl-4, 4' -bipyridine is prepared by a simple and environment-friendly method, and the high-efficiency chemical copper plating solution is obtained by limiting the components and the content of the complexing agent added into the chemical copper plating solution, so that the conductivity of a seed layer is effectively improved, the thickness and the uniformity of a plating layer of the chemical copper plating layer are improved, the efficiency and the speed of electrolytic copper plating are greatly improved, and the bonding capability of a ceramic substrate and a copper layer is improved.
Description
Technical Field
The invention relates to the field of surface treatment, in particular to a method for improving the binding force of electroplated copper on the surface of a ceramic substrate.
Background
With the rapid development of electronic technology, electronic devices are developed to be integrated and multifunctional; the ceramic substrate is most commonly used in the market at present is made of aluminum oxide as a base material, has high thermal stability, chemical stability, low dielectric constant, thermal expansion coefficient and low cost matched with semiconductor silicon, and the aluminum oxide ceramic substrate is used for firstly carrying out metallization on the surface of the aluminum oxide ceramic substrate, wherein the method for metallizing the ceramic substrate mainly comprises the following steps: high temperature sintering silver coating method, vacuum evaporation coating method, magnetron sputtering method, chemical vapor deposition method, chemical plating, etc.
Chemical plating is a method commonly used in industrial production, and has the advantages of simple equipment, low price, convenient mass production and the like; the process of performing autocatalytic and redox reactions on the surface of a ceramic substrate is known as electroless copper plating; however, the following common defects exist when electroless copper plating is performed on the surface of a ceramic substrate in the existing market: the coating thickness is not uniform and reaches the standard, the bonding force between the ceramic substrate and the copper coating is poor, and even the coating is baked at high temperature after being coated, the coating is peeled due to poor bonding force and other bad problems.
Disclosure of Invention
The invention aims to provide a method for improving the binding force of electroplated copper on the surface of a ceramic substrate, so as to solve the problems in the prior art.
The invention provides a method for improving the binding force of electroplated copper on the surface of a ceramic substrate, controlling the thickness and uniformity of a plating layer, and providing a production process combining electroless copper plating and electroplated copper on the surface of the ceramic substrate.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for improving the binding force of electroplated copper on the surface of a ceramic substrate comprises the following steps:
s1: taking water as a solvent, adding 34-36% of sodium hydroxide, 16-18% of phosphate and 2-3% of carbonate into the solvent to prepare etching solution, and putting the ceramic substrate into the etching solution to etch for 1h at 65-70 ℃;
s2: preparing degreasing liquid by taking water as a solvent, wherein the diethylene triamine accounts for 19-20%, the ethylene glycol derivative accounts for 19-20% and the surfactant accounts for 0.1-0.15%, placing the ceramic substrate into the degreasing liquid, and degreasing for 3-5min at 55-60 ℃;
s3: preparing an impregnating solution by taking water as a solvent, wherein the sodium bisulfate accounts for 14-16% and the chloride accounts for 84-86%, and soaking the impregnating solution in the impregnating solution for 0.5-1min after washing;
s4: preparing a pre-activator by taking water as a solvent, wherein stannous chloride accounts for 32-33%, hydrochloric acid accounts for 10-12%, and palladium compound accounts for 0.6%; preparing an activating agent by taking water as a solvent, wherein the sodium bisulfate accounts for 14-16% and the preactivating agent accounts for 84-86%, putting a ceramic substrate into the activating agent, and activating the ceramic substrate with the activating agent for 3-5min at 33-37 ℃;
s5: preparing a sol solution by using water as a solvent, wherein the fluoroboric acid accounts for 19-20% and the boric acid accounts for 0.9-1%, washing with pure water, and soaking in the sol solution for 1-2min;
s6: electroless copper plating is carried out in electroless copper plating solution for 10-15min at 35-36 ℃;
s7: washing with pure water, and copper plating in electrolyte at 50-55deg.C for 170-180min;
s8: after washing with pure water, baking for 30min at 145-150 ℃ to obtain the ceramic substrate after copper plating.
The invention solves the problem of poor binding force of the prior ceramic substrate coating at high temperature, especially the problem of industry hot spot if the good binding force is kept at 300-350 ℃, and solves the problem of binding between ceramic (nonmetal) and copper (metal) coating, especially the problem of keeping the good binding force at 300-350 ℃.
The method for improving the binding force of the invention is to firstly chemically copper-clad the surface of the ceramic substrate, and to change the layer into a seed layer, so that the ceramic substrate is conductive, a thicker plating layer can be obtained only by conductivity, then copper is plated in the electrolyte, the efficiency and the speed of the plating layer can be greatly improved, and the binding capacity of the ceramic substrate and the copper layer can be improved.
Further, the electrolyte is composed of water as a solvent, 60g/L of copper pyrophosphate, 330g/L of potassium pyrophosphate, 0.1-0.3ml/L of ammonium hydroxide and 1-3ml/L of ammonia water.
Further, the electroless copper plating solution was prepared by using water as a solvent, 100ml/L of complexing agent, 50g/L of copper, 14ml/L of additive, 15ml/L of 30% sodium hydroxide, 50ml/L of stabilizer, and 5ml/L of 37% HCHO.
Further, the current density of electrolysis was 0.5ASD.
Further, the additive is one of potassium sodium tartrate and disodium ethylenediamine tetraacetate, and the stabilizer is one of sulfuric acid and hydrochloric acid.
Furthermore, 2' -bipyridine is used as a complexing agent, and a pyridine N coordination point is utilized to form strong complexing with metal, so that the binding force between the ceramic and the copper layer is improved.
The 2,2', 6' -tetra-carboxyl-4, 4' -bipyridine contains not only 2 pyridine N coordination sites, but also 4 carboxyl groups, not only can form strong complexation with the ceramic substrate and copper layers by N, but also can form strong non-covalent bond force between molecules by carboxyl groups, the synergistic effect of the multi-carboxyl groups and the pyridine N coordination sites ensures the bonding strength of the ceramic substrate and the copper layers, the non-covalent bond energy of the multi-carboxyl groups ensures the bonding strength of the bonding layers, and the complexation of N ligands ensures stable deposition on the surface of the ceramic substrate without falling off.
Therefore, the 2,2', 6' -tetracarboxylic-4, 4' -bipyridine is prepared simply and environmentally-friendly, and is limited to be added into the chemical plating solution as a complexing agent for electroless copper plating, so that the high-temperature binding force between the ceramic substrate and the copper layer is greatly improved; the existing preparation method adopts Na to catalyze and couple SO 2 By oxidation, but with SO 2 The toxicity of the oxidant is high and the post-treatment is complicated; or coupling halogenated pyridine under the action of a noble metal catalyst, so that the cost is too high; the invention adopts air as oxidant, which is green, economical and environment-friendly and has high yield.
Further, the complexing agent is 2,2', 6' -tetracarboxylic-4, 4' -bipyridine, and the preparation method comprises the following steps:
(1) Stirring sodium, anhydrous tetrahydrofuran and 2, 6-lutidine at 18-25deg.C under nitrogen protection for 12-16 hr in dark condition;
(2) Steaming to remove anhydrous tetrahydrofuran under reduced pressure, adding deionized water, heating to 45-48deg.C, blowing air for 5-8min, suction filtering, and recrystallizing with dichloromethane and petroleum ether to obtain 2,2', 6' -tetramethyl-4, 4' -bipyridine;
(3) Dissolving chromium trioxide in concentrated sulfuric acid, adding 2,2' -6,6' -tetramethyl-4, 4' -bipyridine for 6-8 times, stirring for 10h, heating to 45-48 ℃ and maintaining for 0.5-1h; and after stopping heating, adding ice cubes and ethanol, cooling to-12 ℃, precipitating, standing, centrifuging, filtering, and washing with cold water to obtain the 2,2', 6' -tetracarboxyl-4, 4' -bipyridine.
Further, the mass molar ratio of sodium to 2, 6-lutidine is (0.22-0.26) g to 10mmol; the mass volume ratio of the sodium to the anhydrous tetrahydrofuran is 0.25 g/20 mL.
Further, the mass molar ratio of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine to chromium trioxide is 1g:28mmol.
Further, the mass-to-volume ratio of ice cubes to ethanol is 4g:4mL.
2, 6-lutidine is used as a raw material, and sodium metal and air are used as a coupling agent and an oxidant to synthesize 2,2', 6' -tetramethyl-4, 4' -bipyridine; the sodium metal is dispersed in THF as very fine particles prior to reaction, otherwise the coupling is slowed down or even stopped rapidly as the intermediate product is deposited on the metal surface; in the feeding process, the feeding ratio of the metal sodium to the 2, 6-lutidine is limited, so that the coupling speed is improved, and the influence of the residual 2, 6-lutidine on the crystallization of the product is reduced; the reaction concentration of the 2, 6-lutidine is 0.4-0.5mol/L, and when the reaction concentration is increased, the deposition of the intermediate product is rapidly increased to prevent the reaction from proceeding; the reaction process is strictly deoxidized and light-proof.
Filtering the redundant metal sodium before oxidizing the intermediate product by air in the oxidation stage to avoid the danger caused by the oxidation of the redundant sodium by air; removing most sodium salt after the reaction of the 2, 6-lutidine is stopped, steaming to remove tetrahydrofuran, dissolving residual solid with dichloromethane, fully removing various possible salts, and avoiding salt residues in the subsequent recrystallization process; the method can prepare the 2,2', 6' -tetramethyl-4, 4' -bipyridine with high yield and good purity at one time, and directly carry out carboxylation reaction.
2,2', 6' -tetramethyl-4, 4' -bipyridine is added into chromium trioxide and 95% concentrated sulfuric acid for carboxylation, the operation sequence is limited, the mild and sufficient carboxylation process is ensured, and partial carbonization is avoided; the reaction temperature is controlled at 18-25 ℃, so that the oxidation of the bipyridine unit is avoided; adding ice cubes and ethanol (v: v=1:1) into the reaction liquid, freezing the mixture to-12 ℃, standing overnight, fully separating out, and reducing the loss in the separation step and the crystallization process; through oxidation, the 2,2', 6' -tetracarboxylic-4, 4' -bipyridine with fully oxidized methyl is obtained.
The invention has the beneficial effects that:
the invention provides a method for improving the copper binding force of electroplated copper on the surface of a ceramic substrate, which combines an ALN ceramic substrate with an electroplating method through chemical plating, so that the metallization of the ceramic surface replaces a magnetron sputtering film method, the prepared ceramic substrate obtains a copper layer with uniform thickness and good performance, the copper binding force of electroplated copper on the surface of the ceramic substrate is greatly improved, and the service life of the ceramic substrate is prolonged.
The ceramic surface is roughened by etching before plating, relevant technological parameters are optimized, the binding force between a ceramic substrate and a copper coating is solved, and the coating is baked for 5-10min at the high temperature of 300-350 ℃ without foaming and peeling; firstly, chemically plating copper on a ceramic substrate to obtain a uniform copper layer with the thickness of 0.5-1 mu m, and combining the uniform copper layer with the copper electroplating process again, wherein the thickness of the plating layer can reach 20-30 mu m to obtain an excellent plating layer;
the 2,2', 6' -tetracarboxyl-4, 4' -bipyridine is prepared by a simple and environment-friendly method, and is limited to be added into the chemical plating solution as a complexing agent for electroless copper plating, so that the high-temperature binding force between the ceramic substrate and the copper layer is greatly improved; optimizing the synthesis of 2,2', 6' -tetracarboxyl-4, 4' -bipyridine, and overcoming the defects of multiple steps, long time consumption and large pollution in the existing synthesis;
the high-efficiency chemical copper plating solution is obtained by limiting the components and the content of the complexing agent added into the chemical copper plating solution, the conductivity of the seed layer is effectively improved, the thickness and the uniformity of the plating layer of the chemical copper plating layer are improved, the efficiency and the speed of electrolytic copper plating are greatly improved, and the bonding capability of the ceramic substrate and the copper layer is improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1
A method for improving the binding force of electroplated copper on the surface of a ceramic substrate comprises the following steps:
s1: taking water as a solvent, adding 34% of sodium hydroxide, 16% of phosphate and 2% of carbonate into the solvent to prepare etching solution, putting the ceramic substrate into the etching solution, and etching for 1h at 65 ℃;
s2: preparing degreasing liquid by taking water as a solvent, wherein the diethylene triamine accounts for 19%, the ethylene glycol derivative accounts for 19% and the surfactant accounts for 0.1%, placing the ceramic substrate into the degreasing liquid, and degreasing for 3min at 55 ℃;
s3: preparing an impregnating solution by taking water as a solvent, wherein the sodium bisulfate accounts for 14% and the chloride accounts for 84%, and soaking the impregnating solution in the impregnating solution for 0.5min after washing;
s4: preparing a pre-activator by taking water as a solvent, wherein the ratio of 60ml/L stannous chloride is 32%, the ratio of hydrochloric acid is 10% and the ratio of palladium compound is 0.6%; preparing an activator by taking water as a solvent, wherein the ratio of 270g/L sodium bisulfate is 14% and the ratio of a preactivator is 84%, putting a ceramic substrate into the activator, and activating the ceramic substrate with the activator for 3min at 33 ℃;
s5: preparing a photoresist solution by using water as a solvent, wherein the ratio of fluoroboric acid is 19% and the ratio of boric acid is 0.9%, flushing the photoresist solution with pure water, and immersing the photoresist solution in the photoresist solution for 1min;
s6: electroless copper plating is carried out in electroless copper plating solution at 35 ℃ for 10min;
the chemical copper plating solution comprises water as a solvent, complexing agent of 100ml/L, copper of 50g/L, additive of 14ml/L,30% sodium hydroxide of 15ml/L, stabilizer of 50ml/L and 37% HCHO of 5ml/L;
the additive is potassium sodium tartrate; the stabilizer is sulfuric acid;
the complexing agent is 2,2', 6' -tetra-carboxyl-4, 4' -bipyridine, and the preparation method comprises the following steps:
(1) Adding 0.22g of sodium into a 100mL flask under the protection of nitrogen, adding 20mL of anhydrous tetrahydrofuran and 10 mmoles of 2, 6-lutidine, and stirring for 12-16h at 18-25 ℃ in dark;
(2) Steaming to remove anhydrous tetrahydrofuran under reduced pressure, adding 10mL of deionized water, heating to 45 ℃, blowing air for 5min, suction filtering, recrystallizing with dichloromethane and petroleum ether to obtain 2,2', 6' -tetramethyl-4, 4' -bipyridine, filtering excessive raw material 2, 6-dimethylpyridine along with a water layer, and separating the water layer to recover the raw material;
(3) 28mmol of chromium trioxide is dissolved in 10mL of 98% concentrated sulfuric acid, 1g of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine is added in 6 times and stirred for 10h, and the temperature is raised to 45 ℃ and kept for 0.5-1h; after stopping heating, adding 4g of ice cubes and 4mL of ethanol, cooling to-12 ℃, precipitating, standing, centrifuging, filtering, and washing with cold water to obtain 2,2', 6' -tetracarboxyl-4, 4' -bipyridine;
s7: after washing with pure water, copper plating is carried out in electrolyte at 50 ℃ for 170-180min;
the electrolyte comprises water as solvent, copper pyrophosphate 60g/L, potassium pyrophosphate 330g/L, ammonium hydroxide 0.1ml/L, and ammonia water 1ml/L; the current density of electrolysis was 0.5ASD;
s8: after washing with pure water, baking at 145 ℃ for 30min to obtain the ceramic substrate after copper plating.
Example 2
A method for improving the binding force of electroplated copper on the surface of a ceramic substrate comprises the following steps:
s1: taking water as a solvent, adding 35% of sodium hydroxide, 17% of phosphate and 3% of carbonate into the solvent to prepare etching solution, putting the ceramic substrate into the etching solution, and etching for 1h at 68 ℃;
s2: preparing degreasing liquid by taking water as a solvent, wherein the diethylene triamine accounts for 19.8%, the ethylene glycol derivative accounts for 19.8% and the surfactant accounts for 0.1%, putting the ceramic substrate into the degreasing liquid, and degreasing for 4min at 58 ℃;
s3: preparing an impregnating solution by taking water as a solvent, wherein the sodium bisulfate accounts for 15% and the chloride accounts for 85%, and soaking the impregnating solution in the impregnating solution for 0.8min after washing;
s4: preparing a pre-activator by taking water as a solvent, wherein the ratio of 60ml/L stannous chloride is 32.8%, the ratio of hydrochloric acid is 11% and the ratio of palladium compound is 0.6%; preparing an activator by taking water as a solvent, wherein the ratio of 270g/L sodium bisulfate is 15% and the ratio of a preactivator is 85%, putting a ceramic substrate into the activator, and activating the ceramic substrate with the activator for 4min at 35 ℃;
s5: preparing a photoresist solution by using water as a solvent, wherein the ratio of fluoroboric acid is 19.3% and the ratio of boric acid is 0.9%, flushing the photoresist solution by pure water, and immersing the photoresist solution in the photoresist solution for 1.5min;
s6: electroless copper plating is carried out in electroless copper plating solution at 35.5 ℃ for 12min;
the chemical copper plating solution comprises water as a solvent, complexing agent of 100ml/L, copper of 50g/L, additive of 14ml/L,30% sodium hydroxide of 15ml/L, stabilizer of 50ml/L and 37% HCHO of 5ml/L;
the additive is disodium ethylenediamine tetraacetate; the stabilizer is sulfuric acid;
the complexing agent is 2,2', 6' -tetra-carboxyl-4, 4' -bipyridine, and the preparation method comprises the following steps:
(1) 0.25g of sodium is added into a 100mL flask under the protection of nitrogen, 20mL of anhydrous tetrahydrofuran and 10 mmoles of 2, 6-lutidine are added, and the mixture is stirred for 14h at 20 ℃ under the dark condition;
(2) Steaming to remove anhydrous tetrahydrofuran under reduced pressure, adding 10mL of deionized water, heating to 46 ℃, blowing air for 5-8min, suction filtering, recrystallizing with dichloromethane and petroleum ether to obtain 2,2', 6' -tetramethyl-4, 4' -bipyridine, filtering excessive raw material 2, 6-lutidine along with a water layer, and separating the water layer to recover the raw material;
(3) 28mmol of chromium trioxide is dissolved in 10mL of 98% concentrated sulfuric acid, 1g of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine is added in 7 times and stirred for 10h, and the temperature is raised to 46 ℃ and kept for 0.8h; after stopping heating, adding 4g of ice cubes and 4mL of ethanol, cooling to-12 ℃, precipitating, standing, centrifuging, filtering, and washing with cold water to obtain 2,2', 6' -tetracarboxyl-4, 4' -bipyridine;
s7: after washing with pure water, copper plating is carried out in electrolyte at 52 ℃ for 170-180min;
the electrolyte comprises water as solvent, copper pyrophosphate 60g/L, potassium pyrophosphate 330g/L, ammonium hydroxide 0.2ml/L, and ammonia water 2ml/L; the current density of electrolysis was 0.5ASD;
s8: after washing with pure water, baking at 148 ℃ for 30min to obtain the ceramic substrate after copper plating.
Example 3
A method for improving the binding force of electroplated copper on the surface of a ceramic substrate comprises the following steps:
s1: taking water as a solvent, adding 36% of sodium hydroxide, 18% of phosphate and 3% of carbonate into the solvent to prepare etching solution, putting the ceramic substrate into the etching solution, and etching for 1h at 70 ℃;
s2: preparing degreasing liquid by taking water as a solvent, wherein the diethylene triamine accounts for 20%, the ethylene glycol derivative accounts for 20%, and the surfactant accounts for 0.15%, placing the ceramic substrate into the degreasing liquid, and degreasing for 5min at 60 ℃;
s3: preparing an impregnating solution by taking water as a solvent, wherein the sodium bisulfate accounts for 16% and the chloride accounts for 86%, and soaking the impregnating solution in the impregnating solution for 1min after washing;
s4: preparing a pre-activator by taking water as a solvent, wherein 60ml/L stannous chloride accounts for 33%, hydrochloric acid accounts for 12% and palladium compound accounts for 0.6%; preparing an activator by taking water as a solvent, wherein the ratio of 270g/L sodium bisulfate is 16% and the ratio of a preactivator is 86%, putting a ceramic substrate into the activator, and activating the ceramic substrate with the activator for 5min at 37 ℃;
s5: preparing a photoresist solution by using water as a solvent, wherein the ratio of fluoroboric acid is 20% and the ratio of boric acid is 1%, flushing the photoresist solution with pure water, and immersing the photoresist solution in the photoresist solution for 2min;
s6: electroless copper plating is carried out in the electroless copper plating solution for 15min at 36 ℃;
the chemical copper plating solution comprises water as a solvent, complexing agent of 100ml/L, copper of 50g/L, additive of 14ml/L,30% sodium hydroxide of 15ml/L, stabilizer of 50ml/L and 37% HCHO of 5ml/L;
the additive is potassium sodium tartrate; the stabilizer is sulfuric acid;
the complexing agent is 2,2', 6' -tetra-carboxyl-4, 4' -bipyridine, and the preparation method comprises the following steps:
(1) 0.26g of sodium is added into a 100mL flask under the protection of nitrogen, 20mL of anhydrous tetrahydrofuran and 10 mmoles of 2, 6-lutidine are added, and the mixture is stirred for 16 hours at 25 ℃ under the dark condition;
(2) Steaming to remove anhydrous tetrahydrofuran under reduced pressure, adding 10mL of deionized water, heating to 48 ℃, blowing air for 8min, suction filtering, recrystallizing with dichloromethane and petroleum ether to obtain 2,2', 6' -tetramethyl-4, 4' -bipyridine, filtering excessive raw material 2, 6-dimethylpyridine along with a water layer, and separating the water layer to recover the raw material;
(3) 28mmol of chromium trioxide is dissolved in 10mL of 98% concentrated sulfuric acid, 1g of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine is added in 8 times and stirred for 10h, and the temperature is raised to 48 ℃ and kept for 1h; after stopping heating, adding 4g of ice cubes and 4mL of ethanol, cooling to-12 ℃, precipitating, standing, centrifuging, filtering, and washing with cold water to obtain 2,2', 6' -tetracarboxyl-4, 4' -bipyridine;
s7: after washing with pure water, copper plating is performed in an electrolyte at 55 ℃ for 180min;
the electrolyte comprises water as solvent, copper pyrophosphate 60g/L, potassium pyrophosphate 330g/L, ammonium hydroxide 0.3ml/L, and ammonia water 3ml/L; the current density of electrolysis was 0.5ASD;
s8: after washing with pure water, baking at 150 ℃ for 30min to obtain the ceramic substrate after copper plating.
Comparative example 1
With example 2 as a control group, electroless copper plating was not performed, and other processes were normal.
Comparative example 2
Using example 2 as a control, 2-bipyridine was used in place of 2,2', 6' -tetracarboxylic-4, 4' -bipyridine, with other procedures being normal.
Comparative example 3
Using example 2 as a control, the mass molar ratio of sodium to 2, 6-lutidine was 0.2 g/10 mmol, and the other procedures were normal.
Comparative example 4
With example 2 as a control group, the mass molar ratio of sodium to 2, 6-lutidine was 0.28g:10mmol, and the other steps were normal.
Performance test: performance tests were conducted on the ceramic substrates prepared in examples 1 to 3 and comparative examples 1 to 4; baking the obtained ceramic substrate at a high temperature of 350 ℃ for 10min, and observing the plating condition; the dielectric constant and dielectric loss of the ceramic substrate were tested with reference to GB 4722-2017; the thermal conductivity of the ceramic substrate was tested with reference to GB/T36476-2018 and the results are shown in Table 1;
TABLE 1
Examples 1-3 are methods for improving the copper binding force of electroplating on the surface of a ceramic substrate according to the invention, and examples 1-3 combine an ALN ceramic substrate with an electroplating method through chemical plating, so that the metallization on the surface of the ceramic replaces a magnetron sputtering film method, the prepared ceramic substrate obtains a copper layer with uniform thickness and good performance, the copper binding force of electroplating on the surface of the ceramic substrate is greatly improved, and the service life of the ceramic substrate is prolonged.
Comparing example 1 with comparative example 1, it is known that by roughening the ceramic surface by etching before plating, optimizing relevant process parameters, the bonding force between the ceramic substrate and the copper plating layer is solved, and the plating layer is baked at a high temperature of 300-350 ℃ for 5-10min without foaming and peeling; firstly, the ceramic substrate is subjected to electroless copper plating to obtain a uniform copper layer with the thickness of 0.5-1 mu m, and then the uniform copper layer is combined with an electroplating copper process again, wherein the thickness of the plating layer can reach 20-30 mu m, so that an excellent plating layer is obtained.
Comparing example 1 with comparative example 2 and comparative example 3, it is known that 2,2', 6' -tetramethyl-4, 4' -bipyridine is synthesized by using 2, 6-lutidine as raw material and sodium metal and air as coupling agent and oxidant; in the feeding process, the feeding ratio of the metal sodium to the 2, 6-lutidine is limited, so that the coupling speed is improved, the influence of the residual 2, 6-lutidine on the crystallization of a product is reduced, the efficient electroless copper plating solution is obtained, the conductivity of a seed layer is effectively improved, the thickness and uniformity of a plating layer of the electroless copper plating layer are improved, the electrolytic copper plating efficiency and speed are greatly improved, and the bonding capability of a ceramic substrate and a copper layer is improved;
comparing example 1 with comparative example 4, it is known that the 2,2', 6' -tetracarboxylic-4, 4 '-bipyridine is prepared by a simple and environment-friendly method, wherein the 2,2',6 '-tetracarboxylic-4, 4' -bipyridine contains not only 2 pyridine N coordination sites but also 4 carboxyl groups, and can form strong complexation with N and ceramic substrate and copper layer, and also form strong non-covalent bond force between molecules with the aid of carboxyl groups, the synergistic effect of the polycarboxylic groups and the pyridine N coordination sites ensures the bonding strength of the ceramic substrate and the copper layer, the non-covalent bond of the polycarboxylic groups can ensure the bonding strength of the bonding layer, and the complexation of N ligand ensures stable deposition on the surface of the ceramic substrate without falling off.
In conclusion, the prepared ceramic substrate copper layer has uniform surface thickness by limiting the added components and the process design, the mechanical strength is improved, the thermal conductivity of the copper-clad ceramic substrate is greatly improved, the service life of the ceramic substrate is prolonged, and the ceramic substrate copper layer has good application prospect.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, but rather, the equivalent structural changes made by the present invention in the light of the inventive concept, or the direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (5)
1. The method for improving the binding force of the electroplated copper on the surface of the ceramic substrate is characterized by comprising the following steps:
s1: taking water as a solvent, adding 34-36% of sodium hydroxide, 16-18% of phosphate and 2-3% of carbonate into the solvent to prepare etching solution, and putting the ceramic substrate into the etching solution to etch for 1h at 65-70 ℃;
s2: preparing degreasing liquid by taking water as a solvent, wherein the diethylene triamine accounts for 19-20%, the ethylene glycol derivative accounts for 19-20% and the surfactant accounts for 0.1-0.15%, placing the ceramic substrate into the degreasing liquid, and degreasing for 3-5min at 55-60 ℃;
s3: preparing an impregnating solution by taking water as a solvent, wherein the sodium bisulfate accounts for 14-16% and the chloride accounts for 84-86%, and soaking the impregnating solution in the impregnating solution for 0.5-1min after washing;
s4: preparing a pre-activator by taking water as a solvent, wherein stannous chloride accounts for 32-33%, hydrochloric acid accounts for 10-12%, and palladium compound accounts for 0.6%; preparing an activating agent by taking water as a solvent, wherein the sodium bisulfate accounts for 14-16% and the preactivating agent accounts for 84-86%, putting a ceramic substrate into the activating agent, and activating the ceramic substrate with the activating agent for 3-5min at 33-37 ℃;
s5: preparing a sol solution by using water as a solvent, wherein the fluoroboric acid accounts for 19-20% and the boric acid accounts for 0.9-1%, washing with pure water, and soaking in the sol solution for 1-2min;
s6: electroless copper plating is carried out in electroless copper plating solution for 10-15min at 35-36 ℃;
the chemical copper plating solution comprises water as a solvent, complexing agent of 100ml/L, copper of 50g/L, additive of 14ml/L,30% sodium hydroxide of 15ml/L, stabilizer of 50ml/L and 37% HCHO of 5ml/L;
the additive is one of potassium sodium tartrate and disodium ethylenediamine tetraacetate; the stabilizer is one of sulfuric acid and hydrochloric acid;
the complexing agent is 2,2', 6' -tetracarboxyl-4, 4' -bipyridine, and the preparation method comprises the following steps:
(1) Stirring sodium, anhydrous tetrahydrofuran and 2, 6-lutidine at 18-25deg.C under nitrogen protection for 12-16 hr in dark condition;
(2) Steaming to remove anhydrous tetrahydrofuran under reduced pressure, adding deionized water, heating to 45-48deg.C, blowing air for 5-8min, suction filtering, and recrystallizing with dichloromethane and petroleum ether to obtain 2,2', 6' -tetramethyl-4, 4' -bipyridine;
(3) Dissolving chromium trioxide in concentrated sulfuric acid, adding 2,2' -6,6' -tetramethyl-4, 4' -bipyridine for 6-8 times, stirring for 10h, heating to 45-48 ℃ and maintaining for 0.5-1h; stopping heating, adding ice cubes and ethanol, cooling to-12 ℃, precipitating, standing, centrifuging, filtering, and washing with cold water to obtain 2,2', 6' -tetracarboxyl-4, 4' -bipyridine;
the mass mol ratio of the sodium to the 2, 6-lutidine is (0.22-0.26) g to 10mmol;
s7: washing with pure water, and copper plating in electrolyte at 50-55deg.C for 170-180min;
the electrolyte comprises water as solvent, copper pyrophosphate 60g/L, potassium pyrophosphate 330g/L, ammonium hydroxide 0.1-0.3ml/L, and ammonia water 1-3ml/L;
s8: after washing with pure water, baking for 30min at 145-150 ℃ to obtain the ceramic substrate after copper plating.
2. The method for improving the copper bonding force of the surface plating of a ceramic substrate according to claim 1, wherein the current density of the electrolysis is 0.5ASD.
3. The method for improving the binding force of electroplated copper on the surface of a ceramic substrate according to claim 1, wherein the mass-to-volume ratio of sodium to anhydrous tetrahydrofuran is 0.25 g/20 mL when preparing the complexing agent.
4. The method for improving the binding force of electroplated copper on the surface of a ceramic substrate according to claim 1, wherein the mass molar ratio of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine to chromium trioxide is 1 g/28 mmol when preparing the complexing agent.
5. The method for improving the binding force of electroplated copper on the surface of a ceramic substrate according to claim 1, wherein when the complexing agent is prepared, the mass-to-volume ratio of the ice cubes to the ethanol is 4g to 4mL.
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