CN110331422B - Method for thickening electroplated copper layer of ceramic substrate - Google Patents
Method for thickening electroplated copper layer of ceramic substrate Download PDFInfo
- Publication number
- CN110331422B CN110331422B CN201910760670.6A CN201910760670A CN110331422B CN 110331422 B CN110331422 B CN 110331422B CN 201910760670 A CN201910760670 A CN 201910760670A CN 110331422 B CN110331422 B CN 110331422B
- Authority
- CN
- China
- Prior art keywords
- ceramic substrate
- copper
- plating
- plating solution
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- 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
-
- 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 method for thickening an electroplated copper layer of a ceramic substrate, belonging to the technical field of ceramic substrates and comprising the following steps of: s1: soaking the ceramic substrate in 8-12% dilute hydrochloric acid for 5-10min, ultrasonically cleaning with deionized water for 10-20min, blow-drying with argon, and oven-drying; s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge the cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 1.5-2.5ASD, controlling the temperature of the plating solution to be 20-25 ℃, adjusting the rotating speed of a motor to control the moving speed of the cathode rod to be 22-30 times/min, and electroplating. By adopting the method of the invention, the plating is carried out for 30min to obtain a plating layer with the thickness of 80-90 microns, the electroplated copper layer has good combination force with the ceramic substrate, the sheet resistance is small, the conductivity is excellent, the plating layer has better thermal shock resistance and stronger reliability.
Description
Technical Field
The invention relates to the technical field of ceramic substrates, in particular to a method for thickening an electroplated copper layer of a ceramic substrate.
Background
Light Emitting Diode (LED) chips have been commonly used in lighting products, heat dissipation capability is an important factor affecting LED efficiency, and a heat dissipation substrate is a key part of an LED heat dissipation channel and should have high thermal conductivity and high electrical insulation. The high-power heat dissipation substrate material is required to have low cost, high electrical insulation, high stability, high thermal conductivity, Coefficient of Thermal Expansion (CTE) matched with a chip, flatness, high strength and the like. In order to meet these requirements, attention has been directed to metal oxides, ceramics, polymers, composites, and the like. The ceramic substrate has the advantages of high thermal conductivity, thermal expansion coefficient matched with a chip, good insulativity, stable mechanical property and the like, and is favored by people. For the high-power LED ceramic substrate, the current carrying capacity determines whether the high-power LED chip can work under rated current, and the effect of making the best use of things is achieved. The key factor determining the current carrying capacity is the thickness of the conductive layer of the ceramic substrate, i.e., the copper layer thickness. The copper layer obtained by sputtering is thin, generally less than 1 micron, cannot bear large current and cannot meet the working requirement of a high-power LED. The thickness of the copper layer is related to its thermal conductivity, and as can be seen from the thermal conductivity formula, the thermal resistance is inversely related to the thickness of the copper layer with the length of the heat transfer path and the thermal conductivity of the material being constant. The thickness of the copper layer is increased, and correspondingly, the thermal resistance is reduced, and the thermal conductivity is enhanced. In consideration, it is necessary to thicken the copper layer to satisfy the electrical and thermal properties of the LED. However, the conventional copper plating process has rough plating surface, poor adhesion and large sheet resistance, and cannot meet the use requirements.
The patent with publication number CN102695370B discloses a method for metallizing the surface of a ceramic profile, in particular to a method for preparing a ceramic circuit board, which comprises the following steps: (1) preparing a ceramic substrate; (2) carving a required circuit pattern on the surface of the ceramic substrate by using laser; (3) placing the ceramic substrate obtained in the step (2) in chemical plating for chemical copper plating and priming; (4) plating nickel or plating gold or silver on the surface of the plating layer to prevent copper oxidation. The ceramic plate is selectively coated with copper by combining a laser engraving technology and chemical copper plating, so that the selectivity is better. However, the bonding force between the plating layer and the substrate is poor, and the plating layer is easy to fall off, so that the technical requirements of the ceramic substrate cannot be met.
Patent document No. CN105472900A discloses a method for processing a circuit board. The method comprises the following steps: and outer layer pattern forming: processing an outer layer pattern on the surface of the laminated board, wherein the outer layer pattern comprises a signal carrying line and a current carrying line; electroplating thickening step: carrying out copper deposition electroplating to form a metal conductive layer on the whole surface of the laminated board; electroplating the current carrying line to thicken by 1-3OZ by taking the metal conducting layer as an electroplating lead; micro-etching to remove the metal conductive layer; a laminating step: laminating an insulating layer having a thickness corresponding to the current carrying line on a region other than the current carrying line on the surface of the circuit board; and repeating the electroplating thickening step and the laminating step until the current carrying line is thickened to a desired thickness. The method does not disclose detailed steps of electroplating thickening, does not disclose components of the plating solution, and the obtained plating layer has poor thermal shock performance, large sheet resistance and rough surface.
Disclosure of Invention
In view of the above, the invention provides a method for thickening an electroplated copper layer of a ceramic substrate, which has good bonding force between the electroplated layer and the ceramic substrate, excellent conductivity, better thermal shock resistance and stronger reliability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for thickening an electroplated copper layer of a ceramic substrate comprises the following steps:
s1: soaking the ceramic substrate in 8-12% dilute hydrochloric acid for 5-10min, ultrasonically cleaning with deionized water for 10-20min, blow-drying with argon, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge the cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 1.5-2.5ASD, controlling the temperature of the plating solution to be 20-25 ℃, adjusting the rotating speed of a motor to control the moving speed of the cathode rod to be 22-30 times/min, and electroplating.
Further, the mass fraction of phosphorus in the phosphorus-copper alloy is 0.12-0.15%.
Further, the plating solution is prepared from the following components in parts by weight: 55-65 parts of copper sulfate, 10-18 parts of sulfuric acid, 5-12 parts of copper chloride, 0.05-0.1 part of 2, 2' -biimidazole, 0.2-0.5 part of brightening agent, 0.1-0.3 part of leveling agent, 0.15-0.2 part of dispersing agent, 0.12-0.2 part of stabilizing agent and 0.03-0.08 part of accelerating agent.
Further, the brightening agent is ethylene thiourea or sodium polydithio-dipropyl sulfonate.
Further, the leveling agent is thioflavin T or polyethyleneimine quaternary ammonium salt.
Further, the dispersing agent is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Further, the stabilizer is 2-mercaptobenzothiophene or methanol.
Further, the accelerator is one of 3-thiol-1-propanesulfonic acid, 3-sulfur-isothiourea propyl sulfonate and N, N-dimethyl-dithiocarbamyl propyl sodium sulfonate.
Since the first silicon integrated circuit was produced in 1958, ceramic substrates have become an important component of hybrid integrated circuits. There are many kinds of metallizations of the substrate surface, such as active metal methods, direct bonding methods, etc. Chemical plating has the advantages of simple technology, uniform plating layer, controllable thickness, low cost and the like, and is widely applied, the chemical copper plating technology is to deposit a layer of high-conductivity copper layer on a substrate, but the stability of plating solution is not high, so for a long time, technicians in the field mainly focus on the research on the stability of the plating solution, and thus, the research on influence factors of the conductivity and the thermal shock performance of the plating layer is not much. For example: the research on electroless copper plating pretreatment of Ninghonglong, Gunn, Majusheng, yellow luck, Qianxigong, Chen China sea and ceramic substrates [ J ] rare metal materials and engineering, 2004,33,3: 321-. For another example: the chemical copper plating and plating layer structure [ J ] of the aluminum oxide ceramic substrate is prepared by carrying out chemical copper plating and plating layer structure [ J ] of the aluminum oxide ceramic substrate, 2007,26,2:40-42, sequentially washing with water, sodium hydroxide solution and water, then carrying out treatments of coarsening, sensitization, activation and the like to obtain a chemical copper plating film layer, and carrying out test analysis on the performance of the plating layer, wherein the bonding between the plating layer and the substrate is good, but the interface of the plating layer and the substrate has bulges and pits, and the thermal shock performance is poor.
In the manufacturing process of the substrate, the quality of plating has an important influence on the yield and reliability of the substrate. It is considered by those skilled in the art that the plating solution can planarize the plated surface by allowing the leveler to block the deposition of copper ions at the cathode tip or projection, but this causes a large amount of charges at the cathode tip to be consumed in the electrochemical reaction, thereby reducing the amount of reduction of copper ions, resulting in a thinner plated layer. Therefore, in order to obtain a thick plating layer, a leveling agent is not generally added to the plating solution. However, leveling agents have an important role in improving the brightness, flatness, and the like of a plating layer in electroplating, and in obtaining a high-toughness plating layer. Therefore, the leveler and convection patterns have been studied by researchers at a later time. For example: the method comprises the following steps of (1) researching the influence of convection and leveling agents on the deep plating capacity of a PCB through hole in cooperation with one another by Reichi 32704A. WangKung Shoudingjun. electroplating and coating, 2016 autumn International PCB technology/information forum: 106-.
However, those skilled in the art have considered that the stronger the convection, the less favorable the deposition of copper ions, and the weaker the convection, the more likely the deposition of copper ions, so that the strength of convection is decreased in order to obtain a thicker plating layer on the premise of further adding a leveling agent, but the obtained plating layer has poor flatness; in order to obtain a coating having good flatness, the strength of convection is increased, and the coating thus obtained is thin. Therefore, a thick plating layer having good flatness cannot be obtained even by the convection increasing method. The person skilled in the art has not yet obtained an effective solution to this problem, which is also an important factor for the limited development of ceramic substrates and related industries.
After many years of intensive research, the inventor of the application carries out hundreds of tests in sequence, and in the face of failure of one time, the inventor also wants to abandon the test for a plurality of times. However, the support of the team, the inner part is not sweet, supports the inventor to walk all the way down, and firmly believes that the technical problem can be solved certainly. Finally, a technical scheme combining an electroplating method and plating solution components is developed, and an excellent technical effect is achieved.
The invention has the beneficial effects that: the method comprises the steps of soaking the ceramic substrate with dilute hydrochloric acid for removing an oxide layer on the surface of the ceramic substrate exposed in the air, and ultrasonically cleaning with deionized water for removing residual hydrochloric acid. And after the ceramic substrate is dried by argon, the ceramic substrate is dried, so that the cleanliness of the surface of the ceramic substrate is maintained, and the influence of surface stains on the subsequent process is prevented. In order to increase the copper layer thickness, after the sputter copper plating, electrolytic copper plating is performed. Under the action of the rectifier, the anode obtains electrons, copper atoms are released to enter the plating solution, the cathode obtains electrons, and the copper atoms are deposited on the ceramic substrate. By adopting the method of the invention, the plating time is 30min, and a plating layer with the thickness of 80-90 microns is obtained.
The invention limits the current density to 1.5-2.5ASD, improves the cathode polarization and increases the overpotential, so that the copper plating layer has fine crystal structure and bright and flat surface. The temperature has great influence on the plating layer, when the temperature is too low, the ion transmission rate is slow, the concentration polarization of the cathode is increased, and simultaneously, the solubility of copper sulfate is reduced, so that the operating current density is reduced, and the electroplating rate is reduced. The operation temperature is too high, the bright range is reduced, even a bright layer is difficult to plate, the plating layer is fogged or rough, the extensibility is reduced, the brittleness is increased, the additive is consumed too fast, and waste is caused. Therefore, the temperature of the plating solution is limited to 20-25 ℃. The invention limits the moving speed of the cathode rod to be 22-30 times/min, has moderate stirring intensity, can meet the consumption of copper ions and additives in the cathode electrodeposition process by electromigration and diffusion mass transfer, and has bright plating surface and good flatness.
The mass fraction of phosphorus in the phosphor copper is 0.12-0.15%, and a layer of brownish black anode mud is generated on the surface of the phosphor copper anode in the electroplating process, so that the rapid dissolution of copper is inhibited. If the phosphorus content in the anode is too high, the produced anode mud is too much, the dissolution of copper is influenced, and Cu in the plating solution2+Supplement cannot be obtained, and the requirement of high current density cannot be met; the content is low, the formed anode mud is thin, the inhibition on the dissolution of copper is not obvious, the content of univalent copper ions in the plating solution is increased, the copper powder is increased, and the consumption of additives is too fast.
Copper sulfate in the plating solution is main salt, sulfuric acid is strong electrolyte, the conductivity of the plating solution can be improved, copper sulfate can be prevented from being hydrolyzed, chloride ions are provided by copper chloride, normal dissolution of the anode is promoted, passivation of the anode is prevented, and the bright and flat plating layer is ensured. The 2, 2' -biimidazole can increase the toughness of the coating and enhance the impact resistance. The brightener ethylene thiourea or sodium polydithio-dipropyl sulfonate is combined with the leveling agent thioflavin T or polyethyleneimine quaternary ammonium salt to improve the brightness of the low current density area. The dispersant sodium dodecyl sulfate or sodium dodecyl benzene sulfonate reduces the surface tension between the plating solution and the solution, eliminates pock spots, enlarges the current density range, ensures that the plated part has good brightness in a low current density area, and reduces the sheet resistance. The stabilizer 2-mercaptobenzothia and methanol can be adsorbed to the surface of the active core to prevent the side reaction of impurity particles in the plating solution and make the plating layer smoother and more compact, and simultaneously the stabilizer is combined with the leveling agent which can prevent the copper ions from depositing at the tip or the convex part of the cathode, and the stabilizer can make the copper ions rapidly deposit at the concave part, thereby obtaining the plating layer with smooth surface and uniform thickness. The accelerators 3-thiol-1-propanesulfonic acid, 3-sulfur-isothiourea propyl sulfonate and N, N-dimethyl-dithiocarbamyl propyl sodium sulfonate improve the deposition rate of chemical copper plating and improve the copper plating efficiency.
The electroplated copper layer of the invention shows good comprehensive properties: the adhesion strength test shows that only a small amount of edge parts fall off, and the falling area is about 2% -3%, which shows that the plating layer and the ceramic substrate have good combination force, the sheet resistance is less than 0.075 omega/□, and the conductivity is excellent; after thermal shock testing and low-temperature and high-temperature alternate circulation, the bonding force of the film/base is tested by a Baige method, and the falling area is about 3% -4%, which shows that the electroplated copper layer has better thermal shock resistance and stronger reliability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
TABLE 1 EXAMPLES 1-6 parts by weight of the components in the plating bath
Example 1
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 8% dilute hydrochloric acid for 10min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz frequency for 10min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 1.5ASD, controlling the temperature of the plating solution to be 20 ℃, and adjusting the rotating speed of a motor to control the moving speed of the cathode rod to be 22 times/min to carry out electroplating. The mass fraction of phosphorus in the phosphor copper is 0.12%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is ethylene thiourea. The leveling agent is thioflavin T. The dispersing agent is sodium dodecyl sulfate. The stabilizer is 2-mercaptobenzothiophene. The accelerator is 3-thiol-1-propanesulfonic acid.
Example 2
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 9% dilute hydrochloric acid for 9min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz for 12min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 1.8ASD, controlling the moving speed of the cathode rod to be 24 times/min by adjusting the rotating speed of a motor, and electroplating. The mass fraction of phosphorus in the phosphor copper is 0.13%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is sodium polydithio-dipropyl sulfonate. The leveling agent is polyethyleneimine quaternary ammonium salt. The dispersant is sodium dodecyl benzene sulfonate. The stabilizer is methanol. The accelerator is 3-sulfur-isothiourea propyl sulfonate.
Example 3
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 10% dilute hydrochloric acid for 8min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz for 14min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, setting the current density to be 2ASD, controlling the moving speed of the cathode rod to be 26 times/min by adjusting the rotating speed of a motor, and electroplating. The mass fraction of phosphorus in the phosphor copper is 0.13%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is ethylene thiourea. The leveling agent is thioflavin T. The dispersing agent is sodium dodecyl sulfate. The stabilizer is 2-mercaptobenzothiophene. The accelerator is N, N-dimethyl-dithiocarbamyl propyl sodium sulfonate.
Example 4
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 11% dilute hydrochloric acid for 7min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz for 16min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 2.1ASD, controlling the moving speed of the cathode rod to be 27 times/min by adjusting the rotating speed of a motor, and electroplating. The mass fraction of phosphorus in the phosphor copper is 0.14%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is sodium polydithio-dipropyl sulfonate. The leveling agent is polyethyleneimine quaternary ammonium salt. The dispersant is sodium dodecyl benzene sulfonate. The stabilizer is methanol. The accelerator is 3-thiol-1-propanesulfonic acid.
Example 5
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 11% dilute hydrochloric acid for 6min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz for 18min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 2.3ASD, controlling the moving speed of the cathode rod to be 28 times/min by adjusting the rotating speed of a motor at the temperature of 24 ℃, and electroplating. The mass fraction of phosphorus in the phosphor copper is 0.14%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is ethylene thiourea. The leveling agent is thioflavin T. The dispersing agent is sodium dodecyl sulfate. The stabilizer is 2-mercaptobenzothiophene. The accelerator is 3-sulfur-isothiourea propyl sulfonate.
Example 6
The embodiment provides a method for thickening an electroplated copper layer of a ceramic substrate, which comprises the following steps:
s1: soaking the ceramic substrate in 12% diluted hydrochloric acid for 5min, ultrasonically cleaning with deionized water at 50 deg.C at 25KHz for 20min, blow-drying with 0.3Mpa argon gas, and oven-drying;
s2: and clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable the plating solution to submerge a cathode plate, arranging phosphorus copper on an anode rod, controlling the current density to be 2.5ASD, controlling the moving speed of the cathode rod to be 30 times/min by adjusting the rotating speed of a motor, and electroplating. The mass fraction of phosphorus in the phosphor copper is 0.15%.
The parts by weight of the components in the plating solution are shown in table 1. The brightener is sodium polydithio-dipropyl sulfonate. The leveling agent is polyethyleneimine quaternary ammonium salt. The dispersant is sodium dodecyl benzene sulfonate. The stabilizer is 2-mercaptobenzothiophene. The accelerator is N, N-dimethyl-dithiocarbamyl propyl sodium sulfonate.
Example 7
This example provides a method for thickening a copper plating layer of a ceramic substrate, which is similar to example 4, but is different from example 4 in that 0.15 parts by weight of cetyltrimethylammonium bromide is added.
Example 8
This example provides a method for thickening a copper plating layer of a ceramic substrate, which is similar to example 5, but is different from example 5 in that 0.16 parts by weight of cetyltrimethylammonium bromide is added.
The hexadecyl trimethyl ammonium bromide can reduce the surface tension of the plating solution, has a thinning effect on the plating layer, enhances the bonding property and obtains the plating layer with uniform thickness.
In examples 1 to 8, sulfuric acid was concentrated sulfuric acid having a concentration of 98%, and the plating solution was prepared by mixing the components, stirring at a rotation speed of 200r/min at 50 ℃ for 30min, and then subjecting the mixture to ultrasonic vibration at room temperature for 1 hour, wherein the ultrasonic frequency was 30 KHz.
Comparative example 1
The comparative example provides a method for thickening an electroplated copper layer of a ceramic substrate, which is different from the method in example 1 in that: the current density is 1ASD, the temperature of the plating solution is 15 ℃, and the moving speed of the cathode rod is controlled to be 18 times/min by adjusting the rotating speed of the motor.
Comparative example 2
The comparative example provides a method for thickening an electroplated copper layer of a ceramic substrate, which is different from the method in example 1 in that: the current density is 3ASD, the temperature of the plating solution is 30 ℃, and the moving speed of the cathode rod is controlled to be 35 times/min by adjusting the rotating speed of the motor.
Comparative example 3
The comparative example provides a method for thickening an electroplated copper layer of a ceramic substrate, which is different from the method in example 1 in that: before electroplating the ceramic substrate, dilute hydrochloric acid soaking and deionized water ultrasonic cleaning are not carried out.
Comparative example 4
The comparative example provides a method for thickening an electroplated copper layer of a ceramic substrate, which is different from the method in example 1 in that: the plating solution lacks a stabilizer.
Test method
The electroplated copper layers of examples 1-8 and comparative examples 1-4 were subjected to performance tests.
Adhesive strength: and (3) scribing 10 multiplied by 10 square grids of 1 multiplied by 1cm by 10 cm on the metal layer by using a hundred-grid knife, brushing 5 times by using a brush along the diagonal direction from the cuts to the substrate, tightly attaching a 3M adhesive tape to the grids, keeping the 3M adhesive tape for 90 +/-30 s, quickly pulling up the adhesive tape perpendicular to the substrate, repeating the actions again, observing the shape of the metal layer, and generally judging that the falling area is less than 5% of the total area to be qualified.
And (3) testing the sheet resistance: the conductivity of the film is usually expressed by sheet resistance (square resistance), and the invention uses a four-probe method to test the sheet resistance of the electroplated layer.
Thermal shock test: the thermal shock test is to test the bonding force between the electroplated copper layer and the ceramic layer under the action of thermal stress generated under the condition of alternating cold and hot cycles. The sample is placed for 1h in a high-temperature (120 ℃) environment, placed for 10min at room temperature, placed for 1h in a low-temperature (-25 ℃) environment, and alternately circulated for 4 times, and the membrane/substrate binding force is tested by using a lattice method.
TABLE 2 results of property test of copper electroplating layers of examples 1 to 8 and comparative examples 1 to 4
When the properties of the copper-plated layers of examples 1 to 8 according to the present invention and comparative examples 1 to 4 were tested in combination with table 2, it can be seen that the copper-plated layers of examples 1 to 8 exhibited good overall properties: the surface is smooth, the adhesion strength is tested, only a small amount of edge parts fall off, and the falling area is about 2% -3%, which shows that the plating layer and the ceramic substrate have good combination force, the sheet resistance is less than 0.075 omega/□, and the conductivity is excellent; after thermal shock test and low-temperature and high-temperature alternate circulation, the bonding force of the film/base is tested by a Baige method, and the falling area is about 3% -4%, which shows that the electroplated copper layer has better thermal shock resistance and stronger reliability. Comparative example 1 reduced the current density, the plating solution temperature, and the cathode rod moving speed. The current density is too low, the cathode polarization is too low, the surface activity of the electrode is not enough, the crystal nucleus formation speed is less than the growth speed, and the surface is rough and dim, the adhesion force is poor, and the sheet resistance is increased. When the temperature is too low, the ion transmission rate is slow, the cathode concentration polarization is increased, and simultaneously, the copper sulfate solubility is reduced, so that the operating current density is reduced, and the electroplating rate is reduced. The moving speed of the cathode is low, the stirring strength is low, electromigration and diffusion mass transfer cannot meet the consumption of copper ions and additives in the cathode electrodeposition process, the copper ions near the cathode cannot be supplemented, and the difference between the concentration of solution particles of an electrode interface layer and the concentration of a plating solution body is increased, so that the cell voltage is increased, the power consumption is increased, and the surface of a plating layer is not compact enough. Comparative example 2 increased the current density, the plating solution temperature, and the cathode rod moving speed. When the current density is too high, the copper hydrated ions are not in time to dehydrate, and water in the hydrated film is carried to deposit on the coating together, so that the normal growth of crystals is hindered, and the coating tissue is influenced. If the temperature is too high, the brightness range is reduced, even a bright layer is difficult to plate, the plating layer is fogged or rough, the ductility is reduced, the brittleness is increased, the additive is consumed too fast, and waste is caused. When the moving speed of the cathode is increased, the moving speed is too high, and the plating solution is easy to splash out. Comparative example 3 no diluted hydrochloric acid immersion and deionized water ultrasonic cleaning, the adhesion strength between the plating and the substrate was affected by impurities such as dust contained on the surface of the ceramic substrate. Comparative example 4 the plating solution lacks a stabilizer, and has a small current density range, a large sheet resistance, and poor adhesion properties.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (1)
1. A ceramic substrate copper-plating layer thickening method is characterized in that: comprises the following steps:
s1: soaking the ceramic substrate in 8-12% dilute hydrochloric acid for 5-10min, ultrasonically cleaning with deionized water for 10-20min, blow-drying with argon, and oven-drying;
s2: clamping the dried ceramic substrate on a cathode rod clamp, placing a cathode rod in an electroplating bath to enable a plating solution to submerge a cathode plate, arranging phosphor copper on an anode rod, controlling the current density to be 1.5-2.5ASD, controlling the temperature of the plating solution to be 20-25 ℃, adjusting the rotating speed of a motor to control the moving speed of the cathode rod to be 22-30 times/min, and electroplating;
the mass fraction of phosphorus in the phosphor copper is 0.12-0.15%;
the plating solution is prepared from the following components in parts by weight: 55-65 parts of copper sulfate, 10-18 parts of sulfuric acid, 5-12 parts of copper chloride, 0.05-0.1 part of 2, 2' -biimidazole, 0.2-0.5 part of brightening agent, 0.1-0.3 part of leveling agent, 0.15-0.2 part of dispersing agent, 0.12-0.2 part of stabilizing agent and 0.03-0.08 part of accelerating agent;
the dispersing agent is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate;
the stabilizer is 2-mercaptobenzothia or methanol;
the accelerator is one of 3-thiol-1-propanesulfonic acid, 3-sulfur-isothiourea propyl sulfonate and N, N-dimethyl-dithiocarbamyl propyl sodium sulfonate;
the brightener is ethylene thiourea or sodium polydithio dipropyl sulfonate;
the leveling agent is thioflavin T or polyethyleneimine quaternary ammonium salt;
the preparation method of the plating solution comprises the steps of mixing the components, stirring for 30min at the rotating speed of 200r/min and the temperature of 50 ℃, and then placing the mixture in ultrasonic waves and vibrating for 1h at normal temperature to obtain the plating solution, wherein the ultrasonic frequency is 30 KHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910760670.6A CN110331422B (en) | 2019-08-16 | 2019-08-16 | Method for thickening electroplated copper layer of ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910760670.6A CN110331422B (en) | 2019-08-16 | 2019-08-16 | Method for thickening electroplated copper layer of ceramic substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110331422A CN110331422A (en) | 2019-10-15 |
| CN110331422B true CN110331422B (en) | 2021-02-12 |
Family
ID=68149763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910760670.6A Expired - Fee Related CN110331422B (en) | 2019-08-16 | 2019-08-16 | Method for thickening electroplated copper layer of ceramic substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110331422B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732455B (en) * | 2020-06-30 | 2022-05-31 | 苏州蓝晶研材料科技有限公司 | Double-tin-layer ceramic conductive material and preparation method thereof |
| CN111732456A (en) * | 2020-06-30 | 2020-10-02 | 苏州蓝晶研材料科技有限公司 | Ceramic conductive material and preparation method and application thereof |
| CN113046805A (en) * | 2021-03-16 | 2021-06-29 | 元六鸿远(苏州)电子科技有限公司 | Surface treatment method for coating thickness homogenization of single-layer ceramic capacitor substrate |
| CN115745666B (en) * | 2022-11-15 | 2024-03-15 | 大富科技(安徽)股份有限公司 | Microwave dielectric ceramic and surface metallization process thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011135716A1 (en) * | 2010-04-30 | 2011-11-03 | 荏原ユージライト株式会社 | Novel compound and use thereof |
| CN103572334B (en) * | 2013-11-20 | 2016-06-22 | 东莞市富默克化工有限公司 | A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method |
| CN105624749B (en) * | 2016-03-28 | 2018-07-10 | 上海申和热磁电子有限公司 | A kind of method of ceramic base plate surface metallization |
| CN107675218A (en) * | 2017-09-30 | 2018-02-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper-plating technique |
| CN107557826A (en) * | 2017-09-30 | 2018-01-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper plating solution |
-
2019
- 2019-08-16 CN CN201910760670.6A patent/CN110331422B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN110331422A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110331422B (en) | Method for thickening electroplated copper layer of ceramic substrate | |
| CN102206098B (en) | Ceramic copper-clad substrate and preparation method thereof | |
| US11655554B2 (en) | Method for preparing electrode of inductive component | |
| US20030201188A1 (en) | Minimizing whisker growth in tin electrodeposits | |
| JP2016065316A (en) | Plated laminate | |
| CN101448364A (en) | Method for producing small-pore-diameter copper-plated through hole on ceramic substrate | |
| CN112635772B (en) | Porous copper foil for lithium battery and preparation method and application thereof | |
| CN113122845B (en) | Preparation method of aluminum alloy metal plating part | |
| JP7302046B2 (en) | Ultra-thin copper foil and its fabrication method | |
| WO2003033776A1 (en) | Electrodeposition of metals in high-aspect ratio cavities using modulated reverse electric fields. | |
| CN103221579B (en) | Process for electroless deposition of metals using highly alkaline plating bath | |
| TW201637527A (en) | Thick copper layer and method for manufacturing the same | |
| CN102424993A (en) | Method for plating ternary alloy layer on aluminum-silicon alloy and product thereof | |
| CN110629259B (en) | Graphene-containing PCB copper composite electroplating solution | |
| KR20000051998A (en) | Method of Silver-plating Microwave Band Pass Cavity Filter Products | |
| WO2023184730A1 (en) | Electroplating method for through and blind holes with high aspect ratio, and pcb | |
| US20020144909A1 (en) | Palladium plating solution | |
| CN116103707A (en) | Electrolytic copper foil and manufacturing method and application thereof | |
| CN116065208A (en) | Preparation method of variable-frequency power ultrasonic electro-deposition nano nickel-based composite layer on magnesium alloy surface | |
| CN115440695A (en) | High-temperature-resistant ultrathin semiconductor lead frame and preparation method thereof | |
| CN1269633C (en) | Novel composite foil and its mfg. method, and copper-coated laminated plate | |
| CN114959814A (en) | Method for quickly electroplating high-conductivity and high-heat-conductivity copper layer | |
| CN113395836A (en) | Method for manufacturing small-spacing high-thickness pure copper circuit board | |
| CN112779574A (en) | Electroplating solution for enhancing conductivity of electronic copper foil, preparation method and electroplating process | |
| CN111690963A (en) | Method for preparing copper/graphite/copper laminated composite material with high thermal conductivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210212 |