CN114351195A - Electro-coppering formula for pulse through hole filling and electro-coppering process thereof - Google Patents
Electro-coppering formula for pulse through hole filling and electro-coppering process thereof Download PDFInfo
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Abstract
The invention discloses an electro-coppering formula for filling a pulse through hole and an electro-coppering process thereof, wherein the electro-coppering formula comprises the following components in mass concentration: 60-90g/L of copper salt, 150-200g/L of concentrated sulfuric acid, 30-90mg/L of inhibitor, 10-30mg/L of leveling aid, 1-8g/L of accelerator, 20-60mg/L of positioning agent, 15-45mg/L of dispersant and 15-45mg/L of brightener. The solution ensures that the orifice of the through hole can not be broken, the deep plating capacity of the plate with the hole thickness-diameter ratio of more than 15:1 is more than 95%, the maximum thickness of the hole filling plate can be more than 3.5mm, and the hole filling rate is kept more than 95%.
Description
Technical Field
The invention relates to the technical field of copper electroplating, in particular to an electroplating copper formula for pulse through hole filling and an electroplating process thereof.
Background
The pulse electroplating process has the advantages of short time length, deep plating capability, good dispersion capability and the like, the existing PCB circuit adopts a cycle-changing pulse electroplating technical method, whether the required performance and the requirement of the product can be achieved or not is often determined by the quality of electroplating liquid medicine, the existing pulse electroplating liquid medicine always takes Ma Demei company as a unique product, and domestic similar products cannot compete with the product, and the important reason is that the deep plating capability and the performance requirement of high thickness-diameter ratio are always short boards of domestic liquid medicine merchants.
Patent CN113881983A discloses a through hole pulse plating solution and a through hole pulse plating coating method, wherein the plating coating method adopts air stirring, so that oxygen can easily enter the solution to cause oxidation corrosion of a chemical copper layer in hole copper, and particularly, fine lines such as an IC carrier plate can cause the problems of circuit disconnection and the like.
In addition, Chui Fangxian et al disclose the application of a pulse plating additive plating solution and plating in patent CN113373482A, which results in the increase of production cost due to the lack of accelerator, and the contained surfactant component has more foam, thus being not beneficial to the operation of inflation and the like.
Therefore, the electroplating copper liquid which can realize high aspect ratio (more than 15: 1) and can not realize more than 95% deep plating and hole filling electroplating on a board with thin lines (the lines are less than 50 microns) is urgently needed in the market to meet the production requirement and remove foreign technical blockages.
Disclosure of Invention
The invention discloses an electro-coppering formula for pulse through hole filling and an electro-coppering process thereof, wherein the electro-coppering formula ensures that a through hole orifice cannot be broken, the deep plating capacity of a plate with the hole thickness-diameter ratio of more than 15:1 is more than 95 percent, the thickest hole filling plate can be more than 3.5mm, and the hole filling rate is kept more than 95 percent.
In order to achieve the above purpose, the invention provides an electrolytic copper plating formula for pulse through hole filling, which comprises the following components in mass concentration:
60-90g/L of copper salt, 150-200g/L of concentrated sulfuric acid and 30-90mg/L of inhibitor; leveling auxiliary agent 10-30 mg/L; 1-8g/L of accelerator; 20-60mg/L of a positioning agent; 15-45mg/L of dispersant; 15-45mg/L of brightener;
the balance of pure water, the pH value is 0.2-0.5;
the operation temperature is 25-35 ℃;
the current density is 0.5-6A/dm2；
The positioning agent is formed by compounding 1, 4-dioxane, ethylene glycol tert-butyl ether and glyoxylic acid, and the mass concentration ratio of the 1, 4-dioxane, the ethylene glycol tert-butyl ether and the glyoxylic acid is 2:1: 1;
the dispersing agent is polyethyleneimine, the brightening agent is a rhodophenazine liquid polymer, and the mass concentration ratio of the brightening agent to the dispersing agent is 1:1 in use.
Wherein the inhibitor is 2-butyl-1-octanol polyoxyethylene ether, the leveling auxiliary agent is 10-15mg/L of thiodiglycol polyoxyethylene ether, and the mass concentration ratio of the inhibitor to the leveling auxiliary agent in use is 3: 1.
Wherein the accelerator is sodium methylenedinaphthalenesulfonate.
The preparation method of the formula of the copper electroplating solution comprises the following steps:
the method comprises the following steps: firstly, adding an inhibitor with the mass concentration of 30-90mg/L and a leveling auxiliary agent with the mass concentration of 10-30mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, and adding pure water for diluting to obtain 200 ml of solution A;
step two: preparing a solution by using an accelerator with the mass concentration of 1-8g/L and a positioning agent with the mass concentration of 20-60mg/L to obtain a solution B with the volume of 200 ml;
step three: placing a dispersing agent with the mass concentration of 15-45mg/L and a brightening agent with the mass concentration of 15-45mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, adding copper salt, and adding pure water for diluting to obtain 200 ml of solution C;
step four: and mixing the solution A, the solution B and the solution C at normal temperature, and diluting to one liter to obtain the copper electroplating solution.
The copper electroplating solution is prepared by adopting the method, and concentrated sulfuric acid is divided into two parts with the same mass concentration and added into the corresponding steps, so that the stability of the plating solution can be improved, and the effects of uniformity, deposition rate and the like of the copper electroplating can be promoted during electroplating.
Wherein, the specific conditions of the step one are as follows: when the concentrated sulfuric acid is prepared, the concentrated sulfuric acid is gradually dripped under magnetic stirring, the dripping speed is 30-50 g per minute, the magnetic stirring speed is 50-60 r/min, and half of the concentrated sulfuric acid is used for preparing a solution A to promote the dissolution and the stability of an inhibitor;
wherein, the concrete conditions of the third step are as follows: the concentrated sulfuric acid is gradually dripped under magnetic stirring at the dripping speed of 70-90 g/min and the magnetic stirring speed of 30-50 r/min, ultrasonic treatment is carried out for 15-20min after dissolution, and the other half of the concentrated sulfuric acid is used for preparing solution C, which is formed by dissolving the concentrated sulfuric acid in water to release heat to promote the uniform mixing of a dispersing agent, a brightening agent and copper ions.
In order to achieve the above object, the present invention further provides an electroplating process of the pulse through hole filling electro-coppering formula, the electroplating process comprises the following specific steps:
step 1, removing oil from the copper plated part after 3-5min, setting the temperature between 40-50 ℃, and washing the copper plated part for three times by pure water until no foam is attached to the copper plated part;
step 2, activating the copper plated part after oil and water removal, and washing the copper plated part for three times by pure water after activation;
step 3, performing steam cleaning on the copper plated part after the activation and water washing, wherein the steam cleaning time is 30-45 s;
and 4, putting the plated copper after steam washing into an electroplating copper tank with the electroplating copper formula, and performing pulse electroplating copper under the irradiation of ultraviolet light until the completion.
Activating by adopting an activating agent in the step 2, wherein the activating temperature is 50-60 ℃, the activating time is 1-2min, and the magnetic stirring speed is 30-60 r/min; the activator consists of 15mg/L silver nitrate, 50mg/L polyethylene glycol and 10mg/L EDTA-4 Nah. The purpose of the activation is to promote better uniform and ordered growth of the copper nuclei.
Wherein, the specific parameter conditions of the steam cleaning in the step 3 are as follows: voltage 220v, frequency 50Hz, temperature 120 ℃.
Wherein, the specific conditions of electroplating in the step 4 are as follows: the amplitude ratio of positive and negative current of pulse waveform is 1:4, the time ratio of positive and negative current is 10-20:1ms, and the forward current density is 0.5-1.5A/dm2Meanwhile, the local temperature rise and the micro-area stirring are realized through ultraviolet irradiation; the forward wavelength of the ultraviolet light irradiation is set to be 100-200nm, the reverse wavelength is set to be 10-50nm, and the scanning speed of the ultraviolet light is between 200nm/s and 1cm/s, so that the light beam moves in the range of 200nm to 1cmThe rate, compared with the existing market, has more excellent uniformity, and can be used for electroplating copper on thin lines such as IC carrier plates and even wafers.
The invention has the beneficial effects that: compared with the prior art, the electro-coppering formula and the electro-coppering process for filling the pulse through hole provided by the invention have the following advantages:
1) 2-butyl-1-octanol polyoxyethylene ether is used as an inhibitor in the components of the plating solution, 10-15mg/L of thiodiglycol polyoxyethylene ether is used as a leveling auxiliary agent, and the mass concentration ratio of the two is 3:1 when the two are used, so that the two special proportions can realize good leveling effect and promote hole filling and deep plating capability, compared with the prior art, the deep plating hole filling capability of the plating solution can reach 95% on a plate with the aspect ratio of 15:1, and the highest plating hole filling capability is only 80-85% in the market.
2) The components of the scheme comprise methylene dinaphthalenesulfonate serving as an accelerator, and the methylene dinaphthalenesulfonate grain refiner can promote the deposition of copper and improve the grain size; the 1, 4-dioxane, ethylene glycol tert-butyl ether and glyoxylic acid are compounded to be used as a positioning agent, and the positioning agent can be adsorbed at a high potential under the action of current by utilizing the coordination of oxygen and copper, so that the inhibitor and the copper are bridged, and are decomposed and reduced into aldehyde groups, and the oxidation of the copper is promoted to be changed into carboxylic acid compounds to be consumed.
3) The polyethyleneimine adopted by the scheme is a dispersant, and can promote copper ions to be uniformly transmitted to a double electric layer of a plated part; the adopted rhodophenazine liquid polymer is a brightening agent, and the mass concentration ratio of the polymer to the dispersant in use is 1:1, compared with the prior art, the two substances have the advantages of low cost, small using amount, less pollution and more obvious effect.
4) The electroplating process of the invention can thoroughly clean adsorbed substances which are difficult to clean and have oil removal, including chemical substances brought by oil removal and microetching by adding steam cleaning, and the specific parameter conditions are voltage 220v, frequency 50Hz and temperature 120 ℃, and simultaneously, ultraviolet light beam irradiation is utilized to ensure that local temperature rise and micro-area stirring are carried out so as to induce or enhance chemical reaction of an irradiation area, so that liquid substances are decomposed, reaction products are deposited on the surface of a solid, and the electroplating efficiency and uniformity are greatly improved.
Drawings
FIG. 1 is a graph showing criteria for evaluation of 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 accompanying drawings.
The invention provides an electro-coppering formula for filling a pulse through hole, which comprises the following components in mass concentration:
60-90g/L of copper salt, 150-200g/L of concentrated sulfuric acid and 30-90mg/L of inhibitor; leveling auxiliary agent 10-30 mg/L; 1-8g/L of accelerator; 20-60mg/L of a positioning agent; 15-45mg/L of dispersant; 15-45mg/L of brightener;
the balance of pure water, the pH value is 0.2-0.5;
the operation temperature is 25-35 ℃;
the current density is 0.5-6A/dm2；
The positioning agent is formed by compounding 1, 4-dioxane, ethylene glycol tert-butyl ether and glyoxylic acid, and the mass concentration ratio of the 1, 4-dioxane, the ethylene glycol tert-butyl ether and the glyoxylic acid is 2:1: 1;
the dispersing agent is polyethyleneimine, the brightening agent is a rhodophenazine liquid polymer, and the mass concentration ratio of the brightening agent to the dispersing agent is 1:1 in use.
In this embodiment, the inhibitor is 2-butyl-1-octanol polyoxyethylene ether, the leveling auxiliary agent is thiodiglycol polyoxyethylene ether 10-15mg/L, and the mass concentration ratio of the two is 3: 1.
In this example, the accelerator is sodium methylenedinaphthalenesulfonate.
The preparation method of the electro-coppering formula comprises the following steps:
the method comprises the following steps: firstly, adding an inhibitor with the mass concentration of 30-90mg/L and a leveling auxiliary agent with the mass concentration of 10-30mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, and adding pure water for diluting to obtain 200 ml of solution A;
step two: preparing a solution by using an accelerator with the mass concentration of 1-8g/L and a positioning agent with the mass concentration of 20-60mg/L to obtain a solution B with the volume of 200 ml;
step three: placing a dispersing agent with the mass concentration of 15-45mg/L and a brightening agent with the mass concentration of 15-45mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, adding copper salt, and adding pure water for diluting to obtain 200 ml of solution C;
step four: and mixing the solution A, the solution B and the solution C at normal temperature, and diluting to one liter to obtain the copper electroplating solution.
In this embodiment, the specific conditions of step one are: the concentrated sulfuric acid is gradually dripped under magnetic stirring when being prepared, the dripping speed is 30-50 g per minute, and the magnetic stirring speed is 50-60 r/min.
In this embodiment, the specific conditions of step three are: the concentrated sulfuric acid is gradually dripped under magnetic stirring at 70-90 g/min and 30-50 r/min, and is dissolved and treated with ultrasonic wave for 15-20 min.
The invention also provides an electroplating process of the pulse through hole filling electro-coppering formula, which comprises the following specific steps:
step 1, removing oil from the copper plated part after 3-5min, setting the temperature between 40-50 ℃, and washing the copper plated part for three times by pure water until no foam is attached to the copper plated part;
step 2, activating the copper plated part after oil and water removal, and washing the copper plated part for three times by pure water after activation;
step 3, performing steam cleaning on the copper plated part after the activation and water washing, wherein the steam cleaning time is 30-45 s;
and 4, putting the plated copper after steam washing into an electrolytic copper plating tank with the electrolytic copper plating solution prepared by the electrolytic copper plating formula, and performing pulse electrolytic copper plating under the irradiation of ultraviolet light until the completion.
In the embodiment, the activating agent is adopted in the step 2 for activation, and the activating agent consists of 15mg/L silver nitrate, 50mg/L polyethylene glycol and 10mg/L EDTA-4Nah, the temperature is 50-60 ℃, the time is 1-2min, and the magnetic stirring speed is 30-60 r/min. The micro silver nitrate in the activating agent can be replaced with copper to generate a micro thin silver seed layer, so that the generation of the number of copper crystal nuclei is facilitated, the copper deposition is catalyzed, the polyethylene glycol can play a role in adjusting and uniformly dispersing silver ions, and the EDTA plays a role in complexing and stabilizing.
In this embodiment, the specific parameter conditions of the step 3 steam cleaning are as follows: voltage 220v, frequency 50Hz, temperature 120 ℃.
In this embodiment, the specific conditions of the step 4 electroplating are as follows: the amplitude ratio of positive and negative current of pulse waveform is 1:4, the time ratio of positive and negative is 10-20:1ms, and the forward current density is 0.5-1.5A/dm2Meanwhile, the local temperature rise and the micro-area stirring are realized through ultraviolet irradiation; the forward wavelength of the ultraviolet light irradiation is set to be 100-200nm, the reverse wavelength is set to be 10-50nm, and the scanning speed of the ultraviolet light is 200 nm/s-1 cm/s, so that the light beam moves within the range of 200nm-1 cm.
The invention has the beneficial effects that: compared with the prior art, the electro-coppering formula and the electro-coppering process for filling the pulse through hole provided by the invention have the following advantages:
1) 2-butyl-1-octanol polyoxyethylene ether is used as an inhibitor in the components of the plating solution, 10-15mg/L of thiodiglycol polyoxyethylene ether is used as a leveling auxiliary agent, and the mass concentration ratio of the two is 3:1 when the two are used, so that the two special proportions can realize good leveling effect and promote hole filling and deep plating capability, compared with the prior art, the deep plating hole filling capability of the plating solution can reach 95% on a plate with the aspect ratio of 15:1, and the highest plating hole filling capability is only 80-85% in the market.
2) The components of the scheme comprise methylene dinaphthalenesulfonate serving as an accelerator, and the methylene dinaphthalenesulfonate grain refiner can promote the deposition of copper and improve the grain size; the 1, 4-dioxane, ethylene glycol tert-butyl ether and glyoxylic acid are compounded to be used as a positioning agent, and the positioning agent can be adsorbed at a high potential under the action of current by utilizing the coordination of oxygen and copper, so that the inhibitor and the copper are bridged, and are decomposed and reduced into aldehyde groups, and the oxidation of the copper is promoted to be changed into carboxylic acid compounds to be consumed.
3) The polyethyleneimine adopted by the scheme is a dispersant, and can promote copper ions to be uniformly transmitted to a double electric layer of a plated part; the adopted rhodophenazine liquid polymer is a brightening agent, and the mass concentration ratio of the polymer to the dispersant in use is 1:1, compared with the prior art, the two substances have the advantages of low cost, small using amount, less pollution and more obvious effect.
4) The electroplating process of the invention can thoroughly clean adsorbed substances which are difficult to clean and have oil removal, including chemical substances brought by oil removal and microetching by adding steam cleaning, and the specific parameter conditions are voltage 220v, frequency 50Hz and temperature 120 ℃, and simultaneously, ultraviolet light beam irradiation is utilized to ensure that local temperature rise and micro-area stirring are carried out so as to induce or enhance chemical reaction of an irradiation area, so that liquid substances are decomposed, reaction products are deposited on the surface of a solid, and the electroplating efficiency and uniformity are greatly improved.
The following are several specific examples of the invention
Example 1
A pulse through hole filling electro-coppering formula comprises the following components in per liter of tank liquor:
60g/L of copper sulfate, 150g/L of concentrated sulfuric acid, 30mg/L of 2-butyl-1-octanol polyoxyethylene ether, 10mg/L of thiodiglycol polyoxyethylene ether, 1g/L of methylene dinaphthalene sodium sulfonate, 20mg/L of 1, 4-dioxane, 10mg/L of ethylene glycol tert-butyl ether, 10mg/L of glyoxylic acid, 15mg/L of polyethyleneimine, 15mg/L of rhodophenazine liquid polymer and the balance of pure water, wherein the pH value is 0.2, the operating temperature is 30 ℃, and the forward current density is 0.5A/dm2Reverse current density 2.0A/dm2The positive and negative pulse time ratio is 10:1ms, and the time is 50 min.
In example 1, the test results were obtained by the criteria of fig. 1: the average deep plating capacity is excellent at 95.8%, the average hole filling capacity is excellent at 96%, the hole opening is excellent without fracture, and the hole opening is bright without pits and copper nodules.
Example 2
A pulse through hole filling electro-coppering formula comprises the following components in per liter of tank liquor:
75g/L of copper sulfate, 175g/L of concentrated sulfuric acid, 60mg/L of 2-butyl-1-octanol polyoxyethylene ether, 20mg/L of thiodiglycol polyoxyethylene ether, 4.5g/L of methylene dinaphthalene sodium sulfonate, 10mg/L of 1, 4-dioxane, 5mg/L of ethylene glycol tert-butyl ether and 5mg/L of glyoxylic acid30mg/L of polyethyleneimine, 30mg/L of rhodophenazine liquid polymer and the balance of pure water, wherein the pH is 0.2, the operating temperature is 30 ℃, and the forward current density is 0.5A/dm2Reverse current density 2.0A/dm2The positive and negative pulse time ratio is 10:1ms, and the time is 50 min.
In example 2, the test results were obtained by the criteria of fig. 1: the average deep plating capacity is excellent at 95.8%, the average hole filling capacity is excellent at 96%, the hole opening is excellent without fracture, and the hole opening is bright without pits and copper nodules.
Example 3
A pulse through hole filling electro-coppering formula comprises the following components in per liter of tank liquor:
90g/L of copper sulfate, 200g/L of concentrated sulfuric acid, 90mg/L of 2-butyl-1-octanol polyoxyethylene ether, 30mg/L of thiodiglycol polyoxyethylene ether, 8g/L of methylene dinaphthalene sodium sulfonate, 30mg/L of 1, 4-dioxane, 15mg/L of ethylene glycol tert-butyl ether, 15mg/L of glyoxylic acid, 45mg/L of polyethyleneimine, 45mg/L of rhodophenazine liquid polymer and the balance of pure water, wherein the pH value is 0.2, the operating temperature is 30 ℃, and the forward current density is 0.5A/dm2Reverse current density 2.0A/dm2The positive and negative pulse time ratio is 10:1ms, and the time is 50 min.
In example 3, the test results were obtained by the criteria of fig. 1: the average deep plating capacity is excellent at 95.8%, the average hole filling capacity is excellent at 96%, the hole opening is excellent without fracture, and the hole opening is bright without pits and copper nodules.
Comparative example
A pulse through hole filling electro-coppering formula comprises the following components in per liter of tank liquor:
60g/L of copper sulfate, 150-g/L of concentrated sulfuric acid, 15-45mg/L of rhodophenazine liquid polymer and the balance of pure water, wherein the pH value is 0.2, the operation temperature is 25 ℃, and the current density is 2.0A/dm2Forward current density 0.5A/dm2Reverse current of 2.0A/dm2The positive and negative pulse time ratio is 10:1ms, and the time is 50 min.
The comparative example test results, by the criteria of figure 1, are: the average deep plating capacity is 74 percent, the average hole filling capacity is 74.2 percent, the hole opening cracks are obvious, and the hollow copper nodules are obvious.
By comparing the comparative example with the examples, the comparative example lacks components such as 2-butyl-1-octanol polyoxyethylene ether, thiodiglycol polyoxyethylene ether, methylene dinaphthalene sodium sulfonate, 1, 4-dioxane, polyethyleneimine and the like; the results obtained by the embodiment are excellent deep plating capability, excellent hole filling capability, excellent uniformity and excellent orifice fracture; the solution of the invention ensures that the hole opening of the through hole cannot be broken, the deep plating capacity of the plate with the hole thickness-diameter ratio of more than 15:1 is more than 95 percent, the maximum thickness of the hole filling plate can be more than 3.5mm, and the hole filling rate is kept more than 95 percent
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 (10)
1. The electrolytic copper plating formula for filling the pulse through hole is characterized by comprising the following components in mass concentration:
60-90g/L of copper salt, 150-200g/L of concentrated sulfuric acid and 30-90mg/L of inhibitor; leveling auxiliary agent 10-30 mg/L; 1-8g/L of accelerator; 20-60mg/L of a positioning agent; 15-45mg/L of dispersant; 15-45mg/L of brightener;
the balance of pure water, the pH value is 0.2-0.5;
the operation temperature is 25-35 ℃;
the current density is 0.5-6A/dm2；
The positioning agent is formed by compounding 1, 4-dioxane, ethylene glycol tert-butyl ether and glyoxylic acid, and the mass concentration ratio of the 1, 4-dioxane, the ethylene glycol tert-butyl ether and the glyoxylic acid is 2:1: 1;
the dispersing agent is polyethyleneimine, the brightening agent is a rhodophenazine liquid polymer, and the mass concentration ratio of the brightening agent to the dispersing agent is 1:1 in use.
2. The formulation of claim 1, wherein the inhibitor is 2-butyl-1-octanol polyoxyethylene ether, the leveling aid is thiodiglycol polyoxyethylene ether 10-15mg/L, and the ratio of the mass concentration of the two in use is 3: 1.
3. The formulation of claim 1, wherein the accelerator is sodium methylenedinaphthalenesulfonate.
4. The formulation of claim 1, wherein the formulation of the copper electroplating solution is as follows:
the method comprises the following steps: firstly, adding an inhibitor with the mass concentration of 30-90mg/L and a leveling auxiliary agent with the mass concentration of 10-30mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, and adding pure water for diluting to obtain 200 ml of solution A;
step two: preparing a solution by using an accelerator with the mass concentration of 1-8g/L and a positioning agent with the mass concentration of 20-60mg/L to obtain a solution B with the volume of 200 ml;
step three: placing a dispersing agent with the mass concentration of 15-45mg/L and a brightening agent with the mass concentration of 15-45mg/L into about 50 ml of pure water, adding 75-100g/L of concentrated sulfuric acid for dissolving, cooling, adding copper salt, and adding pure water for diluting to obtain 200 ml of solution C;
step four: and mixing the solution A, the solution B and the solution C at normal temperature, and diluting to one liter to obtain the copper electroplating solution.
5. The formulation of claim 1, wherein the specific conditions of step one are: the concentrated sulfuric acid is gradually dripped under magnetic stirring when being prepared, the dripping speed is 30-50 g per minute, and the magnetic stirring speed is 50-60 r/min.
6. The formulation of claim 1, wherein the specific conditions in step three are: the concentrated sulfuric acid is gradually dripped under magnetic stirring at 70-90 g/min and 30-50 r/min, and is dissolved and treated with ultrasonic wave for 15-20 min.
7. An electroplating process of an electroplating copper formula for filling a pulse through hole is characterized by comprising the following specific steps:
step 1, removing oil from the copper plated part after 3-5min, setting the temperature between 40-50 ℃, and washing the copper plated part for three times by pure water until no foam is attached to the copper plated part;
step 2, activating the copper plated part after oil and water removal, and washing the copper plated part for three times by pure water after activation;
step 3, performing steam cleaning on the copper plated part after the activation and water washing, wherein the steam cleaning time is 30-45 s;
and 4, putting the plated part copper subjected to steam water washing into an electrolytic copper plating tank with the electrolytic copper plating formula of any one of claims 1 to 6, and performing pulse electrolytic copper plating under the irradiation of ultraviolet light until the plating is finished.
8. The plating process of the pulse through hole filling electro-coppering formulation as claimed in claim 7, wherein said step 2 is activated by activating agent with activating temperature between 50-60 ℃, activating time between 1-2min, magnetic stirring speed 30-60 rpm; the activator consists of 15mg/L silver nitrate, 50mg/L polyethylene glycol and 10mg/L EDTA-4 Nah.
9. The electroplating process of the pulse through hole filling electro-coppering formula according to claim 7, wherein the specific parameter conditions of the step 3 steam cleaning are as follows: voltage 220v, frequency 50Hz, temperature 120 ℃.
10. The plating process of the pulse through hole filled electroplated copper formula as claimed in claim 7, wherein the specific conditions of the step 4 plating are: the amplitude ratio of positive and negative current of pulse waveform is 1:4, the time ratio of positive and negative current is 10-20:1ms, and the forward current density is 0.5-1.5A/dm2Meanwhile, the local temperature rise and the micro-area stirring are realized through ultraviolet irradiation; the forward wavelength of the ultraviolet light irradiation is set to be 100-200nm, the reverse wavelength is set to be 10-50nm, the ultraviolet light scanning speed is between 200nm/s and 1cm/s, and the light beam is in the range of 200nm-1cmMoving in the inner direction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114990647A (en) * | 2022-08-01 | 2022-09-02 | 深圳市创智成功科技有限公司 | Environment-friendly through hole filling pulse copper electroplating solution and electroplating method thereof |
| CN115418686A (en) * | 2022-11-07 | 2022-12-02 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1313197A (en) * | 1970-02-12 | 1973-04-11 | Udylite Corp | Copper electrodeposition bath and method |
| US4923576A (en) * | 1988-07-06 | 1990-05-08 | Technic, Inc. | Additives for electroplating compositions and methods for their use |
| US20020112964A1 (en) * | 2000-07-12 | 2002-08-22 | Applied Materials, Inc. | Process window for gap-fill on very high aspect ratio structures using additives in low acid copper baths |
| US20030000850A1 (en) * | 2001-06-18 | 2003-01-02 | Horkans Wilma Jean | Method of controlling additives in copper plating baths |
| US20080269395A1 (en) * | 2007-04-03 | 2008-10-30 | Rohm And Haas Electronic Materials Llc | Metal plating compositions |
| DE102007040005A1 (en) * | 2007-08-23 | 2009-02-26 | Ewh Industrieanlagen Gmbh & Co. Kg | Depositing functional layers from electroplating bath, circulates zinc-nickel electrolyte between bath and regeneration unit providing ozone- and ultraviolet light treatment |
| CN101899687A (en) * | 2010-08-03 | 2010-12-01 | 济南德锡科技有限公司 | Single dye type bright acidic copper plating additive and preparation method and application thereof |
| CN102817051A (en) * | 2012-09-14 | 2012-12-12 | 中国科学院半导体研究所 | Laser pulse electroplating system |
| CN103252505A (en) * | 2013-05-21 | 2013-08-21 | 昆明理工大学 | Preparation method of silver-plated copper powder |
| CN104789999A (en) * | 2015-04-24 | 2015-07-22 | 深圳市崇辉表面技术开发有限公司 | Acid copper direct-electroplating solution for iron part |
| CN105316713A (en) * | 2015-10-26 | 2016-02-10 | 苏州福莱盈电子有限公司 | Copper electroplating dissolving solution and rapid high-depth blind hole filling process |
| CN105568326A (en) * | 2015-12-31 | 2016-05-11 | 深圳市鑫鸿顺科技有限公司 | Coppering solution special for vertical and continuous electroplating of PCB |
| US20160190007A1 (en) * | 2013-08-08 | 2016-06-30 | Shanghai Sinyang Semiconductor Materials Co., Ltd. | A method for microvia filling by copper electroplating with tsv technology for 3d copper interconnection at high aspect ratio |
| US20160194760A1 (en) * | 2013-09-25 | 2016-07-07 | Atotech Deutschland Gmbh | Method for depositing a copper seed layer onto a barrier layer and copper plating bath |
| CN106887640A (en) * | 2017-03-15 | 2017-06-23 | 苏州大学 | A kind of lithium-sulfur cell electrolyte for improving battery capacity and preparation method thereof |
| CN107268043A (en) * | 2017-07-04 | 2017-10-20 | 电子科技大学 | A kind of inhibitor and electrolytic copper plating bath that filling perforation is electroplated for copper-connection HDI |
| CN107770969A (en) * | 2017-10-31 | 2018-03-06 | 广东骏亚电子科技股份有限公司 | A kind of pcb board washes copper method |
| CN108166028A (en) * | 2017-12-20 | 2018-06-15 | 深圳市板明科技有限公司 | A kind of subtle blind hole direct current electrode position filling perforation liquid medicine |
| CN108166030A (en) * | 2017-12-20 | 2018-06-15 | 深圳市板明科技有限公司 | A kind of through-hole direct current electrode position filling perforation liquid medicine |
| CN108914171A (en) * | 2018-07-19 | 2018-11-30 | 广东工业大学 | A kind of acceleration copper deposition additive and its preparation method and application |
| CN109989079A (en) * | 2019-05-22 | 2019-07-09 | 四川海英电子科技有限公司 | A kind of technique of high aspect ratio blind hole electro-coppering filling perforation |
| CN111424296A (en) * | 2020-05-18 | 2020-07-17 | 深圳市创智成功科技有限公司 | Electroplating copper solution for filling through holes of IC carrier plate and electroplating method |
| US20200347504A1 (en) * | 2017-11-09 | 2020-11-05 | Atotech Deutschland Gmbh | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
| CN112030203A (en) * | 2020-08-28 | 2020-12-04 | 生益电子股份有限公司 | Through hole electroplating filling method and preparation method of printed circuit board |
| CN112210801A (en) * | 2019-07-09 | 2021-01-12 | 江西博泉化学有限公司 | Electroplating solution for electroplating through hole of circuit board with high aspect ratio and electroplating method thereof |
| CN112899736A (en) * | 2021-01-15 | 2021-06-04 | 深圳中科利尔科技有限公司 | PCB high-longitudinal-transverse-through-hole electro-coppering additive and preparation method thereof |
-
2022
- 2022-03-19 CN CN202210273777.XA patent/CN114351195A/en active Pending
Patent Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1313197A (en) * | 1970-02-12 | 1973-04-11 | Udylite Corp | Copper electrodeposition bath and method |
| US4923576A (en) * | 1988-07-06 | 1990-05-08 | Technic, Inc. | Additives for electroplating compositions and methods for their use |
| US20020112964A1 (en) * | 2000-07-12 | 2002-08-22 | Applied Materials, Inc. | Process window for gap-fill on very high aspect ratio structures using additives in low acid copper baths |
| US20030000850A1 (en) * | 2001-06-18 | 2003-01-02 | Horkans Wilma Jean | Method of controlling additives in copper plating baths |
| US20080269395A1 (en) * | 2007-04-03 | 2008-10-30 | Rohm And Haas Electronic Materials Llc | Metal plating compositions |
| CN101302632A (en) * | 2007-04-03 | 2008-11-12 | 罗门哈斯电子材料有限公司 | Metal plating compositions |
| DE102007040005A1 (en) * | 2007-08-23 | 2009-02-26 | Ewh Industrieanlagen Gmbh & Co. Kg | Depositing functional layers from electroplating bath, circulates zinc-nickel electrolyte between bath and regeneration unit providing ozone- and ultraviolet light treatment |
| CN101899687A (en) * | 2010-08-03 | 2010-12-01 | 济南德锡科技有限公司 | Single dye type bright acidic copper plating additive and preparation method and application thereof |
| CN102817051A (en) * | 2012-09-14 | 2012-12-12 | 中国科学院半导体研究所 | Laser pulse electroplating system |
| CN103252505A (en) * | 2013-05-21 | 2013-08-21 | 昆明理工大学 | Preparation method of silver-plated copper powder |
| US20160190007A1 (en) * | 2013-08-08 | 2016-06-30 | Shanghai Sinyang Semiconductor Materials Co., Ltd. | A method for microvia filling by copper electroplating with tsv technology for 3d copper interconnection at high aspect ratio |
| US20160194760A1 (en) * | 2013-09-25 | 2016-07-07 | Atotech Deutschland Gmbh | Method for depositing a copper seed layer onto a barrier layer and copper plating bath |
| CN104789999A (en) * | 2015-04-24 | 2015-07-22 | 深圳市崇辉表面技术开发有限公司 | Acid copper direct-electroplating solution for iron part |
| CN105316713A (en) * | 2015-10-26 | 2016-02-10 | 苏州福莱盈电子有限公司 | Copper electroplating dissolving solution and rapid high-depth blind hole filling process |
| CN105568326A (en) * | 2015-12-31 | 2016-05-11 | 深圳市鑫鸿顺科技有限公司 | Coppering solution special for vertical and continuous electroplating of PCB |
| CN106887640A (en) * | 2017-03-15 | 2017-06-23 | 苏州大学 | A kind of lithium-sulfur cell electrolyte for improving battery capacity and preparation method thereof |
| CN107268043A (en) * | 2017-07-04 | 2017-10-20 | 电子科技大学 | A kind of inhibitor and electrolytic copper plating bath that filling perforation is electroplated for copper-connection HDI |
| CN107770969A (en) * | 2017-10-31 | 2018-03-06 | 广东骏亚电子科技股份有限公司 | A kind of pcb board washes copper method |
| US20200347504A1 (en) * | 2017-11-09 | 2020-11-05 | Atotech Deutschland Gmbh | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
| CN108166028A (en) * | 2017-12-20 | 2018-06-15 | 深圳市板明科技有限公司 | A kind of subtle blind hole direct current electrode position filling perforation liquid medicine |
| CN108166030A (en) * | 2017-12-20 | 2018-06-15 | 深圳市板明科技有限公司 | A kind of through-hole direct current electrode position filling perforation liquid medicine |
| CN108914171A (en) * | 2018-07-19 | 2018-11-30 | 广东工业大学 | A kind of acceleration copper deposition additive and its preparation method and application |
| CN109989079A (en) * | 2019-05-22 | 2019-07-09 | 四川海英电子科技有限公司 | A kind of technique of high aspect ratio blind hole electro-coppering filling perforation |
| CN112210801A (en) * | 2019-07-09 | 2021-01-12 | 江西博泉化学有限公司 | Electroplating solution for electroplating through hole of circuit board with high aspect ratio and electroplating method thereof |
| CN111424296A (en) * | 2020-05-18 | 2020-07-17 | 深圳市创智成功科技有限公司 | Electroplating copper solution for filling through holes of IC carrier plate and electroplating method |
| CN112030203A (en) * | 2020-08-28 | 2020-12-04 | 生益电子股份有限公司 | Through hole electroplating filling method and preparation method of printed circuit board |
| CN112899736A (en) * | 2021-01-15 | 2021-06-04 | 深圳中科利尔科技有限公司 | PCB high-longitudinal-transverse-through-hole electro-coppering additive and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 丁飞等: "1,4-二氧六环预处理对锂电极的钝化作用", 《稀有金属材料与工程》 * |
| 杨培霞等: "《现代电化学表面处理专论》", 31 October 2016, 哈尔滨工业大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990647A (en) * | 2022-08-01 | 2022-09-02 | 深圳市创智成功科技有限公司 | Environment-friendly through hole filling pulse copper electroplating solution and electroplating method thereof |
| CN115418686A (en) * | 2022-11-07 | 2022-12-02 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
| CN115418686B (en) * | 2022-11-07 | 2023-01-10 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
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