CN110642731A - Leveling agent for blind hole full-copper electroplating, preparation method thereof and electroplating solution - Google Patents
Leveling agent for blind hole full-copper electroplating, preparation method thereof and electroplating solution Download PDFInfo
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- CN110642731A CN110642731A CN201911046805.9A CN201911046805A CN110642731A CN 110642731 A CN110642731 A CN 110642731A CN 201911046805 A CN201911046805 A CN 201911046805A CN 110642731 A CN110642731 A CN 110642731A
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- leveling agent
- tertiary amine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
The invention provides a leveling agent for blind hole full-copper filling electroplating, a preparation method thereof and electroplating liquid, wherein the leveling agent for blind hole full-copper filling electroplating is quaternary ammonium salt formed by polymerizing polyether and tertiary amine compound under an alkaline condition. The leveling agent for blind hole full copper filling electroplating can bear high current density of 4-5 ASD, can improve electrochemical deposition efficiency, reduce the occurrence of cathode hydrogen evolution, and realize strong leveling effect, and the leveling agent, the accelerator and the inhibitor can realize full copper filling electroplating through synergistic effect, and can be used for full copper filling of blind holes with the diameter of 100-150 um and the depth of 75-125 um.
Description
Technical Field
The invention relates to the technical field of applied electrochemistry, in particular to a leveling agent for blind hole full-copper electroplating, a preparation method thereof and electroplating liquid.
Background
Along with the development of moore's law, the integration degree of chips is higher and higher, and in chip packaging, the packaging function of the chips borne by a circuit board or a packaging substrate is stronger and higher, and the requirement on the reliability of the chips is higher and higher, and the full copper filling is an important requirement in the chip packaging. These package carriers achieve layer-to-layer interconnection through various holes that have been metallized. In the early stage, the hole plugging can be carried out by adopting an electric-conduction heat-conduction high polymer material due to the large aperture in the packaging carrier. However, as the integration degree increases and the aperture becomes smaller, the process of plugging the hole by using the conductive and heat conductive polymer material is more and more important. In addition, the production efficiency of the ordinary hole plugging process is very low, and the electric conduction and the heat conduction of the high polymer material cannot be comparable to those of pure metal at all.
Therefore, it is very important to develop a preparation technology which has simple process, low requirements on environment and equipment, relatively low cost and is suitable for large-area industrial production.
Electroplating hole filling is a new technology developed in the electronic industry, and is originally derived from a TSV (through silicon via) technology in a chip, but at present, the technologies have problems in the industries of circuit boards and packaging substrates, such as too low deposition rate, and generally only 1-2A/dm2If the current density is forcibly increased, problems of poor reliability such as hole wrapping and plating missing occur. The main reason for this is that the current plating additives currently available do not carry too high a current density.
To achieve higher current density in via-fill electroplating, a leveling agent is required to have a strong leveling effect, and to be capable of adsorbing in a high current density region and inhibiting the multiplication of copper ions in the high current density region. In addition, the electrochemical deposition efficiency is improved, and the generation of cathode hydrogen evolution is reduced. Leveling agents are particularly critical for achieving this.
Disclosure of Invention
In view of the above, the present invention provides a leveling agent for blind via all copper electroplating, which can carry high current density and can realize high electrodeposition rate.
The invention also provides a preparation method of the leveling agent for the blind hole full-copper electroplating.
The invention further provides electroplating solution containing the leveling agent for blind hole full-copper electroplating.
In order to solve the technical problems, the invention adopts the following technical scheme:
the leveling agent for blind hole full copper electroplating according to the embodiment of the first aspect of the invention is a quaternary ammonium salt formed by polymerizing polyether and tertiary amine compound under alkaline conditions, and has a structure shown in a formula (1):
wherein R1, R2 and R3 represent saturated or unsaturated alkyl and aryl groups with 1-10 carbon atoms.
Further, the polyether is selected from the group consisting of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, o-methylphenyl glycidyl ether, and mixtures thereof.
Further, the tertiary amine is selected from the group consisting of dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and mixtures thereof.
According to the preparation method of the leveling agent for blind hole full copper electroplating provided by the embodiment of the second aspect of the invention, the leveling agent for blind hole full copper electroplating is quaternary ammonium salt with a structure shown in a formula (1):
the preparation method comprises the following steps:
step 1, weighing polyether and aqueous hydrogen bromide, putting the polyether and aqueous hydrogen bromide into a flask of a rotary evaporator, heating the polyether and aqueous hydrogen bromide to 40-50 ℃ in a water bath, reacting to obtain an intermediate,
step 2, adding alkali into the reaction system, and adjusting the pH value to 8-10;
and 3, adding tertiary amine into the reaction system, heating to 60-80 ℃ through a water bath while rotating and stirring to obtain the quaternary ammonium salt.
Further, the polyether is selected from the group consisting of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, o-methylphenyl glycidyl ether, and mixtures thereof.
Further, the tertiary amine is selected from the group consisting of dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and mixtures thereof.
Further, in the step 1, the molar ratio of the polyether to the hydrogen bromide is 1 (1.5-3), and the reaction is carried out for 2-4 hours to obtain the intermediate.
Preferably, in the step 2, the alkali is selected from ammonia water, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
Further, the molar ratio of the polyether to the tertiary amine is 1 (1.5-3), and the water bath in the step 3 is heated to 60-80 ℃ for reaction for 3-6 hours.
Further, the method also comprises the following steps:
and 4, carrying out vacuum rotary evaporation on the reaction system, and drying solid precipitates to obtain the quaternary ammonium salt.
The plating solution according to the third aspect of the invention contains:
a base solution;
the leveling agent is the leveling agent for blind hole full copper electroplating, and the content of the leveling agent in the electroplating solution is 20-500 mg/L.
The basic solution further contains copper sulfate pentahydrate, sulfuric acid and chloride ions, wherein the concentration of the copper sulfate pentahydrate in the basic solution is 40-100 g/L, the concentration of the sulfuric acid in the basic solution is 160-240 g/L, the concentration of the chloride ions in the basic solution is 30-80 mg/L, and the content of the leveling agent in the electroplating solution is 20-500 mg/L.
Further, the plating solution further contains:
an accelerator with the content of 2-15 mg/L;
the content of the inhibitor is 200-2000 mg/L.
Further, the accelerator is selected from one or more of sodium polydithio dipropyl sulfonate (SPS), sodium 3-mercapto-1-propane sulfonate (MPS), sodium 3- (benzothiazole-2-mercapto) propane sulfonate (ZPS), sodium N, N-dimethyl-dithio carbonyl propane sulfonate (DPS) and thiourea propyl sulfate (UPS).
The inhibitor is polyethylene glycol or polyether.
Preferably, the molecular weight of the polyethylene glycol is 600-.
Preferably, the polyether is selected from tridecanol polyoxyethylene allyl ether, fatty alcohol polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether and allyl alcohol polyoxypropylene ether, and the molecular weight of the polyether is 400-20000.
Preferably, DC electroplating is used with a current density of 2-4 ASD, i.e., 2-4A/dm2。
The technical scheme of the invention at least has one of the following beneficial effects:
the leveling agent provided by the embodiment of the invention has a symmetrical molecular structure, so that the leveling agent can be adsorbed in a high current density area, namely can bear high current density, and the leveling agent molecule can bear 4-5 ASD at most;
in addition, when blind hole filling electroplating is about to finish, namely when the difference of high and low current density areas is about to disappear, the leveling agent of the embodiment of the invention adopts chain-shaped molecules, compared with cyclic molecules, the chain-shaped molecules are diffused in a solution more quickly, so that the leveling agent can be desorbed from the surface of copper as soon as possible, the content of organic impurities in the copper is reduced, the electrochemical deposition efficiency can be improved, the generation of cathodic hydrogen evolution is reduced, and the strong leveling effect is realized;
the leveling agent for blind hole full copper electroplating is applied to copper sulfate-sulfuric acid system electroplating solution, and the leveling agent, the accelerator and the inhibitor are used together to realize electroplating hole filling under the synergistic action, so that the blind hole full copper filling with the diameter of 100-150 mu m and the depth of 75-125 mu m can be realized;
in addition, the blind hole is filled with all copper by an electroplating method, the process is simple, and equipment can use a vertical hanging plating line and a vertical or horizontal continuous plating line;
and secondly, the circuit board or the packaging substrate forms a copper framework inside through full copper filling, so that the mechanical property is stable, and meanwhile, the heat conductivity of the circuit board or the packaging substrate is very good due to the copper in the circuit board or the packaging substrate, so that the circuit board or the packaging substrate is particularly suitable for occasions with high power, and the service life or the durability of the device is excellent.
Drawings
FIG. 1 is a photograph of a cut after a blind via full copper fill in an electroplating bath according to example 2 of the present invention;
FIG. 2 is a photograph of a section of a blind via according to comparative example 1 after full copper filling;
fig. 3 is a photograph of a section after the blind hole according to comparative example 2 has been filled with all copper.
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 will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. 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.
The following first describes the preparation method of the leveling agent for blind hole full copper electroplating according to the embodiment of the invention with reference to the accompanying drawings.
The leveling agent for blind hole full copper electroplating is quaternary ammonium salt with a structure shown in a formula (1):
wherein R1, R2 and R3 represent saturated or unsaturated alkyl and aryl groups with 1-10 carbon atoms.
The preparation method of the leveling agent for the blind hole full copper electroplating according to the embodiment of the invention comprises the following steps:
step 1, weighing polyether and aqueous hydrogen bromide, putting the polyether and aqueous hydrogen bromide into a flask of a rotary evaporator, heating the mixture to 40-50 ℃ through water bath, and reacting to obtain an intermediate.
Specifically, the reaction formula is shown as the following formula (2):
wherein the polyether may be selected from polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, o-methylphenyl glycidyl ether, and mixtures thereof.
In addition, the molar ratio of the polyether to the hydrogen bromide can be 1 (1.5-3), and is preferably 1:2, and the reaction time can be set to 2 to 4 hours, so as to obtain the intermediate.
And 2, adding alkali into the reaction system, and adjusting the pH value to 8-10.
The base may be selected from ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc., and among them, ammonia is preferable.
And 3, adding tertiary amine into the reaction system, heating to 60-80 ℃ through a water bath while rotating and stirring to obtain the quaternary ammonium salt.
Specifically, the reaction formula is represented by the following formula (3):
wherein R1, R2 and R3 represent saturated or unsaturated alkyl and aryl groups with 1-10 carbon atoms.
Wherein the tertiary amine may be selected from the group consisting of dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and mixtures thereof.
Wherein, the molar ratio of the polyether to the tertiary amine can be 1 (1.5-3), preferably 1:2, and the water bath in the step 3 is heated to 60-80 ℃, and the reaction time can be set to 3-6 hours.
Preferably, the preparation method of the leveling agent for blind hole full copper electroplating according to the embodiment of the invention can further comprise the following steps:
and 4, carrying out vacuum rotary evaporation on the reaction system, and drying solid precipitates to obtain the quaternary ammonium salt.
Specifically, for example: and starting vacuum, performing rotary evaporation to remove residual liquid impurities, and drying the product to obtain the quaternary ammonium salt.
Further, the product may be purified to obtain a purified quaternary ammonium salt.
The method for preparing the leveler for blind via full copper plating and the plating solution of the present invention will be described in detail with reference to the following examples.
Example 1
Weighing polyethylene glycol diglycidyl ether and aqueous hydrogen bromide (wherein the molar ratio of the polyethylene glycol diglycidyl ether to the hydrogen bromide is 1:2), putting into a flask of a rotary evaporator, heating in a water bath to 50 ℃, stirring while rotating, and reacting for 2 hours to obtain an intermediate.
Thereafter, ammonia was added to adjust the pH to 8.
And finally, adding dodecyl dimethyl tertiary amine (wherein the molar ratio of the polyethylene glycol diglycidyl ether to the dodecyl dimethyl tertiary amine is 1:2), continuously rotating and stirring, heating in a water bath to 60 ℃, and reacting for 4 hours to obtain the quaternary ammonium salt.
And (3) carrying out rotary evaporation on the reaction system, and carrying out reflux purification to obtain the refined quaternary ammonium salt.
Example 2
A plating solution was prepared using the quaternary ammonium salt obtained in example 1.
Firstly, preparing a base solution mainly comprising a mixed solution of copper sulfate pentahydrate and sulfuric acid, wherein the concentration of the copper sulfate pentahydrate in the base solution is 100g/L, the concentration of the sulfuric acid in the base solution is 200g/L, and the concentration of chloride ions in the base solution is 60 mg/L.
Thereafter, the quaternary ammonium salt obtained in example 1, sodium polydithio dipropyl sulfonate as an accelerator, and tridecanol polyoxyethylene allyl ether as an inhibitor were added to the base solution.
Wherein the concentration of the quaternary ammonium salt in the whole plating solution is 30ppm, the concentration of the accelerator in the whole plating solution is 10ppm, and the concentration of the inhibitor in the whole plating solution is 600 ppm.
And mixing uniformly to obtain the electroplating solution.
The plating test described below was performed using the obtained plating solution.
Firstly, a copper-clad plate or a packaging substrate to be electroplated and filled with holes, which is provided with blind holes (the diameter is 120 mu m, the thickness of a dielectric layer is 80 mu m) and the hole wall of which is processed by a conducting layer, is provided as a sample to be electroplated, and the thickness of initial surface copper is 5 mu m.
Then, the sample to be electroplated is subjected to conventional electroplating pretreatment processes such as spraying, rinsing, acid degreasing, hot water washing twice, cold water washing twice, micro-etching, acid leaching and the like, and then enters an electroplating process. Specifically, a layer of thin copper is deposited on the inner wall of the hole of a sample to be electroplated through chemical deposition, namely, the conductive treatment is carried out, so that the subsequent electroplating is convenient.
Thereafter, electroplating was carried out as follows:
thereafter, the pretreated sample was placed in a plating line, the current output of a rectifier was set in advance, a constant current plating mode was used, and the current density was 3ASD, i.e., 2.5A/dm2The current was adjusted so that the current was equal to the plating area multiplied by the current density, and 23 minutes after plating, the rectifier was turned off and the sample was taken out.
And finally, carrying out post-treatment on the electroplated sample, namely cold water washing, oxidation resistance, cold air blow-drying and hot air blow-drying.
Wherein, the plating bath is internally provided with a plating solution injection device to ensure the plating solution exchange rate.
The results of the full copper fill of the blind holes were examined for dicing and are shown in FIG. 1. As can be seen from FIG. 1, the electroplating bath according to the invention, owing to the leveler according to the invention, enables full copper filling without any defects in the holes.
The total thickness of the surface copper is 20 μm, the thickness of the electroplated surface copper is reduced by 5 μm, namely the thickness of the electroplated surface copper is increased by 15 μm, and the thickness of the copper in the hole is 100 μm which is the total thickness of the copper after electroplating and the thickness of the medium layer, namely 20 μm plus 80 μm, so that the deposition rate of the copper in the hole is 6.6 times of that of the copper outside the hole.
Comparative example 1
For comparison, a plating solution was prepared in the same manner as in example 2 using a commercially available dye-based leveling agent (Janus Green B, JGB).
Thereafter, the same plating process as in example 2 was employed, and the plating results are shown in fig. 2. As can be seen from fig. 2, the existence of voids, i.e., holes, in the blind hole does not meet the quality requirement. The porosity is generally due to the fact that levelers do not adapt to high current densities. In addition, there is a significant depression at the top of the hole. It is obvious that the currently commonly used JGB is not suitable for high current density via-filling electroplating.
Comparative example 2
For comparison, a plating solution was prepared in the same manner as in example 2 using a commercially available dye-based leveling agent (Janus Green B, JGB).
Thereafter, electroplating was carried out in the same manner as in example 2 except that the current density was reduced to 1.5ASD, and the result of electroplating is shown in FIG. 3. As can be seen from fig. 3, although there is no void in the hole, the blind hole is not completely filled, and there is a certain depression at the top.
The thickness of the surface copper is 23 μm, the thickness of the surface copper minus the initial surface copper is 5 μm, and the thickness of the copper added after electroplating is 18 μm; meanwhile, since the depth of the recess in the hole is about 8 μm, the thickness of the copper in the hole is increased to the thickness of the dielectric layer plus the total thickness of the copper on the surface minus the depth of the recess, i.e. 80 μm plus 23 μm minus 8 μm, i.e. 95 μm, and thus it can be known that the deposition rate of the copper ions in the hole is 5.3 times that of the copper ions outside the hole and is far lower than 6.6 times of that of embodiment 2.
As can be seen from comparison, the plating solution of example 2 of the present invention can be used at a rate of 2.0 to 4.0A/dm, since the novel quaternary ammonium salt of the present invention is used as a leveling agent2The current density of the copper-filled blind holes is used for electroplating and filling through holes with the diameter of 100-150 mu m and blind holes with the depth of 75-125 mu m, and no defect exists in the through holes.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The leveling agent for blind hole full copper electroplating is characterized by being a quaternary ammonium salt formed by polymerizing polyether and a tertiary amine compound under an alkaline condition, and having a structure shown in a formula (1):
wherein R1, R2 and R3 represent saturated or unsaturated alkyl and aryl groups with 1-10 carbon atoms.
2. The leveler for blind via all copper electroplating of claim 1, wherein the polyether is selected from the group consisting of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, o-methylphenyl glycidyl ether, and mixtures thereof.
3. The leveler for blind via all copper electroplating of claim 1, wherein the tertiary amine is selected from the group consisting of dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and mixtures thereof.
4. The preparation method of the leveling agent for the blind hole full copper electroplating is characterized in that the leveling agent for the blind hole full copper electroplating is quaternary ammonium salt with a structure shown in a formula (1):
wherein R1, R2 and R3 represent saturated or unsaturated alkyl and aryl groups with 1-10 carbon atoms,
the preparation method comprises the following steps:
step 1, weighing polyether and aqueous hydrogen bromide, putting the polyether and aqueous hydrogen bromide into a flask of a rotary evaporator, heating the mixture to 40-50 ℃ through water bath, reacting to obtain an intermediate,
step 2, adding alkali into the reaction system, and adjusting the pH value to 8-10;
and 3, adding tertiary amine into the reaction system, heating to 60-80 ℃ through a water bath while rotating and stirring to obtain the quaternary ammonium salt.
5. The method of claim 4, wherein the polyether is selected from the group consisting of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, o-methylphenyl glycidyl ether, and mixtures thereof.
6. The method of claim 4, wherein the tertiary amine is selected from the group consisting of dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and mixtures thereof.
7. The method for preparing the leveling agent for the blind hole all-copper electroplating according to claim 4, wherein in the step 1, the molar ratio of the polyether to the hydrogen bromide is 1 (1.5-3), and the intermediate is obtained after the reaction for 2-4 hours,
preferably, in the step 2, the alkali is selected from ammonia water, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
8. The method for preparing the leveling agent for the full copper electroplating of the blind holes as claimed in claim 4, wherein the molar ratio of the polyether to the tertiary amine is 1 (1.5-3), and the water bath in the step 3 is heated to 60-80 ℃ for reaction for 3-6 hours.
9. The method for preparing the leveling agent for the blind hole full copper electroplating according to claim 4, characterized by further comprising the following steps:
and 4, carrying out vacuum rotary evaporation on the reaction system, and drying solid precipitates to obtain the quaternary ammonium salt.
10. An electroplating bath, comprising:
a base solution;
the leveling agent for the blind hole full copper electroplating according to claim 1, wherein the content of the leveling agent in the electroplating solution is 20-500 mg/L.
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| CN113373482A (en) * | 2021-05-26 | 2021-09-10 | 深圳市贝加电子材料有限公司 | Pulse electro-plating additive, electroplating solution and application of electroplating solution |
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| CN114150351A (en) * | 2021-12-03 | 2022-03-08 | 武汉利之达科技股份有限公司 | High-speed copper electroplating solution and ceramic substrate pattern electroplating method thereof |
| CN114276256A (en) * | 2021-12-29 | 2022-04-05 | 安庆北化大科技园有限公司 | Polyquaternary ammonium compound and preparation method and application thereof |
| CN117026316A (en) * | 2023-07-17 | 2023-11-10 | 中山博美新材料科技有限公司 | Hole-filling copper plating solution, preparation method thereof and hole-filling copper plating method |
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| CN113423194A (en) * | 2021-04-27 | 2021-09-21 | 厦门理工学院 | Roll-to-roll copper foil blind hole filling method |
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| CN114150351A (en) * | 2021-12-03 | 2022-03-08 | 武汉利之达科技股份有限公司 | High-speed copper electroplating solution and ceramic substrate pattern electroplating method thereof |
| CN114276256A (en) * | 2021-12-29 | 2022-04-05 | 安庆北化大科技园有限公司 | Polyquaternary ammonium compound and preparation method and application thereof |
| CN117026316A (en) * | 2023-07-17 | 2023-11-10 | 中山博美新材料科技有限公司 | Hole-filling copper plating solution, preparation method thereof and hole-filling copper plating method |
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