KR101647715B1 - Nano-silver Colloidal Catalyst Composition For Electroless Cupper Plating, making method therefor, and Electroless Cupper Plating Method Using The Same - Google Patents
Nano-silver Colloidal Catalyst Composition For Electroless Cupper Plating, making method therefor, and Electroless Cupper Plating Method Using The Same Download PDFInfo
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- KR101647715B1 KR101647715B1 KR1020150189895A KR20150189895A KR101647715B1 KR 101647715 B1 KR101647715 B1 KR 101647715B1 KR 1020150189895 A KR1020150189895 A KR 1020150189895A KR 20150189895 A KR20150189895 A KR 20150189895A KR 101647715 B1 KR101647715 B1 KR 101647715B1
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- South Korea
- Prior art keywords
- catalyst
- copper plating
- nano
- electroless copper
- catalyst composition
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000007747 plating Methods 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 6
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims description 74
- 229910052802 copper Inorganic materials 0.000 claims description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 235000006708 antioxidants Nutrition 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- -1 pyridine poly carboxylic acid Chemical class 0.000 claims description 10
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000003750 conditioning effect Effects 0.000 claims description 9
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
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- 150000003839 salts Chemical class 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- USNDJVGIYZJHOD-UHFFFAOYSA-N tetrapotassium;dioxidophosphanyl phosphite Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])OP([O-])[O-] USNDJVGIYZJHOD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B01J35/0013—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemically Coating (AREA)
Abstract
The present invention relates to an Ag catalyst capable of replacing a Pd catalyst. The present invention utilizes an organic dispersion supporting material to disperse Ag into nano-sized particles and to form a colloid to form a nano-Ag colloid catalyst. Nano Ag colloids provide more than Pd catalyst activity. In addition, in the case of Ag, since there is no bridge generation, the production yield of the printed circuit board product of the fine circuit is greatly improved. The nano-Ag colloid dispersed in nano-scale and supported by the organic support material can prevent agglomeration phenomenon and is suitable for horizontal spraying equipment because the stability of liquid is high due to low oxidation and long bath life.
Description
The present invention relates to a method for producing a catalyst for electroless copper plating and an electroless copper plating method using the same. More particularly, the present invention relates to a method of preparing an Ag catalyst capable of replacing a Pd catalyst, and to a method of preparing a nano-Ag colloid catalyst using Ag as an organic dispersion supporting material.
Electroless copper plating is a technique for metallizing the surface of nonconductive materials to form a copper coating on resins, ceramics, glass, and fibers. The electroless copper plating of printed circuit board is done through several steps as follows. Of the electroless copper plating processes, the catalysts used in the catalytic process are commercially available as Pd as three types.
(1) Acid Pd / Sn colloid type
Pd is used as a catalyst by making a colloid shape using SnCl 2 . Acid Pd / Sn colloid has been used for a long time, and studies are underway to improve the activity, stability, and the consumption reduction method continuously. Relevant documents related to this are US3099608, US4120822, US4593016, US4790913, US4952286, US5071517, US5017742, US5595789, US6790334, US7858146.
(2) Alkaline Pd ion type
SnCl 2 used in the Pd / Sn colloid catalyst Instead, a Pd ++ -Complex is produced using an organic nitrogen ligand to produce a catalyst in a Pd ++ ionic state. In a related literature, US4248632 the PdCl 2, pyridine-3-Sulfonic acid, were prepared using sodium hypophosphite, in US4966786 were prepared using PdSO 4, 2-aminopyridine, sodium Borohydride, US5165971 the PdCl 2, 3- sulfopropyl-2-vinylpyridine, dimethyl formamide was used to prepare Pd ++ -complex.
(3) Acid Pd Colloidal type
Pd is combined with a water-soluble organic polymer to form a colloid and used as a catalyst. Recently, many studies have been made. Thus in a related document US4725314 was prepared using Polyvinyl Pyrrolidon, US6325910 the PdCl 2, it was prepared using the Poly (4-vinyl Pyrrolidon) Sodium Hyphoposphite, US7514476 the final compound using a PdCl 2, Polyacrylate, US0140242287A in Dichlorodiamine Palladium , Butadien-malic acid, and dimethylamine borane. In US8828131, acid Pd colloids were prepared using Catechol, PdCl 2 , and Sodium Hypophosphite.
The catalysts of the above three types of Pd type are expensive due to expensive Pd, and the catalyst process cost exceeds 60% of the total electroless copper plating process cost. In the case of the fine circuit product, due to the residual Pd on the substrate surface after the etching process There has been a need for a catalyst to replace Pd due to the problem that the bridge phenomenon between circuits is increased during electroless Ni / Au plating.
(4) Cu colloid type
Many researches have been conducted on a catalyst system using low cost metals such as Cu, Fe, Co, and Ni, and in particular, studies on Cu have been mainly conducted. However, since the activity of the catalyst is lowered and the stability is limited, there is a limit that can not be actually used. Studies on stabilizers to improve the stability of Cu colloid and studies on Cu corrosion inhibitor to prevent Cu oxidation have been carried out concurrently, but satisfactory results have not been obtained. The documents related to this are US4384893, US4327125, US4820547, US4440805, US5009965, US4273804.
(5) Ag colloid type
Recently, studies for using Ag as a catalyst have been continuing. In US 6,645,557, silver nitrate, methane sulfonic acid and triethanol amine were used, and silver sulfate, tin sulfate and potassium pyrophosphite were used in US 7166152. In US7892317, silver nitrate, linear alkylbenzene sulfonate and hydrazine were used . It was prepared by using silver nitrate, histidine and formaldehyde in US20140083860A, hesperidin, sliver p-toluene sulfonate and ascorbic acid in US20140272144A, US20150004323A Were prepared using 5.5-dimethyl hydantoin, silver nitrate and dimethylamine borane. Ag catalyst has been extensively studied. However, the Ag catalyst has not yet been developed and can not exceed the activity and stability of the Pd catalyst.
In the case of the Pd catalyst, the problem of residual Pd residue on the etched substrate surface after etching causes a failure due to a bridge phenomenon between the circuit and the circuit during electroless Ni / Au plating. In addition, since the electroless copper plating method is changed from a deepening method to a spray method using a horizontal type apparatus, Pd oxidation is generated by nozzle injection, which reduces the stability of the catalyst and shortens the bath life .
The present invention provides a method for replacing a Pd catalyst with a catalyst system using Ag, and it is an object of the present invention to provide an organic dispersion supporting material capable of forming nano-sized Ag particles to support Ag particles to form a colloid shape, Suitable stabilizers, antioxidants, catalytic activity and stability for long-term maintenance of the nano-Ag colloids provide the same catalyst as the Pd catalyst. Further, the present invention provides a catalyst free of bridge residue during electroless Ni / Au plating because no Ag residue remains in the etching process.
The present invention relates to a catalyst composition for electroless copper plating comprising a water-soluble Ag compound, a reducing agent, an antioxidant, and an organic dispersion-supporting material for supporting the water-soluble Ag compound in a nano- The supported material is a catalyst composition for electroless copper plating using a heterocyclic aromatic compound of the following formula (1).
(1)
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, -COOH, -CH 3 , -C 2 H 5 , -CH = CHCOOH, -CONH 2 , or -NH 2 , except when all of R 1 , R 2 and R 3 are hydrogen atoms)
In another embodiment of the present invention, the compound represented by the formula (1) is at least one selected from the group consisting of 3- (2-amino-3-pyridyl) acrylic acid, 3- 2-aminopyridine-4-carboxylic acid, polyalkyl pyridine mono (2-aminopyridine-4-carboxylic acid) carboxylic acid, polyalkyl pyridine polycarboxylic acid, hydroxy methyl cellulose, hydroxy ethyl cellulose, poly vinyl pyrrolidone, , Polyvinylimidazole, and the like. The present invention relates to a catalyst composition for electroless copper plating.
In another embodiment of the present invention, the water-soluble Ag compound is silver nitrate, silver acetate, silver sulfate, silver oxide, silver methane sulfate, silver cyanide silver potassium cyanide, silver perchlorate, silver tetrafluoroborate, and the like. The present invention relates to a catalyst composition for electroless copper plating.
In another embodiment of the present invention, the reducing agent is selected from the group consisting of dimethylamine borane, sodium borohydride, sodium hypophosphite, hydrazin hydrate, hydroxylamine sulfate hydroxylamine sulfate, formic acid, and formaldehyde. The present invention also relates to a catalyst composition for electroless copper plating.
In another embodiment of the present invention, the antioxidant is selected from the group consisting of citric acid, gallic acid, acetic acid, ascorbic acid, malic acid, Benzoic acid, and the like. The present invention also relates to a catalyst composition for electroless copper plating.
Another embodiment of the present invention relates to a catalyst composition for electroless copper plating, wherein the catalyst composition for electroless copper plating is a nano silver colloid catalyst composition, wherein the Ag particles have a size of 10 nm to 50 nm.
Another embodiment of the present invention is a nano silver colloid catalyst composition for electroless copper plating characterized in that the concentration of Ag is 500 ppm to 1500 ppm.
Another embodiment of the present invention is directed to a water-soluble Ag compound, an organic dispersion-supporting material for dispersing the water-soluble Ag compound in nano-scale, a first step of mixing and mixing the solvent; A second step of mixing the first step product with a reducing agent at a high temperature; A third step of mixing an antioxidant with the second-step product; Wherein the organic dispersion supporting material comprises a heterocyclic aromatic compound represented by the following formula (1): < EMI ID = 1.0 > will be.
(1)
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, -COOH, -CH 3 , -C 2 H 5 , -CH = CHCOOH, -CONH 2 , or -NH 2 , except when all of R 1 , R 2 and R 3 are hydrogen atoms)
In another embodiment of the present invention, the pH is controlled to 3 to 6 by the third step of mixing the antioxidant, and a catalyst for electroless copper plating capable of preventing the occurrence of a bridge phenomenon during electroless Ni / Au plating To a process for preparing the composition.
According to another aspect of the present invention, there is provided a method of manufacturing a printed circuit board, comprising: forming a through hole or a via hole in a printed circuit board to 50 to 100 占 퐉; A swelling step of treating the interior of the hole using one or more solvents selected from dimethyl sulfoxide, ketone, ethyl acetate and glycol ether; Removing the smear or burr formed in the through hole or the via hole using a compound containing MnO 4 - group after the bacteriostatic process; Neutralizing the through hole or the inside of the via hole; Conditioning with a compound containing a cationic or nonionic surfactant and -NH2 group after the neutralization step; After the conditioning process, one or more species selected from the group consisting of sodium persulfate, ammonium persulfate, and sodium oxymonopersulfate may be added to the through hole or the inside of the via hole and the surface of the substrate A micro-etching step of etching; A pre-dipping step of diluting the micro-etching solution with a solvent; A catalyst treatment step of treating the inside of the through hole or the inside of the via hole by using a catalyst composition for electroless copper plating; Electroless copper plating with a solution containing a Cu metal source, a complexing agent, a reducing agent, a pH adjusting agent and an organic additive after the catalyst treatment.
The nano-Ag colloid according to the present invention provides a similar effect as the Pd catalyst. The average particle size of Ag produced using the organic dispersion supporting material according to the present invention may be 10 to 50 nm on average. This is a very small size and serves to compensate for the deterioration of the catalytic activity of Ag compared to Pd, thus providing the same catalytic activity. Compared to the Pd catalyst, the amount of Ag can be increased, but it has an effect of replacing expensive Pd. In addition, using Ag particle size of 10 to 50 nm, it is excellent in dispersibility and activity as a catalyst, can maintain the stability of the catalyst for a long time, and can maintain the life of the catalyst bath, and is also suitable for horizontal type spray equipment Do. In addition, since there is no residual Ag on the surface after the printed circuit board is etched, there is an advantage that bridge failure does not occur during electroless Ni / Au plating.
The present invention relates to an Ag catalyst capable of replacing a Pd catalyst. The present invention utilizes an organic dispersion supporting material to disperse Ag into nano-sized particles and to form a colloid to form a nano-Ag colloid catalyst. Nano Ag colloids provide more than Pd catalyst activity. In addition, in the case of Ag, since there is no bridge generation, the production yield of the printed circuit board product of the fine circuit is greatly improved. The nano-Ag colloid dispersed in nano-scale and supported by the organic support material can prevent agglomeration phenomenon and is suitable for horizontal spraying because the stability of the liquid is high due to low oxidation and long life of the bath.
The present invention relates to a catalyst composition for electroless copper plating comprising a water-soluble Ag compound, a reducing agent, an antioxidant, and an organic dispersion-supporting material for supporting the water-soluble Ag compound in a nano- The supported material is a catalyst composition for electroless copper plating using a heterocyclic aromatic compound of the following formula (1). The compound represented by the formula (1) or (2) can disperse Ag in a nano-scale, and can carry out a function of supporting a Ag particle to generate a safe colloid state.
(1)
(2)
(1) or (2), R 1 , R 2 and R 3 are each independently a hydrogen atom, -COOH, -CH 3 , -C 2 H 5 , -CH = CHCOOH, -CONH 2 , or -NH 2 , except when all of R 1 , R 2 and R 3 are hydrogen atoms)
Specific examples of the amino acid include 3- (2-amino-3-pyridyl) acrylic acid, 2-aminopyridine-4-carboxylamide 2-aminopyridine-4-carboxylic acid, polyalkylpyridine mono carboxylic acid, polyalkylpyridine polycarboxylic acid, polyvinylpyrrolidone, polyvinylimidazole, and the like, which are selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone, polycarboxylic acid, hydroxy methyl cellulose, hydroxy ethyl cellulose, polyvinyl pyrrolidone, Or two or more.
Nitrogen atoms such as amino, amide, and amine have a property of easily binding to Ag nanoparticles, and the carboxyl group plays a role of keeping bound Ag particles stable. Particularly preferred are compounds represented by the following formula (3) in that Ag particles are dispersed and the ability to support Ag particles is excellent.
(3)
The water-soluble Ag compounds are silver nitrate, silver acetate, silver sulfate, silver oxide, silver methane sulfate, silver potassium cyanide, perchloric acid, silver perchlorate, silver tetrafluoroborate, and the like.
The molar ratio of the water-soluble Ag compound to the organic dispersion-supporting material may be 1: 0.5 to 1: 5. More preferably from 1: 1 to 1: 3.
The reducing agent may be selected from the group consisting of dimethylamine borane, sodium borohydride, sodium hypophosphite, hydrazin hydrate, hydroxylamine sulfate, formic acid ), Formaldehyde, and the like.
The molar ratio of the water-soluble Ag compound to the reducing agent may be from 1: 0.3 to 1: 3. More preferably from 1: 0.5 to 1: 2.
Antioxidant is selected from citric acid, gallic acid, acetic acid, ascorbic acid, malic acid, hydroxybenzoic acid, and the like. And may be one kind or two or more kinds. It is preferable to adjust the pH to 3 to 6 by adding an antioxidant. More preferably, the pH may be 4 to 5. The amount of the antioxidant may be appropriately selected in order to adjust the pH.
The catalyst composition for electroless copper plating is a nano silver colloid catalyst composition, wherein the size of the Ag particles may be 10 nm to 50 nm. And more preferably from 20 nm to 40 nm. The reason for this is that the dispersibility and activity of the catalyst are excellent within the above range, the stability of the catalyst can be maintained for a long period of time, and the life of the catalyst bath can be maintained for a long time.
The catalyst composition for electroless copper plating is a nano silver colloid catalyst composition, and the concentration of Ag may be 500 ppm to 1500 ppm. More preferably 800 ppm to 1200 ppm. In the case of the Pd catalyst, the Pd concentration is suitably in the range of 200 to 500 ppm, and in the case of the Ag catalyst, the same activity as the Pd catalyst and the same catalyst addition result in the through hole and the via hole can be obtained at the above concentration. Ag can be used 3 to 4 times as much as Pd, but it can have an effect of substituting Pd.
Since the Ag particles have a negative electric potential and the holes have a positive electric potential, the zeta potential is preferably -40 mV to -20 mV in order to be able to adhere to the hole in the range of Ag concentration of 500 ppm to 1500 ppm.
Accordingly, the present invention relates to a water-soluble Ag compound, a reducing agent, an antioxidant, and an Ag dispersion-supporting material for supporting the water-soluble Ag compound in a nano- It is excellent in ability to do.
A water-soluble Ag compound, an organic dispersion-supporting material for dispersing and supporting the water-soluble Ag compound in a nano-scale, and a solvent; A second step of mixing the first step product with a reducing agent at a high temperature; A third step of mixing an antioxidant with the second-step product; Wherein the organic dispersion-supporting material is a catalyst composition for electroless copper plating using a heterocyclic aromatic compound represented by the following formula (1) or (2) Can be prepared. Here, the step of stirring the water-soluble Ag compound, the organic dispersion supporting material and the solvent is preferably performed at room temperature.
(1)
(2)
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, -COOH, -CH 3 , -C 2 H 5 , -CH = CHCOOH, -CONH 2 , or -NH 2 , except when all of R 1 , R 2 and R 3 are hydrogen atoms)
The third step of mixing the antioxidant may control the pH to 3 to 6, more preferably 4 to 5, and prevent bridge phenomenon during electroless Ni / Au plating . As the solvent, DI water can be used. The concentration can be adjusted by adding DI water as a solvent in the second or third step.
It is possible to obtain a stable catalyst excellent in the pH range. The reaction between the water-soluble Ag compound and the organic dispersion-supporting material is carried out at room temperature, and the temperature for reducing Ag ions to Ag particles is preferably 50 ° C to 70 ° C.
The following <electroless copper plating process> represents a process for electroless copper plating. A desmearing step and a plating through hole (PTH) step. The above process will be described in detail.
Forming through holes or via holes in the printed circuit board to 50 to 100 占 퐉; A swelling step of treating the interior of the hole using one or more solvents selected from dimethyl sulfoxide, ketone, ethyl acetate and glycol ether; Removing the smear or burr formed in the through hole or the via hole by using a compound containing MnO4 group after the belling process; Neutralizing the through hole or the inside of the via hole; Conditioning with a compound containing a cationic or nonionic surfactant and -NH2 group after the neutralization step; After the conditioning process, one or more species selected from the group consisting of sodium persulfate, ammonium persulfate, and sodium oxymonopersulfate may be added to the through hole or the inside of the via hole and the surface of the substrate A micro-etching step of etching; A pre-dipping step of diluting the micro-etching solution with a solvent; A catalyst treatment step of treating the inside of the through hole or the inside of the via hole by using a catalyst composition for electroless copper plating; Electroless copper plating with a solution containing a Cu metal source, a complexing agent, a reducing agent, a pH adjusting agent and an organic additive after the catalytic treatment.
The present invention relates to an electroless copper plating for manufacturing a printed circuit board, wherein the nonconductive material used for the printed circuit board is an epoxy resin, a polyimide resin, a phenol resin, a cyanate resin, or the like, .
Before the printed circuit board is subjected to the catalytic process, a pretreatment process must be performed. Through holes or via holes are processed by a laser drilling process using a laser drill or a bit in a printed circuit board. The minimum hole size is 50 ㎛ for laser drill and 100 ㎛ (0.1 mm) for bit use.
In order to attach the catalyst to the drilled small hole, the smear or burr generated in the hole must be removed. As the swelling step, the interior of the hole is treated with a solvent, and one or two or more selected from dimethyl sulfoxide, ketone, ethyl acetate and glycol ether can be selected as the solvent. The solvent can be selected depending on the type of resin used in the printed circuit board. In the examples of the present invention, MK-600H manufactured by MK Chemtech Co., Ltd. was used.
As the desmearing step, after the briquetting step, the alkali permanganate can be used to remove and remove the smear in the hole. In the example of the present invention, MK-601D, a product of MK Chem & In the neutralization step, the hole can be neutralized after the desmearing step. In the examples of the present invention, MK-602N was used.
After the neutralization process, a conditioning process is performed, and a negative charge (-) formed on the inner wall surface of the hole is converted into a (+) charge with a cationic or nonionic surfactant to smooth the adhesion of the catalyst in the catalytic process And an amine compound can additionally be used. In the examples of the present invention, MK-CIW-2, a product of MK Chem &
The micro-etching process increases the roughness by etching the Cu region in the hole or the Cu surface of the substrate in the micro-range after the conditioning process, thereby assisting adhesion of the catalyst and enhancing the adhesion of the electroless copper plating. One or more selected from the group consisting of sodium persulfate, ammonium persulfate and sodium oxymonopersulfate may be selected. In the examples of the present invention, MKS-3000, a product of MK Chem &
The catalytic process is specifically described in the examples.
After pretreatment and catalytic treatment with the nano Ag colloid catalyst of the present invention, electroless copper plating is carried out. The amount of electroless copper plating may be composed of a Cu metal source, a complexing agent, a reducing agent, a pH adjusting agent, an organic additive, and the like. The copper ions of the plating solution are reduced and attached to the Ag catalyst by the electrons generated by the oxidation reaction of the plating solution by the reducing agent to obtain the copper thin film. Thereafter, electroless copper plating is carried out by oxidation / reduction, which is a chemical reaction by the autocatalytic reaction of Cu. Cu metal salts include CuSO 4 , or CuCl 2 EDTA, DTPA, THPED, or NTA may be used as the complexing agent. As the reducing agent, formaldehyde, hydrazine, glyoxylic acid and the like can be used. NaOH or KoH may be used as the pH adjusting agent. Organic additives include NaCN, KCN, 2.2-bipyridyl, 1.10-phenanthroline, thiourea, 2-mercaptobenzothiazole, etc. Can be used. In the embodiment of the present invention, MK-ME, a product of MK Chem &
(Example 1)
1700 mg of 3- (2-amino-3-pyridyl) acrylic acid is dissolved in 500 ml of DI water. 1600 mg of silver nitrate is dissolved in 100 ml of DI water, and silver nitrate solution is added over 2 hours with vigorous stirring using an agitator of 1000 RPM or more. After raising the temperature to 60 ° C, a solution of 600 mg of dimethylamine borane in 100 ml of DI water is added over 1 hour. About 300 ml of DI water is added to make 1000 ml. The pH is adjusted to 4 by adding ascorbic acid. 1000ppm nano Ag colloid was produced. According to a particle size analyzer (PSS, NICOMP 380 / ZLS), the average Ag particle size was 25 nm. The coupon of the printed circuit board prepared in advance is pre-processed in the order of the electroless copper plating process described above.
Here, the swelling process is MK-600 product, MK-600H, the dispensing process is MK-Chemtech product MK-601D, the neutralization process is MK-Chemtech product MK-602N and the conditioning process is MKChemec product MK CIW- Micro etch is MKE Chemtech product MKS. 3000 was used.
The pretreated test coupon is dipped in a 1000ppm nano Ag colloidal solution at room temperature for 5 minutes. Electroless copper plating was performed using a test coupon with a catalyst treatment using MK-Chem product MK-ME. The completed test coupons were backlight tested to ensure that the Ag catalyst of the nano-Ag colloid catalyst was fully adhered to complete the electroless copper plating. As a result, it was found that both the through hole and the via hole proceeded 100%.
(Example 2)
200 ml of the 1000ppm nano-Ag colloid solution prepared in Example 1 was diluted 2-fold with DI water to prepare a 500ppm nano-Ag colloid solution. Then, the same procedure as in Example 1 was carried out by using a test coupon such as pretreatment, catalytic treatment, electroless copper plating As a result of confirming the degree of adhesion of the catalyst to the catalyst by the back light test, it was confirmed that both the through hole and the via hole proceeded 100%.
(Comparative Example 1)
200 ml of the 1000ppm nano-Ag colloid solution prepared in Example 1 was diluted 4-fold with DI water to prepare a 250ppm nano-Ag colloid solution. Then, pretreated, catalyst-treated, electroless copper plating . As a result of confirming the degree of adhesion of the catalyst to the catalyst by the back light test, it was confirmed that the through hole and the via hole proceeded by about 80%. When the Ag catalyst is used at 250 ppm, there is a risk of void formation in the electroplating, which is not suitable.
(Example 3)
2-amino pyridine-4-carboxylamide is dissolved in 500 ml of DI water. 1600 mg of silver nitrate was dissolved in 100 ml of DI water, and the solution was added over a period of 2 hours with stirring using a stirring device of 1000 RPM or more. The temperature was raised to 60 ° C and a solution of 600 mg of dimethyl amine borane in 100 ml of DI water was added over 1 hour. About 300 ml of DI water is added to make 1000 ml. Acetic acid was added to adjust the pH to about 4. 1000 ppm of nano Ag colloid was produced. The average size of the nano-Ag colloids dispersed and supported by 2-amino pyridine-4-carboxylamide (PSS, NICOMP 380 / ZLS) was 45 mm. The prepared coupon was pretreated in the same manner as in Example 1, treated with the catalyst solution at 20 ° C for 5 minutes, and then subjected to electroless copper plating, and then subjected to a back light test. As a result, 100% I can confirm that it has been done.
(Example 4)
200 ml of the solution prepared in Example 3 was diluted 2 times with Di water to prepare a 500 ppm solution of nano-Ag colloid. The solution was pretreated with a test coupon in the same manner as in Example 1, and then treated with 500 ppm of a catalyst solution at 20 ° C for 5 minutes And then electroless copper plating was carried out. As a result of checking the back light test, it was confirmed that 90% of the through hole and the via hole proceeded. This is an acceptable level of use.
(Comparative Example 2)
Amino diacetic acid (1400 mg) was dissolved in DI water (500 ml), silver nitrate (1600 mg) was dissolved in DI water (100 ml), and a silver nitrate solution was added over a period of 2 hours with stirring using a stirring device of 1000 RPM or more. After raising the temperature to 60 ° C, a solution of 400 mg of sodium borohydride in 100 ml of DI water was added over 1 hour. About 300 ml of DI water was added to make 1000 ml. The pH was adjusted to about 4 with ascorbic acid, and 1000 ppm of nano Ag colloid was produced. The particle size of the nano - Ag - colloidal Ag particles dispersed and supported by the generated amino diacetic acid was determined to be 175 nm by particle size analysis (PSS, NICOMP 380 / ZLS).
Test coupons were pretreated in the same manner as in Example 1, treated with the above-mentioned 1000ppm nano-Ag colloid solution at 20 ° C for 5 minutes, and then subjected to electroless copper plating. As a result of the back light test, it was confirmed that 80% of the through hole and the via hole proceeded. This is an unavailable criterion.
(Comparative Example 3)
200 ml of the 1000 ppm solution prepared in Comparative Example 2 was diluted 2 times with DI water to prepare an Ag colloid solution of 500 ppm. The solution was pretreated with a test coupon in the same manner as in Example 1, and then subjected to a catalytic treatment with a 500 ppm Ag colloid solution ° C for 5 minutes and then electroless copper plating was performed. As a result of the back light test, it was confirmed that the through hole and the via hole proceeded by about 60%. This is an unusable level.
As shown in Table 1, when the nano-Ag particle size is 25 nm as in Examples 1, 2, 3 and 4 of the present invention, the activity of the catalyst and the degree of catalyst addition are 1000 ppm at 1000 ppm of Ag, 500 ppm of Ag, Good results are obtained. It can be confirmed that the Ag catalyst of the present invention can replace the existing Pd catalyst.
[Table 2] and [Table 3] are photographs of plating coverage and backlight test. Here, EPOXY plate (0.4T, FR-4) was used as a sample for plating coverage evaluation, and a CCL substrate (0.8T, hole diameter 200um) was used as a sample for back light test evaluation.
[Table 4] shows the Ag particle size obtained from the average particle distribution.
[Table 5] and [Table 6] show a photograph of the copper plating of the test substrate (SEM, 25,000 magnification).
1000ppm
500ppm
250ppm
-4-carboxylic amide
1000ppm
500ppm
1000ppm
500ppm
Claims (11)
Wherein the organic dispersion supporting material is a heterocyclic aromatic compound having the following formula (1):
The Pd catalyst is not used in the catalyst composition for electroless copper plating,
Wherein the Ag particle size is 20 nm to 40 nm, the Ag concentration is 500 ppm to 1500 ppm,
Wherein the Ag particles have negative electric potential and the zeta potential of the Ag particles is from -40 mV to -20 mV.
(1)
(Wherein R 1 and R 3 are hydrogen atoms and R 2 is -CONH 2 or -COOH)
The organic dispersion-supporting material may be selected from the group consisting of polyalkyl pyridine mono carboxylic acid, polyalkyl pyridine poly carboxylic acid, In the catalyst composition for copper plating,
The Pd catalyst is not used in the catalyst composition for electroless copper plating,
Wherein the Ag particle size is 20 nm to 40 nm, the Ag concentration is 500 ppm to 1500 ppm,
Wherein the Ag particles have negative electric potential and the zeta potential of the Ag particles is from -40 mV to -20 mV.
The water-soluble Ag compound may be at least one selected from the group consisting of silver nitrate, silver acetate, silver sulfate, silver oxide, silver methane sulfate, silver potassium cyanide, Silver perchlorate, and silver tetrafluoroborate. The catalyst composition for electroless copper plating according to claim 1,
The reducing agent may be selected from the group consisting of dimethylamine borane, sodium borohydride, sodium hypophosphite, hydrazin hydrate, hydroxylamine sulfate, formic acid, acid, and formaldehyde. The present invention relates to a catalyst composition for electroless copper plating,
The antioxidant may be at least one selected from the group consisting of citric acid, gallic acid, acetic acid, ascorbic acid, malic acid, and hydroxybenzoic acid. Wherein the catalyst composition is one or more selected from the group consisting of iron and iron.
A second step of mixing the first step product with a reducing agent;
A third step of mixing an antioxidant with the second-step product;
In a method for producing a catalyst composition for electroless copper plating,
Wherein the organic dispersion-supporting material is a heterocyclic aromatic compound having the following formula (1): < EMI ID =
The Pd catalyst is not used in the method for producing the catalyst composition for electroless copper plating,
Wherein the Ag particle size is 20 nm to 40 nm, the Ag concentration is 500 ppm to 1500 ppm,
Wherein the Ag particles have negative electric potential and the zeta potential of the Ag particles is from -40 mV to -20 mV.
(1)
(Wherein R 1 and R 3 are hydrogen atoms and R 2 is -CONH 2 or -COOH)
Wherein the pH is controlled to 3 to 5 by the third step of mixing the antioxidant to prevent the occurrence of a bridge phenomenon during electroless Ni / Au plating.
A swelling step of treating the interior of the hole using one or more solvents selected from dimethyl sulfoxide, ketone, ethyl acetate and glycol ether;
Removing the smear or burr formed in the through hole or the via hole by using a compound containing MnO4 group after the swelling step;
Neutralizing the through hole or the inside of the via hole;
Conditioning with a compound containing a cationic or nonionic surfactant and -NH2 group after the neutralization step;
After the conditioning process, one or more species selected from the group consisting of sodium persulfate, ammonium persulfate, and sodium oxymonopersulfate may be added to the through hole or the inside of the via hole and the surface of the substrate A micro-etching step of etching;
A pre-dipping step of diluting the micro-etching solution remaining in the through hole or the via hole with a solvent;
A catalyst treatment step of treating the inside of the through hole or the inside of the via hole using the catalyst composition for electroless copper plating according to claim 1 or 2;
After the catalyst treatment, electroless copper plating with a solution containing a Cu metal source, a complexing agent, a reducing agent, a pH adjusting agent, and an organic additive;
The method comprising the steps of:
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| CN106591907A (en) * | 2016-10-14 | 2017-04-26 | 江门崇达电路技术有限公司 | Copper plating method for PCB production process |
| CN108267412A (en) * | 2018-03-20 | 2018-07-10 | 东北大学 | The quick repeatable hexavalent chromium detecting system and method utilized |
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| KR20120066607A (en) * | 2010-12-14 | 2012-06-22 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Plating catalyst and method |
| KR20130020640A (en) * | 2011-08-17 | 2013-02-27 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Stable catalysts for electroless metallization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20120066607A (en) * | 2010-12-14 | 2012-06-22 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Plating catalyst and method |
| KR20130020640A (en) * | 2011-08-17 | 2013-02-27 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Stable catalysts for electroless metallization |
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| CN106591907A (en) * | 2016-10-14 | 2017-04-26 | 江门崇达电路技术有限公司 | Copper plating method for PCB production process |
| CN108267412A (en) * | 2018-03-20 | 2018-07-10 | 东北大学 | The quick repeatable hexavalent chromium detecting system and method utilized |
| CN108267412B (en) * | 2018-03-20 | 2020-09-29 | 东北大学 | Rapid and reusable hexavalent chromium ion detection system and method |
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