CN111876799A - Hole metallization composition suitable for back plate and hole metallization method thereof - Google Patents
Hole metallization composition suitable for back plate and hole metallization method thereof Download PDFInfo
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- CN111876799A CN111876799A CN202010654256.XA CN202010654256A CN111876799A CN 111876799 A CN111876799 A CN 111876799A CN 202010654256 A CN202010654256 A CN 202010654256A CN 111876799 A CN111876799 A CN 111876799A
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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
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/06—Filtering particles other than ions
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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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
- C25D7/00—Electroplating characterised by the article coated
Abstract
The invention relates to the field of electroplating, in particular to a composition suitable for back plate hole metallization and a hole metallization method thereof, wherein the composition comprises 30000-350000 ppm of copper ions, 5000-350000 ppm of inorganic acid and 1-10000 ppm of polymer formed by polymerizing epoxide and/or alcohol. The hole metallization composition provided by the invention can improve the thickness distribution of hole copper and surface copper, reduce material consumption, can use higher current density for reverse pulse electroplating, increase the productivity of electroplating lines, and has the advantages of fine and compact plating layer, good ductility, low internal stress and good thermal shock resistance, is particularly suitable for electroplating of through holes of printed circuit boards with high aspect ratio apertures, can improve the deep plating capability of copper plating of the through holes of the printed circuit boards with high aspect ratio apertures, and improves the production efficiency, thereby improving the copper plating quality of the printed circuit boards with high aspect ratio apertures, and ensuring the quality and reliability of products.
Description
Technical Field
The invention relates to the field of electroplating, in particular to a hole metallization composition suitable for a back plate and a hole metallization method thereof.
Background
The back board is also called a motherboard (Backplane), belongs to a high-end PCB product, and is mainly applied to communication equipment, a supercomputer, a military base station and other very important equipment. All the daughter boards or the user boards are connected through the backplane to achieve the working function thereof, so functionally, the backplane is a key core component of these devices, and not only bears the bearing function of single boards such as switching, radio frequency, power supply and the like, but also provides signal transmission for the switch station and the network device, which can be called as a "neural center" of the electronic system.
Hole metallization refers to plating a layer of copper on the inner walls of the through-hole between the top and bottom layers of the circuit board so that the top and bottom layers of the circuit board are connected to each other. Hole metallization of circuit boards is usually achieved by means of conventional dc plating. However, the back plate has the characteristics of high layer number (about 60 layers at most), overlarge size (762 mm multiplied by 1300mm at most), super thickness (4 mm-13 mm), overweight (about 20Kg of each piece), fine lines and intervals, plate thickness and aperture ratio (16: 1-20: 1) and the like, so that the technical difficulty of hole metallization processing is increased, and particularly, higher requirements on deep plating capability and copper plating reliability of holes with high thickness-diameter ratio are provided. The traditional direct current copper plating technology cannot meet the requirement of hole metallization of a circuit board with a high thickness-diameter ratio due to insufficient deep plating capacity, and particularly for the circuit board with through holes having assembly requirements, the traditional electroplating mode is difficult to meet the requirement of hole diameter tolerance.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides, in a first aspect, a hole metallization composition comprising 30000 to 350000ppm of copper ions, 5000 to 350000ppm of inorganic acids, and 1 to 10000ppm of polymers polymerized from epoxides and/or alcohols.
In a preferred embodiment of the present invention, the polymer polymerized from an epoxide and/or an alcohol comprises at least one of polypropylene glycol, polyethylene glycol, an ethylene oxide-propylene oxide copolymer, and a butanol-ethylene oxide-propylene oxide copolymer.
In a preferable embodiment of the present invention, the weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is 100 to 100000.
As a preferable technical scheme of the invention, the weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is 500-10000.
As a preferred embodiment of the present invention, the hole metallization composition further comprises 0.001ppm to 1000ppm of a brightener; the brightener includes N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propyl sulfonic acid and its corresponding salt, dithio-O-ethyl ester-S-carbonate, 3-mercapto-1-propane sulfonate, bis-sulfopropyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) propyl sulfonate, pyridinium propyl sulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, N-dimethyl-dithioformamide propane sulfonate sodium, N-dimethyl-dithiocarbamic acid ester, N-dimethyl-dithiocarbamic acid ester, 3-mercapto-ethylpropylsulfonic acid- (3-sulfoethyl) ester, 3-mercapto-ethylsulfonate, carbonic acid-dithio-O-ethyl ester-S-ester, 3-mercapto-1-ethanesulfonate, bis-sulfoethyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) ethanesulfonate, pyridinium ethylsulfobetaine, 1-sodium-3-mercaptoethane-1-sulfonate.
As a preferable technical scheme of the invention, the hole metallization composition also comprises 1-5000 ppm of leveling agent; the leveling agent is a heterocyclic compound and/or an ethylene oxide copolymer; the ethylene oxide copolymer is a polymer of a heterocyclic compound and ethylene oxide; the heterocyclic compound has the following structure:
the Xe and Rn can be the same or different and are respectively selected from hydrogen and C1～C10One or more of alkyl, alkoxy, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo group.
As a preferable technical solution of the present invention, the R is1And R2May be the same or differentIndependently selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C2～C12One or more of alkenyl, substituted or unsubstituted aryl, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo.
In a preferred embodiment of the present invention, B and Y may be the same or different and are each selected from C, N, P, O, S.
As a preferred embodiment of the present invention, the substituted aryl group is C1～C4Alkyl and/or hydroxy substituted aryl.
As a preferable embodiment of the present invention, the aryl group is any one selected from a phenyl group, a xylyl group, and a naphthyl group.
In a second aspect the present invention provides a method of hole metallisation comprising: and (3) placing the hole metallization composition on a printed circuit board with a plurality of through holes at 25-60 ℃, and plating copper by adopting a reverse pulse method for 120-225 min.
As a preferable technical solution of the present invention, the forward-reverse current density ratio of the reverse pulse method is 1: (1.5-3.5).
Compared with the prior art, the invention has the following beneficial effects:
the hole metallization composition provided by the invention can improve the thickness distribution of hole copper and surface copper, reduce material consumption, can use higher current density for reverse pulse electroplating, increase the productivity of electroplating lines, and has the advantages of fine and compact plating layer, good ductility, low internal stress and good thermal shock resistance, is particularly suitable for electroplating of through holes of printed circuit boards with high aspect ratio apertures, can improve the deep plating capability of copper plating of the through holes of the printed circuit boards with high aspect ratio apertures, and improves the production efficiency, thereby improving the copper plating quality of the printed circuit boards with high aspect ratio apertures, and ensuring the quality and reliability of products.
Drawings
FIG. 1 is a schematic cross-sectional view of a through-hole of a printed circuit board;
a1, A2, A3 and A4-the plating thickness of the copper on the surface of the through hole section of the printed circuit board; b1, B2, B3 and B4-the plating thickness of hole copper on the cross section of the through hole of the printed circuit board; c1, C2-thickness of electroplated copper in the middle of hole of through hole section of printed circuit board
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Unless otherwise explicitly stated, the following abbreviations in this specification have the following meanings:
min: the method comprises the following steps of (1) taking minutes; ms: milliseconds; um: micron size; ASD: ampere per square decimeter; ASF: amperes per square inch; AH: ampere hours; ppm: parts per million; ppb: parts per billion; DEG C: c, centigrade degree; g/L: g/l; a: ampere; dm: dividing the rice; DI: deionizing; wt%: the weight percentage is as follows; tg: glass transition temperature.
Aperture ratio of through-hole: height of via/diameter of via.
Deep plating capability: the ability to plate the same thickness in the low current density region as the higher current density region.
All amounts are in weight percent unless otherwise indicated. All numerical ranges are inclusive and combinable with each other in any order, the sum of the numerical ranges being limited to 100%.
Hole metallization: the hole metallization refers to a process of plating a layer of conductive metal on the insulated hole wall in the hole by using an electroless plating and electroplating method so as to ensure that the conductive metal is reliably communicated with each other. The core problem of the metallized hole double-sided printed board manufacturing process is the hole metallization process. The requirements of the metallized hole are strict, the metallized hole has good mechanical toughness and electrical conductivity, the metallized copper layer is uniform and complete, the thickness is 5-10 mu m, the plating layer is not allowed to have serious oxidation phenomenon, no delamination, no bubble, no drilling cutting and no crack are generated in the hole, and the hole resistance is below 1000 mu omega.
Hole copper: the hole copper is a hole with a metallization requirement, a layer of copper is plated in the hole through electroplating, two sides of the hole can be conducted, and the layer of copper in the hole is called the hole copper.
Solder resist ink: is an ink used in the welding process.
DC: and is represented by direct current. Direct Current (DC) is also called constant Current.
AC: representing an alternating current. Alternating Current (AC) means that the direction of Current changes periodically with time and is an Alternating Current.
The hole metallization composition of the present invention is an electroplating solution for hole metallization.
In a first aspect the present invention provides a pore metallising composition comprising 30000 to 350000ppm copper ions, 5000 to 350000ppm inorganic acid, 1 to 10000ppm polymer formed by polymerisation of an epoxide and/or an alcohol.
In one embodiment, the hole metallization composition further comprises 0.001ppm to 1000ppm of a brightener.
In one embodiment, the pore metallization composition further comprises from 1 to 5000ppm of a leveler.
In a preferred embodiment, the pore metallisation composition comprises 30000 to 250000ppm copper ions, 80000 to 270000ppm inorganic acid, 5 to 10000ppm polymer formed by polymerisation of epoxides and/or alcohols, 0.001 to 500ppm brightener, 1 to 5000ppm levelling agent.
In a preferred embodiment, the pore metallisation composition comprises 30000-250000 ppm copper ions, 80000-270000 ppm inorganic acid, 5-10000 ppm polymer polymerized from epoxide and/or alcohol, 0.05-10 ppm brightener, 1-5000 ppm leveler.
In a more preferred embodiment, the pore metallising composition comprises 40000ppm copper ions, 260060ppm mineral acid, 1000ppm polymer polymerised from epoxides and/or alcohols, 1ppm brightener, 20ppm leveller.
Copper ion
In one embodiment, the copper ions comprise at least one source of copper ions.
In one embodiment, the source of copper ions for the copper ions includes, but is not limited to, water-soluble halides, nitrates, acetates, sulfates of copper, and other organic or inorganic copper salts.
Examples of the copper ion source include copper sulfate, copper sulfate pentahydrate, copper chloride, copper nitrate, copper hydroxide, and copper sulfamate.
Preferably, the source of copper ions is anhydrous copper sulfate.
Inorganic acid
In one embodiment, the inorganic acid includes, but is not limited to, sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid, sulfamic acid, alkyl sulfonic acids.
Preferably, the inorganic acids are sulfuric acid and hydrochloric acid; further preferably, the concentration ratio of the sulfuric acid to the hydrochloric acid is (4300-4500): 1; more preferably, the concentration ratio of sulfuric acid to hydrochloric acid is 4333: 1.
polymers polymerized from epoxides and/or alcohols
In one embodiment, the polymer polymerized from an epoxide and/or an alcohol comprises at least one of polypropylene glycol, polyethylene glycol, ethylene oxide-propylene oxide copolymer, and butanol-ethylene oxide-propylene oxide copolymer.
In one embodiment, the weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is 100 to 100000.
Preferably, the weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is 500-10000.
Brightening agent
In one embodiment, the brighteners include, but are not limited to, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propyl sulfonic acid and its corresponding sodium salt, dithio-O-ethyl ester-S-carbonate with 3-mercapto-1-propane sulfonate, bis-sulfopropyl disulfide and its corresponding salt, 3- (benzothiazyl-S-thio) propyl sulfonate, pyridinium propyl sulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, N, sodium N-dimethyldithioformamide propane sulfonate, 3-mercapto-ethylpropyl sulfonic acid- (3-sulfoethyl) ester, 3-mercapto-ethylsulfonate, carbonic acid-dithio-O-ethyl ester-S-ester, 3-mercapto-1-ethanesulfonate, bis-sulfoethyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) ethanesulfonate, pyridinium ethylsulfobetaine, 1-sodium-3-mercaptoethane-1-sulfonate, 2-mercapto-ethanesulfonic acid and its corresponding sodium salt, 3- (benzothiazolyl-2-thio) propanesulfonic acid and its corresponding sodium salt, 3-mercaptopropane-1-sulfonic acid and its corresponding salt, sodium N-dimethyldithioformamide propane sulfonate, 3-mercapto-ethyl propyl sulfonic acid- (3-sulfoethyl) ester, 3-mercapto-ethyldisulfate, 3-mercapto-ethyl-sulfobetaine, 3, Ethylenebisthiodipropanesulfonic acid and its corresponding salts, bis (p-sulfophenyl) disulfide disodium salt, bis (ω -sulfobutyl) -disulfide disodium salt, bis (ω -sulfohydroxypropyl) -disulfide disodium salt, bis (ω -sulfopropyl) -sulfide disodium salt, methyl- (ω -sulfopropyl) -disulfide disodium salt, methyl- (ω -sulfopropyl) -trisulfide disodium salt, O-ethyl-dithiocarbonic acid-S- (ω -sulfopropyl) -ester, sylthioglycolic acid, thiophosphoric acid-O-ethyl-bis- (ω -sulfopropyl) -ester and its corresponding salts, thiophosphoric acid-tris (ω -sulfopropyl) -ester and its corresponding salts, thiophosphoric acid-bis (ω -sulfopropyl) -ester, bis (ω -sulfobutyl) -disulfide disodium salt, bis (, At least one of (3-sulfopropyl) N, N-dimethyldithiocarbamate and a salt thereof, (O-ethyldithiocarbonic acid) -S- (3-sulfopropyl) -ester and a salt thereof, 3- [ (amino-iminomethyl) -thio ] -1-propanesulfonic acid, 3- (2-benzothiazolylthio) -1-propanesulfonic acid and a salt thereof.
Preferably, the brightener includes N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propyl sulfonic acid and its corresponding salt, dithio-O-ethyl carbonate-S-ester, 3-mercapto-1-propane sulfonate, bis-sulfopropyl disulfide and its corresponding salt, 3- (benzothiazyl-S-thio) propyl sulfonate, pyridinium propyl sulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, sodium N, N-dimethyldithioformamide propane sulfonate, sodium N, N-dimethyldithiocarbamic acid, N-dimethyldithioformamide, 3-mercapto-ethylpropyl sulfonic acid- (3-sulfoethyl) ester, 3-mercapto-ethylsulfonate, carbonic acid-dithio-O-ethyl ester-S-ester, 3-mercapto-1-ethanesulfonate, bis-sulfoethyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) ethanesulfonate, pyridinium ethylsulfobetaine, 1-sodium-3-mercaptoethane-1-sulfonate; more preferably, the brightener is bis sulfopropyl disulfide and/or the corresponding salt of bis sulfopropyl disulfide.
Leveling agent
In one embodiment, the leveler is a heterocyclic compound and/or an ethylene oxide copolymer; the ethylene oxide copolymer is a polymer of a heterocyclic compound and ethylene oxide; the heterocyclic compound has the following structure:
the Xe and Rn can be the same or different and are respectively selected from hydrogen and C1～C10One or more of alkyl, alkoxy, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo group.
C1～C10Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2- (2-methyl) butyl group, a 2- (2, 3-dimethyl) butyl group, a 2- (2-methyl) pentyl group, and a neopentyl group.
In one embodiment, the R is1And R2May be the same or different and are each selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C2～C12One or more of alkenyl, substituted or unsubstituted aryl, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo.
In the present invention, substituted aryl is C1～C4Alkyl and/or hydroxy substituted aryl.
Examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a xylyl group, a hydroxytoluene group, a phenol group, a naphthyl group, a furyl group, and a phenylthio group.
Preferably, the aryl group is phenyl, xylyl or naphthyl.
Substituted or unsubstituted C1～C12The alkyl radical mayExamples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2- (2-methyl) butyl group, 2- (2, 3-dimethyl) butyl group, 2- (2-methyl) pentyl group, neopentyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, cyclopentyl group, hydroxycyclopentyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexyl group, cyclohexylmethyl group, hydroxycyclohexyl group, benzyl group, phenethyl group, naphthylmethyl group, tetrahydronaphthyl group, tetrahydronaphthylmethyl group and the like.
Substituted or unsubstituted C2～C12Examples of the alkenyl group include allyl, styryl, cyclopentenyl, cyclopentenylmethyl, cyclopentenylethyl, cyclohexenyl, cyclohexenylmethyl, and indenyl.
In one embodiment, B and Y may be the same or different and are each selected from any one of C, N, P, O, S.
The method of preparation of the ethylene oxide copolymers of the present invention can be routinely selected by those skilled in the art.
In a second aspect the present invention provides a method of hole metallisation comprising: and (3) placing the hole metallization composition on a printed circuit board with a plurality of through holes at 25-60 ℃, and plating copper by adopting a reverse pulse method.
In one embodiment, the hole metallization method comprises the steps of placing the hole metallization composition on a printed circuit board with a plurality of through holes for 20-200 min at 25-60 ℃, and carrying out copper plating by adopting a reverse pulse method, wherein the plating time is 120-225 min.
Preferably, the hole metallization method comprises the steps of placing the hole metallization composition on a printed circuit board with a plurality of through holes for 150min at 25-40 ℃, and plating copper by adopting a reverse pulse method.
In one embodiment, the reverse pulse has a positive-to-negative current density ratio of 1: (1.5-3.5).
In one embodiment, the power supply reverse current time of the reverse pulse is 0.5-1.5 s; preferably, the power supply reverse current time of the reverse pulse is 1 s.
The method of placing the hole-metallizing composition on the printed circuit board having a plurality of through-holes in the present invention is not particularly limited, and there may be exemplified a method of immersing or immersing the printed circuit board in the hole-metallizing composition, spraying the hole-metallizing composition onto the printed circuit board, and placing the hole-metallizing composition on the printed circuit board by means of a sprayer.
In one embodiment, the printed circuit board is plated with an electroless copper layer such that the electroless copper layer is adjacent to the surface of the printed circuit board and the walls of the through hole.
Preferably, the thickness of the electroless plating layer is 0.25-6 um; more preferably, the thickness of the electroless plating layer is 0.25 to 3 um.
In one embodiment, the electroless plating is further plated with an electroplating layer.
Preferably, the thickness of the electroplated copper layer on the electroless copper plating layer is 0.5-15 um; further preferably, the thickness of the electroplated copper layer on the electroless copper layer is 1-10 um; more preferably, the thickness of the electroplated copper layer on the electroless copper layer is 1-5 um.
In one embodiment, the thickness of the printed circuit board is 0.5-10 mm.
In one embodiment, the through-hole passes through the width of the printed circuit board.
Preferably, the length of the through hole is 2-6 mm.
Preferably, the diameter of the through hole is 100-1000 um; more preferably, the diameter of the through hole is 100-500 um.
In one embodiment, the material of the printed circuit board includes at least one of a thermosetting resin, a thermoplastic resin, and a fiber.
Thermoplastic resins include, but are not limited to, acetal resins, acrylic resins, cellulosic resins, polyethers, nylons, polyethylenes, polystyrenes, styrene blends, polycarbonates, polychlorotrifluoroethylene, vinyl polymers.
Examples of the cellulose resin include cellulose propionate, cellulose acetate butyrate, and cellulose nitrate.
Examples of the styrene blend include an acrylonitrile-styrene copolymer and an acrylonitrile-butadiene-styrene copolymer.
Examples of the vinyl polymer include vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride-acetate copolymer, vinylidene chloride, and vinyl formaldehyde.
Thermosetting resins include, but are not limited to, allyl phthalate, furan, melamine-formaldehyde, phenol-formaldehyde copolymers, phenol-furfural copolymers.
In one embodiment, the thermosetting resin further comprises at least one of butadiene acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyacrylate, silicone, urea-formaldehyde, epoxy resin, allyl resin, glyceryl phthalate, polyester.
In one embodiment, the material of the printed circuit board includes a low Tg resin or a high Tg resin.
Low Tg resin: a resin having a Tg of less than 160 ℃.
High Tg resin: resins with a Tg higher than 160 ℃.
High Tg resins include, but are not limited to, polytetrafluoroethylene blends, epoxy resins, bismaleimide/triazine, epoxy resins, epoxy/polyphenylene oxide resins, acrylonitrile butadiene styrene, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyamide, polyester, polyether ketone, liquid crystal polymers, polyurethane, polyetherimide.
The polytetrafluoroethylene blends include, but are not limited to, PTFE, polyphenylene oxide, and cyanate esters.
The polyester includes, but is not limited to, polyethylene terephthalate, polybutylene terephthalate.
The electroplating process of the present invention is a routine choice for one skilled in the art.
The solvent for the metallization composition of the present invention is deionized water.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
Example 1 of the present invention provides a hole metallization composition comprising copper ions, a mineral acid, a polymer polymerized from an epoxide and/or an alcohol, a leveler, a brightener.
The copper ion source is copper sulfate pentahydrate; the inorganic acid is sulfuric acid and hydrochloric acid, the polymer polymerized by epoxide and/or alcohol is ethylene oxide-propylene oxide copolymer which is purchased from Pasteur and has the trade mark of Pluronic RPE 2520; the levelling agents were carboxypyridine/ethylene oxide copolymer, 100mmol of 1, 4-butanediol diglycidyl ether, 25mmol of carboxypyridine, added to a round-bottomed reaction flask at room temperature, followed by 30ml of deionized water in the flask, and carboxypyridine/ethylene oxide copolymer, the initially formed white suspension eventually disappeared with increasing reaction temperature and turned into a phase separated mixture. The resulting reaction mixture was heated for 2 hours using an oil bath set at 98 ℃. After 2ml of concentrated sulfuric acid was added to the reaction flask, the solution became transparent and pale yellow. The mixture was heated for a further 3 hours and stirred at room temperature for a further 8 hours, and the amber-colored reaction product obtained was transferred into a volumetric flask, washed with 0.5% by weight of sulfuric acid and diluted. The reaction product solution was used without further purification; the CAS number of the carboxypyridine is 59-67-6, namely 3-pyridinecarboxylic acid; the brightener is bis-sulfopropyl disulfide and sodium salt thereof and N, N-dimethyl-dithioformamide propane sodium sulfonate, and the bis-sulfopropyl disulfide and the sodium salt thereof are purchased from Jiangsu Mengde and Shenzhen proud new source.
The preparation method of the carboxypyrrole/ethylene oxide copolymer is the same as that of a carboxypyridine/ethylene oxide copolymer in the specific embodiment, except that the carboxypyridine is replaced by the carboxypyrrole, and the CAS number of the carboxypyrrole is 1898-66-4.
The concentration composition of the pore metal composition is as follows:
the hole metallization method comprises: the hole metallization composition was placed on a printed circuit board having a plurality of through holes at 25 c and copper plated using a reverse pulse method.
The electroplating steps are as follows:
1. liquid medicine addition
a. 2/3 volumes of DI water were added;
b. starting a circulation, filtration and temperature control system;
c. slowly adding sulfuric acid, wherein the sulfuric acid is heated and needs to be added for several times, and the temperature in the bath cannot exceed 50 ℃;
d. adding copper sulfate;
e. hanging the titanium basket which is sleeved with the titanium basket bag and filled with the copper balls;
f. supplementing water level, analyzing and adjusting sulfuric acid, copper sulfate and chloride ions, and then starting to drag the cylinder;
g. a carbon core is filled in the filter barrel to filter liquid medicine, so that organic pollutants are removed;
h. current density 5ASF cylinder dragging for 2 hours;
i. current density 10ASF cylinder dragging for 2 hours;
j. after the cylinder dragging is finished, confirming the tank liquor pollutants by using a Hull cell sheet;
hull cell sheets were electrolyzed at 2 amps for 5 minutes with no light to remove. If it is bright, electrolysis and carbon core filtration are needed to be continued.
2. Copper ball treatment
a, soaking copper balls for 1.5 hours by using AR-grade sulfuric acid with the concentration of 4% V/V and hydrogen peroxide with the concentration of 2.5% V/V;
b. draining off acid solution, and washing with DI water.
3. Additive hole metallization composition and mop cylinder
a. Sequentially adding the corresponding amount of each component of the pore metallization composition;
b. d, direct-current cylinder dragging:
5ASF for 2 hours;
dragging for 2 hours by 10 ASF;
15ASF for 2 hours;
20ASF for 2 hours, and pulse the cylinder after the direct current cylinder dragging is finished
c. Pulse cylinder dragging step:
(1) parameter of cylinder
Forward current density: 20 ASF;
reverse current density: 52 ASF;
positive and negative time ratio: 20 ms: 1 ms;
cylinder dragging time: 2 hours
(2) Parameter of cylinder
Forward current density: 25 ASF;
reverse current density: 65 ASF;
positive and negative time ratio: 20 ms: 1 ms;
cylinder dragging time: continuously dragging the cylinder to 12 AH/L;
after the cylinder dragging is finished, the test production can be carried out.
The plating conditions were as follows:
working temperature: 25 ℃; the positive current density is 5-40 ASF, the reverse current density is 10-120 ASF, the positive current time is 10-200 ms, the reverse current time is 0.5-30 ms, and the anode is a phosphor-copper ball or a phosphor-copper corner (containing 0.03-0.06 wt% of phosphor) containing 99.9% of copper. The area ratio of the cathode to the anode is 1: 2; the stirring mode is air stirring (a low-pressure oil-free blower is adopted and passes through an oil-water separation device and a filtering device) and cathode moving stirring; the filtration mode is continuous filtration with 5-10 μm cotton core.
The present embodiment is directed at different forward pulse current densities, and the forward pulse current is experimentally designed as follows: 8ASF, 10ASF, 12ASF and 15ASF, and the ratio of positive pulse current to reverse pulse current is 1:2, the forward pulse time is 100ms, the forward/reverse pulse time ratio is 100:5, the electroplating time is 120-225 min, and the specific experimental conditions are as follows:
and (3) carrying out plating solution maintenance in the electroplating process:
1. the plating solution lost due to evaporation can be supplemented by deionized water;
2. periodically analyzing the copper sulfate content, the sulfuric acid content and the chloride content;
3. adjusting the additive according to the hercules test;
4. in normal production, 0.8g of brightener is added for every 1000AH operation.
The printed circuit board conditions were as follows:
| plate item | Range of |
| Plate material | FR4-S1000 |
| Thickness of plate | 4～10mm |
| Minimum pore diameter | 0.35～0.45mm |
| Thickness to diameter ratio | 12～15 |
Example 2
Example 2 of the present invention provides a hole metallization composition comprising copper ions, mineral acid, polymer polymerized from epoxide and/or alcohol, leveler, brightener.
The copper ion source is copper sulfate pentahydrate; the inorganic acid is sulfuric acid and hydrochloric acid, the polymer polymerized by epoxide and/or alcohol is ethylene oxide-propylene oxide copolymer which is purchased from Sanyo chemical and has the mark of 50 HB; the leveling agent is an aminopyrrole-ethylene oxide copolymer, purchased from Shenzhen proud new source and has the brand name of VMF; the brightener was disulfopropyl disulfide and its sodium salt, purchased from Jiangsu dream.
The concentration composition of the pore metal composition is as follows:
| components | Content (wt.) |
| Blue vitriod | 40000ppm |
| Sulfuric acid | 260000ppm |
| Hydrochloric acid | 60ppm |
| Ethylene oxide-propylene oxide copolymer | 1000ppm |
| Aminopyrrole-ethylene oxide copolymers | 20ppm |
| Disulfopropyl disulfide and its sodium salt | 1ppm |
The specific implementation of the hole metallization method is the same as that in example 1, except that the reverse pulse method has the following specific operating parameters:
example 3
Example 3 of the present invention provides a hole metallising composition as in examples 2 to 3, except that the polymer polymerised from an epoxide and/or an alcohol is a butanol-ethylene oxide-propylene oxide copolymer having a weight average molecular weight of 200, available from basf.
Example 4
Example 4 of the present invention provides a hole metallization composition in accordance with the specific embodiment of examples 2-3, except that the polymer polymerized from epoxides and/or alcohols is a butanol-ethylene oxide-propylene oxide copolymer having a weight average molecular weight of 500, available from Sanyo chemical.
Example 5
Example 5 of the present invention provides a hole metallization composition, which is similar to examples 2-3, except that the polymer polymerized from an epoxide and/or an alcohol is a butanol-ethylene oxide-propylene oxide copolymer having a weight average molecular weight of 100000, which is commercially available from the ancient field chemical industry.
Example 6
Example 6 of the present invention provides a hole metallization composition, which is similar to examples 2-3, except that the polymer polymerized from an epoxide and/or an alcohol is a butanol-ethylene oxide-propylene oxide copolymer, which has a weight average molecular weight of 10000 and is commercially available from ancient field chemical industry.
Example 7
Example 7 of the present invention provides a hole metallising composition as in examples 2 to 3 except that the brightener is sodium N, N-dimethyldithioformamide propane sulphonate.
The method of hole metallization is as described in examples 2-3.
Example 8
Example 8 of the present invention provides a hole metallization composition, which is substantially the same as examples 2-3, except that the leveling agent is thiazoline-based sodium dithiopropane sulfonate, available from new wuhanelon materials ltd, under the designation SH 110.
The method of hole metallization is as described in examples 2-3.
Example 9
Example 9 of the present invention provides a pore metallising composition as in examples 2 to 3 except that the levelling agent is a 2-imidazolidinethione.
The method of hole metallization is as described in examples 2-3.
Performance evaluation
Fig. 1 is a schematic cross-sectional view of a printed circuit board through hole, wherein a1, a2, A3 and a4 represent the plating thickness of copper on the surface of the through hole cross-section of the printed circuit board, B1, B2, B3 and B4 represent the plating thickness of copper on the hole cross-section of the printed circuit board through hole, and C1 and C2 represent the plating thickness of copper in the middle of the hole of the through hole cross-section of the printed circuit board.
1. Average throwing power TPAvg
Average throwing power ═ [ (B1+ B2+ B3+ B4+ C1+ C2)/6 ]. 100%/[ (A1+ A2+ A3+ A4)/4]
2. Minimum throwing power TPmin
Minimum throwing power ═ C1+ C2)/2] × 100%/[ (a1+ a2+ A3+ a4)/4]
TABLE 1
| Examples | Average throwing power (%) | Minimum throwing power (%) |
| Examples 1 to 1 | 104.88 | 101.63 |
| Examples 1 to 2 | 102.32 | 109.05 |
| Examples 1 to 3 | 88.03 | 78.32 |
| Examples 1 to 4 | 90.43 | 81.64 |
| Example 2-1 | 82.08 | 73.53 |
| Examples 2 to 2 | 107.95 | 92.89 |
| Examples 2 to 3 | 115.82 | 110.68 |
| Examples 2 to 4 | 85.38 | 76.71 |
| Example 3 | 92.11 | 88.34 |
| Example 4 | 97.46 | 91.11 |
| Example 5 | 88.32 | 78.43 |
| Example 6 | 102.22 | 98.01 |
| Example 7 | 107.2 | 100.15 |
| Example 8 | 85.31 | 76.93 |
| Example 9 | 75.32 | 64.87 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A hole metallization composition is characterized by comprising 30000-350000 ppm of copper ions, 5000-350000 ppm of inorganic acid and 1-10000 ppm of polymer polymerized by epoxide and/or alcohol.
2. The hole metallization composition of claim 1 wherein the polymer polymerized from an epoxide and/or an alcohol comprises at least one of polypropylene glycol, polyethylene glycol, ethylene oxide-propylene oxide copolymer, butanol-ethylene oxide-propylene oxide copolymer.
3. The hole metallization composition of claim 2, wherein the weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is 100 to 100000.
4. The hole metallization composition of claim 3 wherein the butanol-ethylene oxide-propylene oxide copolymer has a weight average molecular weight of 500 to 10000.
5. The hole metallization composition of claim 1, further comprising 0.001ppm to 1000ppm of a brightener; the brightener includes N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propyl sulfonic acid and its corresponding salt, dithio-O-ethyl ester-S-carbonate, 3-mercapto-1-propane sulfonate, bis-sulfopropyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) propyl sulfonate, pyridinium propyl sulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, N-dimethyl-dithioformamide propane sulfonate sodium, N-dimethyl-dithiocarbamic acid ester, N-dimethyl-dithiocarbamic acid ester, 3-mercapto-ethylpropylsulfonic acid- (3-sulfoethyl) ester, 3-mercapto-ethylsulfonate, carbonic acid-dithio-O-ethyl ester-S-ester, 3-mercapto-1-ethanesulfonate, bis-sulfoethyl disulfide and its corresponding salt, 3- (benzothiazolyl-S-thio) ethanesulfonate, pyridinium ethylsulfobetaine, 1-sodium-3-mercaptoethane-1-sulfonate.
6. The hole metallization composition of any one of claims 1 to 5, further comprising 1 to 5000ppm of a leveler; the leveling agent is a heterocyclic compound and/or an ethylene oxide copolymer; the ethylene oxide copolymer is a polymer of a heterocyclic compound and ethylene oxide; the heterocyclic compound has the following structure:
the Xe and Rn can be the same or different and are respectively selected from hydrogen and C1～C10One or more of alkyl, alkoxy, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo group; the R is1And R2May be the same or different and are each selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C2～C12One or more of alkenyl, substituted or unsubstituted aryl, cyano, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl and azo; the B and the Y may be the same or different and are each selected from C, N, P, O, S.
7. The hole metallization composition of claim 6, wherein the substituted aryl group is C1～C4Alkyl and/or hydroxy substituted aryl.
8. The hole metallization composition of claim 7, wherein the aryl group is selected from any of phenyl, xylyl, and naphthyl.
9. A method of hole metallization, comprising: placing the hole metallization composition on a printed circuit board with a plurality of through holes at 25-60 ℃, and plating copper by adopting a reverse pulse method, wherein the plating time is 120-225 min; the pore metallising composition is as claimed in any one of claims 1 to 8.
10. The hole metallization method of claim 9, wherein the reverse pulse method has a forward to reverse current density ratio of 1: (1.5-3.5).
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| CN113463074A (en) * | 2021-06-03 | 2021-10-01 | 广东硕成科技有限公司 | Copper deposition composition and copper deposition method |
| CN113881983A (en) * | 2021-10-19 | 2022-01-04 | 广州市慧科高新材料科技有限公司 | Through hole pulse electroplating liquid and through hole pulse electroplating coating method |
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