CN115341250A - HDI board hole-filling copper plating solution composition - Google Patents
HDI board hole-filling copper plating solution composition Download PDFInfo
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- CN115341250A CN115341250A CN202211078854.2A CN202211078854A CN115341250A CN 115341250 A CN115341250 A CN 115341250A CN 202211078854 A CN202211078854 A CN 202211078854A CN 115341250 A CN115341250 A CN 115341250A
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- 238000007747 plating Methods 0.000 title claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000000080 wetting agent Substances 0.000 claims abstract description 17
- 238000005282 brightening Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 75
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 50
- 229920000570 polyether Polymers 0.000 claims description 50
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 239000002202 Polyethylene glycol Substances 0.000 claims description 38
- 229920001223 polyethylene glycol Polymers 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 30
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 18
- -1 polydithio-dipropyl Polymers 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- WCHFOOKTKZYYAE-UHFFFAOYSA-N ethoxyperoxyethane Chemical compound CCOOOCC WCHFOOKTKZYYAE-UHFFFAOYSA-N 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 33
- 230000000996 additive effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
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Classifications
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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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a HDI board hole-filling copper plating solution composition, which belongs to the technical field of electroplating and comprises a hole-filling copper plating solution base solution, a leveling agent, a brightening agent and a wetting agent.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a hole-filling copper plating solution composition for an HDI board.
Background
HDI is an abbreviation for High Density interconnect (High Density interconnect) and is a technique for producing printed circuit boards, a relatively High line Density circuit board using micro-blind buried via technology. HDI is a compact product designed specifically for small volume users. The manufacturing process of the HDI board usually needs to fill and level up the blind hole after the chemical copper plating through the way of electroplating copper, and the advantages of electroplating filling hole have: (1) facilitating the design of stacked and tray holes; (2) improving electrical performance, facilitating high frequency design; (3) to aid in heat dissipation; (4) completing the hole plugging and the electrical interconnection in one step; (5) The blind holes are filled with the electro-plated copper, so that the reliability is higher, and the conductivity is better than that of the conductive adhesive.
The hole filling and copper plating scheme in the prior art is as follows: leveling agent, brightening agent and wetting agent are added into a hole-filling copper-plating basic working solution, a blind hole with the thickness of 40-100 mu m of a blind hole dielectric layer is filled with copper at the cathode current density of 1.0-2.5ASD, the blind hole is required to be almost filled or filled until the depression value is lower than 10 mu m (the lower the better) within a certain time of electroplating, the board surface is plated with copper while the hole is filled with copper, and finally after the electroplating is finished, the hole-filling copper-plating additive with excellent performance is required to ensure that the hole-filling copper-plating efficiency is higher, the physical performance of a copper-plated layer can meet the requirement, and the deep plating capacity of the hole-filling copper-plating is excellent.
The copper plating additive for filling holes in the prior art has the following defects in the using process:
1. the hole filling efficiency is not high, so that the hole filling electroplating cost is high, the qualified hole filling rate is achieved, larger current and longer electroplating time are needed, the copper plating on the plate surface is thicker, and a large amount of unnecessary copper raw materials are consumed;
2. when hole filling electroplating is carried out, holes are formed in the board surface for through hole electroplating, and certain thinning and sharpening images can be generated at the hole openings during through hole electroplating, so that the reliability of the through holes is reduced;
3. when hole filling electroplating is carried out, the deep plating capability of the through holes on the board is low, and the reliability of the whole board is influenced
4. Occasionally, some hole filling defects are generated, which has a certain influence on the quality stability.
Disclosure of Invention
The embodiment of the invention provides a HDI board hole-filling copper plating solution composition, which is used for solving the technical problem of the hole-filling copper plating additive in the using process and comprises the following specific contents:
the invention aims to provide a HDI board pore-filling copper plating solution composition, which comprises a pore-filling copper plating solution base solution, a leveling agent, a brightening agent and a wetting agent and has the technical points that,
the leveling agent comprises 1-2% (v/v) of polyether, 0.1-0.5% (w/v) of polyethylene glycol 20000, 2-3% (v/v) of leveling aid, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite and 93-96% (v/v) of deionized water;
the brightener comprises 1-2% (v/v) of polyether, 0.1-0.5% (w/v) of polyethylene glycol 20000, 0.1-0.5% (v/v) of sodium polydithio-dipropyl sulfonate, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite and 95.5-97.9% (v/v) of deionized water;
the wetting agent comprises 12-20% (v/v) polyether, 2-5% (w/v) polyethylene glycol 20000, 0.4-0.6% (v/v) sulfuric acid, 0.4-0.6% (v/v) formaldehyde, 0.2-0.3% (w/v) chalcanthite, 73.5-85% (v/v) deionized water.
In some embodiments of the present invention, in the HDI board hole-filling copper plating solution composition, the leveling agent is prepared by:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether, polyethylene glycol 20000 and leveling aid into the reaction kettle, and stirring until completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the leveling agent.
In some embodiments of the present invention, in the HDI board hole-filling copper plating solution composition, the brightening agent is prepared by:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether, polyethylene glycol 20000 and sodium polydithio-dipropyl sulfonate into a reaction kettle, and stirring until the polyether, the polyethylene glycol 20000 and the sodium polydithio-dipropyl sulfonate are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
In some embodiments of the present invention, in the HDI board hole-filling copper plating solution composition, the wetting agent is prepared by:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether and polyethylene glycol 20000 into the reaction kettle, and stirring until completely dissolving;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
In one embodiment of the present invention, in the HDI board hole-filling copper plating solution composition, the hole-filling copper plating solution base solution includes 30 to 50g/L of sulfuric acid, 200 to 250g/L of copper sulfate, and 30 to 70ppm of chloride ions.
In an embodiment of the present invention, in the HDI board via-filling copper plating solution composition, an addition amount of the leveling agent is 15 to 25mL/L.
In some embodiments of the present invention, the brightening agent is added in an amount of 1-2mL/L in the HDI board hole-filling copper plating solution composition.
In one embodiment of the present invention, in the HDI board hole-filling copper plating solution composition, the wetting agent is added in an amount of 10 to 20mL/L.
In some embodiments of the present invention, in the HDI board hole-filling copper plating solution composition, the polyether is any one of propylene glycol block polyether, polyether F-6, polyether NPE-108, polyether NPE-105, and random polyether.
In some embodiments of the present invention, in the HDI board hole-filling copper plating solution composition, the leveling assistant is butynediol diethoxy ether.
Compared with the prior art, the HDI board hole-filling copper plating solution composition has the following beneficial effects:
the HDI board hole-filling copper plating solution composition comprises a hole-filling copper plating solution base solution (30-50 g/L of sulfuric acid, 200-250g/L of copper sulfate and 30-70ppm of chloride ions), a leveling agent (1-2% (v/v) of polyether, 0.1-0.5% (w/v) of polyethylene glycol 20000, 2-3% (v/v) of a leveling aid, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite, 93-96% (v/v) of deionized water, a brightening agent (1-2% (v/v) of polyether, a stabilizer 0.1-0.5% (w/v) of polyethylene glycol 20000, 0.1-0.5% (v/v) of sodium polydithiodipropionate, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite, 95.5-97.9% (v/v) of deionized water, and a wetting agent (12-20% (v/v) of polyether, 2-5% (w/v) of polyethylene glycol 20000, 0.4-0.6% (v/v) of sulfuric acid, 0.4-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite, 0.1-0.5% (v/v), 73.5-85% (v/v) deionized water, when VCP (vertical continuous plating) is adopted to plate copper on the HDI board blind hole substrate, the plated board has high hole filling rate, low depression value, low hole filling defect rate, high hole filling efficiency, excellent uniform plating capacity and through hole deep plating capacity, excellent ductility of the copper-plated surface, smooth and bright surface and stress-free plating layer.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a hole-filling copper plating process of an HDI board according to the present invention;
FIG. 2 is an SEM photograph of plating using the HDI board hole-filling copper plating solution of example 1 (a blind via board having a hole depth of 75 μm and a hole diameter of 110 μm);
FIG. 3 is a schematic diagram illustrating the calculation of the hole filling ratio and the dishing value;
FIG. 4 is a schematic view of a hole filling defect;
FIG. 5 is a schematic view of a plating uniformity calculation;
fig. 6 is a diagram illustrating the calculation of the depth capability TP.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical solutions provided by the embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example 1
The embodiment of the invention provides a HDI board hole-filling copper plating solution composition, which is used for solving the technical problem of the hole-filling copper plating additive in the using process and comprises the following specific contents:
a HDI board hole-filling copper plating solution composition comprises
40g/L sulfuric acid;
225g/L copper sulfate;
50ppm of chloride ion;
leveling agent of 10 mL/L: comprises 1.5% (v/v) of propylene glycol block polyether (F38), 0.3% (w/v) of polyethylene glycol 20000, 2.5% (v/v) of butynediol diethoxy ether, 0.5% (v/v) of sulfuric acid, 0.45% (v/v) of formaldehyde, 0.25% (w/v) of chalcanthite, 94.5% (v/v) of deionized water; the preparation method of the leveling agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding propylene glycol block polyether (F38), polyethylene glycol 20000 and butynediol diethoxy ether into the reaction kettle, and stirring until the propylene glycol block polyether, the polyethylene glycol 20000 and the butynediol diethoxy ether are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the leveling agent.
1.5mL/L of brightener: comprises 1.5% (v/v) of propylene glycol block polyether (F38), 0.3% (w/v) of polyethylene glycol 20000, 0.3% (v/v) of sodium polydithio-dipropyl sulfonate, 0.5% (v/v) of sulfuric acid, 0.45% (v/v) of formaldehyde, 0.25% (w/v) of chalcanthite, 96.7% (v/v) of deionized water; the preparation method of the brightener comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding propylene glycol block polyether (F38), polyethylene glycol 20000 and sodium polydithio-dipropyl sulfonate into a reaction kettle, and stirring until the materials are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
15mL/L of wetting agent: comprises 16% (v/v) propylene glycol block polyether (F38), 3.5% (w/v) polyethylene glycol 20000, 0.5% (v/v) sulfuric acid, 0.5% (v/v) formaldehyde, 0.25% (w/v) chalcanthite, and 79.25% (v/v) deionized water. The preparation method of the wetting agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding propylene glycol block polyether (F38) and polyethylene glycol 20000 into the reaction kettle, and stirring until the propylene glycol block polyether and the polyethylene glycol are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
Example 2
The embodiment of the invention provides a HDI board hole-filling copper plating solution composition, which is used for solving the technical problem of the hole-filling copper plating additive in the using process and comprises the following specific contents:
a HDI board hole-filling copper plating solution composition comprises
30g/L sulfuric acid;
200g/L of copper sulfate;
30ppm of chloride ions;
15mL/L of leveler: comprises 1% (v/v) of polyether NPE-108, 0.1% (w/v) of polyethylene glycol 20000, 2% (v/v) of butynediol diethoxy ether, 0.4% (v/v) of sulfuric acid, 0.3% (v/v) of formaldehyde, 0.2% (w/v) of chalcanthite, and 96% (v/v) of deionized water; the preparation method of the leveling agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-108, polyethylene glycol 20000 and butynediol diethoxy ether into the reaction kettle, and stirring until the mixture is completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the leveling agent.
1mL/L of brightener: comprises 1% (v/v) of polyether NPE-108, 0.1% (w/v) of polyethylene glycol 20000, 0.1% (v/v) of sodium polydithio dipropyl sulfonate, 0.4% (v/v) of sulfuric acid, 0.3% (v/v) of formaldehyde, 0.2% (w/v) of chalcanthite and 97.9% (v/v) of deionized water; the preparation method of the brightener comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-108, polyethylene glycol 20000 and sodium polydithio dipropyl sulfonate into a reaction kettle, and stirring until the mixture is completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
10mL/L of wetting agent: comprises 12% (v/v) of polyether NPE-108, 2% (w/v) of polyethylene glycol 20000, 0.4% (v/v) of sulfuric acid, 0.4% (v/v) of formaldehyde, 0.2% (w/v) of chalcanthite and 85% (v/v) of deionized water. The preparation method of the wetting agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-108 and polyethylene glycol 20000 into the reaction kettle, and stirring until completely dissolving;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
Example 3
The embodiment of the invention provides a HDI board hole-filling copper plating solution composition, which aims to solve the technical problems existing in the use process of the hole-filling copper plating additive, and the invention comprises the following specific contents:
a HDI board hole-filling copper plating solution composition comprises
50g/L sulfuric acid;
250g/L of copper sulfate;
70ppm of chloride ion;
25mL/L of leveling agent: comprises 2% (v/v) of polyether NPE-105, 0.5% (w/v) of polyethylene glycol 20000, 3% (v/v) of butynediol diethoxy ether, 0.6% (v/v) of sulfuric acid, 0.6% (v/v) of formaldehyde, 0.3% (w/v) of chalcanthite, and 93% (v/v) of deionized water; the preparation method of the leveling agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-105, polyethylene glycol 20000 and butynediol diethoxy ether into the reaction kettle, and stirring until the mixture is completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the leveling agent.
2mL/L of brightener: comprises 2% (v/v) of polyether NPE-105, 0.5% (w/v) of polyethylene glycol 20000, 0.5% (v/v) of sodium polydithio dipropyl sulfonate, 0.6% (v/v) of sulfuric acid, 0.6% (v/v) of formaldehyde, 0.3% (w/v) of chalcanthite and 95.5% (v/v) of deionized water; the preparation method of the brightener comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-105, polyethylene glycol 20000 and sodium polydithio-dipropyl sulfonate into a reaction kettle, and stirring until the materials are completely dissolved;
c. adding formaldehyde into the reaction kettle and stirring uniformly;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
20mL/L of wetting agent: comprises 20% (v/v) of polyether NPE-105, 5% (w/v) of polyethylene glycol 20000, 0.6% (v/v) of sulfuric acid, 0.6% (v/v) of formaldehyde, 0.3% (w/v) of chalcanthite, 73.5% (v/v) of deionized water; the preparation method of the wetting agent comprises the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether NPE-105 and polyethylene glycol 20000 into the reaction kettle, and stirring to dissolve completely;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
Test examples
The HDI board hole-filling copper-plating additive is replaced by a code J with a certain famous American brand additive, and a code B with a certain domestic brand additive for omnibearing performance comparison, and specific samples are prepared as follows: 25 PCB substrates drilled with holes, 5 plates of each additive are used as a test plate, the average value of each test result is taken, the plate thickness is 1.2mm, the minimum aperture of a through hole is 0.225mm, and the thickness-diameter ratio of the through hole is 5.3:1; the depth of the blind hole is 60 μm, the aperture is 100 μm, the thickness of the substrate copper is 14 μm, the size is 603mm × 518mm, the current density is 1.2ASD, the total flow of specific Cao is 50min for electroplating, and the test results are shown in the following table:
the test project industry standard requirements are as follows: the appearance is bright and smooth, and no copper particles exist; no or minimal hole-filling defects; the larger the pore filling rate is, the better the pore filling rate is; the smaller the filling hole depression value is, the better the filling hole depression value is; COV ≦ 5%: the smaller the copper thickness range, the better; the larger the TP value, the better; thermal shock reaches 3 times of non-porous copper fracture; ductility ≧ 14%, the larger the ductility, the better the physical properties, and the more excellent the additive properties.
As shown in fig. 3, the filling ratio and the dishing value are calculated by: porosity = B/a 100%; hole filling depression value (sample) = a-B.
As shown in fig. 4, the hole-filling defect has the following condition 6;
as shown in fig. 5, COV (uniformity) test mode;
as shown in fig. 6, TP (throwing power) test mode;
thermal shock: immersing the electroplated board into the yellow rice model No. \675at 288 ℃ for 10S in 292005, taking out and placing the board in the air for 10S as thermal shock, performing the cycle for 3-6 times, and making slices after testing for at least 3 times, and checking that the copper layer is not broken.
Ductility test of this test: tested according to IPC-TM-650.2.4.18.1.
As shown in FIG. 2, which is an SEM image of the copper solution composition for pore-filling copper plating of an example of a blind via board having a hole depth of 75 μm and a hole diameter of 110 μm, the HDI board was plated with copper in a thickness of 10.7 μm at a porosity of more than 95% and a dishing value of less than 3 μm.
The test examples show that the scheme of the invention greatly improves the hole-filling and copper-plating efficiency of the plating solution and enhances the performances of various aspects while ensuring the excellent physical performance of the hole-filling and copper-plating, so that the hole-filling and copper-plating process has better quality, lower cost and stronger reliability.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A HDI board hole-filling copper plating solution composition comprises a hole-filling copper plating solution base solution, a leveling agent, a brightening agent and a wetting agent,
the leveling agent comprises 1-2% (v/v) of polyether, 0.1-0.5% (w/v) of polyethylene glycol 20000, 2-3% (v/v) of leveling aid, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite and 93-96% (v/v) of deionized water;
the brightener comprises 1-2% (v/v) of polyether, 0.1-0.5% (w/v) of polyethylene glycol 20000, 0.1-0.5% (v/v) of sodium polydithio-dipropyl sulfonate, 0.4-0.6% (v/v) of sulfuric acid, 0.3-0.6% (v/v) of formaldehyde, 0.2-0.3% (w/v) of chalcanthite and 95.5-97.9% (v/v) of deionized water;
the wetting agent comprises 12-20% (v/v) polyether, 2-5% (w/v) polyethylene glycol 20000, 0.4-0.6% (v/v) sulfuric acid, 0.4-0.6% (v/v) formaldehyde, 0.2-0.3% (w/v) chalcanthite, 73.5-85% (v/v) deionized water.
2. The HDI board hole-filling copper plating solution composition according to claim 1, wherein the leveling agent is prepared by the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether, polyethylene glycol 20000 and leveling aid into the reaction kettle, and stirring until the materials are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the leveling agent.
3. An HDI board hole-filling copper plating solution composition according to claim 1, characterized in that the brightener is prepared by the method comprising the following steps:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether, polyethylene glycol 20000 and sodium polydithio-dipropyl sulfonate into a reaction kettle, and stirring until the polyether, the polyethylene glycol and the sodium polydithio-dipropyl sulfonate are completely dissolved;
c. adding formaldehyde into the reaction kettle and uniformly stirring;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
4. An HDI board hole-filling copper plating solution composition according to claim 1, characterized in that the wetting agent is prepared by the following method:
a. adding deionized water into a reaction kettle, starting stirring, slowly adding sulfuric acid, and uniformly stirring;
b. sequentially adding polyether and polyethylene glycol 20000 into the reaction kettle, and stirring until the polyether and the polyethylene glycol are completely dissolved;
c. adding formaldehyde into the reaction kettle and stirring uniformly;
d. adding chalcanthite into the reaction kettle, and stirring until the chalcanthite is completely dissolved uniformly to obtain the brightener.
5. An HDI board hole-filling copper plating solution composition as claimed in claim 1, wherein the hole-filling copper plating solution base solution comprises 30-50g/L sulfuric acid, 200-250g/L copper sulfate and 30-70ppm chloride ion.
6. An HDI board hole-filling copper plating solution composition as recited in claim 5, wherein the leveling agent is added in an amount of 15-25mL/L.
7. An HDI board hole-filling copper plating solution composition according to claim 6, wherein the brightener is added in an amount of 1-2mL/L.
8. An HDI board hole-filling copper plating solution composition as claimed in claim 7, wherein the wetting agent is added in an amount of 10-20mL/L.
9. An HDI board hole-filling copper plating solution composition as claimed in claim 1, wherein the polyether is any one of propylene glycol block polyether, polyether F-6, polyether NPE-108, polyether NPE-105 and random polyether.
10. An HDI board hole-filling copper plating solution composition according to claim 1, characterized in that the leveling aid is butynediol diethoxy ether.
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