CN115537885A - Hole filling conductive liquid and application thereof - Google Patents
Hole filling conductive liquid and application thereof Download PDFInfo
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- CN115537885A CN115537885A CN202211295404.9A CN202211295404A CN115537885A CN 115537885 A CN115537885 A CN 115537885A CN 202211295404 A CN202211295404 A CN 202211295404A CN 115537885 A CN115537885 A CN 115537885A
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- hole
- conductive liquid
- filling
- filling conductive
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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
- C25D7/00—Electroplating characterised by the article coated
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a hole filling conductive liquid and application thereof, wherein the hole filling conductive liquid comprises an electroplating additive shown in a formula I and a base liquid. The hole filling conductive liquid has excellent performance in blind hole filling, and is particularly characterized by thin copper on the surface after filling, small diameter value and excellent long-term use stability.
Description
Technical Field
The invention relates to the technical field of electroplating liquid, in particular to hole filling conductive liquid and application thereof.
Background
In recent years, the method of filling blind holes by electroplating has been widely applied to the production of printed circuit board substrates in electronic devices such as personal wear, mobile phones, flat panel lamps. The copper electroplating solution requires the addition of many organic additives to enable control of the appearance and functional characteristics of the electroplated layer, especially the addition of a carrier, leveler and accelerator to the electroplating solution, which have corresponding effects, and by formulating different kinds or proportions of additives to enable deposition of copper on the surface of the circuit board or on specific structures such as blind vias, through-holes, X-type through-holes or tapered through-holes, etc. during electroplating.
CN114232041A discloses a high depth-diameter ratio blind hole filling electroplating solution and a preparation method thereof, wherein the electroplating solution comprises the following components in parts by mass: 165-210 g/L of copper salt, 70-125 g/L of sulfuric acid, 20-60 mg/L of potassium chloride, 2.0-5.0 g/L of complexing agent, 50-200 mg/L of accelerator JL-1 and 10-50 mg/L of Janus green B. The accelerator JL-1 is a compound accelerator comprising 2-S-thiourea sodium propanesulfonate, polyethylene glycol and chitosan. The electroplating solution disclosed by the invention can be used for electroplating blind holes of circuit boards, and has good stability; the method has strong deep plating capability and the hole filling rate is more than 95 percent; the preparation process has high production efficiency, is suitable for industrial production, and can play an important role in the industries of printed circuit boards, integrated circuits, semiconductors and the like.
However, it is difficult to uniformly deposit copper in the filling of the tiny blind holes, and because the aperture of the blind holes is small, the diffusion of metal ions and common organic additives is greatly limited, so that the electroplated structure is usually abnormal, such as a large depression value (Dmiple) and a large gap (core-spun) in the blind holes, which results in the rejection of the whole circuit board. Some additives can exhibit good pore filling ability at the beginning of application, but the electrolytic copper plating solution is unstable with time, for example, filling ability becomes weak during electroplating, and copper nodules, surface roughness, and discoloration occur. In addition, the ability to reliably withstand subsequent thermal shock also deteriorates.
US5972192a discloses a method by which electroplated copper can reliably fill openings in dielectric layers, particularly high aspect ratio openings for contacts, vias and/or trenches. A plating solution is employed that includes a leveler and optionally a brightener. The leveling agent may be selected from the group consisting of polyethyleneimine, polyglycine acid, 2-amino-1-propanesulfonic acid, 4-aminotoluene-2-sulfonic acid, and other compounds. A suitable brightener may be 2,5-dimercapto-1,3,4-thiodiazole.
In summary, it is important to develop more hole-filling conductive liquids that can be used for filling minute blind holes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the hole filling conductive liquid and the application thereof, the hole filling conductive liquid can be used for electroplating tiny blind holes, and the hole filling conductive liquid has excellent performance in blind hole filling, and is particularly characterized in that the filled blind holes are small in pore space, small in diameter value and excellent in long-term use stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a hole-filling conductive liquid, which comprises an electroplating additive shown in a formula I and a base liquid;
Z-R-(CH 2 ) n -R-Z is of formula i;
wherein n is an integer of 1 to 5, such as 2, 3,4, etc.;
r is selected from S or CH 2 ；
Z is selected from- ((C) 2 H 4 O) a -(C 3 H 6 O) b -A-CH 2 -M) y ；
a and b are each independently an integer from 1 to 10, such as 2, 3,4, 5, 6, 7, 8, 9, etc.;
a is selected from NH or CH 2 ；
y is an integer from 1 to 3, such as 1, 2, 3;
m is selected from-CH 2 -CHOH-CH 2 -NH-CH＝CH 2 or-CH 2 -CHOH-CH 2 -NH-CH-CH 3 。
In the invention, the electroplating additive contains ether bond, vinyl and amino, the formed electroplating solution has stable quality, and can reduce the surface tension of the hole filling conductive liquid and promote solution exchange in the process of electroplating the micro blind holes, and simultaneously can inhibit/adsorb a surface area and inhibit the growth of a copper surface, so that the blind holes are well filled.
Preferably, the electroplating additive comprises any one of formula I-1 to formula I-4 or a combination of at least two of the same;
in formulas I-1-I-4, a and b are each independently an integer from 1 to 10 (e.g., 2, 3,4, 5, 6, 7, 8, 9, etc.), and y is each independently an integer from 1 to 3 (e.g., 1, 2, 3).
Preferably, the concentration of the plating additive in the electrolyte is 1-1000mg/L, such as 10mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L, and the like.
Preferably, the auxiliaries include wetting agents and brighteners.
Preferably, the wetting agent comprises any one of polyethylene glycol, polypropylene glycol or polyethylene glycol methyl ether or a combination of at least two thereof; combinations of polyethylene glycol and polypropylene glycol, polypropylene glycol and polyethylene glycol methyl ether, polyethylene glycol, polypropylene glycol and polyethylene glycol methyl ether, and the like.
Preferably, in the hole filling conductive liquid, the concentration of the wetting agent is 10-10000mg/L, such as 100mg/L, 500mg/L, 1000mg/L, 2000mg/L, 4000mg/L, 6000mg/L, 8000mg/L, and the like.
Preferably, the brightener comprises SPS.
Preferably, the concentration of the brightening agent in the hole-filling conductive liquid is 0.1-10mg/L, such as 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L, 8mg/L, 9mg/L, and the like.
Preferably, the base liquid comprises a combination of hydrogen ions, copper ions and halogen ions
In a second aspect, the present invention provides a use of the conductive liquid for filling holes in the first aspect in blind hole filling.
Preferably, the blind holes have a diameter of 50-200 μm, such as 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, and the like.
Preferably, the blind holes have a depth of 20-200 μm, such as 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the hole filling conductive liquid has excellent performance in blind hole filling, and is characterized in that the surface copper after filling is thin, the diameter value is within 9 mu m, the diameter value is small, the diameter value is within 4 mu m, the diameter value is still within 5 mu m when the stable electric quantity is accumulated to 200AH/L after long-term use, and the long-term use stability is excellent and can reach more than 1 year.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-1,a =1,b =1,n =2,y = 3) 500mg/L
Wetting agent (polyethylene glycol 8000) 500mg/L
Brightener (SPS) 2mg/L
Base solution (copper ion: 50g/L, sulfuric acid: 50g/L, chloride ion: 60 mg/L).
Example 2
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-2,a =5,b =5,n =3,y = 2) 500mg/L
Wetting agent (polyethylene glycol 8000) 600mg/L
Brightener (SPS) 2mg/L
Base solution (copper ion: 60g/L, sulfuric acid: 40g/L, chloride ion: 50 mg/L).
Example 3
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-3,a =7,b =7,n =2,y = 2) 500mg/L
Wetting agent (polyethylene glycol 8000) 300mg/L
Brightener (SPS) 1mg/L
Base solution (copper ion: 45g/L, sulfuric acid: 60g/L, chloride ion: 40 mg/L).
Example 4
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-4,a =2,b =2,n =2,y = 1) 500mg/L
Wetting agent (polyethylene glycol 8000) 700mg/L
Brightener (SPS) 2mg/L
Base solution (copper ion: 40g/L, sulfuric acid: 40g/L, chloride ion: 50 mg/L).
Example 5
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-1,a =8,b =7,n =1,y = 1) 10mg/L
Wetting agent (polyethylene glycol 8000) 600mg/L
Brightener (SPS) 2mg/L
Base solution (copper ion: 60g/L, sulfuric acid: 40g/L, chloride ion: 55 mg/L).
Example 6
The embodiment provides a hole-filling conductive liquid, which is composed of the following components:
electroplating additive (formula 1-4,a =2,b =4,n =3,y = 3) 1000mg/L
Wetting agent (polyethylene glycol 800) 400mg/L
Brightener (SPS) 2mg/L
Base solution (copper ion: 55g/L, sulfuric acid: 55g/L, chloride ion: 65 mg/L).
Comparative example 1
This comparative example differs from example 1 in that compound 1 is replaced by an equal mass of Janus green T, the rest being the same as example 1.
Performance testing
The hole-filling conductive liquids described in examples 1 to 6 and comparative example 1 were subjected to a blind hole filling test: the circuit board with blind holes is used as a cathode, the insoluble titanium mesh is used as an anode, the current density is 1.5ASD, and the electroplating time is 40min.
(1) Thickness value of plane copper
(2) Value of double
(3) The sample value at 200AH/L of long-term use stability/electric quantity accumulation: medium thickness of 60um, aperture of 100 um blind hole, current density of 1.5ASD.
The test results are summarized in table 1.
TABLE 1
The data in the table 1 are analyzed, and it is known that the hole-filling conductive liquid has excellent performance in blind hole filling, and specifically shows that the filled blind hole has small pore size within 9 μm and small double value within 4 μm, the double value is within 5 μm when the stable electricity quantity accumulation for long-term use is 200AH/L, and the stability for long-term use is excellent and can reach more than 1 year.
As can be seen from the analysis of comparative example 1 and example 1, the performance of comparative example 1 is inferior to that of example 1, and the hole filling conductive liquid additive provided by the invention is proved to be more beneficial to blind hole filling.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The hole filling conductive liquid is characterized by comprising an electroplating additive and a base liquid, wherein the electroplating additive is shown in a formula I;
Z-R-(CH 2 ) n -R-Z is of formula i;
wherein n is an integer of 1 to 5;
r is selected from S or CH 2 ；
Z is selected from- ((C) 2 H 4 O) a -(C 3 H 6 O) b -A-CH 2 -M) y ；
a and b are each independently an integer from 1 to 10;
a is selected from NH or CH 2 ；
y is an integer of 1 to 3;
m is selected from-CH 2 -CHOH-CH 2 -NH-CH＝CH 2 or-CH 2 -CHOH-CH 2 -NH-CH-CH 3 。
2. The hole-filling conductive solution of claim 1, wherein the plating additive comprises any one of formulas i-1 to i-4 or a combination of at least two thereof;
in the formula I-1 to formula I-4, a and b are each independently an integer of 1 to 10, and y is each independently an integer of 1 to 3.
3. The hole-filling conductive liquid according to claim 1 or 2, wherein the concentration of the plating additive in the electrolytic solution is 1 to 1000mg/L.
4. The hole-filling conductive liquid according to any one of claims 1 to 3, wherein the auxiliary agent includes a wetting agent and a brightening agent.
5. The conductive, via-fill fluid of claim 4, wherein the wetting agent comprises any one of polyethylene glycol, polypropylene glycol, or polyethylene glycol methyl ether, or a combination of at least two thereof.
6. The conductive liquid for filling holes of claim 4 or 5, wherein the concentration of the wetting agent in the conductive liquid for filling holes is 10-10000mg/L.
7. The hole-filling conductive liquid according to any one of claims 4 to 6, wherein the brightener comprises SPS;
preferably, the concentration of the brightener in the hole filling conductive liquid is 0.1-10mg/L.
8. The hole-filling conductive liquid according to any one of claims 1 to 7, wherein the base liquid includes hydrogen ions, copper ions, and halogen ions.
9. Use of a hole-filling conductive fluid according to any one of claims 1 to 8 in blind hole filling.
10. Use according to claim 9, wherein the diameter of the blind holes is 50-200 μm;
preferably, the depth of the blind hole is 20-200 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211295404.9A CN115537885A (en) | 2022-10-21 | 2022-10-21 | Hole filling conductive liquid and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211295404.9A CN115537885A (en) | 2022-10-21 | 2022-10-21 | Hole filling conductive liquid and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115537885A true CN115537885A (en) | 2022-12-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211295404.9A Pending CN115537885A (en) | 2022-10-21 | 2022-10-21 | Hole filling conductive liquid and application thereof |
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| CN (1) | CN115537885A (en) |
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- 2022-10-21 CN CN202211295404.9A patent/CN115537885A/en active Pending
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