CN116282949A - Glass through hole copper electroplating solution for radio frequency device and copper electroplating process thereof - Google Patents
Glass through hole copper electroplating solution for radio frequency device and copper electroplating process thereof Download PDFInfo
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- 238000009713 electroplating Methods 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 65
- 239000011521 glass Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000007747 plating Methods 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- 239000000080 wetting agent Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000002441 reversible effect Effects 0.000 claims description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MPZDNIJHHXRTIQ-UHFFFAOYSA-N 6-chloroimidazo[1,2-b]pyridazine Chemical compound N1=C(Cl)C=CC2=NC=CN21 MPZDNIJHHXRTIQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004142 Polyoxypropylene-polyoxyethylene polymer Substances 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 5
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000013527 degreasing agent Substances 0.000 claims description 3
- 238000005237 degreasing agent Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- WRXFJKBQZVRPHI-UHFFFAOYSA-N 2-methoxy-6-nitrophenol Chemical compound COC1=CC=CC([N+]([O-])=O)=C1O WRXFJKBQZVRPHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- JHOFQKBMEIVICM-UHFFFAOYSA-L CS(=O)(=O)O.CS(=O)(=O)[O-].[Cu+2].CS(=O)(=O)[O-] Chemical compound CS(=O)(=O)O.CS(=O)(=O)[O-].[Cu+2].CS(=O)(=O)[O-] JHOFQKBMEIVICM-UHFFFAOYSA-L 0.000 claims 1
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical group [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 36
- 238000000151 deposition Methods 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000001465 metallisation Methods 0.000 abstract description 9
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 abstract description 7
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 abstract 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 244000241796 Christia obcordata Species 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- KBRKFTKQRMYINW-UHFFFAOYSA-M sodium;2-methoxy-5-nitrophenolate Chemical group [Na+].COC1=CC=C([N+]([O-])=O)C=C1[O-] KBRKFTKQRMYINW-UHFFFAOYSA-M 0.000 description 4
- IVJQGBHYRPCKGH-UHFFFAOYSA-N 2-methoxy-4-nitrophenol;sodium Chemical compound [Na].COC1=CC([N+]([O-])=O)=CC=C1O IVJQGBHYRPCKGH-UHFFFAOYSA-N 0.000 description 3
- YWIQISNBXFTDJS-UHFFFAOYSA-N C(C1=C(C=CC2=CC=CC=C12)C)C1=C(C=CC2=CC=CC=C12)C.[Na] Chemical compound C(C1=C(C=CC2=CC=CC=C12)C)C1=C(C=CC2=CC=CC=C12)C.[Na] YWIQISNBXFTDJS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- -1 quaternary ammonium salt compound Chemical class 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- TUGYIMVHPWPMBE-UHFFFAOYSA-N C=CC1=C(C=CC2=CC=CC=C12)C.[Na] Chemical compound C=CC1=C(C=CC2=CC=CC=C12)C.[Na] TUGYIMVHPWPMBE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004475 heteroaralkyl group Chemical group 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
- C03C2217/253—Cu
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/115—Deposition methods from solutions or suspensions electro-enhanced deposition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention discloses a glass through hole copper electroplating solution for a radio frequency device and a copper electroplating process thereof, wherein the copper electroplating solution comprises the following components: 250-330g/L copper methylsulfonate, 15-35g/L methylsulfonate, 40-90mg/L chloride ion, 120-300mg/L composite accelerator, 10-80mg/L wetting agent, 20-50mg/L composite leveling agent and 1-8mg/L composite nucleating agent. The technology adopts S1 pulse square wave current to carry out preferential nucleation butterfly filling in the middle of the hole and S2 unidirectional direct current to carry out filling and leveling deposition of the blind hole, ensures void-free filling of the through hole, can finish metallization of the whole through hole only by setting different current output modes, does not need to replace a plating tank, and improves the production efficiency.
Description
Technical Field
The invention relates to the technical field of copper electroplating, in particular to a glass through hole copper electroplating solution for a radio frequency device and a copper electroplating process thereof.
Background
The Glass Via (TGV) has better high frequency characteristics than the Through Silicon Via (TSV) at high frequencies, and the glass substrate has the advantages of lower manufacturing cost and thickness as low as 100 μm in the large panel manufacturing process. TGV in a 3D packaging System (SiP) integrated antenna enables wireless in-plane/out-of-plane and in-chip/inter-chip communication. The wireless interconnection can reduce signal delay and increase communication distance with little dispersion, compared with the wired method.
When the traditional copper electroplating solution formula adopts direct current electroplating during through hole electroplating, the control range of the electroplating solution is narrower, the problems of cavity, dissatisfaction of hole metal and the like easily occur in the through hole metallization filling process, the electroplating time is longer, the surface copper thickness is thicker, and the subsequent polishing difficulty is increased. When pulse electroplating is adopted, two blind holes are formed at two ends after butterfly-shaped filling of the middle part of the hole, filling cannot be continued, and the blind holes are generally required to be electroplated and filled by replacing electroplating bath solution, so that the working procedures are increased.
In addition, patent CN111441071a discloses a double-sided copper plating technique for glass through holes, in which the current density range is narrow due to defects of a leveling agent and a brightening agent system, and the technique is not suitable for high-speed production efficiency. In order to solve the drawbacks of leveling agents and brightening agents, there have been many efforts made by commercial manufacturers, such as the application of a copper acid leveling agent disclosed in patent CN103924268A, which is a quaternary ammonium salt compound, with the anion x=cl - Or Br (Br) - The method comprises the steps of containing one of S or N, alkyl, alkenyl, aralkyl, heteroaralkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaralkyl, and is mainly applied to wafer electroplating with adjustable surface morphology. However, the leveling agent still does not achieve satisfactory results.
Aiming at the problems, the invention develops a novel through hole electroplating solution formula, which can form a state that copper in a hole is thick and copper in an orifice is thin under proper pulse conditions, and takes copper protruding from the middle position of the hole as a plating starting point of hole filling liquid medicine to form butterfly wings. The pulse waveform can be changed to realize the continuous filling of the blind holes. The production replacement of the electroplating bath is avoided while the void filling in the hole is effectively ensured, and the production efficiency is improved.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides the glass through hole copper plating solution for the radio frequency device and the copper plating process thereof, the technology adopts S1 pulse square wave current to carry out preferential nucleation butterfly-shaped filling in the middle part of the hole and S2 unidirectional direct current to carry out filling deposition of the blind hole, thereby ensuring void-free filling of the through hole, completing metallization of the whole through hole only by setting different current output modes, avoiding replacement of a plating tank and improving production efficiency.
In order to achieve the above purpose, the invention provides a glass through hole copper electroplating solution for a radio frequency device, which comprises the following components in mass concentration:
250-330g/L copper methylsulfonate
Methanesulfonic acid 15-35g/L
Chloride ion 40-90mg/L
120-300mg/L of composite accelerator
10-80mg/L of wetting agent
20-50mg/L of composite leveling agent
1-8mg/L composite nucleating agent
DI pure water balance.
The temperature is 22-26 DEG C
The chloride ions are provided by hydrochloric acid.
The composite accelerator is methylene sodium dimethylnaphthalene sulfonate and 5-chloro-2-methyl-4-isothiazolin-3-ketone, and the mass ratio of the two is 5:1 when the composite accelerator is used, the composite accelerator can be adsorbed on a high potential area on the surface of a through hole, inhibit the growth of holes and surface copper, and is beneficial to preferentially depositing copper in the through hole in a low potential area, so that an ideal growth mode is achieved.
The wetting agent is triblock polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F127, the molecular formula of which is PEO106-PPO70-PEO106, and the wetting agent is used for reducing the surface tension of plating solution and increasing the uniform distribution effect of the plating solution in holes, so that metal copper is orderly plated and deposited on a seed layer of a through hole.
The composite leveling agent is a composite formed by dithiophene-pyrrolopyrrole diketone and sodium carboxymethyl cellulose, and the mass concentration ratio of the dithiophene-pyrrolopyrrole diketone and the sodium carboxymethyl cellulose is 4:1 when the composite leveling agent is used, so that the copper coating is fine and smooth in crystallization and bright in coating; meanwhile, the copper plating in the high current density area is inhibited, and the copper plating and other components are combined to achieve an ideal butterfly-shaped filling mode of the through hole.
The compound nucleating agent is 5-nitro guaiacol sodium and 6-chloroimidazo [1,2-b ] pyridazine, and the mass concentration ratio of the 5-nitro guaiacol sodium and the 6-chloroimidazo [1,2-b ] pyridazine is 1:1 when the compound nucleating agent is used, so that the compound nucleating agent can assist the additives to be adsorbed in different potential areas, plays corresponding accelerating and leveling inhibiting functions, and enhances the preferential nucleation filling of electroplated copper in the middle of a hole in the initial stage.
The copper electroplating process for the glass through hole of the radio frequency device comprises the following specific steps:
firstly, degreasing and cleaning a through hole glass plate plated with a corresponding seed layer for 5-10min, removing greasy dirt on the surface, and then leaching with DI pure water for 3 times to remove redundant degreasing agent;
step two, fixing the cleaned through hole glass plate on a double-sided electroplating device, and immersing the through hole glass plate in the copper electroplating solution according to any one of claims 1-5;
turning on a power supply, and applying an S1 current, wherein the applied S1 current is a periodic reversing pulse electroplating square wave current with a turn-off time of 10-60 ms;
and step four, applying S2 current, wherein the applied current is unidirectional direct current.
The specific conditions of the step 3 are as follows: the current density is 0.5-1.5ASD, the circulation rate of the plating solution is 0.5-2TO/h, the electroplating time is 0.5-1.0h, the current forward and reverse current density ratio in each period is 1:2-5, and the forward and reverse pulse time ratio is 40-60:1.
The specific conditions of the step 4 are as follows: the current density is 2-5ASD, the circulation rate of the plating solution is 3-4TO/h, and the electroplating time is 1.0-2.5h.
In the S1 stage, pulse square wave current is used for electroplating, so that the effects of low surface deposition speed and relatively high in-hole deposition speed can be achieved, electroplated copper is firstly connected in the middle of the inside of the through hole to form butterfly wings, and then gradually deposited to the orifices on the two sides of the through hole, and the generation of holes or cracks in the through hole in other growth modes is effectively avoided. In S2 stage, the blind holes are regulated to unidirectional DC output, and the blind holes are continuously filled up, thereby completing the metallization filling of the whole through holes
The beneficial effects of the invention are as follows: compared with the prior art, the glass through hole copper electroplating solution for the radio frequency device and the copper electroplating process thereof have the following advantages:
1) The novel formula is adopted in the electroplating solution, and the composite accelerator is compounded by adopting the sodium methylene dimethylnaphthalene sulfonate and the 5-chloro-2-methyl-4-isothiazolin-3-ketone, so that the electroplating solution can be adsorbed on a high potential area on the surface of a through hole, inhibit the growth of copper on the hole opening and the surface, is beneficial to the preferential deposition of copper in the through hole in a low potential area, and achieves an ideal growth mode; the wetting agent is triblock polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F127, which is used for reducing the surface tension of the plating solution and increasing the uniform distribution effect of the plating solution in the holes, so that the metal copper is orderly electrodeposited on the seed layer of the through holes.
2) The composite leveling agent is prepared by mixing the following 2 components: the sodium carboxymethyl cellulose is compounded, so that the copper coating is fine and smooth in crystallization and bright; meanwhile, copper plating in a high current density area is inhibited, an ideal through hole butterfly filling mode is achieved through combined action with other components, and on the basis, a trace amount of compound nucleating agent 5-nitro guaiacol sodium and 6-chloroimidazo [1,2-b ] pyridazine are added, so that the respective action of compound additives can be enhanced, and the preferential nucleation filling of electroplated copper in the middle of a hole can be enhanced in the initial stage.
3) In the S1 stage, pulse square wave current is used for electroplating, so that the effects of low surface deposition speed and relatively high in-hole deposition speed can be achieved, electroplated copper is firstly connected in the middle of the inside of the through hole to form butterfly wings, and then gradually deposited to the orifices on the two sides of the through hole, and the generation of holes or cracks in the through hole in other growth modes is effectively avoided. And in the S2 stage, the single-direction direct current output is regulated, and the formed blind holes are continuously filled up, so that the metallization filling of the whole through holes is completed.
4) By adopting a specific electroplating solution formula and adjusting the corresponding electroplating output current, the rapid void-free filling of the glass through holes can be realized in the same bath solution, the replacement of the bath solution is avoided while the void-free metallization manufacturing is ensured, the process flow is reduced, and the production efficiency is improved.
Drawings
FIG. 1 is a graph of the X-Ray diffraction pattern obtained in the present invention after filling with TGV Kong Zhengchang;
FIG. 2 is a cross-sectional view of a TGV hole S1 stage butterfly filling in example 1 of the present invention;
FIG. 3 is a cross-sectional view of the invention after filling the TGV holes S2 stage in example 1;
FIG. 4 is a cross-sectional view of a TGV hole S1 stage butterfly filling in example 2 of the present invention;
FIG. 5 is a cross-sectional view of the embodiment 2 of the present invention after filling the TGV holes S2;
FIG. 6 is a cross-sectional view of a TGV hole S1 stage butterfly filling in example 3 of the present invention;
FIG. 7 is a cross-sectional view of the invention after filling the TGV holes S2 stage in example 3;
FIG. 8 is a cross-sectional view of a TGV hole S1 stage butterfly filling in a comparative example of the present invention;
FIG. 9 is a cross-sectional view of the comparative example of the present invention after filling the TGV holes S2 stage;
FIG. 10 is a surface plot of the comparative example of the present invention after complete filling of the TGV holes.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to the accompanying drawings and text, wherein the X-Ray diffraction pattern of the filled TGV Kong Zhengchang obtained by the present invention is shown in fig. 1.
The invention provides a glass through hole copper electroplating solution for a radio frequency device, which comprises the following components in mass concentration:
250-330g/L copper methylsulfonate
Methanesulfonic acid 15-35g/L
Chloride ion 40-90mg/L
120-300mg/L of composite accelerator
10-80mg/L of wetting agent
20-50mg/L of composite leveling agent
1-8mg/L composite nucleating agent
DI pure water balance
The temperature is 22-26 DEG C
The chloride ions are provided by hydrochloric acid.
In the embodiment, the composite accelerator is methylene sodium dimethylnaphthalene sulfonate and 5-chloro-2-methyl-4-isothiazolin-3-one, and the mass ratio of the two is 5:1 when the composite accelerator is used.
In this embodiment, the wetting agent is a triblock polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F127 having the molecular formula PEO106-PPO70-PEO106.
In this embodiment, the composite leveling agent is a composite formed by dithiophene-pyrrolopyrrole dione and sodium carboxymethyl cellulose, and the mass concentration ratio of the dithiophene-pyrrolopyrrole dione to sodium carboxymethyl cellulose is 4:1 when in use.
In the embodiment, the compound nucleating agent is 5-sodium nitroguaiacol and 6-chloroimidazo [1,2-b ] pyridazine, and the mass concentration ratio of the two is 1:1 when the compound nucleating agent is used.
The copper electroplating process for the glass through hole of the radio frequency device comprises the following specific steps:
firstly, degreasing and cleaning a through hole glass plate plated with a corresponding seed layer for 5-10min, removing greasy dirt on the surface, and then leaching with DI pure water for 3 times to remove redundant degreasing agent;
step two, fixing the cleaned through hole glass plate on a double-sided electroplating device, and immersing the through hole glass plate in the copper electroplating solution according to any one of claims 1-5;
turning on a power supply, and applying an S1 current, wherein the applied S1 current is a periodic reversing pulse electroplating square wave current with a turn-off time of 10-60 ms;
and step four, applying S2 current, wherein the applied current is unidirectional direct current.
In this embodiment, the specific conditions of step 3 are: the current density is 0.5-1.5ASD, the circulation rate of the plating solution is 0.5-2TO/h, the electroplating time is 0.5-1.0h, the current forward and reverse current density ratio in each period is 1:2-5, and the forward and reverse pulse time ratio is 40-60:1.
In this embodiment, the specific conditions of step 4 are: the current density is 2-5ASD, the circulation rate of the plating solution is 3-4TO/h, and the electroplating time is 1.0-2.5h.
In the S1 stage, pulse square wave current is used for electroplating, so that the effects of low surface deposition speed and relatively high in-hole deposition speed can be achieved, electroplated copper is firstly connected in the middle of the inside of the through hole to form butterfly wings, and then gradually deposited to the orifices on the two sides of the through hole, and the generation of holes or cracks in the through hole in other growth modes is effectively avoided. In S2 stage, the blind holes are regulated to unidirectional DC output, and the blind holes are continuously filled up, thereby completing the metallization filling of the whole through holes
The beneficial effects of the invention are as follows: compared with the prior art, the glass through hole copper electroplating solution for the radio frequency device and the copper electroplating process thereof have the following advantages:
1) The novel formula is adopted in the electroplating solution, and the composite accelerator is compounded by adopting the sodium methylene dimethylnaphthalene sulfonate and the 5-chloro-2-methyl-4-isothiazolin-3-ketone, so that the electroplating solution can be adsorbed on a high potential area on the surface of a through hole, inhibit the growth of copper on the hole opening and the surface, is beneficial to the preferential deposition of copper in the through hole in a low potential area, and achieves an ideal growth mode; the wetting agent is triblock polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F127, which is used for reducing the surface tension of the plating solution and increasing the uniform distribution effect of the plating solution in the holes, so that the metal copper is orderly electrodeposited on the seed layer of the through holes.
2) The composite leveling agent is prepared by mixing the following 2 components: the sodium carboxymethyl cellulose is compounded, so that the copper coating is fine and smooth in crystallization and bright; meanwhile, copper plating in a high current density area is inhibited, an ideal through hole butterfly filling mode is achieved through combined action with other components, and on the basis, a trace amount of compound nucleating agent 5-nitro guaiacol sodium and 6-chloroimidazo [1,2-b ] pyridazine are added, so that the respective action of compound additives can be enhanced, and the preferential nucleation filling of electroplated copper in the middle of a hole can be enhanced in the initial stage.
3) In the S1 stage, pulse square wave current is used for electroplating, so that the effects of low surface deposition speed and relatively high in-hole deposition speed can be achieved, electroplated copper is firstly connected in the middle of the inside of the through hole to form butterfly wings, and then gradually deposited to the orifices on the two sides of the through hole, and the generation of holes or cracks in the through hole in other growth modes is effectively avoided. And in the S2 stage, the single-direction direct current output is regulated, and the formed blind holes are continuously filled up, so that the metallization filling of the whole through holes is completed.
4) By adopting a specific electroplating solution formula and adjusting the corresponding electroplating output current, the rapid void-free filling of the glass through holes can be realized in the same bath solution, the replacement of the bath solution is avoided while the void-free metallization manufacturing is ensured, the process flow is reduced, and the production efficiency is improved.
Example 1
Preparing an electrolytic copper plating solution with the following concentration components:
copper methylsulfonate 250g/L, methylsulfonic acid 15g/L, chloride ion 40mg/L, sodium methylenebis (methylnaphthalene) sulfonate 100mg/L, 5-chloro-2-methyl-4-isothiazolin-3-one 20mg/L, polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F12710mg/L, dithienyl-pyrrolopyrrole dione 16mg/L, sodium carboxymethylcellulose 4mg/L, sodium 5-nitroguaiacol 0.5mg/L, 6-chloroimidazo [1,2-b ] pyridazine 0.5mg/L
DI pure water balance
At 25 DEG C
S1 electroplating conditions: applying periodic reversing pulse electroplating square wave current with a turn-off time of 40ms in each period, wherein the current forward and reverse current density ratio in each period is 1:3, the forward and reverse pulse time ratio is 50:1, the current density is 1.0ASD, the circulation rate of the plating solution is 1.5TO/h, and the electroplating time is 1.0h.
S2, electroplating conditions: unidirectional direct current, current density is adjusted TO 3.5ASD, plating solution circulation rate is 3.5TO/h, and electroplating time is 1.5h.
Example two
Preparing an electrolytic copper plating solution with the following concentration components:
copper methylsulfonate 330g/L, methylsulfonic acid 35g/L, chloride ion 90mg/L, sodium methylenebis (methylnaphthalene) sulfonate 250mg/L, 5-chloro-2-methyl-4-isothiazolin-3-one 50mg/L, polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F12780mg/L, dithienyl-pyrrolopyrrole dione 40mg/L, sodium carboxymethylcellulose 10mg/L, sodium 5-nitroguaiacol 4mg/L, 6-chloroimidazo [1,2-b ] pyridazine 4mg/LDI, the balance of pure water
At 25 DEG C
DI pure water balance
S1 electroplating conditions: and applying periodic reversing pulse electroplating square wave current with a turn-off time of 50ms in each period, wherein the current forward and reverse current density ratio in each period is 1:2, the forward and reverse pulse time ratio is 40:1, the current density is 1.5ASD, the plating solution circulation rate is 2TO/h, and the electroplating time is 1.0h.
S2, electroplating conditions: unidirectional direct current, current density is adjusted TO 4ASD, plating solution circulation rate is 4TO/h, and electroplating time is 2.5h.
Example III
Preparing an electrolytic copper plating solution with the following concentration components:
copper methylsulfonate 300g/L, methylsulfonic acid 30g/L, chloride ion 60mg/L, sodium methylenebis (methylnaphthalene) sulfonate 150mg/L, 5-chloro-2-methyl-4-isothiazolin-3-one 30mg/L, polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F12750mg/L, dithienyl-pyrrolopyrrole dione 20mg/L, sodium carboxymethylcellulose 5mg/L, sodium 5-nitroguaiacol 2mg/L, 6-chloroimidazo [1,2-b ] pyridazine 2mg/LDI, the balance of pure water
At 25 DEG C
S1 electroplating conditions: applying periodic reversing pulse electroplating square wave current with a turn-off time of 45ms in each period, wherein the current forward and reverse current density ratio in each period is 1:3, the forward and reverse pulse time ratio is 45:1, the current density is 1.5ASD, the circulation rate of the plating solution is 1.5TO/h, and the electroplating time is 1.0h.
S2, electroplating conditions: unidirectional direct current, current density is adjusted TO 3.5ASD, plating solution circulation rate is 3TO/h, and electroplating time is 2.0h.
Comparative example one
Copper methylsulfonate 250g/L, methylsulfonic acid 15g/L, chloridion 40mg/L
DI pure water balance
At 25 DEG C
S1 electroplating conditions: applying periodic reversing pulse electroplating square wave current with a turn-off time of 50ms in each period, wherein the current forward and reverse current density ratio in each period is 1:4, the forward and reverse pulse time ratio is 60:1, the current density is 1.5ASD, the circulation rate of the plating solution is 0.5TO/h, and the electroplating time is 1.0h.
S2, electroplating conditions: unidirectional direct current, current density is adjusted TO 4.5ASD, plating solution circulation rate is 3TO/h, and electroplating time is 2.0h.
The standard index of judgment is as follows:
| group of experiments | Kong Naqing condition | Orifice sag value | Filling rate in hole | Service life of the product |
| Example 1 | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example two | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example III | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Comparative example one | Difference of difference | Difference of difference | Difference of difference | Difference of difference |
The results obtained in examples 1-3 are excellent, the graphs of the experimental results corresponding to example 1 are shown in fig. 2-3, the experimental results corresponding to example 2 are shown in fig. 4-5, the experimental results corresponding to example 3 are shown in fig. 6-7, the orifice recess value is excellent, the hole filling rate is excellent, and the service life is excellent; the experimental results corresponding to the comparative examples are shown in fig. 8-10, and the comparative examples are poor in the absence of the composite nucleating agent, the wetting agent, the composite leveling agent, and the composite accelerator, poor in the orifice dent value, poor in the hole filling rate, and poor in the service life.
The embodiments of the present invention are disclosed only, but the present invention is not limited thereto, and any variations that can be considered by those skilled in the art should fall within the scope of the present invention.
Claims (8)
1. The glass through hole copper electroplating solution for the radio frequency device is characterized by comprising the following components in mass concentration:
250-330g/L copper methylsulfonate
Methanesulfonic acid 15-35g/L
Chloride ion 40-90mg/L
120-300mg/L of composite accelerator
10-80mg/L of wetting agent
20-50mg/L of composite leveling agent
1-8mg/L composite nucleating agent
DI pure water balance
The temperature is 22-26 DEG C
The chloride ions are provided by hydrochloric acid.
2. The copper electroplating solution for glass through holes of radio frequency devices according to claim 1, wherein the composite accelerator is sodium methylenebis naphthalene sulfonate and 5-chloro-2-methyl-4-isothiazolin-3-one, and the mass ratio of the two is 5:1.
3. The copper electroplating solution for glass via of radio frequency device according to claim 1, wherein the wetting agent is triblock polyoxyethylene-polyoxypropylene-polyoxyethylene polymer F127 having a molecular formula of PEO106-PPO70-PEO106.
4. The copper electroplating solution for glass through holes of radio frequency devices according to claim 1, wherein the composite leveling agent is a composite formed by dithiophene-pyrrolopyrrole dione and sodium carboxymethyl cellulose, and the mass concentration ratio of the dithiophene-pyrrolopyrrole dione to sodium carboxymethyl cellulose is 4:1 when the copper electroplating solution is used.
5. The glass through hole copper electroplating solution for the radio frequency device according to claim 1, wherein the compound nucleating agent is 5-sodium nitroguaiacol and 6-chloroimidazo [1,2-b ] pyridazine, and the mass concentration ratio of the two is 1:1 when the compound nucleating agent is used.
6. The copper electroplating process for the glass through hole of the radio frequency device is characterized by comprising the following specific steps of:
firstly, degreasing and cleaning a through hole glass plate plated with a corresponding seed layer for 5-10min, removing greasy dirt on the surface, and then leaching with DI pure water for 3 times to remove redundant degreasing agent;
step two, fixing the cleaned through hole glass plate on a double-sided electroplating device, and immersing the through hole glass plate in the copper electroplating solution according to any one of claims 1-5;
turning on a power supply, and applying an S1 current, wherein the applied S1 current is a periodic reversing pulse electroplating square wave current with a turn-off time of 10-60 ms;
and step four, applying S2 current, wherein the applied current is unidirectional direct current.
7. The electrolytic copper plating process for glass through holes of radio frequency devices according to claim 1, wherein the specific conditions of step 3 are: the current density is 0.5-1.5ASD, the circulation rate of plating solution is 0.5-2TO/h, and the electroplating time is 0.5-1.0h ， The current density ratio of the forward current to the reverse current in each period is 1:2-5, and the pulse time ratio of the forward current to the reverse current is 40-60:1.
8. The electrolytic copper plating process for glass through holes of radio frequency devices according to claim 1, wherein the specific conditions of step 4 are: the current density is 2-5ASD, the circulation rate of the plating solution is 3-4TO/h, and the electroplating time is 1.0-2.5h.
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| CN116499401A (en) * | 2023-06-29 | 2023-07-28 | 深圳市圭华智能科技有限公司 | X-ray-based wafer-level glass through hole TGV detection device and method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116499401A (en) * | 2023-06-29 | 2023-07-28 | 深圳市圭华智能科技有限公司 | X-ray-based wafer-level glass through hole TGV detection device and method |
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