CN104561955A - Chemical copper plating solution for ceramic substrate and metallization process of ceramic substrate - Google Patents
Chemical copper plating solution for ceramic substrate and metallization process of ceramic substrate Download PDFInfo
- Publication number
- CN104561955A CN104561955A CN201410771640.2A CN201410771640A CN104561955A CN 104561955 A CN104561955 A CN 104561955A CN 201410771640 A CN201410771640 A CN 201410771640A CN 104561955 A CN104561955 A CN 104561955A
- Authority
- CN
- China
- Prior art keywords
- ceramic substrate
- plating solution
- copper plating
- chemical copper
- metallization process
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
Abstract
The invention relates to the technical field of production of ceramic substrate circuit boards and in particular relates to a chemical copper plating solution for a ceramic substrate and a metallization process of the ceramic substrate. According to the chemical copper plating solution for the ceramic substrate and the metallization process of the ceramic substrate, various components and additives are added into the chemical copper plating solution, the bubbling of a plating layer can be avoided, and the copper deposition rate can be increased; in the electroplating process, the ceramic substrate circuit boards are manufactured by using a laser modification method, the chemical copper plating in a palladium-free activation manner can be implemented; and noble metals are saved.
Description
Technical field
The present invention relates to ceramic substrate board production technical field, refer in particular to the metallization process of a kind of ceramic substrate chemical copper plating solution and ceramic substrate.
Background technology
Along with electronic product is towards miniaturization, density and the functional requirement of electronic circuit also improve thereupon, and this just causes circuit temperature constantly to rise, so, there is high heat conductance, the board substrate of good electrical properties of heat dispersion just becomes active demand.It is high that ceramic substrate has thermal conductivity, coefficient of thermal expansion and Si sheet close, the superior electrical properties such as the large and dielectric loss of insulation resistance is little, ideal heat radiation and the packaged material of large-scale integrated circuit of new generation, semiconductor module circuit and high power device, be mainly used at present in the products such as high-density hybrid circuit, microwave power device, there is application prospect widely.
The ceramic metalizing process developed at present mainly contains thick-film metalliz, membrane process metallization, Direct Bonding copper metallization (DBC) and electroless metallization plating.When making ceramic substrate, above technique usually needs to make mask plate, and technological process is numerous and diverse, and the cycle is long, and flexibility degree is very low, and figure difficulty becomes more meticulous.
Disclose a kind of making method of ceramic base wiring board in patent CN 103188877 A, adopt laser modified pottery (comprising aluminium nitride, alumina-ceramic), then electroless plating makes modification area metallize, quick high flexibility makes ceramic base wiring board.
This mode possesses following advantage, adopt laser modified method to make ceramic base wiring board, on the one hand, ceramic surface is because absorbing high energy beam generation physics, the chemical reaction of laser, generate activation source, can be used as the active center of subsequent chemistry plating, direct electroless plating copper, does not need the precious metal activation such as palladium, silver.On the other hand, through the region of laser modified mistake, roughness increases, and hydrophilicity improves, and this adds increased the bonding force between coating and matrix.Meanwhile, laser processing has regioselectivity, and can be deposited metal by the region of laser modified mistake, unmodified region does not then deposit, or deposition is few, and laser facula is little, and working accuracy is high, is applicable to make hyperfine circuit.
But there is following drawback: pottery is after absorbing laser energy, if it is less to absorb energy, surface roughness Ra is generally below 3 μm, when electroless copper, mechanical snap ability between coating and matrix is more weak, the phenomenon of coating " foaming " will be there is when the gas tension reacting generation exceedes the sticking power between copper plate and matrix, have a strong impact on the performances such as the compactness of coating, planarization and sticking power.
Summary of the invention
The present invention is directed to the deficiency that current ceramic substrate circuit fabrication exists, and provide the metallization process of a kind of ceramic substrate chemical copper plating solution and ceramic substrate, for realizing above object, the present invention adopts following technical scheme:
A kind of ceramic substrate chemical copper plating solution, described chemical copper plating solution is made up of following composition, soluble Cu
2+salt; With Cu
2+complexing forms the complexing agent of metastable title complex; PH adjusting agent containing hydroxide ion source; Prevent the stablizer of plating solution Auto-decomposition; Suppress the additive that coating foaming is suitable; And reductive agent.
Preferably, described soluble Cu
2+salt is CuSO
45H
2o, Cu (NO
3)
2, CuCl
2wherein a kind of or arbitrary combination.
Preferably, described complexing agent is tartrate, EDTA, quadrol, and ammonia, Whitfield's ointment, trolamine be a kind of or arbitrary combination wherein.
Preferably, described pH adjusting agent is sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide wherein a kind of or arbitrary combination.
Preferably, described stablizer is the bistable agent of 2-2 ' dipyridyl and prussiate, and described stabilizer concentration is respectively 2-2 ' dipyridyl: 5 ~ 30mg/L, prussiate: 8 ~ 70mg/L.
Preferably, described additive is P-benzoquinones, cyanogen quinone, anthraquinone, O ~ benzoquinones, Isosorbide-5-Nitrae ~ naphthoquinone and polyatomic phenol: Resorcinol, pyrocatechol, Resorcinol and hydrogen radical trapping agent.
Preferably, described reductive agent is sodium hypophosphite, dimethylin borane, formaldehyde one wherein.
A metallization process for ceramic substrate, comprises following processing step:
(1) oil removing: organic solvent ceramic substrate being put into not phosphorous alkalescence, coordinates ultrasonic cleaning, and remove surface and oil contaminant, the present invention adopts alcohol washes;
(2) laser modified making circuit pattern: by the line pattern designed, transfer on ceramic substrate by laser;
(3) clean: laser modified metacoxa is put into alcohol and cleans, then carry out washed with de-ionized water and remove in modifying process the residue produced;
(4) electroless copper: substrate is put into above-mentioned chemical bronze plating liquid plating; Bath temperature controls at about 50 DEG C by thermostat water bath, plating time 50 ~ 90min; In plating process, continuous stirred solution, forms ceramic circuit board.
Preferably, the parameters in described step 2 in laser modified process: wavelength X=248nm, λ=266nm, λ=355nm, λ=532nm, λ=1064nm; Laser power is at 1 ~ 20w; Sweep velocity is 80 ~ 4000mm/s, and pulse-repetition frequency is 60 ~ 400KHz, obtains the circuit pattern that surface roughness Ra is 0.5 ~ 2 μm.
Beneficial effect of the present invention is: the metallization process of ceramic substrate chemical copper plating solution of the present invention and ceramic substrate, adds various composition and additive in described chemical copper plating solution in the plating solution, can prevent coating from bubbling, improve copper sedimentation rate; In electroplating technology, adopt laser modified legal system to make ceramic substrate circuit, " no-palladium activating " electroless copper can be realized, save precious metal.
Accompanying drawing explanation
Fig. 1. be the ceramic substrate wiring board enlarged view of a prior art chemical copper plating solution and explained hereafter
Fig. 2. the ceramic substrate wiring board of chemical copper plating solution of the present invention and explained hereafter with the identical magnification of Fig. 1 ceramic substrate wiring board
Fig. 3. the circuit enlarged view of the ceramic substrate wiring board of chemical copper plating solution of the present invention and explained hereafter
Embodiment:
Below in conjunction with accompanying drawing 1 ~ 3 and specific embodiment, the present invention is further described:
Below the several embodiment about chemical copper plating solution of the present invention:
Embodiment 1:
The chemical copper plating solution of the present embodiment is made up of following composition:
Soluble Cu
2+salt: CuSO
45H
2o is 10 ~ 30g/L in the concentration of chemical copper plating solution
Complexing agent: EDTA and tartrate mixed twine mixture are respectively 12 ~ 35g/L in chemical copper plating solution concentration.
PH adjusting agent: by sodium hydroxide, the lithium hydroxide mixing conditioning agent of originating containing hydroxide ion, be 12.5 ~ 13.5 at chemical copper plating solution pH.
Stablizer: in order to prevent plating solution Auto-decomposition, add the bistable agent of 2-2 ' dipyridyl and prussiate, concentration is respectively 2-2 ' dipyridyl: 5 ~ 30mg/L, prussiate: 8 ~ 70mg/L.
Additive: P-benzoquinones, cyanogen quinone are 0.11 ~ 11g/L in the concentration of chemical copper plating solution;
Reductive agent: formaldehyde is 5 ~ 20ml/L in the concentration of chemical copper plating solution.
As better embodiment, complexing agent and CuSO
45H
2preferred 2:1 ~ the 5:1 of mass ratio of O; HCHO (37%) and CuSO
45H
2preferred 1:1.1 ~ the 1:1.7 of mass ratio of O.
Embodiment 2:
Soluble Cu
2+salt: Cu (NO
3)
2, CuCl
2;
Complexing agent: quadrol, ammonia, Whitfield's ointment, trolamine;
PH adjusting agent: the adjustments such as potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, pH preferably 12.5 ~ 13.5 under room temperature;
Stablizer: the bistable agent of 2-2 ' dipyridyl and prussiate, concentration is respectively 2-2 ' dipyridyl: 5 ~ 30mg/L, prussiate: 8 ~ 70mg/L;
Additive: suppress the suitable additive of coating foaming to have quinones: anthraquinone, O-benzoquinones, Isosorbide-5-Nitrae-naphthoquinone;
Reductive agent: optional sodium hypophosphite, dimethylin borane;
Embodiment 3:
Soluble Cu
2+salt: Cu (NO
3)
2; Complexing agent: quadrol, ammonia, Whitfield's ointment; PH adjusting agent: ammonium hydroxide, tetramethylammonium hydroxide; Stablizer: be prussiate; Additive: Resorcinol, pyrocatechol, Resorcinol polyatomic phenol; Reductive agent: dimethylin borane.
Embodiment 4:
Soluble Cu
2+salt: CuCl
2; Ammonia, Whitfield's ointment, trolamine; Complexing agent is O-quinone, Isosorbide-5-Nitrae-quinone; PH adjusting agent: ammonium hydroxide, tetramethylammonium hydroxide; Stablizer: 2-2 ' dipyridyl; Additive: Resorcinol, pyrocatechol, the derivative of Resorcinol: the hydrogen radical trapping agent such as dicyan quinone; Reductive agent: optional sodium hypophosphite.
In embodiment 2,3,4, about the content of wherein each component, those skilled in the art can regulate according to demand, therefore the present embodiment limits.
The metallization process of a kind of ceramic substrate of the present invention, comprises following processing step:
(1) oil removing: organic solvent ceramic substrate being put into not phosphorous alkalescence, coordinates ultrasonic cleaning, and remove surface and oil contaminant, the present invention adopts alcohol washes;
(2) laser modified making circuit pattern: by the line pattern designed, transfer on ceramic substrate by laser;
(3) clean: laser modified metacoxa is put into alcohol and cleans, then carry out washed with de-ionized water and remove in modifying process the residue produced;
(4) electroless copper: the chemical bronze plating liquid plating of substrate being put into the present invention's formula; Bath temperature controls at about 50 DEG C by thermostat water bath, plating time 50 ~ 90min; In plating process, continuous stirred solution, forms ceramic circuit board.
Parameters in step 2 in laser modified process is preferred: wavelength X=248nm, λ=266nm, λ=355nm, λ=532nm, λ=1064nm; Laser power is at 1 ~ 20w; Sweep velocity is 80 ~ 4000mm/s, and pulse-repetition frequency is 60 ~ 400KHz, obtains the circuit pattern that surface roughness Ra is 0.5 ~ 2 μm.
Through measuring, wiring board wire plating scooter is to 0.01 ~ 0.1 μm/min, and specific conductivity is at 1.8 ~ 2.3 μ Ω cm, and the present invention is applicable to thickness of coating at the ceramic base wiring board of 0.1 ~ 20 μm.
The metallization process of ceramic substrate chemical copper plating solution of the present invention and ceramic substrate, adds various composition and additive in chemical copper plating solution in the plating solution, can prevent coating from bubbling, improve copper sedimentation rate; In electroplating technology, laser modified legal system is adopted to make ceramic substrate circuit, " no-palladium activating " electroless copper can be realized, save precious metal, have obvious foaming phenomena in the ceramic substrate wiring board of prior art chemical copper plating solution and explained hereafter in fig. 1, and in Fig. 2, the coating of the ceramic substrate of chemical copper plating solution of the present invention and explained hereafter is even, gained ceramic base wiring board coating light, plated layer compact, strong adhesion; Fig. 3 is the ceramic base wire line pattern of minimum feature/distance between centers of tracks arrival 20um/15um that the present invention obtains, circuit is still clear, the present invention obtains wiring board plating scooter 0.01 ~ 0.1 μm/min, specific conductivity is at 1.8 ~ 2.3 μ Ω cm, be applicable to thickness of coating at the ceramic base wiring board of 0.1 ~ 20 μm, in prior art, do not have the product of live width like this and line-spacing.
The above embodiment, just preferred embodiments of the present invention, be not limit the scope of the present invention, therefore all equivalences done according to structure, feature and the principle described in the present patent application the scope of the claims change or modify, and all should be included in patent claim of the present invention.
Claims (9)
1. a ceramic substrate chemical copper plating solution, is characterized in that: described chemical copper plating solution is made up of following composition, soluble Cu
2+salt; With Cu
2+complexing forms the complexing agent of metastable title complex; PH adjusting agent containing hydroxide ion source; Prevent the stablizer of plating solution Auto-decomposition; Suppress the additive that coating foaming is suitable; And reductive agent.
2. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, is characterized in that, described soluble Cu
2+salt is CuSO
45H
2o, Cu (NO
3)
2, CuCl
2wherein a kind of or arbitrary combination.
3. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, is characterized in that, described complexing agent is tartrate, EDTA, quadrol, and ammonia, Whitfield's ointment, trolamine be a kind of or arbitrary combination wherein.
4. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, it is characterized in that, described pH adjusting agent is sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide wherein a kind of or arbitrary combination.
5. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, it is characterized in that, described stablizer is the bistable agent of 2-2 ' dipyridyl and prussiate, described stabilizer concentration is respectively 2-2 ' dipyridyl: 5 ~ 30mg/L, prussiate: 8 ~ 70mg/L.
6. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, it is characterized in that, described additive is P-benzoquinones, cyanogen quinone, anthraquinone, O-benzoquinones, Isosorbide-5-Nitrae-naphthoquinone and polyatomic phenol: Resorcinol, pyrocatechol, Resorcinol and hydrogen radical trapping agent.
7. the metallization process of a kind of ceramic substrate chemical copper plating solution according to claim 1 and ceramic substrate, is characterized in that, described reductive agent is sodium hypophosphite, dimethylin borane, formaldehyde one wherein.
8. a metallization process for ceramic substrate, comprises following processing step:
(1) oil removing: organic solvent ceramic substrate being put into not phosphorous alkalescence, coordinates ultrasonic cleaning, and remove surface and oil contaminant, the present invention adopts alcohol washes;
(2) laser modified making circuit pattern: by the line pattern designed, transfer on ceramic substrate by laser;
(3) clean: laser modified metacoxa is put into alcohol and cleans, then carry out washed with de-ionized water and remove in modifying process the residue produced;
(4) electroless copper: substrate is put into the chemical bronze plating liquid plating described in claim 1 ~ 7 any one; Bath temperature controls at about 50 DEG C by thermostat water bath, plating time 50 ~ 90min; In plating process, continuous stirred solution, forms ceramic circuit board.
9. the metallization process of a kind of ceramic substrate according to claim 8, is characterized in that, the parameters in described step 2 in laser modified process: wavelength X=248nm, λ=266nm, λ=355nm, λ=532nm, λ=1064nm; Laser power is at 1 ~ 20w; Sweep velocity is 80 ~ 4000mm/s, and pulse-repetition frequency is 60 ~ 400KHz, obtains the circuit pattern that surface roughness Ra is 0.5 ~ 2 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771640.2A CN104561955A (en) | 2014-12-11 | 2014-12-11 | Chemical copper plating solution for ceramic substrate and metallization process of ceramic substrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771640.2A CN104561955A (en) | 2014-12-11 | 2014-12-11 | Chemical copper plating solution for ceramic substrate and metallization process of ceramic substrate |
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|---|---|
| CN104561955A true CN104561955A (en) | 2015-04-29 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040044A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Electroplating solution for copper plating and preparation method thereof |
| CN107723691A (en) * | 2017-09-25 | 2018-02-23 | 江苏时瑞电子科技有限公司 | A kind of chemically plating for copper electrode negative tempperature coefficient thermistor method |
| CN114163259A (en) * | 2021-12-14 | 2022-03-11 | 东莞智昊光电科技有限公司 | Method for metallizing ceramic surfaces and metallized ceramics |
| CN114990533A (en) * | 2022-04-13 | 2022-09-02 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper electroplating binding force of ceramic substrate surface |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191491A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Chemical copper-plating solution and chemical copper-plating method |
| CN102695370A (en) * | 2012-06-18 | 2012-09-26 | 惠州市富济电子材料有限公司 | Preparation method of ceramic circuit board |
-
2014
- 2014-12-11 CN CN201410771640.2A patent/CN104561955A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191491A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Chemical copper-plating solution and chemical copper-plating method |
| CN102695370A (en) * | 2012-06-18 | 2012-09-26 | 惠州市富济电子材料有限公司 | Preparation method of ceramic circuit board |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040044A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Electroplating solution for copper plating and preparation method thereof |
| CN107723691A (en) * | 2017-09-25 | 2018-02-23 | 江苏时瑞电子科技有限公司 | A kind of chemically plating for copper electrode negative tempperature coefficient thermistor method |
| CN114163259A (en) * | 2021-12-14 | 2022-03-11 | 东莞智昊光电科技有限公司 | Method for metallizing ceramic surfaces and metallized ceramics |
| CN114990533A (en) * | 2022-04-13 | 2022-09-02 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper electroplating binding force of ceramic substrate surface |
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Application publication date: 20150429 |