CN106676502A - Palladium-free copper deposition preparation process of printed circuit board - Google Patents
Palladium-free copper deposition preparation process of printed circuit board Download PDFInfo
- Publication number
- CN106676502A CN106676502A CN201710036102.2A CN201710036102A CN106676502A CN 106676502 A CN106676502 A CN 106676502A CN 201710036102 A CN201710036102 A CN 201710036102A CN 106676502 A CN106676502 A CN 106676502A
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- Prior art keywords
- palladium
- heavy copper
- concentration
- printed circuit
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- 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
- C23C18/405—Formaldehyde
-
- 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
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a palladium-free copper deposition preparation process of a printed circuit board and belongs to the field of preparation of printed circuit boards. Dinitrogen heterocyclic benzenoid pyridine is added into a CuSO4 solution, excitation is performed through electromagnetic waves, Cu<2+> ions are dissociated from a CuETDA complex during excitation and then guided into dinitrogen heterocyclic benzenoid pyridine holes to be assembled into Cu<3+> ions, the assembled Cu<3+> ions are dissociated from the dinitrogen heterocyclic benzenoid pyridine holes, and the rest of Cu<2+> ions in the solution continuously enter the dinitrogen heterocyclic benzenoid pyridine to be assembled into Cu<3+> ions inside under the action of electric waves. According to the palladium-free copper deposition preparation process, the activation procedure and the accelerating procedure are omitted, so that the preparation process time is shortened; Cu<3+> ions are used as an activating agent and expensive palladium is replaced, so that the production cost is reduced; and adopted bioactive dinitrogen heterocyclic benzenoid pyridine supermolecules can be repeatedly used in the copper deposition process, the inversion frequency is reduced, and the liquid waste disposal cost is reduced.
Description
Technical field
The present invention relates to printed circuit board without the heavy copper preparation technology of palladium, belong to the preparation field of printed circuit board (PCB).
Background technology
In the manufacturing process of printed circuit board (PCB), needs carry out heavy copper operation, and the purpose of heavy copper is former using chemical reaction
Reason deposits the copper of one layer of 0.3um-0.5um on hole wall, and the hole wall for making insulation originally has electric conductivity, is easy to follow-up panel plating
And graphic plating is smoothed out, so as to completing the electrical intercommunication between PCB circuit networks.Heavy copper principle is in highly basic using formaldehyde
Property environment in the reproducibility that has and make Cu under Pd effects2+It is reduced into copper.
Traditional heavy process for copper specifically includes the steps such as bulk, removing glue, neutralization, microetch, whole hole, activation, acceleration, heavy copper.
Wherein, it is bulk：Because substrate resin is macromolecular compound, inter-molecular binding force is very strong, in order that bore dirty resin effectively being removed
Go, its bulk softening is made by expansion process, consequently facilitating MnO4 -The immersion of ion, makes Long carbon chain crack and reach the mesh of removing glue
's.Removing glue：Produce hole wall epoxy resin surface coarse on microcosmic, to improve the engaging force between hole wall and chemical copper, and
Adsorbance of the hole wall to activating solution can be improved, its principle is to utilize KMnO4The characteristic of strong oxidizing property is by hole wall in alkaline environment
Surface resin oxidation Decomposition.Neutralization：Jing alkalescence KMnO4Plate after process, carries substantial amounts of MnO in plate face and hole4 -、MnO4 2-、
MnO2Deng liquid medicine residue, because of MnO4 -Itself has extremely strong oxidisability, is a kind of poison to the degreaser and reactivity of rear operation
Thing, therefore the plate after removing glue neutralized must be processed MnO4 -Reduced, to eliminate its strong oxidizing property.Microetch：By this work
The copper of 0.8-3um is etched on Copper substrate, and makes copper face that rough matsurface is shown as on microcosmic, on the one hand can be with
Matrix polluted by copper is set more to activate palladium colloid, another Main Function is the adhesion for improving base copper and chemical copper.The work of activation
With being to adsorb one layer of metal with catalytic capability on the matrix of insulation, make the matrix surface through activating that there is catalysis reduction
The ability of metal.What is adsorbed on matrix surface after activation is the micelle with Metal Palladium as core, is surrounded around micelle
Alkali formula stannate.The printed board processed more than enters copper liquid, Cu in heavy copper liquid2+With reducing agent in catalyst metals palladium and
There is redox reaction in the presence of copper in new deposition, in matrix surface the thin copper of one layer of 0.3-0.5um is deposited, make itself
The hole wall of insulation produces electric conductivity, makes follow-up panel plating smooth.
Find in use, existing process process is complicated, and need to use expensive palladium in preparation process, cause to produce into
This height, in addition, the palladium-containing waste liquid produced during heavy copper can cause environmental pollution.
The content of the invention
For the problem that above-mentioned prior art is present, the present invention provide printed circuit board without the heavy copper preparation technology of palladium, it is raw
Production. art is simple, and the palladium of costliness, effective reduces cost are not required the use of in production.
To achieve these goals, a kind of printed circuit board (PCB) that the present invention is adopted it is without the heavy process for copper of palladium including bulk, remove
Glue, neutralization, microetch, whole hole and without the heavy copper process of palladium, it is described to specifically include following operation without the heavy copper process of palladium：
After by the copper-clad plate etching of FR-4, some little sections are cut into, are hung in heavy copper tank liquor, it is pre- in the heavy copper tank liquor
First added with HCHO, CuSO4·5H2O, EDTA-2Na, dinitrogen heterocyclic arene pyridine, K [Fe (CN) 3] and α α ' bipyridyls, to heavy copper
Add NaOH to adjust pH value to 11-13 in tank liquor, then HCHO concentration is adjusted to into 6-9g/L, CuSO4·5H2O concentration is adjusted to 5-
15g/L, EDTA-2Na concentration is adjusted to 28g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to 1.2-1.5g/L, K [Fe (CN)3]
Concentration is adjusted to 100g/L, and the concentration of α α ' bipyridyls is 10g/L, then heavy copper tank liquor is excited with electromagnetic wave, and will be heavy
Copper tank liquor temperature is set as 25-30 DEG C, takes out after little section deposition 50-70min, is then placed in the ammonia-ammonium buffering of PH=10
In liquid, plus hydrogen peroxide, heat after its all dissolving and drive excessive hydrogen peroxide, plus 2-3 drop PAN indicator away, use 0.05mol/
LEDTA is titrated to yellow green.
As improvement, the concentration of NaOH is adopted for 12-15g/L.
Used as improvement, the copper-clad plate is cut into the little section of 6 × 6cm.
Used as improvement, during the electromagnetic wave is excited to heavy copper tank liquor, the wave frequency for adopting swashs for 0.78-0.85GHz
The time of sending out is the 18-25 seconds.
Used as improvement, the HCHO concentration is adjusted to 7.5g/L, CuSO4·5H2O concentration is adjusted to 7.5g/L, dinitrogen heterocycle
Aromatic hydrocarbons pyridine concentration is adjusted to 1.5g/L.
As improvement, NaOH is added to adjust pH value to 12.5 in the heavy copper tank liquor.
Used as improvement, the heavy copper tank liquor temperature is set as 30 DEG C.
The reaction mechanism of the present invention, it is specific as follows：
, in the case where electromagnetic wave is excited, the coefficient of stability of dinitrogen heterocyclic arene pyridine is from original lgk=16.75 for chemical copper liquid
Lgk=20.3 is raised to, and the coefficient of stability of CuETDA complex compounds then drops to lgk=16.50 from original lgk=18.80, it is real
Show two kinds of complex coefficients of stability once to reverse, the part Cu being so complexed by ETDA originally2+Ion " will seize the opportunity " from
Dissociate in ETDA complex compounds and, enter into chemical copper liquid, then dissociate Cu in solution2+Increase, wherein some
Free Cu2+The hole of dinitrogen heterocyclic arene pyridine will be entered into, to maintain chemical copper liquid in dissociate Cu2+Revenue and expenditure is put down
Weighing apparatus, and the void diameter of dinitrogen heterocyclic arene pyridine compares Cu about between 770pm-810pm2+The diameter 730pm of ion is omited
Greatly, this is exactly just Cu2+One micro- space posted is provided, high activity, high-spin Cu are assembled them in the presence of electric wave3 +With low spin Cu3+Two kinds of ions, because assembling successful Cu3+Diameter little (540pm), it will be from dinitrogen heterocyclic arene pyridine
Discharge in hole, replace activation palladium ion to carry out the electroless deposition (sink copper) of copper, and remaining Cu in solution2+Ion exists
Under electric wave effect, and continuously enter in dinitrogen heterocyclic arene pyridine, to fill up Cu3+Dissociate the vacancy for, while inner
While being assembled into Cu3+Ion (current potential is 747.5mV), the Cu for assembling afterwards3+Ion is released once again, completes one
Circulation, the Cu in this cyclic process3+Itself is also regenerated, and the Cu entered in chemical copper liquid3+Because diameter is little, negative
Lotus high (about 1.8066 × 1024E/mol), it will quickly be adsorbed to whole hole and cross on insulating substrate under electric wave effect.
From Cu2+In entering into the hole of dinitrogen heterocyclic arene pyridine, then to Cu3+The 12-18 seconds are taken around on adsorbed insulating substrate
Clock, this time is exactly Cu3+The grappling phase.Afterwards formaldehyde in the basic conditions, with aqueous solubilized symphysis into methene glycol CH2
(OH)2, and methene glycol is not by Cu3+It is do not possess strong reducing power (lgK=-4) before activation, when by Showed Very Brisk
Cu3+After activation, the tendency on effusion surface is just provided with so that elecrtonegativity in its surface band, thus by electronegative work
Change Cu3+Surface is adsorbed soon, and has influence on the polarization of methene glycol molecules due to electronegative, near Cu3+Part band is just
Electricity, away from Cu3+Part is negatively charged.So, away from the hydroxyl (OH on position-) on hydrogen atom have the tendency of separate out, and
Become the methene glycol anion with strong negative electricity, the copper ion Cu with positive electricity2+Attracted by electronegative methene glycol, accumulated
In Cu3+Near surface, is then formed Bockris-Serpinski electric double layers.
Compared with the heavy process for copper of tradition, the present invention's has lacked two links without the heavy process for copper of palladium, that is, activate and accelerate, so as to
Processing time is reduced, the present invention adopts Cu3+For activator, the palladium of costliness is instead of, activation responsibility is performed, so as to reduce life
Produce cost；In addition, the present invention is using the dinitrogen heterocyclic arene pyridine supermolecule with biologically active, it can be anti-in heavy copper process
Use again, so reduce inverted engine frequency, and Cu is adopted in activation process3+Activation Cu2+, without the need for introducing palladium colloidal solution, this
Sample just reduces liquid waste processing expense indirectly.
Description of the drawings
Fig. 1 is the KIO-77255-E brassboards adopted in the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, below by drawings and Examples, to this
Invention is further elaborated.However, it should be understood that specific embodiment described herein is only to explain the present invention,
It is not limited to the scope of the present invention.
Unless otherwise defined, all of technical term used herein and scientific terminology and the technology neck for belonging to the present invention
The implication that the technical staff in domain is generally understood that is identical, and the term for being used in the description of the invention herein is intended merely to retouch
State the purpose of specific embodiment, it is not intended that of the invention in limiting.
Embodiment one
A kind of printed circuit board without the heavy copper preparation technology of palladium, including bulk, removing glue, neutralization, microetch, whole hole and heavy without palladium
Copper process, it is described to specifically include following operation without the heavy copper process of palladium：
After by the copper-clad plate etching of FR-4, the little sections of some 6 × 6cm are cut into, are hung in heavy copper tank liquor, the heavy copper groove
In advance added with HCHO, CuSO in liquid4·5H2O, EDTA-2Na, dinitrogen heterocyclic arene pyridine, K [Fe (CN) 3] and α α ' bipyridyls,
Add NaOH (concentration is 12g/L) to adjust pH value to 11 into heavy copper tank liquor, then HCHO concentration is adjusted to into 6g/L, CuSO4·
5H2O concentration is adjusted to 5g/L, and EDTA-2Na concentration is adjusted to 28g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to 1.2g/L, K
[Fe(CN)3] concentration is adjusted to 100g/L, the concentration of α α ' bipyridyls is 10g/L, then heavy copper tank liquor is swashed with electromagnetic wave
Send out, for 0.78GHz, firing time is 18 seconds to the wave frequency for adopting, and heavy copper tank liquor temperature is set as into 25 DEG C, treats little cutting
Take out after piece deposition 50min, in being then placed in the ammonia of PH=10-ammonium buffer solution, plus hydrogen peroxide, heat after its all dissolving and catch up with
Excessive hydrogen peroxide is walked, plus 2 and is dripped PAN indicator, with 0.05mol/lEDTA yellow green is titrated to, that is, complete heavy copper process.
Embodiment two
A kind of printed circuit board without the heavy copper preparation technology of palladium, including bulk, removing glue, neutralization, microetch, whole hole and heavy without palladium
Copper process, it is described to specifically include following operation without the heavy copper process of palladium：
After by the copper-clad plate etching of FR-4, the little sections of some 6 × 6cm are cut into, are hung in heavy copper tank liquor, the heavy copper groove
In advance added with HCHO, CuSO in liquid4·5H2O, EDTA-2Na, dinitrogen heterocyclic arene pyridine, K [Fe (CN) 3] and α α ' bipyridyls,
Add NaOH (concentration is 13.5g/L) to adjust pH value to 12.5 into heavy copper tank liquor, then HCHO concentration be adjusted to into 7.5g/L,
CuSO4·5H2O concentration is adjusted to 7.5g/L, and EDTA-2Na concentration is adjusted to 28g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to
1.5g/L, K [Fe (CN)3] concentration is adjusted to 100g/L, the concentration of α α ' bipyridyls is 10g/L, then with electromagnetic wave to heavy copper groove
Liquid is excited, and for 0.83GHz, firing time is 20 seconds to the wave frequency for adopting, and heavy copper tank liquor temperature is set as into 30
DEG C, take out after little section deposition 60min, in being then placed in the ammonia of PH=10-ammonium buffer solution, plus a little hydrogen peroxide, treat that its is complete
Excessive hydrogen peroxide, plus 2-3 drop PAN indicator are driven in heating after portion's dissolving away, are titrated to yellow green with 0.05mol/lEDTA, i.e.,
Complete heavy copper process.
Embodiment three
A kind of printed circuit board without the heavy copper preparation technology of palladium, including bulk, removing glue, neutralization, microetch, whole hole and heavy without palladium
Copper process, it is described to specifically include following operation without the heavy copper process of palladium：
After by the copper-clad plate etching of FR-4, the little sections of some 6 × 6cm are cut into, are hung in heavy copper tank liquor, the heavy copper groove
In advance added with HCHO, CuSO in liquid4·5H2O, EDTA-2Na, dinitrogen heterocyclic arene pyridine, K [Fe (CN) 3] and α α ' bipyridyls,
Add NaOH (concentration is 15g/L) to adjust pH value to 13 into heavy copper tank liquor, then HCHO concentration is adjusted to into 9g/L, CuSO4·
5H2O concentration is adjusted to 15g/L, and EDTA-2Na concentration is adjusted to 28g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to 1.5g/L,
K[Fe(CN)3] concentration is adjusted to 100g/L, the concentration of α α ' bipyridyls is 10g/L, then heavy copper tank liquor is carried out with electromagnetic wave
Excite, for 0.85GHz, firing time is 25 seconds to the wave frequency for adopting, and heavy copper tank liquor temperature is set as into 30 DEG C, treats little
Take out after section deposition 70min, in being then placed in the ammonia of PH=10-ammonium buffer solution, plus a little hydrogen peroxide, after its all dissolving
Excessive hydrogen peroxide, plus 2-3 drop PAN indicator are driven in heating away, and with 0.05mol/lEDTA yellow green is titrated to, that is, it is heavy to complete
Copper process.
When using, we devise a model KIO-77255-E plank, as shown in figure 1, we are pre- on the plank
A series of aperture has been put, then bulk → removing glue → neutralization → microetch → whole has been sequentially passed through by the new technological flow of embodiment two
Behind hole → without the heavy Copper treatment of palladium, it is taken out cleaning, processing procedure section, it can be seen that heavy copper works well.
The present invention's has lacked two links without the heavy copper preparation technology of palladium, that is, activate and accelerate, so as to reduce processing time,
The present invention adopts Cu3+For activator, the palladium of costliness is instead of, activation responsibility is performed, so as to reduce production cost；In addition, this
Using the dinitrogen heterocyclic arene pyridine supermolecule with biologically active, it can so subtract in heavy copper process Reusability for invention
Few inverted engine frequency, and Cu is adopted in activation process3+Activation Cu2+, without the need for introducing palladium colloidal solution, thus reduce indirectly
Liquid waste processing expense.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent or improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (7)
1. printed circuit board without the heavy copper preparation technology of palladium, it is characterised in that including bulk, removing glue, neutralization, microetch, whole hole and
It is described to specifically include following operation without the heavy copper process of palladium without the heavy copper process of palladium：
After by the copper-clad plate etching of FR-4, some little sections are cut into, are hung in heavy copper tank liquor, added in advance in the heavy copper tank liquor
There are HCHO, CuSO4·5H2O, EDTA-2Na, dinitrogen heterocyclic arene pyridine, K [Fe (CN) 3] and α α ' bipyridyls, to heavy copper tank liquor
Interior plus NaOH adjusts pH value to 11-13, then HCHO concentration is adjusted to into 6-9g/L, CuSO4·5H2O concentration is adjusted to 5-15g/
L, EDTA-2Na concentration is adjusted to 28g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to 1.2-1.5g/L, K [Fe (CN)3] concentration
It is adjusted to 100g/L, the concentration of α α ' bipyridyls is 10g/L, then heavy copper tank liquor is excited with electromagnetic wave, and by heavy copper groove
Liquid temp is set as 25-30 DEG C, takes out after little section deposition 50-70min, in being then placed in the ammonia of PH=10-ammonium buffer solution,
Plus hydrogen peroxide, heat after its all dissolving and drive excessive hydrogen peroxide, plus 2-3 drop PAN indicator away, use 0.05mol/lEDTA
It is titrated to yellow green.
2. printed circuit board according to claim 1 without the heavy copper preparation technology of palladium, it is characterised in that using the dense of NaOH
Spend for 12-15g/L.
3. printed circuit board according to claim 2 without the heavy copper preparation technology of palladium, it is characterised in that the copper-clad plate is cut out
It is cut into the little section of 6 × 6cm.
4. printed circuit board according to claim 3 without the heavy copper preparation technology of palladium, it is characterised in that the electromagnetic wave pair
During heavy copper tank liquor is excited, for 0.78-0.85GHz, firing time is the 18-25 seconds to the wave frequency for adopting.
5. printed circuit board according to claim 4 without the heavy copper preparation technology of palladium, it is characterised in that the HCHO concentration
It is adjusted to 7.5g/L, CuSO4·5H2O concentration is adjusted to 7.5g/L, and dinitrogen heterocyclic arene pyridine concentration is adjusted to 1.5g/L.
6. printed circuit board according to claim 1 without the heavy copper preparation technology of palladium, it is characterised in that the heavy copper tank liquor
Interior plus NaOH adjusts pH value to 12.5.
7. printed circuit board according to claim 1 without the heavy copper preparation technology of palladium, it is characterised in that the heavy copper tank liquor
Temperature is set as 30 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710036102.2A CN106676502A (en) | 2017-01-17 | 2017-01-17 | Palladium-free copper deposition preparation process of printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710036102.2A CN106676502A (en) | 2017-01-17 | 2017-01-17 | Palladium-free copper deposition preparation process of printed circuit board |
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| CN106676502A true CN106676502A (en) | 2017-05-17 |
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ID=58859275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710036102.2A Pending CN106676502A (en) | 2017-01-17 | 2017-01-17 | Palladium-free copper deposition preparation process of printed circuit board |
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Citations (6)
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|---|---|---|---|---|
| US1035227A (en) * | 1911-11-25 | 1912-08-13 | Diamond Electric Company | Electric connector. |
| US3902907A (en) * | 1973-08-17 | 1975-09-02 | Kazutaka Kishita | System for electroless plating of copper and composition |
| CN101580953A (en) * | 2008-05-14 | 2009-11-18 | 深圳市迪凯鑫科技有限公司 | Electroless copper plating solution composition and preparation method thereof |
| CN102051607A (en) * | 2009-10-29 | 2011-05-11 | 比亚迪股份有限公司 | Electroless copper plating solution |
| CN103668138A (en) * | 2012-09-24 | 2014-03-26 | 比亚迪股份有限公司 | Chemical copper plating solution and chemical copper plating method |
| CN104651814A (en) * | 2014-11-28 | 2015-05-27 | 广东致卓精密金属科技有限公司 | Chemical copper plating solution and chemical copper plating method |
-
2017
- 2017-01-17 CN CN201710036102.2A patent/CN106676502A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1035227A (en) * | 1911-11-25 | 1912-08-13 | Diamond Electric Company | Electric connector. |
| US3902907A (en) * | 1973-08-17 | 1975-09-02 | Kazutaka Kishita | System for electroless plating of copper and composition |
| CN101580953A (en) * | 2008-05-14 | 2009-11-18 | 深圳市迪凯鑫科技有限公司 | Electroless copper plating solution composition and preparation method thereof |
| CN102051607A (en) * | 2009-10-29 | 2011-05-11 | 比亚迪股份有限公司 | Electroless copper plating solution |
| CN103668138A (en) * | 2012-09-24 | 2014-03-26 | 比亚迪股份有限公司 | Chemical copper plating solution and chemical copper plating method |
| CN104651814A (en) * | 2014-11-28 | 2015-05-27 | 广东致卓精密金属科技有限公司 | Chemical copper plating solution and chemical copper plating method |
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| Title |
|---|
| 钨通芳等: ""无钯沉铜新思路"", 《印制电路信息》 * |
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Application publication date: 20170517 |
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| RJ01 | Rejection of invention patent application after publication |