CN104955262A - Circuit board and manufacturing method thereof - Google Patents
Circuit board and manufacturing method thereof Download PDFInfo
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- CN104955262A CN104955262A CN201410120355.4A CN201410120355A CN104955262A CN 104955262 A CN104955262 A CN 104955262A CN 201410120355 A CN201410120355 A CN 201410120355A CN 104955262 A CN104955262 A CN 104955262A
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Abstract
The invention discloses a circuit board and a manufacturing method thereof. The circuit board comprises an aluminum nitride ceramic substrate and a copper circuit layer and protection layers attached to at least one surface of the aluminum nitride ceramic substrate, wherein the protection layers comprise a nickel layer, a palladium layer and a gold layer; the nickel layer is connected with the copper circuit layer; and two surfaces of the palladium layer are respectively connected with the nickel layer and the gold layer. According to the circuit board of the invention, a black nickel phenomenon can be avoided, and gold wire bonding test at a high temperature can be completed. The circuit board of the invention has a high cooling performance. In addition, each protection layer in the circuit layer is thin, and the cost of the circuit board can be reduced.
Description
Technical field
The present invention relates to the manufacture method of a kind of wiring board and this wiring board.
Background technology
Along with country payes attention to and input the increasing of energy-saving and emission-reduction, LED(light-emitting diode) demand of product is increasing, and traditional LED product is mainly using epoxy resin such as FR-4 as heat sink material, its lower conductive coefficient can not meet the demand of high-capacity LED product.Ceramic material has become a kind of heat sink material preferably owing to having higher conductive coefficient, and the conductive coefficient of part pottery even reaches more than 200W/mK, is 1000 times of traditional printed circuit board (PCB) plate (that is, FR-4 epoxy resin board) conductive coefficient.
Further, in order to the copper face on protection circuit plate, need to carry out surface treatment to wiring board.At present, process of surface treatment market being applicable to wiring board mainly contains four kinds: 1) chemical wicking; 2) electroless immersion silver; 3) organic solder protective agent; 4) chemical nickel and gold (ENIG).And use more general to be in the circuit board chemical nickel and gold process, in this technique, to utilize golden low contact resistance and not oxidizable characteristic, provide good conduction and protective effect to circuit; And nickel is as the resilient coating between copper and gold, prevent the migration between copper and gold and diffusion.But because layer gold surface has certain hole in this technique, cause the scaling powder in layer gold or acid easily to migrate in nickel dam, thus make circuit board occur the phenomenon of black nickel (nickel corrosion), and make its dozen of gold thread abilities poor.
Therefore, a kind of new wiring board of exploitation and manufacture method thereof is needed badly.
Summary of the invention
The object of the invention is to solve the black nickel phenomenon of wiring board in prior art, beat the problem of gold thread ability and wiring board poor radiation, a kind of wiring board and manufacture method thereof are provided.
According to a first aspect of the invention; the invention provides a kind of wiring board; described wiring board comprises aluminum nitride ceramic substrate and the copper wire layer that is attached at least one surface of described aluminum nitride ceramic substrate and protective layer; described protective layer contains nickel dam, palladium layers and layer gold; described nickel dam connects with described copper wire layer, and two surfaces of described palladium layers connect with described nickel dam and described layer gold respectively.
According to a second aspect of the invention, present invention also offers the manufacture method of above-mentioned wiring board, the method be included in be attached to aluminum nitride ceramic substrate at least one surface on copper wire layer surface on form nickel dam, palladium layers and layer gold successively.
Wiring board of the present invention avoids black nickel phenomenon, and at high temperature can complete dozen gold thread test.Wiring board of the present invention also has higher heat dispersion.In addition, the thinner thickness of each protective layer in line layer of the present invention, also reduces the cost of wiring board.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to a first aspect of the invention; the invention provides a kind of wiring board; described wiring board comprises aluminum nitride ceramic substrate and the copper wire layer that is attached at least one surface of described aluminum nitride ceramic substrate and protective layer; described protective layer contains nickel dam, palladium layers and layer gold; described nickel dam connects with described copper wire layer, and two surfaces of described palladium layers connect with described nickel dam and described layer gold respectively.
According to the present invention, the adhesion between the protective layer that the thickness of described nickel dam, palladium layers and layer gold can be expected according to described wiring board is selected.In the present invention, the Thickness Ratio of described nickel dam, described palladium layers and described layer gold can be 1:0.005-0.1:0.002-0.1.Preferably, the Thickness Ratio of described nickel dam, described palladium layers and described layer gold is 1:0.01-0.05:0.01-0.03, so both can ensure the electric conductivity of described wiring board, turn avoid when manufacturing wiring board simultaneously, peeling off between described palladium layers and nickel dam.
According to one embodiment of the present invention, the thickness of described nickel dam can be 2-7 μm.Preferably, the thickness of described nickel dam is 3-5 μm, can play the effect stopping phase counterdiffusion between copper wire layer with layer gold described in wiring board so further.
The thickness of described palladium layers can be 0.05-0.2 μm.Preferably, the thickness of described palladium layers is 0.05-0.15 μm, layer gold in the process manufacturing described wiring board can be avoided on the one hand further simultaneously to replace with nickel dam and palladium layers, can avoid golden liquid and nickel generation displacement reaction further on the other hand.
The thickness of described layer gold can be 0.02-0.2 μm.Preferably, the thickness of described layer gold is 0.05-0.1 μm, layer gold surface can be avoided on the one hand further to occur more hole, can reduce the cost of described wiring board on the other hand further.
According to the present invention, the gross thickness of described protective layer and the Thickness Ratio of described copper wire layer can be 0.01-0.4:1.Preferably, the gross thickness of described protective layer and the Thickness Ratio of described copper wire layer are 0.06-0.1:1, and that can improve described wiring board so further beats gold thread ability.
The thickness of described copper wire layer can be selected according to the function of wiring board and the mechanical load born, and usually, can be 20-100 μm.Under preferable case, the thickness of described copper wire layer is 20-50 μm, can ensure that the rigidity of described wiring board can reduce again the cost of described wiring board like this.
In the present invention, in described wiring board, the thickness of each metal level all can adopt x-ray fluorescence spectrometry.
According to a second aspect of the invention, the invention provides a kind of manufacture method of wiring board, the method be included in be attached to aluminum nitride ceramic substrate at least one surface on copper wire layer surface on form nickel dam, palladium layers and layer gold successively.
Copper wire layer on aluminum nitride ceramic substrate of the present invention can obtain according to the method for this area routine.Usually, can thick film technology be adopted, namely utilize print process that copper slurry is coated substrate surface, then sinter through heat treatment, metallic copper slurry and obtain copper wire layer; Or use thin film technique, namely shaping by vacuum maskings such as sputtering, vacuum evaporations, ceramic base plate surface is metallized, forms described copper wire layer through photoetching, etching work procedure.The concrete steps that described copper wire layer is formed are the selection of this area routine, do not repeat them here.
Chemical nickel plating can be carried out to form described nickel dam to the surface of copper wire layer by chemical nickel-plating liquid.Usually, aluminum nitride ceramic substrate can be placed in the chemical nickel-plating liquid that temperature is 80-90 DEG C (as 83-86 DEG C), thus form nickel dam on the surface of the copper wire layer of substrate.The time of chemical nickel plating can be selected according to the thickness of the nickel dam of expection, can be generally 20-40min.
Nickel salt and hypophosphites can be contained in described chemical nickel-plating liquid.The content of described hypophosphites and described nickel salt can be the customary amount of this area.Such as, the content of described hypophosphites can be 15-50g/L, and the content of described nickel salt can be 12-45g/L.Under preferable case, the content of described hypophosphites is 20-45g/L, the content of described nickel salt is 20-35g/L, and described chemical nickel-plating liquid can be made like this to have higher stability, and makes to have higher adhesion between the copper wire layer on the nickel dam of formation and aluminum nitride ceramic substrate.
The kind of the present invention to described nickel salt and hypophosphites has no particular limits, and can be conventional selection.
Particularly, described nickel salt can be one or more in nickelous sulfate, nickel chloride and nickel acetate, is preferably nickelous sulfate.
Described hypophosphites can be sodium hypophosphite and/or potassium hypophosphite.From the angle reducing described chemical nickel-plating liquid cost, described hypophosphites is preferably sodium hypophosphite.
According to the present invention, described chemical nickel-plating liquid can also contain stabilizer, buffer and complexing agent, to avoid decomposition and the precipitation of chemical nickel-plating liquid.The present invention is not particularly limited the kind of described stabilizer, buffer and complexing agent and content thereof.
Described stabilizer can be at least one in sodium thiosulfate, potassium thiosulfate, thiocarbamide and xanthate.Preferably, described stabilizer is thiocarbamide.The content of described stabilizer can be 0.5-5mg/L.
Described buffer can be at least one in sodium acetate, sodium succinate and natrium hydrocitricum.Preferably, described buffer is sodium acetate.The content of described buffer can be 5-20g/L.
Described complexing agent can be at least one in succinic acid, sodium succinate, citric acid, natrium citricum, lactic acid, malic acid, glycine, is preferably natrium citricum.The content of described complexing agent can be 25-45g/L.
According to the present invention, in order to meet the requirement of chemical plating process, the pH of described chemical nickel-plating liquid is 4-5.
Be placed in by aluminum nitride ceramic substrate before chemical nickel-plating liquid carries out chemical nickel plating, the surface of method to described copper wire layer that this area can be adopted to commonly use activates.The present invention is not particularly limited for the method for being carried out activating in the surface of described copper wire layer, and the conventional method of this area can be adopted to carry out.
Usually, aluminum nitride ceramic substrate can be put into containing palladium activator and aqueous acid, so that will the copper wire layer activation forming coating be needed.Described palladium activator can be palladium bichloride, palladium sulfate one or both, be preferably palladium bichloride, described acid is preferably hydrochloric acid, and more preferably concentration is the hydrochloric acid of 37 % by weight.
The content of described palladium activator and acid can be conventional selection.Usually, the content of described palladium activator can be 0.2-2.5g/L, and concentration is the content of the hydrochloric acid of 37 % by weight can be 180-250mL/L.PH value containing palladium activator and aqueous acid can be generally 3-5.
When activating, the temperature containing palladium activator and aqueous acid can be 25-35 DEG C.The time of described palladium activation can be generally 30-90 second.
According to the present invention, after the surface of described copper wire layer forms nickel dam, described method can also be included in nickel dam surface successively plating palladium layers and the layer gold of formation, and the method for plating palladium layers and layer gold is the method for this area routine.
Particularly, the substrate that chemical nickel plating obtains can be placed in chemical palladium plating solution and carry out chemical palladium-plating, to form palladium layers on the surface of described nickel dam.Described chemical palladium plating solution can contain palladium salt, reducing agent, complexing agent and stabilizer.Described palladium salt can be one or more in palladium bichloride, palladium bromide and palladium sulfate, described reducing agent can be sodium hypophosphite, hydrazine or dimethylamine borane, described complexing agent can be ethylenediamine tetra-acetic acid and/or ethylenediamine, and described stabilizer can be one or more in ammonium chloride, sodium thiosulfate and THIOGLYCOL acid.
In described chemical palladium plating solution, the content of described palladium salt can be 3-10g/L, and the content of described reducing agent can be 0.5-15g/L, and the content of described complexing agent can be 15-35g/L, and the content of described stabilizer can be 15-30mg/L.
The condition of described chemical palladium-plating can comprise: pH value is 7-8, and temperature is 40-60 DEG C (as 45-55 DEG C).The processing time of described chemical palladium-plating can be 7-20min, is preferably 8-10min.
The substrate that chemical palladium-plating obtains can be placed in chemical gold plating liquid, to form layer gold further on palladium layers surface.Described chemical gold plating liquid can contain golden salt, reducing agent and complexing agent.Described golden salt can be one or more in potassium auricyanide, gold potassium cyanide and gold chloride, described reducing agent can be sodium hypophosphite, potassium borohydride, hydrazine or dimethylamine borane, and described complexing agent can be one or more in potassium cyanide, ethylenediamine tetra-acetic acid and monoethanolamine.
In described chemical gold plating liquid, the content of described golden salt can be 2-7g/L, and the content of described reducing agent can be 4-12g/L, and the content of described complexing agent can be 3-8g/L.
The condition of described chemical gilding can comprise: pH value is 7-8, and temperature is 80-85 DEG C.The processing time of described chemical gilding can be 8-11min.
In addition, before activating the surface of described copper wire layer, the method that this area can be adopted to commonly use carries out degreasing to the copper wire layer surface on substrate, and carries out microetch to the copper wire layer after degreasing.The method of described degreasing can be the routine selection of this area, no longer describes in detail herein.
The method of described microetch can comprise: carry out microetch with micro-etching agent to described copper wire layer, can contain sulfuric acid, hydrogen peroxide and copper chloride in described micro-etching agent.In the present invention, described sulfuric acid is preferably the sulfuric acid that concentration is more than 70 % by weight, and more preferably concentration is the sulfuric acid of 98 % by weight.
In described micro-etching agent, sulfuric acid, hydrogen peroxide and copper chloride content can be the customary amount of this area.Under preferable case, the content of sulfuric acid is 70-160g/L, and the content of hydrogen peroxide is 15-40g/L, and the content of copper chloride is 15-35g/L, has higher adhesive force between the nickel dam formed and copper wire layer after can making like this.
According to the present invention, in described micro-etching agent, stabilizer can also be contained.The present invention is not particularly limited the weight of described stabilizer and content, and usually, described stabilizer can be BTA and/or salicylic acid, and the content of described stabilizer can be 0.1-1.2g/L.
According to the present invention, in order to improve the speed of described microetch, the pH value of described micro-etching agent can be 2-4.
When carrying out microetch, the temperature of described microetch can be 15-35 DEG C; The time of described microetch can be 20-40s.
After carrying out each step chemical plating, conventional method can be adopted to wash the substrate through chemical plating.Particularly, the tertiary effluent washing trough substrate after each step process can being put into lasting overflow processes 50-70s.
After chemical plating completes, can also comprise and the wiring board of preparation is carried out drying.The condition of described drying can be conventional selection.Such as, can first be dried up by the moisture of PCB surface, the baking oven then putting into 80-100 DEG C is dried.
In more detail the present invention will be described by embodiment below.
In following examples and comparative example, acid degreasing agent is purchased from Shenzhen Success Technology Co., Ltd., and the trade mark is CG-1551; The composition of chemical palladium plating solution and chemical gold plating liquid and content thereof are as shown in Table 1.
The composition of the chemical nickel-plating liquid of embodiment 1-4 is as shown in table 2.
The thickness measuring of each protective layer on wiring board: according to x-ray fluorescence spectrometry.
The thermal conductivity test of wiring board: adopt laser Conduction Coefficient Detector Basing (originating from German Nai Chi company, LFA447 type), probe temperature is 25 DEG C.
Stretch (PULL) strength test: wiring board sample is cut into 3mm foursquare each 5 pieces (chessboard trellis) in length and breadth, amount to 25 fritters, then in layer gold, a nailhead-shaped lead is welded, (to be paused Mechanical Equipment Company purchased from Shanghai Songyuan by tensile testing machine after leaving standstill, model WDW-2) hot strength test is carried out to sample and records tensile strength values, pulling rate is 10mm/min, peels off position and is designated as defective between layers of copper and nickel dam, record underproof number.
Gold thread binding ability (WB) is tested: wiring board sample is cut into 3mm foursquare each 5 pieces (chessboard trellis) in length and breadth, amount to 25 fritters, by bracing wire tester (purchased from RHESCA society, model is PRT-30) sample is tested at 25 DEG C and 250 DEG C and records strength values, test speed is 500 μm/s, and test load is 20.4g, wherein, the diameter of gold thread is 45 μm, and gold content is 99.99%.The alloy situation that compound part occurs to rupture and gold thread cannot be adhered altogether is all designated as defective, records underproof sample number.
Be confirmed whether to occur nickel black by the tangent plane of scanning electron microscopic observation wiring board.
Table 1
Table 2
Embodiment 1-4
Embodiment 1-4 is for illustration of wiring board provided by the invention and preparation method thereof.
Step 1 a: acid degreasing agent surface attachment being had the aluminum nitride ceramic substrate (76mm × 12.5mm × 0.5mm) of copper wire layer (thickness is 50 μm) to put into 100mL/L carries out degreasing, with the Temperature Treatment 6min of 45 DEG C.
Step 2: be placed with successively by the substrate after degreasing in the tertiary effluent washing trough of lasting overflow and process 50s, with processing procedure liquid medicine before thorough cleaning base plate remained on surface.
Step 3: salicylic mixed solution substrate being put into sulfuric acid (concentration 98 % by weight), the hydrogen peroxide of 20g/L, 30g/L copper chloride and the 0.7g/L being furnished with 55mL/L carries out microetch, the pH controlling mixed solution is 2-3, with room temperature treatment 20s, the cupric oxide that removing copper surface oxidation is formed, to obtain fresh copper circuit surface.
Step 4: the substrate after microetch is placed with successively in the tertiary effluent washing trough of lasting overflow and processes 60s, processing procedure liquid medicine before residual with thorough clean plate face.
Step 5: the hydrochloric acid solution (concentration is 37 % by weight) substrate being put into 120mL/L carries out acidification, and the processing time is 40s, the substrate surface after activation microetch.
Step 6: the substrate after activation microetch is placed with in the tertiary effluent washing trough of lasting overflow successively and processes 60s, processing procedure liquid medicine before residual with thorough clean plate face.
Step 7: hydrochloric acid (concentration is 37 % by weight) mixed solution substrate being put into palladium bichloride and the 180mL/L being furnished with 2g/L, the pH controlling mixed solution is 4-5, processes 40s, to cause the deposition of nickel metal at the temperature of 30 DEG C.
Step 8: be placed with successively by substrate in the tertiary effluent washing trough of lasting overflow and process 60s, with processing procedure liquid medicine before residual between thorough cleaning base plate line layer.
Step 9: substrate is put into chemical nickel-plating liquid, controlling the pH of chemical nickel-plating liquid is 4-5, at the temperature of 85 DEG C, process 20min, thus at the copper wire layer surface deposition nickel dam of substrate.
Step 10: the substrate that deposited nickel dam is placed with successively in the tertiary effluent washing trough of lasting overflow and processes 60s, processing procedure liquid medicine before residual with thorough clean plate face.
Step 11: substrate is put into chemical palladium plating solution, controlling chemical palladium plating solution pH is 7-8, processes 10min, in nickel dam surface deposition palladium layers at the temperature of 48 DEG C.
Step 12: the substrate that deposited palladium layers is placed with successively in the tertiary effluent washing trough of lasting overflow and processes 60s, processing procedure liquid medicine before residual with thorough clean plate face.
Step 13: substrate is put into chemical gold plating liquid, the pH controlling chemical gold plating liquid is 7.5-8, processes 10min, in palladium layers surface deposition layer gold at the temperature of 85 DEG C.
Step 14: the substrate that deposited layer gold is placed with successively in the tertiary effluent washing trough of lasting overflow and processes 60s, processing procedure liquid medicine before residual with thorough clean plate face.
Step 15: baking oven substrate being put into 80 DEG C dries 12min, the moisture on removing substrate.
Thus the wiring board of obtained embodiment 1-4, the thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, replaces aluminum nitride ceramic substrate with the FR-4 epoxy resin base plate of same size, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Comparative example 2
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, does not carry out step 11-12, that is, do not carry out chemical palladium-plating to substrate, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Comparative example 3
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, replaces aluminum nitride ceramic substrate with the aluminium oxide ceramic substrate of same size, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Embodiment 5
The present embodiment is for illustration of wiring board of the present invention and manufacture method thereof.
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, the thickness of the copper wire layer on aluminum nitride ceramic substrate is 23 μm, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Embodiment 6
The present embodiment is for illustration of wiring board of the present invention and manufacture method thereof.
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, the thickness of the copper wire layer on aluminum nitride ceramic substrate is 65 μm, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Embodiment 7
The present embodiment is for illustration of wiring board of the present invention and manufacture method thereof.
Adopt the method identical with embodiment 1 to prepare wiring board, difference is, in step 11, the time of chemical palladium-plating is 20min, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Embodiment 8
The method identical with embodiment 1 is adopted to prepare wiring board, difference is, in step 3, salicylic mixed solution substrate being put into sulfuric acid (concentration 98 % by weight), the hydrogen peroxide of 39g/L, 32g/L copper chloride and the 1.5g/L being furnished with 100mL/L carries out microetch, the pH controlling mixed solution is 2-3, with room temperature treatment 20s, and the cupric oxide that removing copper surface oxidation is formed, to obtain fresh copper circuit surface, thus obtained wiring board.The thickness of each protective layer of wiring board and character are respectively as shown in Table 3 and Table 4.
Table 3
*: the Thickness Ratio of protective layer refers to the Thickness Ratio of nickel dam, palladium layers and layer gold.
Table 4
As can be seen from Table 4, wiring board of the present invention does not have black nickel to occur, and has higher gold thread binding ability, even 250 DEG C time, can meet gold thread bonding, and wiring board of the present invention has higher heat-sinking capability yet.In addition, between protective layer of the present invention and copper wire layer, there is higher adhesion.This shows, the scolding tin that wiring board of the present invention stands good in LED punch die welds.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a wiring board; this wiring board comprises aluminum nitride ceramic substrate and the copper wire layer that is attached at least one surface of described aluminum nitride ceramic substrate and protective layer; described protective layer contains nickel dam, palladium layers and layer gold; described nickel dam connects with described copper wire layer, and two surfaces of described palladium layers connect with described nickel dam and described layer gold respectively.
2. wiring board according to claim 1, wherein, the Thickness Ratio of described nickel dam, described palladium layers and described layer gold is 1:0.005-0.1:0.002-0.1.
3. wiring board according to claim 1, wherein, the gross thickness of described protective layer and the Thickness Ratio of described copper wire layer are 0.01-0.4:1.
4. according to the wiring board in claim 1-3 described in any one, wherein, the thickness of described nickel dam is 2-7 μm, and the thickness of described palladium layers is 0.05-0.2 μm, and the thickness of described layer gold is 0.02-0.2 μm.
5. according to the wiring board in claim 1-3 described in any one, wherein, the thickness of described copper wire layer is 20-100 μm.
6. the manufacture method of wiring board described in any one in claim 1-5, the method be included in be attached to aluminum nitride ceramic substrate at least one surface on copper wire layer surface on form nickel dam, palladium layers and layer gold successively.
7. method according to claim 6, wherein, by chemical nickel-plating liquid, chemical nickel plating is carried out to form nickel dam to the surface of copper wire layer, containing nickel salt, hypophosphites, stabilizer, buffer and complexing agent in described chemical nickel-plating liquid, and the content of described nickel salt is 12-45g/L, the content of described hypophosphites is 15-50g/L, and the content of described stabilizer is 0.5-5mg/L, the content of described buffer is 5-20g/L, and the content of described complexing agent is 25-45g/L; The pH value of described chemical nickel-plating liquid is 4-5.
8. the method according to claim 6 or 7, wherein, before the described protective layer of formation, the method also comprises carries out microetch with micro-etching agent to described copper wire layer, containing sulfuric acid, hydrogen peroxide and copper chloride in described micro-etching agent; And the content of sulfuric acid is 70-160g/L, the content of hydrogen peroxide is 15-40g/L, and the content of copper chloride is 15-35g/L; The pH value of described micro-etching agent is 2-4.
9. method according to claim 8, wherein, the temperature of described microetch is 15-35 DEG C; The time of described microetch is 20-40s.
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| CN201410120355.4A CN104955262A (en) | 2014-03-27 | 2014-03-27 | Circuit board and manufacturing method thereof |
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| CN201410120355.4A CN104955262A (en) | 2014-03-27 | 2014-03-27 | Circuit board and manufacturing method thereof |
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