CN109023448A - Filling perforation electro-plating method - Google Patents
Filling perforation electro-plating method Download PDFInfo
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- CN109023448A CN109023448A CN201811004521.9A CN201811004521A CN109023448A CN 109023448 A CN109023448 A CN 109023448A CN 201811004521 A CN201811004521 A CN 201811004521A CN 109023448 A CN109023448 A CN 109023448A
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- Prior art keywords
- filling perforation
- copper
- dummy
- plate body
- electro
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Abstract
The invention discloses a kind of filling perforation electro-plating methods, by adding formaldehyde in copper sulphate filling perforation electroplate liquid, and Dummy electrolysis is carried out in two times before starting filling perforation plating, the electrolysis of first time Dummy is electrolysed a few hours to add progress Dummy after cupric sulfate pentahydrate, sulfuric acid, hydrochloric acid in the plating solution, second of Dummy electrolysis is electrolysed a few hours to add progress Dummy after gloss agent, leveling agent, wetting agent, formaldehyde in the plating solution, it carries out formal filling perforation plating again by the electrolysis of Dummy twice, can be realized ideal filling perforation effect.
Description
Technical field
The present invention relates to electroplating technologies, in particular to a kind of filling perforation electro-plating method.
Background technique
Currently, industry of printed circuit boards either multi-layer PCB, HDI, FPC, Rigid-flex or LED/OLED and
Semiconductor can all be related to the electro-coppering fill process of blind hole or through-hole, because constructing the requirement of multilayer circuit, it is necessary to pass through
Blind hole or through-hole are filled up (hereinafter referred to as filling perforation or Via Filling) by the mode of electro-coppering, need to lead to before filling perforation
The mode for crossing chemistry or physics forms conductive seed layer (copper, carbon, Ni, Ni-Cr, Organic Conductive Films etc.) in hole wall, to ensure
It the circulation of electric current when plating and is uniformly distributed.
At this stage, the electroplating device for being mostly used in filling perforation is insoluble anode copper sulphate filling perforation electroplating device, this sets
For using insoluble anode, that is, there is IrO2There are anode or anode diaphragm package in the titanium net or titanium plate of coating, outside,
Agitating mode is jet flow stirring in slot, by the constant current output of motor-generator set substrate two sides electricity plated with copper.Such equipment plating
Stability is preferable, the easy maintenance in use process, but the copper oxide (CuO) as used in Ni―Ti anode and supplement copper ion
With copper carbonate (CuCO3) costly, so whole operating cost can be higher.
For insoluble anode copper sulphate filling perforation electroplating device, resolvability anode copper sulphate filling perforation plating is set
Standby operating cost is lower, however, resolvability anode copper sulphate filling perforation electroplating device has, the earth of positive pole is more, maintenance work amount
Greatly, the disadvantages of copper particle abnormal risk is big, medical fluid stability is poor is generated.Figure 1A and Figure 1B is existing resolvability anode
The filling effect schematic diagram of copper sulphate filling perforation electroplating device, it can be seen that the filling effect that Figure 1A is shown is very undesirable, Figure 1B
Then almost without filling effect.
For some medium-sized and small enterprises, in the high speed development of PCB industry, the ability that constantly upgrades and improve is needed
It survives, filling perforation electroplating technology is their the only way which must be passed, however, insoluble anode copper sulphate filling perforation electroplating device great number
Operating cost make them be difficult to bear, therefore, many electroplate liquid manufacturers attempt solvable to solve by developing new electroplate liquid
The undesirable problem of the filling effect of solution property anode copper sulphate filling perforation electro-plating method, however the effect is unsatisfactory.
Summary of the invention
It is an object of the invention to propose a kind of filling perforation electro-plating method, can more be managed for the blind hole realization in copper-clad plate
The landfill effect thought.
In order to achieve the above object, the present invention provides a kind of filling perforation electro-plating method, comprising:
Step 1 provides copper-clad plate, and the copper-clad plate includes dielectric layer and is covered each by the in the dielectric layer two sides
One copper foil and the second copper foil；
Step 2 forms blind hole using bore process in the copper-clad plate, and the blind hole is through first copper foil and is situated between
Electric layer；
Step 3, the shape on first copper foil, the hole wall of the blind hole and the second copper foil positioned at the blind via bottom
At copper conductive layer, first copper foil is connected with the second copper foil using the copper conductive layer, obtains copper sheet to be plated；
Step 4 fills the blind hole on the copper sheet to be plated by the way of electro-coppering；The step 4 is specifically wrapped
It includes:
Step 41 provides resolvability anode copper sulphate filling perforation electroplating device, the resolvability anode copper sulphate filling perforation
Electroplating device includes electroplating bath, power supply, the copper sulphate filling perforation electroplate liquid in the electroplating bath, the positive phase with the power supply
Company and the resolvability anode immersed in the copper sulphate filling perforation electroplate liquid, the Dummy plate being connected with the cathode of the power supply；
The copper sulphate filling perforation electroplate liquid includes water, cupric sulfate pentahydrate, sulfuric acid, hydrochloric acid；
It opens power supply and carries out first time Dummy electrolysis a few hours；
Leveling agent, gloss agent, wetting agent and formaldehyde is added in the copper sulphate filling perforation electroplate liquid in step 42, carries out the
After secondary Dummy electrolysis a few hours, Dummy plate is removed, the copper sheet to be plated is connect with the cathode of the power supply, starts filling perforation
Plating.
Optionally, first time Dummy is electrolysed 3-6 hours in the step 41, second of Dummy electrolysis in the step 42
8-12 hours.
Optionally, the resolvability anode includes titanium basket and the P-Containing Copper Ball in the titanium basket；It is described phosphorous
The phosphorus content of copper ball is 0.03wt%~0.08wt%.
Optionally, the diameter of the P-Containing Copper Ball is 25-60mm.
Optionally, agitating device, the stirring dress are additionally provided in the resolvability anode copper sulphate filling perforation electroplating device
Set include: pump outside the electroplating bath, inlet tube, outlet tube and the first plate body inside the electroplating bath with
Second plate body；
First plate body is oppositely arranged with the second plate body, is equipped with first jet on first plate body, and described second
Second nozzle is installed, first plate body and the second plate body are immersed in the copper sulphate filling perforation electricity in the electroplating bath on plate body
In plating solution；
The fluid passage being connected to the first jet is equipped in first plate body；It is equipped with and institute in second plate body
State the fluid passage of second nozzle connection；
The electroplating bath is equipped with inlet and liquid outlet, and the pump has liquid sucting port and leakage fluid dram, the imbibition of the pump
Mouthful be connected to the liquid outlet of the electroplating bath by inlet tube, the leakage fluid dram of the pump pass through outlet tube and the electroplating bath into
The connection of liquid mouth, and the fluid passage of first plate body and the second plate body is connected by the inlet of pipeline and the electroplating bath
It is logical；
In first time Dummy electrolysis with second of Dummy electrolytic process, the Dummy plate is located at first plate body
Between the second plate body；
In filling perforation electroplating process, the copper sheet to be plated is between first plate body and the second plate body.
Optionally, the power supply includes motor-generator set；The Dummy plate is to drag cylinder plate.
Optionally, in the electroplating process of the step 4, it is solid that cupric sulfate pentahydrate is added in the copper sulphate filling perforation electroplate liquid
Body and/or in the titanium basket add P-Containing Copper Ball with to the copper sulphate filling perforation electroplate liquid supplement copper ion.
Optionally, in the copper sulphate filling perforation electroplate liquid, the concentration of cupric sulfate pentahydrate molecule is 100~280g/L, sulfuric acid
The concentration of molecule is 10~200g/L, and the concentration of chloride ion is 20~100mg/L, the concentration of formaldehyde molecule is 850~
20000mg/L, the concentration of oxygen are 6~10mg/L.
Optionally, in the copper sulphate filling perforation electroplate liquid, the concentration of formaldehyde molecule is 850~5000mg/L.
Optionally, in the copper sulphate filling perforation electroplate liquid, the additive amount of gloss agent is 0.5-2ml/L, the addition of leveling agent
Amount is 10-30ml/L, and the additive amount of wetting agent is 10-20ml/L.
Beneficial effects of the present invention: the present invention provides a kind of filling perforation electro-plating method, by copper sulphate filling perforation electroplate liquid
Formaldehyde is added, and carries out Dummy electrolysis in two times before starting filling perforation plating, first time Dummy, electrolysis is in the plating solution
It is carried out Dummy electrolysis a few hours after adding cupric sulfate pentahydrate, sulfuric acid, hydrochloric acid, second of Dummy electrolysis is to add light in the plating solution
Dummy is carried out after damp agent, leveling agent, wetting agent, formaldehyde and is electrolysed a few hours, carries out formal fill out again by the electrolysis of Dummy twice
Hole plating, can be realized ideal filling perforation effect.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, letter will be made to attached drawing needed in the embodiment below
It singly introduces, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as to the present invention
The restriction of protection scope.
Figure 1A and Figure 1B is the effect signal that filling perforation is carried out using existing soluble anode copper sulphate filling perforation electroplating device
Figure；
Fig. 2 is the flow chart of filling perforation electro-plating method of the invention；
Fig. 3 is the schematic diagram of filling perforation electro-plating method step 1 of the invention；
Fig. 4 is the schematic diagram of filling perforation electro-plating method step 2 of the invention；
Fig. 5 is the schematic diagram of filling perforation electro-plating method step 3 of the invention；
Fig. 6 is the schematic diagram of filling perforation electro-plating method step 4 of the invention；
Fig. 7 is the resolvability anode copper sulphate filling perforation electroplating device that filling perforation electro-plating method step 4 of the invention uses
Structural schematic diagram；
Fig. 8 is the action principle schematic diagram of gloss agent and inhibitor in the present invention and existing filling perforation electro-plating method；
Fig. 9 is the instrumentation plan of blind hole related data after filling perforation plating in filling perforation electro-plating method embodiment 1 of the invention；
Figure 10 is the schematic diagram for failing to fill in phenomenon in the present invention and existing filling perforation electro-plating method；
Figure 11 is the schematic diagram of the present invention and the hole metallization abnormal phenomenon in existing filling perforation electro-plating method.
Main element symbol description:
10, copper-clad plate；11, dielectric layer；12, the first copper foil；13, the second copper foil；20, blind hole；30, copper conductive layer；40, to
Plate copper sheet；50, resolvability anode copper sulphate filling perforation electroplating device；51, electroplating bath；52, power supply；53, resolvability anode；
54, agitating device；531, titanium basket；532, P-Containing Copper Ball；541, the first plate body；542, the second plate body；543, first jet；544,
Second nozzle；61, it pumps；62, inlet tube；63, outlet tube；64, pipeline；71, secondary slot；72, inflating pump；73, air-inflating tube；74, it follows
Endless tube.
Specific embodiment
Term as used herein:
" by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing "
Or its any other deformation, it is intended that cover non-exclusionism includes.For example, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step
Suddenly, method, product or the intrinsic element of device.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim,
This phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
" mass parts " refer to the basic measurement unit for indicating the mass ratio relationship of multiple components, and 1 part can indicate arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
Measuring part is b parts, then it represents that the quality of component A and the mass ratio a:b of B component.Alternatively, indicating that the mass ratio of component A is aK, B
The mass ratio of component is bK (K is arbitrary number, indicates multiplying factor).It can not misread, unlike mass fraction, own
The sum of mass parts of component are not limited to 100 parts of limitation.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B)；
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
Referring to Fig. 2, the present invention provides a kind of filling perforation electro-plating method, comprising:
Step 1, as shown in figure 3, providing copper-clad plate 10, the copper-clad plate 10 includes dielectric layer 11 and being covered each by institute
Give an account of the first copper foil 12 and the second copper foil 13 of 11 two sides of electric layer.
It is formed specifically, the dielectric layer 11 makees reinforcing material leaching by wood pulp paper or glass-fiber-fabric etc. with resin.
Step 2, as shown in figure 4, forming blind hole 20 in the copper-clad plate 10 using bore process, the blind hole 20 runs through
First copper foil 12 and dielectric layer 11.
Specifically, the bore process is laser drilling process.
Step 3, as shown in figure 5, first copper foil 12, the blind hole 20 hole wall and be located at 20 bottom of blind hole
Copper conductive layer 30 is formed on second copper foil 13 in portion, using the copper conductive layer 30 by first copper foil 12 and the second copper foil 13
Conducting, obtains copper sheet 40 to be plated.
Specifically, in the step 3, using electroless copper, DMSE (Organic Conductive Films), black holes (Black hole) or
The techniques such as shadow (shadow) prepare the copper conductive layer 30.
Step 4, as shown in fig. 6, being filled by the way of electro-coppering to the blind hole 20 on the copper sheet 40 to be plated；Institute
Step 4 is stated to specifically include:
Step 41, as shown in fig. 7, provide resolvability anode copper sulphate filling perforation electroplating device 50, resolvability sun
Pole copper sulphate filling perforation electroplating device 50 includes electroplating bath 51, power supply 52, the copper sulphate filling perforation plating in the electroplating bath 51
Liquid is connected with the anode of the power supply 52 and immerses the resolvability anode 53 in the copper sulphate filling perforation electroplate liquid and institute
State connected Dummy (false cathode) plate of the cathode of power supply 52；The copper sulphate filling perforation electroplate liquid includes water, cupric sulfate pentahydrate
(CuSO4·5H2O), sulfuric acid (H2SO4), hydrochloric acid (HCl)；
It opens power supply 52 and carries out first time Dummy electrolysis a few hours；
Leveling agent, gloss agent, wetting agent and formaldehyde (HCHO) is added in the copper sulphate filling perforation electroplate liquid in step 42,
After carrying out second of Dummy electrolysis a few hours, Dummy plate is removed, the cathode of the copper sheet 40 to be plated and the power supply 52 is connected
It connects, starts filling perforation plating.
As shown in figure 5, filling perforation electro-plating method of the invention can be realized extraordinary filling perforation effect, blind hole 20 is filled out by copper
It is full, and copper-plated smooth surface in blind hole 20.
Specifically, the resolvability anode copper sulphate filling perforation electroplating device 50 is before the use, first in the step 41
First electroplating bath 51 is cleaned, after cleaning, be added in electroplating bath 51 first a certain amount of deionized water (DI water,
Deionized Water), the cupric sulfate pentahydrate, sulfuric acid, hydrochloric acid of specified amount are sequentially added, copper sulphate filling perforation electroplate liquid is obtained.
Specifically, the step 41 is capable of forming the black film on covering phosphorus-copper anode surface simultaneously by first time Dummy electrolysis
Remove impurities in material；The step 42 is able to ascend the copper sulphate filling perforation electroplate liquid by second of Dummy electrolysis
Activity, to obtain better filling perforation effect.
Specifically, the Dummy plate can be to drag cylinder plate.
Optionally, first time Dummy is electrolysed 3-6 hours (such as 3 hours, 4 hours, 5 hours, 6 hours in the step 41
Deng), second of Dummy is electrolysed 8-12 hours (such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours in the step 42
Deng).
Preferably, Dummy is electrolysed 4 hours in the step 41, and Dummy is electrolysed 10 hours in the step 42, at this
Very excellent filling perforation effect, hole surface recess value≤3 μm can be obtained under part.
Specifically, the resolvability anode 53 includes in the resolvability anode copper sulphate filling perforation electroplating device 50
Titanium basket 531 and the P-Containing Copper Ball 532 in the titanium basket 531, the phosphorus content of the P-Containing Copper Ball 532 be 0.03wt%~
0.08wt%, such as 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt% etc..Specifically,
Anode (not shown) is also arranged with outside the titanium basket 531.
Specifically, the diameter of the P-Containing Copper Ball 532 can be 25-60mm, such as 25mm, 30mm, 35mm, 40mm,
45mm、50mm、55mm、60mm。
Specifically, it is additionally provided with agitating device 54 in the resolvability anode copper sulphate filling perforation electroplating device 50, it is described to stir
Device 54 is mixed to include: pump 61 outside the electroplating bath 51, inlet tube 62, outlet tube 63 and be set to the electroplating bath 51
Internal the first plate body 541 and the second plate body 542；
First plate body 541 is oppositely arranged with the second plate body 542, is equipped with first jet on first plate body 541
543, second nozzle 544 is installed on second plate body 542, first plate body 541 and the second plate body 542 are immersed in institute
It states in the copper sulphate filling perforation electroplate liquid in electroplating bath 51；
The fluid passage (not shown) being connected to the first jet 543 is equipped in first plate body 541；Described second
The fluid passage (not shown) being connected to the second nozzle 544 is equipped in plate body 542；
The electroplating bath 51 is equipped with inlet and liquid outlet, and the pump 61 has liquid sucting port and leakage fluid dram, the pump 61
Liquid sucting port be connected to the liquid outlet of the electroplating bath 51 by inlet tube 62, the leakage fluid dram of the pump 61 pass through outlet tube 63 and
The inlet of the electroplating bath 51 is connected to, and the fluid passage of first plate body 541 and the second plate body 542 passes through pipeline 64
It is connected to the inlet of the electroplating bath 51；
In first time Dummy electrolysis with second of Dummy electrolytic process, the Dummy plate is located at first plate body
541 and second between plate body 542；
In filling perforation electroplating process, the copper sheet 40 to be plated is between first plate body 541 and the second plate body 542.
Optionally, the pump 61 is jet-pump.
The copper sulphate filling perforation electroplate liquid is flowed into first via pump 61 by sucking and the discharge effect of pump 61 by the present invention
Nozzle 543 and second nozzle 544 simultaneously spray the mixing effect for realizing the copper sulphate filling perforation electroplate liquid.
Specifically, the resolvability anode copper sulphate filling perforation electroplating device 50 further includes secondary slot 71, inflating pump 72, inflates
Pipe 73, the copper sulphate filling perforation electroplate liquid in the pair slot 71 pass through the copper sulphate filling perforation electricity in circulation pipe 74 and the electroplating bath 51
Plating solution connection, the inflating pump 72 is for sucking air and the air of sucking being discharged into the secondary slot 71 via the air-inflating tube 73
In interior copper sulphate filling perforation electroplate liquid.
Specifically, the circulation pipe 74 is that common PVC (polyvinyl chloride) is managed.
The present invention passes through the inflating pump 72 that pair slot 71 is arranged and air-inflating tube 73 carries out air stirring and electroplating bath 51 and pair
The mode that slot 71 recycles is mixed into the air containing oxygen in the copper sulphate filling perforation electroplate liquid, promotes the copper sulphate filling perforation electricity
Cu in plating solution+It is oxidized to Cu2+, eliminate Cu+Adverse effect to plating.
Specifically, five water sulfuric acid can be added in the copper sulphate filling perforation electroplate liquid in the electroplating process of the step 4
Copper solid and/or in the titanium basket 531 add P-Containing Copper Ball 532 with to the copper sulphate filling perforation electroplate liquid supplement copper ion,
Since the price of copper ball and cupric sulfate pentahydrate solid is lower, the resolvability anode copper sulphate filling perforation that the present invention uses is electroplated
The operating cost of equipment 50 is lower, is far below and uses CuO or CuCO3It is filled out to supplement the insoluble anode copper sulphate of copper ion
Hole electroplating device.
In addition, since cost is relatively low for soluble anode, not relative to the Ti anode of use price costly
For dissolubility anode copper sulphate filling perforation electroplating device, resolvability anode copper sulphate filling perforation electroplating device 50 that the present invention uses
Production cost it is lower, price is more cheap.
Specifically, the power supply 52 includes motor-generator set in the resolvability anode copper sulphate filling perforation electroplating device 50, lead to
Two sides electricity plated with copper of the constant current output of over commutation machine in copper sheet 40 to be plated.
In the actual production process, copper sulphate filling perforation electroplate liquid needs maintain good work by being continuously electroplated
Property, when there are end-of-life state, again carry out filling perforation electroplating technology before, need in copper sulphate filling perforation electroplate liquid add 10~
The formaldehyde of 1000mg/L, then 0.5~12 hour (determining according to practical halt production situation) is persistently electroplated, copper sulphate filling perforation can be restored
The filling perforation performance of electroplate liquid.The content of formaldehyde in copper sulphate filling perforation electroplate liquid can be analyzed by ultraviolet specrophotometer,
It can repeatedly be added on a small quantity when content of formaldehyde deficiency.
Specifically, the concentration of cupric sulfate pentahydrate molecule is 100~280g/L, sulfuric acid in the copper sulphate filling perforation electroplate liquid
Molecule (H2SO4) concentration be 10~200g/L, chloride ion (Cl-) concentration be 20~100mg/L, the concentration of formaldehyde molecule is
850~20000mg/L, the concentration of oxygen are 6~10mg/L.
Preferably, in the copper sulphate filling perforation electroplate liquid, the concentration of formaldehyde molecule is 850~5000mg/L.
Specifically, the leveling agent, gloss agent and wetting agent are the common used material of this field, therefore the present invention is not to it
Ingredient is specifically limited.
Optionally, in the copper sulphate filling perforation electroplate liquid, the additive amount of gloss agent is 0.5-2ml/L, such as 0.5ml/L,
1ml/L, 1.5ml/L, 2ml/L etc., the additive amount of leveling agent are 10-30ml/L, for example, 10ml/L, 15ml/L, 20ml/L,
25ml/L, 30ml/L etc., the additive amount of wetting agent are 10-20ml/L, such as 10ml/L, 15ml/L, 20ml/L etc..
The present invention can obtain by the way that formaldehyde is added in copper sulphate filling perforation electroplate liquid and inhibit in copper deposition to surface and add
The good result of fast recess (in such as blind hole 20 or through-hole) copper deposition is made a concrete analysis of as follows:
When carrying out copper sulphate filling perforation plating using soluble anode electroplating device, Cu can be generated since anode copper is oxidized+, it may occur that following redox reaction:
Cu+-e-→Cu2+(oxidation reaction), SPS+e-→ MPS (reduction reaction), wherein e-For electronics, SPS is gloss agent master
Ingredient is wanted, MPS is the reduction-state of SPS.The content of MPS in copper sulphate filling perforation electroplate liquid is caused to increase since above-mentioned reaction occurs,
And MPS, to 20 times or so that the acceleration of copper deposition rate in electroplating process is SPS, the acceleration effect of such gloss agent is with regard to remote
It is described far more than the effect (inhibitor plays the role of that copper is inhibited to deposit on 40 surface of copper sheet to be plated) of inhibitor
Copper fast deposition at a same speed in 40 surface of copper sheet to be plated and the blind hole 20, therefore blind hole 20 can not just be filled out；
As shown in figure 8, inhibitor, since molecular weight is big, primary attachment plays inhibition copper on 40 surface of copper sheet to be plated
The effect of deposition, gloss agent can then enter in the blind hole 20 while being adsorbed in 40 surface of copper sheet to be plated, work as gloss
The content of agent far super inhibitor when, inhibitor can not play a role, and copper deposition thickness b can not far surmount always in the blind hole 20
The 40 surface deposition thickness a of copper sheet to be plated, the height c of 20 depressed area of blind hole can not be filled up, and filling perforation is caused to fail；
After the present invention adds formaldehyde in the copper sulphate filling perforation electroplate liquid, since formaldehyde has reproducibility, lead to anode
Copper is in oxidation process, the Cu that can generate originally+(reaction 1) can not be generated, anode copper is direct oxidation into Cu2+(reaction 2), no Cu+It generates, is just converted to the process of MPS without SPS naturally, effect of the gloss agent on 40 surface of copper sheet to be plated would not be too
By force, inhibitor can play its effect, and for copper deposition rate much larger than copper deposition rate on face, 20 depressed area of blind hole will in hole
It is filled；
Cu-e-→Cu+(reaction 1), Cu-2e-→Cu2+(reaction 2).
Filling perforation electro-plating method of the invention and its effect are described in detail in the form of specific embodiment below.
Embodiment 1
The evaluation of 20 filling perforation plating performance of blind hole.
For 100 μm of diameter, the blind hole 20 of 80 μm of depth, first make to lead in hole with the mode of horizontal electroless copper (PTH)
Electrification, carry out Quality Detection, confirm 20 hole of blind hole in copper deposition OK when, using following 6 kinds of plating solutions (plating solution 1~3 of the present invention, than
Compared with plating solution 1~3) carry out electro-coppering filling perforation.25 DEG C of bath temperature, anode is 0.03%~0.08% phosphorous copper balls of phosphorus content, yin
Pole (copper sheet 40 to be plated) side current density 2.0A/dm2, jet flow is opened using pump 61 and is stirred, and secondary slot 71 opens air stirring to protect
Plating solution oxygen content is demonstrate,proved in 6~10ppm, electroplating time 36min, first with dragging cylinder plate to carry out 1A/dm before test2Dummy electrolysis 1
Hour.After the completion of plating, section (section at 20 middle position of blind hole) grinding and observation are carried out to blind hole 20, measure blind hole 20
Aperture a, hole depth b, face copper c, recess value d, face copper e confirm filling perforation performance with real data.
(filling perforation copper sulfate bath composition)
Plating solution 1 of the present invention
CuSO4·5H2O:230g/L
H2SO4: 70g/L
Cl-: 50mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
HCHO:1000mg/L
Plating solution 2 of the present invention
CuSO4·5H2O:200g/L
H2SO4: 100g/L
Cl-: 60mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
HCHO:1000mg/L
Plating solution 3 of the present invention
CuSO4·5H2O:270g/L
H2SO4: 30g/L
Cl-: 70mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
HCHO:1000mg/L
Compare plating solution 1
CuSO4·5H2O:230g/L
H2SO4: 70g/L
Cl-: 50mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
Compare plating solution 2
CuSO4·5H2O:200g/L
H2SO4: 100g/L
Cl-: 60mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
Compare plating solution 3
CuSO4·5H2O:270g/L
H2SO4: 30g/L
Cl-: 70mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
As shown in figure 9, blind hole 20 related data a, b, c, d, e (unit μm) after measurement filling perforation plating, the result is as follows:
From the point of view of upper table result, the plating solution 1-3 of the present invention for adding HCHO has excellent performance in filling perforation aspect of performance, compares
Plating solution 1-3 is then substantially without filling perforation effect.
Embodiment 2
The implementation result comparative evaluation of different HCHO concentration.
Using test substrate totally 70, having a size of 510mm*410mm, every 20 quantity 600,000 of chip base board blind hole, 20 hole of blind hole
110 μm of diameter, 80 μm of hole depth.First make conducting in hole with the mode of horizontal electroless copper, carry out Quality Detection, confirms blind hole 20
In hole when copper deposition OK, electro-coppering filling perforation, every kind of 10 plate base of condition are carried out using the plating solution of following 7 kinds of differences HCHO concentration
(copper sheet 40 to be plated).25 DEG C of bath temperature, anode is 0.03%~0.08% phosphorous copper balls of phosphorus content, cathode (copper sheet 40 to be plated) side
Current density 2.0A/dm2, open jet flow using pump 61 and stir, secondary slot 71 open air stirring with guarantee plating solution oxygen content 6~
In 10ppm, electroplating time 43min, first with dragging cylinder plate to carry out 1A/dm before test2Dummy is electrolysed 1 hour.After the completion of plating,
Filling perforation situation is detected using AOI, statistics blind hole 20 fails to fill in quantity, and carries out section confirmation, and hole metallization is bad to lead to exclude
What is caused fails to fill in exception.
Bath composition:
CuSO4·5H2O:230g/L
H2SO4: 80g/L
Cl-: 50mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
Such as there is phenomenon as shown in Figure 10 after filling perforation plating, blind hole 20 substantially without filling perforation effect, is referred to as in the industry
Phenomenon is failed to fill in, can be detected by AOI.But problem corresponding to Figure 11 is hole metallization caused by abnormal, therefore is not counted in
It fails to fill in abnormal results statistics.By carrying out AOI scanning to the substrate after the completion of above each condition plating, as a result record is seen below
Table:
From the point of view of upper table, when HCHO concentration is within the scope of 850~20000mg/L, it is qualified to fail to fill in rate；HCHO concentration is lower than
When 800mg/L, fails to fill in rate and obviously rise.For comprehensive filling perforation effect with from the point of view of Environmental Factors, the most preferred concentration range of HCHO is 850
~5000mg/L.
Embodiment 3
Whether need to carry out the verifying of Dummy electrolysis after addition HCHO.
Plating solution compound concentration is as follows:
CuSO4·5H2O:230g/L
H2SO4: 80g/L
Cl-: 50mg/L
Gloss agent: 1ml/L
Leveling agent: 20ml/L
Wetting agent: 15ml/L
HCHO:1000mg/L
Test comparison condition:
The blind hole 20 of 100 μm of diameter, 80 μm of depth first makes conducting in hole with the mode of horizontal electroless copper, carries out
Quality Detection is filled out when confirming copper deposition OK in 20 hole of blind hole using above-mentioned 4 kinds of condition plating solutions (condition 1~4) to carry out electro-coppering
Hole.25 DEG C of bath temperature, anode is 0.03%~0.08% phosphorous copper balls of phosphorus content, and cathode side current density 2.0A/dm2 is utilized
Pump 61 opens jet flow stirring, and secondary slot 71 opens air stirring to guarantee plating solution oxygen content in 6~10ppm, and electroplating time is
36min.After the completion of plating, section (section at 20 middle position of blind hole) grinding and observation are carried out to blind hole 20, measure blind hole
20 aperture a, hole depth b, face copper c, recess value d, face copper e confirm filling perforation performance with real data.
Reference implementation example 1 measures blind hole 20 related data a, b, c, d, e (unit μm) after filling perforation plating, the result is as follows:
In upper table, OK represents d≤10 μm, and filling perforation effect is more satisfactory, and NG represents 10 μm of d >, and filling perforation effect is undesirable.
From the point of view of upper table result, newly match plating solution, must be carried out after addition gloss agent, leveling agent, wetting agent, HCHO
Dummy electrolysis, could obtain good filling perforation performance；Before carrying out filling perforation electroplating activity again after halt production, it need to add certain
The HCHO of amount and dummy electrolysis is carried out, can just restore filling perforation performance.
Existing Normal practice (i.e. condition 2) is to add VMS (CuSO in the plating solution4·5H2O、H2SO4, HCl) carry out afterwards
Dummy electrolysis then directly carries out filling perforation electroplating operations after adding gloss agent, leveling agent, wetting agent, HCHO in the plating solution, however,
The filling perforation effect of this operation is very undesirable；The present invention after addition gloss agent, leveling agent, wetting agent, HCHO by continuing
Filling perforation electroplating operations are carried out again after carrying out Dummy electrolysis a few hours, can be realized preferable filling perforation effect.
The numberical range of each parameter as involved in the present invention can not all embody in the above-described embodiments, but this
As long as the technical staff in the field envisioned any numerical value fallen into above-mentioned each numberical range completely can be implemented the present invention,
It certainly also include any combination of occurrence in several numberical ranges.Herein, due to space considerations, be omitted provide it is a certain
The embodiment of occurrence in item or multinomial numberical range, this is not to be construed as the insufficient disclosure of technical solution of the present invention.
It should be clear to those skilled in the art, any improvement in the present invention, to each raw material of product of the present invention
Equivalence replacement and auxiliary element addition, concrete mode selection etc., fall within the scope of protection of the present invention.
Claims (10)
1. a kind of filling perforation electro-plating method characterized by comprising
Step 1 provides copper-clad plate, and the copper-clad plate includes dielectric layer and is covered each by the first bronze medal of the dielectric layer two sides
Foil and the second copper foil；
Step 2 forms blind hole using bore process in the copper-clad plate, and the blind hole runs through first copper foil and dielectric
Layer；
Step 3 forms copper on first copper foil, the hole wall of the blind hole and the second copper foil positioned at the blind via bottom
First copper foil is connected with the second copper foil using the copper conductive layer, obtains copper sheet to be plated by conductive layer；
Step 4 fills the blind hole on the copper sheet to be plated by the way of electro-coppering；The step 4 specifically includes:
Step 41 provides resolvability anode copper sulphate filling perforation electroplating device, the resolvability anode copper sulphate filling perforation plating
Equipment includes electroplating bath, power supply, the copper sulphate filling perforation electroplate liquid in the electroplating bath, is connected simultaneously with the anode of the power supply
And the resolvability anode immersed in the copper sulphate filling perforation electroplate liquid, the Dummy plate being connected with the cathode of the power supply；It is described
Copper sulphate filling perforation electroplate liquid includes water, cupric sulfate pentahydrate, sulfuric acid, hydrochloric acid；
It opens power supply and carries out first time Dummy electrolysis a few hours；
Leveling agent, gloss agent, wetting agent and formaldehyde is added in the copper sulphate filling perforation electroplate liquid in step 42, carries out second
After Dummy is electrolysed a few hours, Dummy plate is removed, the copper sheet to be plated is connect with the cathode of the power supply, starts filling perforation electricity
Plating.
2. filling perforation electro-plating method as described in claim 1, which is characterized in that first time Dummy is electrolysed 3-6 in the step 41
Hour, second of Dummy is electrolysed 8-12 hours in the step 42.
3. filling perforation electro-plating method as described in claim 1, which is characterized in that the resolvability anode includes titanium basket and sets
P-Containing Copper Ball in the titanium basket；The phosphorus content of the P-Containing Copper Ball is 0.03wt%~0.08wt%.
4. filling perforation electro-plating method as claimed in claim 3, which is characterized in that the diameter of the P-Containing Copper Ball is 25-60mm.
5. filling perforation electro-plating method as described in claim 1, which is characterized in that the resolvability anode copper sulphate filling perforation plating
Be additionally provided with agitating device in equipment, the agitating device include: pump outside the electroplating bath, inlet tube, outlet tube with
And the first plate body and the second plate body inside the electroplating bath；
First plate body is oppositely arranged with the second plate body, and first jet, second plate body are equipped on first plate body
On second nozzle is installed, first plate body and the second plate body are immersed in the copper sulphate filling perforation electroplate liquid in the electroplating bath
In；
The fluid passage being connected to the first jet is equipped in first plate body；It is equipped in second plate body and described the
The fluid passage of two nozzles connection；
The electroplating bath is equipped with inlet and liquid outlet, and the pump has liquid sucting port and leakage fluid dram, and the liquid sucting port of the pump is logical
It crosses inlet tube to be connected to the liquid outlet of the electroplating bath, the leakage fluid dram of the pump passes through the inlet of outlet tube and the electroplating bath
Connection, and first plate body is connected to by pipeline with the inlet of the electroplating bath with the fluid passage of the second plate body；
In first time Dummy electrolysis with second Dummy electrolytic process, the Dummy plate is located at first plate body and the
Between two plate bodys；
In filling perforation electroplating process, the copper sheet to be plated is between first plate body and the second plate body.
6. filling perforation electro-plating method as described in claim 1, which is characterized in that the power supply includes motor-generator set；The Dummy plate
To drag cylinder plate.
7. filling perforation electro-plating method as claimed in claim 3, which is characterized in that in the electroplating process of the step 4, in the sulphur
Cupric sulfate pentahydrate solid is added in sour copper filling perforation electroplate liquid and/or P-Containing Copper Ball is added in the titanium basket to the copper sulphate
Filling perforation electroplate liquid supplements copper ion.
8. filling perforation electro-plating method as described in claim 1, which is characterized in that in the copper sulphate filling perforation electroplate liquid, five water sulphur
The concentration of sour copper molecule is 100~280g/L, and the concentration of sulfuric acid molecule is 10~200g/L, the concentration of chloride ion is 20~
100mg/L, the concentration of formaldehyde molecule are 850~20000mg/L, and the concentration of oxygen is 6~10mg/L.
9. filling perforation electro-plating method as claimed in claim 8, which is characterized in that in the copper sulphate filling perforation electroplate liquid, formaldehyde point
The concentration of son is 850~5000mg/L.
10. filling perforation electro-plating method as described in claim 1, which is characterized in that in the copper sulphate filling perforation electroplate liquid, gloss agent
Additive amount be 0.5-2ml/L, the additive amount of leveling agent is 10-30ml/L, and the additive amount of wetting agent is 10-20ml/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113597143A (en) * | 2021-07-28 | 2021-11-02 | 恒赫鼎富(苏州)电子有限公司 | Copper plating and hole filling process for blind hole of flexible circuit board |
| CN114411214A (en) * | 2022-01-27 | 2022-04-29 | 四会富仕电子科技股份有限公司 | Method for electroplating copper on copper substrate |
| CN114457396A (en) * | 2022-02-15 | 2022-05-10 | 江西博泉化学有限公司 | Acidic copper plating process suitable for carrier plate electroplating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108085722A (en) * | 2017-12-07 | 2018-05-29 | 江西博泉化学有限公司 | A kind of acid copper-plating technique and method |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108085722A (en) * | 2017-12-07 | 2018-05-29 | 江西博泉化学有限公司 | A kind of acid copper-plating technique and method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113597143A (en) * | 2021-07-28 | 2021-11-02 | 恒赫鼎富(苏州)电子有限公司 | Copper plating and hole filling process for blind hole of flexible circuit board |
| CN114411214A (en) * | 2022-01-27 | 2022-04-29 | 四会富仕电子科技股份有限公司 | Method for electroplating copper on copper substrate |
| CN114411214B (en) * | 2022-01-27 | 2023-05-05 | 四会富仕电子科技股份有限公司 | Method for electroplating copper on copper substrate |
| CN114457396A (en) * | 2022-02-15 | 2022-05-10 | 江西博泉化学有限公司 | Acidic copper plating process suitable for carrier plate electroplating |
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| CN109023448B (en) | 2019-11-05 |
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