CN107604391A - A kind of plating agent for electro-coppering and its related plating metal copper combination agent - Google Patents
A kind of plating agent for electro-coppering and its related plating metal copper combination agent Download PDFInfo
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- CN107604391A CN107604391A CN201710799771.5A CN201710799771A CN107604391A CN 107604391 A CN107604391 A CN 107604391A CN 201710799771 A CN201710799771 A CN 201710799771A CN 107604391 A CN107604391 A CN 107604391A
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Abstract
The invention discloses a kind of plating agent for electro-coppering and its related plating metal copper formula, belongs to plating and electro-deposition techniques field.It is one or more kinds of organic matters containing first kind active function groups or the second class active function groups that the present invention, which plates agent, the first kind active function groups and the second class active function groups conjugation, reduction potential of the organic matter containing active function groups under electrochemical system is not higher than copper electro-deposition reduction potential, so that the present invention, which plates active function groups in agent, competitive reaction occurs with copper ion, reduce the copper deposition current efficiency of negative electrode, so contribute to the reduction of face copper thickness, the covering power being particularly suitable for use in when improving plating and blind hole filling high thickness to diameter ratio through hole, and then improve the circuit fineness of printed circuit board now.
Description
Technical field
The invention belongs to electroplate and electro-deposition techniques field, to improve plating solution during more particularly to a kind of plating metal copper
Covering power and the electroplating additive used and its related plating metal copper combination agent.
Background technology
Direction with electronic product to multi-functional, high density, light and fast is developed, printed circuit board (Printed
Circuit board, PCB) also develop therewith as carrier indispensable in electronic product, high density interconnection (High
Density interconnection, HDI) technology arises at the historic moment.HDI technologies are carried by modes such as through hole, blind hole and buried via holes
The Manufacturing Technology for PCB of high wiring density.In HDI printed board processing procedures, hole metallization is a mostly important work
Skill, with the increase of HDI flaggy numbers, through hole, the radius-thickness ratio of blind hole are increasing (>=10), to realize through hole conformal plating and
Being filled up completely with for blind hole is more and more difficult.Especially, in the conformal plating of through hole and in blind hole filling, in the aperture and hole of through hole
The CURRENT DISTRIBUTION of the heart, the aperture of blind hole and bottom hole is uneven, wants the layers of copper of depositing homogeneous in high thickness to diameter ratio through hole and will be blind
Hole is filled up completely with, and only relies upon existing plating copper technology far from meeting the needs of electronic product is to high reliability.
Plating metal copper is the general technology in printed circuit board and IC substrate manufactures, can realize conducting, interlayer interconnection
Or form the function of the electrical connections such as screen layer.Now most-often used copper plating process is acid copper sulfate electroplating technology, this
The composition of kind of technique is simple, solution-stabilized, current efficiency is high, and adding applicable organic additive just can obtain the plating of uniform light
Layers of copper.Above-mentioned organic additive be it is a kind of can be by the synergy of all kinds of materials so as to improve copper plate quality, and can
Improve a kind of organic compound of through hole and blind hole covering power (Throwing power, TP).Usual acid copper plating is organic
Additive has three classes：Accelerator, inhibitor and leveling agent.Accelerator is also known as grain refiner or brightener, mainly small molecule
Sulfur-containing compound, in plating beneficial to the formation of nucleus, make layers of copper bright.Inhibitor is mostly macromolecule oxygenatedchemicals, can
To suppress the deposition of face copper, while wetting agent can also be used as, reduce the surface tension at interface.The leveling agent now reported is typically each
For itrogenous organic substance, there is very strong electropositive, be easy to absorption in areas of high current density, can will be surface flattening.It is and right
For the plating of high thickness to diameter ratio through hole and blind hole filling, because the electric current distribution at hole center and aperture is uneven, cause
In hole and the uneven situation of face copper thickness, and blocked up face copper is difficult to making fine-line.Existing plating addition at present
Agent can not solve this problem, so the thickness of face copper how is effectively reduced in plating and blind hole filling high thickness to diameter ratio through hole,
And then the circuit fineness of printed circuit board now is improved, become this area technical problem urgently to be resolved hurrily.
The content of the invention
The technical problems to be solved by the invention are：There is provided it is a kind of based on competitive reaction come reduce copper deposition electric current effect
Rate causes face copper thickness to reduce and then plates the novel electroplating additive of purpose, prepares to be formed with novel electroplating additive
Plating metal copper combination agent be advantageous to improve base material covering power.The present invention is high thick effectively to reduce plating and blind hole filling
Face copper thickness when footpath is than through hole provides solution, is advantageous to improve the circuit fineness of printed circuit board now.
To achieve these goals, this hair provides following technical scheme：
On the one hand the present invention provide a kind of plating agent for electro-coppering, it is characterised in that it is described plate agent for one kind or
The a variety of organic matters containing first kind active function groups or the second class active function groups of person；Contain first kind active function groups
Material is conjugated with the material containing the second class active function groups, and the organic matter containing active function groups is under electrochemical system
Reduction potential be not higher than copper electro-deposition reduction potential.
Further, the present invention in the material containing first kind active function groups chemical general formula as shown in formula I：
Separate between R1, R2, R3, R4 or any bonding in formula I；
The chemical general formula of material containing the second class active function groups in the present invention is as shown in formula II：
Separate between R1 ', R2 ', R3 ', R4 ' or any bonding in formula II.
Preferably, in the present invention in the material containing first kind active function groups between R1 and R2 and R3
Form phenyl ring respectively between R4, obtain 9,10- anthraquinone derivatives, its chemical general formula is as shown in formula III：
X1, X2, X3, X4, X5, X6, X7, X8 are independently of each other or any cyclic in formula III；
In material containing the second class active function groups in the present invention between R1 ' and R2 ' and between R3 ' and R4 ' respectively
Phenyl ring is formed, its chemical general formula is as shown in formula IV：
X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ' are independently of each other or any cyclic in formula IV.
Preferably, naphthalene is formed between R3 and R4 in the material containing first kind active function groups in the present invention
Ring, Isosorbide-5-Nitrae-anthraquinone derivatives are obtained, its chemical general formula is as shown in formula V：
Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 are independently of each other or any cyclic in formula V.
Naphthalene nucleus is formed between R3 ' and R4 ' in material containing the second class active function groups in the present invention, its chemical general formula is such as
Shown in formula VI：
Y1 ', Y2 ', Y3 ', Y4 ', Y5 ', Y6 ', Y7 ', Y8 ' are independently of each other or any cyclic in formula VI.
Further, agent is plated in the present invention and contains the functional group for playing leveling agent effect；Meet the plating of this condition
Agent includes but is not limited to：Containing the material of any one functional group in nitrogen imidazoles, pyridine, pyrimidine, pyrazoles and pyrroles or with being good for
That green (JGB), it is good for the material that the dye class leveling agents such as that black, methylene violet, methylene blue, gentian violet, phenolphthalein mutually bond together to form；
Further, agent is plated in the present invention and contains the functional group for playing inhibitor effect；Meet the plating of this condition
Agent includes but is not limited to：Contain polyether compound, polyethylene glycol and polyethylene glycol block polymer, polypropylene glycol or hydroxyl first
The material of the free polyvinyl alcohol of base fiber.
Further, during the Y1 in the organic matter in the present invention as shown in formula IV, V, VI is to Y8 or Y1 ' to Y8 ' at least
Contain a sodium sulfonate substituent.
Furthermore the present invention also provides a kind of method that covering power is improved in plating metal process for copper, use is square as described above
Additive of the agent as electroplate liquid is plated disclosed in case, base material to be plated is placed in plating metal copper electrochemical solution system and carried out
Plating.
Further, also including any one in accelerator, leveling agent and inhibitor or any a variety of in the present invention
Combination.
On the other hand present invention also offers a kind of plating metal copper combination agent, including copper source, it is characterised in that also includes
Plate agent, it is described to plate agent to be one or more kinds of organic containing first kind active function groups or the second class active function groups
Thing；Material containing first kind active function groups is conjugated with the material containing the second class active function groups, described to contain active official
Reduction potential of the organic matter that can be rolled into a ball under electrochemical system is not higher than copper electro-deposition reduction potential.
Further, the present invention in plating metal copper combination agent also include accelerator, leveling agent and inhibitor in it is any
One or any a variety of combination.
Further, the present invention in the material containing first kind active function groups chemical general formula as shown in formula I：
Separate between R1, R2, R3, R4 or any bonding in formula I；
The chemical general formula of material containing the second class active function groups in the present invention is as shown in formula II：
Separate between R1 ', R2 ', R3 ', R4 ' or any bonding in formula II.
Preferably, in the present invention in the material containing first kind active function groups between R1 and R2 and R3
Form phenyl ring respectively between R4, obtain 9,10- anthraquinone derivatives, its chemical general formula is as shown in formula III：
X1, X2, X3, X4, X5, X6, X7, X8 are independently of each other or any cyclic in formula III；
In material containing the second class active function groups in the present invention between R1 ' and R2 ' and between R3 ' and R4 ' respectively
Phenyl ring is formed, its chemical general formula is as shown in formula IV：
X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ' are independently of each other or any cyclic in formula IV.
Preferably, naphthalene is formed between R3 and R4 in the material containing first kind active function groups in the present invention
Ring, Isosorbide-5-Nitrae-anthraquinone derivatives are obtained, its chemical general formula is as shown in formula V：
Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 are independently of each other or any cyclic in formula V.
Naphthalene nucleus is formed between R3 ' and R4 ' in material containing the second class active function groups in the present invention, its chemical general formula is such as
Shown in formula VI：
Y1 ', Y2 ', Y3 ', Y4 ', Y5 ', Y6 ', Y7 ', Y8 ' are independently of each other or any cyclic in formula VI.
Further, agent is plated in the present invention and contains the functional group for playing leveling agent effect；Meet the plating of this condition
Agent includes but is not limited to：Containing the material of any one functional group in nitrogen imidazoles, pyridine, pyrimidine, pyrazoles and pyrroles or with being good for
That green (JGB), it is good for the material that the dye class leveling agents such as that black, methylene violet, methylene blue, gentian violet, phenolphthalein mutually bond together to form；
Further, agent is plated in the present invention and contains the functional group for playing inhibitor effect；Meet the plating of this condition
Agent includes but is not limited to：Contain polyether compound, polyethylene glycol and polyethylene glycol block polymer, polypropylene glycol or hydroxyl first
The material of the free polyvinyl alcohol of base fiber.
Further, the X1 in the present invention in organic matter as shown in formula III, IV, V, VI to X8, X1 ' to X8 ', Y1 extremely
At least contain a sodium sulfonate substituent in Y8 or Y1 ' to Y8 '.
Compared with prior art, beneficial effects of the present invention are as follows：
The invention provides a kind of novel electroplating additive, this kind of novel electroplating additive contains active function groups, a side
In electrochemical reaction system with copper ion competitive reaction can occur for active function groups described in face, so as to reduce tough cathode deposition
Current efficiency, and then reduce face copper thickness and improve the purpose plated to reach；On the other hand, because high thickness to diameter ratio through hole is conformal
In plating and blind hole filling, the current density of plate face causes CURRENT DISTRIBUTION uneven commonly greater than in through hole hole and hole bottom
It is even, cause in through hole hole, face copper thickness blocked up phenomenon be present when blind hole is filled up completely with or deposited certain thickness copper, and
The present invention causes active function groups in the electroplating additive to target by being introduced into the strong functional group of electropositive on new additive agent
The big position of cathode-current density, reduction can be participated in by active function groups in areas of high current density (plate face) improves and plates agent
Kinetic current density accounting, therefore plating agent is better than in hole in the action effect of plate face, and due in through hole hole and hole bottom
Mass transfer be far below plate face, i.e., plate density of the agent in hole and be less than plate face, it is strong in the effect of plate face to further result in plating agent
In its effect in hole.Therefore, by above-mentioned technological means, what the present invention plated that agent is capable of selectivity acts on face copper, drop
Bottom surface copper thickness, the covering power being particularly suitable for use in when improving plating and blind hole filling high thickness to diameter ratio through hole, and then improve now
The circuit fineness of printed circuit board.
Brief description of the drawings
Fig. 1 is the principle schematic of electroplating additive provided by the invention；I plates agent, I to be provided by the invention in figure-
Ionic condition after being reduced for plating agent provided by the invention.
Fig. 2 is CV image of the 1,4-benzoquinone provided in an embodiment of the present invention in acid copper sulfate.
Embodiment
The principle and characteristic of the present invention are described in detail with reference to embodiment：
Idea of the invention is：There is provided a kind of causes face copper thick based on competitive reaction to reduce the current efficiency of copper deposition
Degree reduces and then plates the novel electroplating additive of purpose and its related plating metal copper combination agent.
On the one hand, the invention provides one kind to plate agent, and it is the material containing active function groups that this, which plates agent, the activity
Functional group is divided into first kind active function groups and the second class active function groups；Material containing first kind active function groups is with containing
The material of second class active function groups is conjugated, i.e., the two can form oxidation-reduction pair；
Assuming that the oxidisability of the material containing first kind active function groups is stronger, it is in following electroplating process as oxidant
Reaction is participated at negative electrode, is competed with copper ion, has the invention enables the material containing first kind active function groups and is not higher than
Copper ion is reduced to the current potential of copper, is easily reduced so the material containing first kind active function groups compares copper ion, therefore energy
Enough reduce the copper deposition current efficiency of negative electrode；And the reproducibility of the material containing the second class active function groups is stronger, due to its with
The material conjugation of the active function groups containing the first kind, therefore first can be oxidized in following electroplating process at anode containing the first kind
The material of active function groups, then competed as described above with copper ion.Therefore, the material containing active group passes through in negative electrode
Between anode constantly occur redox reaction, reduce copper deposition current efficiency, and then reduce face copper thickness with
Improve the purpose plated.
The present embodiment provides a kind of material containing first kind active function groups, specially to benzene diketone derivative, its
Chemical general formula is as shown in formula A：
Wherein：Separate between R1, R2, R3, R4 or any bonding in formula I；The present invention does not limit for substituent
It is fixed, remaining atom beyond also being may be present in R1, R2, R3, R4 in addition to C, such as S, N, O；There can be saturation in R1, R2, R3, R4
Side chain, it is possibility to have unsaturated side chain, can also there is ring-type side chain, also including unsaturated side chain or saturation side chain and ring-type branch
The combination chain that chain is formed.
The present embodiment provides a kind of material containing the second class active function groups, specially Pyrogentisinic Acid's analog derivative, and it is changed
Formula is learned as shown in formula II：
Wherein：R1 ', R2 ', R3 ', R4 ' are independently of each other or any cyclic in formula II；The present invention does not limit for substituent
It is fixed, remaining atom beyond also being may be present in R1 ', R2 ', R3 ', R4 ' in addition to C, such as S, N, O；Can in R1 ', R2 ', R3 ', R4 '
To there is saturation side chain, it is possibility to have unsaturated side chain, can also there is ring-type side chain, also including unsaturated side chain or saturation side chain
The combination chain formed with ring-type side chain.
A kind of material containing first kind active function groups of the present embodiment offer, specially 9,10- anthraquinone derivatives, i.e.,
Form phenyl ring in formula I between R1 and R2 and between R3 and R4 respectively, its chemical general formula is as shown in formula III：
Wherein：X1, X2, X3, X4, X5, X6, X7, X8 are independently of each other or any cyclic in formula III；The present invention is for substitution
Base does not limit, remaining atom beyond also being may be present in X1, X2, X3, X4, X5, X6, X7, X8 in addition to C, such as S, N, O；X1、
There can be saturation side chain in X2, X3, X4, X5, X6, X7, X8, it is possibility to have unsaturated side chain, there can also be ring-type side chain, also wrap
Include the combination chain that unsaturated side chain or saturation side chain are formed with ring-type side chain.
The present embodiment provides a kind of material containing the second class active function groups, i.e., in formula II between R1 ' and R2 ' and
Phenyl ring is formed between R3 ' and R4 ' respectively, its chemical general formula is as shown in formula IV：
Wherein：X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ' are independently of each other or any cyclic in formula IV；The present invention
Do not limited for substituent, remaining beyond also being may be present in X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ' in addition to C is former
Son, such as S, N, O；There can be saturation side chain in X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ', it is possibility to have unsaturation branch
Chain, there can also be ring-type side chain, the combination chain also formed including unsaturated side chain or saturation side chain with ring-type side chain.
Quinones substance and aldehydes matter that above-mentioned formula is covered all are the organic compounds that nature is stabilized, phenolic material
Matter is a kind of organic compound containing the hydroxyl being joined directly together with aromatic hydrocarbons core, and quinones substance be containing with cyclohexadiene or virtue
Fragrant cycle compound is directly connected with a kind of organic compound of two carbonyls.Carbonyl in quinones substance is changed into hydroxyl after carrying out reduction,
Quinones substance is caused to be changed into aldehydes matter through reduction；And the hydroxyl of aldehydes matter it is oxidized after can be changed into carbonyl, cause phenol
Class material is oxidized to be changed into quinones substance, and this is the redox characteristic of quinone/phenol.
The present embodiment provides a kind of material containing first kind active function groups, i.e., naphthalene nucleus is formed between R3 and R4 in formula I,
Isosorbide-5-Nitrae-anthraquinone derivatives are obtained, its chemical general formula is as shown in formula V：
Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 are independently of each other or any cyclic in formula V.
The present embodiment provides a kind of material containing the second class active function groups, i.e., naphthalene is formed between R3 ' and R4 ' in formula II
Ring, its chemical general formula is as shown in formula VI：
Y1 ', Y2 ', Y3 ', Y4 ', Y5 ', Y6 ', Y7 ', Y8 ' are independently of each other or any cyclic in formula VI.
Preferably, the X1 in the present invention in organic matter as shown in formula III, IV, V, VI to X8, X1 ' extremely
X8 ', Y1 to Y8 or Y1 ' to Y8 ' in containing be no less than a sodium sulfonate substituent when, be favorably improved through hole plating and blind hole
Covering power during filling.
It is proposed by the present invention to plate agent as the 4th class electro-coppering addition different from accelerator, inhibitor and leveling agent
Agent, its mechanism of action and Lothrus apterus with existing three class plating copper additives.Moreover, it is proposed by the present invention to plate agent
On can pass through to introduce and play the group that inhibitor or leveling agent act on and form the electroplating additive with complex function.
Specifically, it is proposed by the present invention that there is the plating agent for playing inhibitor effect to include but is not limited to：Contain polyethers
The material of compound, polyethylene glycol and polyethylene glycol block polymer, polypropylene glycol or the free polyvinyl alcohol of hydroxylmethyl cellulose.
Specifically, it is proposed by the present invention that there is the plating agent for playing leveling agent effect to include but is not limited to：Contain imidazoles, pyrrole
In pyridine, pyrimidine, pyrazoles and pyrroles the material of any one functional group or be good for that green (JGB), be good for that black, methylene violet, Asia
The material that the dye class leveling agent such as methyl blue, gentian violet, phenolphthalein mutually bonds together to form；
It should be further stated that the nitrogen heterocyclic ring class such as imidazoles, pyridine, pyrimidine, pyrazoles and pyrroles leveling agent has
There is very strong electropositive, be easy to absorption in areas of high current density, therefore be bonded to the present invention and propose to plate the structure of agent
On can cause to plate the big position of active function groups targeting cathode-current density in agent, so being advantageous to improve active function groups
Reduction reaction current density accounting, so as to realize reduce metallic copper deposition efficiency, further have by this technological means
Help the reduction of face copper thickness, the covering power being particularly suitable for use in when improving plating and blind hole filling high thickness to diameter ratio through hole, finally
Reach the purpose for improving the circuit fineness of printed circuit board now.
On the other hand, the invention provides a kind of plating metal copper combination agent, including copper source is characterized in that, also include such as
Upper described plating agent.According to being actually needed, can also add in accelerator, leveling agent and inhibitor any one or it is any
A variety of combinations.
The applicable electroplating substrate of plating metal copper combination agent of the present invention can be any suitable base material, be opened on usual base material
Provided with intensive through hole and blind hole；The base material includes but is not limited to：Printed circuit board, package substrate, integrated circuit and silicon chip,
The material of the base material includes but is not limited to：Resin material, ceramic material, metal material and semi-conducting material.
In a specific embodiment, need to carry out conductive processing before being electroplated；The mode present invention of conductive processing is not
Limit, can be any suitable conductive processing mode, including：Electroless copper, vapour deposition, direct plating, sputter and lead
Electric particulate absorption；The preferred electroless copper of the present embodiment.
In a specific embodiment, material to be electroplated needs to be surface-treated；Surface treatment is generally included to wash, removed
Some processes such as oil, microetch, preimpregnation, the present invention are not limited this, can adopted for the process of surface treatment of material to be electroplated
With existing any suitable processing mode.
In a specific embodiment, selection of the present invention for the electroplate liquid residing for electroplating additive does not limit, and electroplates
Additive is applied to any kind of electrolytic copper plating solution, can be copper sulfate bath, cyanide bath or cupric pyrophosphate plating solution；This
Preferably sulfuric acid copper electrolyte is specific as follows as electrolytic copper plating solution, its formula in implementation：
In a specific embodiment, the present invention for used in plating metal copper combination agent accelerator (also referred to as brightener,
Accelerator) do not limit；It is preferred that polysulfide organic sulfonate, it be A1-S-S-A2 to define its logical knowledge, and wherein A1 can be alkane, organic
Heterocycle, aromatic hydrocarbon or alkylsulfonate, A2 can be alkane, organic heterocyclic, aromatic hydrocarbon or alkylsulfonate；It is excellent in the present embodiment
Sodium polydithio-dipropyl sulfonate (SPS) is selected, preferable amount is 1~20mg/L.
In a specific embodiment, the present invention does not limit for the inhibitor used in plating metal copper combination agent；Tool
Body, inhibitor includes but is not limited to：Polyether compound, polyethylene glycol and polyethylene glycol block polymer, polypropylene glycol or
The free polyvinyl alcohol of person's hydroxylmethyl cellulose；Preferably polyethylene glycol (PEG), preferably its molecular weight are 600~12000, and dosage is
100~1000mg/L.
In a specific embodiment, the present invention does not limit for the leveling agent used in plating metal copper combination agent；Tool
Body, leveling agent includes but is not limited to：The nitrogen heterocyclic ring class that imidazoles, pyridine, pyrimidine, pyrazoles or pyrroles bond together to form with side chain
Leveling agent and the dye class leveling agent such as strong that green (JGB), strong that black, methylene violet, methylene blue, gentian violet, phenolphthalein.
In a specific embodiment, plating metal copper combination agent of the present invention is applied to any suitable electroplating temperature, preferably
Electroplating temperature is 15~45 DEG C.
In a specific embodiment, the current type that the present invention uses for plating does not limit；It is usually used during plating
Current type have direct current electrode position, pulse plating etc., the present invention is applied to above-mentioned current type, but is not limited only to above-mentioned current capacity
Type.
In a specific embodiment, the anode that the present invention uses for plating does not limit；Plating piece conduct is used in plating
Negative electrode, anode can be soluble anode and insoluble anode, and plating metal copper combination agent of the invention is applied to above-mentioned anode,
But it is not limited only to above-mentioned anode.
In a specific embodiment, for the mass transfer in electroplating process, prior art is mainly by stirring plating solution come real
It is existing；Any suitable agitating mode can be used in plating for plating metal copper combination agent of the present invention, such as be passed through air, injection,
It is of the invention to this and unrestricted.
In a specific embodiment, the present invention is not limited for current density workable for plating metal copper combination agent；
As the method that is preferable to carry out, the scope of current density is 0.5~8A/dm2。
The principle and characteristic of the present invention are further illustrated with reference to Figure of description：
Shown in Fig. 1, I provides one kind in plating agent for the present invention has compound.Plating agent I is reduced in negative electrode is changed into
I-, plating agent I is close or lower so as to form competition reduction in the reduction potential of negative electrode and the reduction potential of copper ion, reduces
The current efficiency of copper deposition；And I-By convection current and anode is diffused into, in anode I-It is oxidized again and is changed into I, completes circulation.
The technique effect of the present invention is further illustrated with reference to specific embodiment：
Embodiment 1：
200mg/L benzoquinones and 10% copper sulphate are formed mixed solution system by the present embodiment, using three-electrode system, wherein
Platinum electrode is used as to electrode as working electrode, copper electrode, and mercuric sulfate electrode is as reference electrode；Work station is set to scan current potential
For 0.5~-0.6V, sweep speed 0.1V/S, the circle of experiment scanning 200 finds to occur without peak attenuation.
Normal electrode reduction potential-the 0.342V of copper electro-deposition (i.e. copper ion is changed into copper), but consider in real process
Overpotential and other influences factor (such as electroplating additive) be present, the copper electro-deposition potential range in acid copper sulfate baths
For -0.4~-0.78V vs.SSE.Copper ion can obtain electronics in negative electrode and be changed into copper atom in this potential region, work as reduction
When current potential exceedes -0.78V vs.SSE, evolving hydrogen reaction will occur.200mg/L benzoquinones is illustrated in figure 2 in 10%H2SO4In
CV images, reduction potential is -0.43V in figure, and oxidizing potential is -0.5V.Current potential when benzoquinones is reduced to phenol is less than copper electricity
Sedimentation potential, in contrast it is easier to reduce, so the reduction reaction that can be competed with copper ion, so as to reduce negative electrode
Copper deposition current efficiency.After benzoquinones is reduced to phenol in negative electrode, reaches anode region further through mass transfer and be oxidized to benzoquinones.Cause
This, this is just circulated quinone/phenol to redox materials between anode and cathode, reduces the current efficiency of copper electro-deposition.Due to this turn
Change and do not consume therefore need not add to be recycled for multiple times.
Embodiment 2：
The present embodiment is provided using the present invention using Hull cell plating measurement and plates influence of the agent for current efficiency.
The present embodiment is 4A/dm using current density2, electroplating time 10min, electroplating temperature is normal temperature, and plating uses
Hall tankage be 250mL；Plating piece be 10cm × 5cm latten(-tin), before being electroplated, latten(-tin) need to carry out oil removing,
Microetch, preimpregnation, washing process.The anode used in plating is phosphorus-copper anode.The plating metal copper combination that Hull cell plating uses
Agent and calculating gained current efficiency are as shown in table 1.
The basic plating solution formula that the present embodiment uses is as follows：
The calculating of current efficiency is according to obtained by Faraday's law M=k × I × t in the present embodiment, and wherein k is the electricity of copper
Chemical equivalent, its value are 1.86g/Ah, and I is current density, and t is electroplating time.
The present embodiment is tested using electroplating additive shown in table 2, and is obtained as shown in the results summarized in table 1.SPS is in table 1
Double (3- sulfopropyls) sodium disulfides of brightener, PEG-8000 are the polyethylene glycol that molecular weight is 8000, and JGB is green to be good for that.
The plating of the Hull cell of table 1. uses additive and current efficiency
As it can be seen from table 1 being electroplated using compound under general formula III, current efficiency can be made significantly to decline.
Embodiment 3：
The electroplating formula that this implementation plates agent using Haring cell test with being provided containing the present invention is electroplated containing the two-sided of through hole
The covering power of printed circuit board.
The test plate thickness that the present embodiment uses is 1.6mm, and through-hole aperture is 250 μm.Test board is dual platen and its is big
Small is 10cm × 5cm；The temperature of plating solution is normal temperature, and plating density is 2A/dm2, electroplating time 70min, agitating mode is negative electrode
Bubbling；Haring cell capacity used in plating is 1.5L.
The basic electroplating formula that the present embodiment uses is same as Example 1 as follows.
Before implementing to electroplate, test board will pass through acid deoiling, preimpregnated process and be stain with removing test plate surface.
The present embodiment is tested using electroplating additive shown in table 2, and obtains result as shown in table 2.In table 2, EO/PO
For the block copolymer of epoxy ethane-epoxy propane.
The average thickness that covering power refers to measure through hole center institute copper plate in the present embodiment on plating piece surface with being plated
The ratio of the average thickness of layers of copper, recorded according to the form of percentage.
The Haring cell electroplating additive of table 2. and TP values
Contrast sequence number 4 to 6 is as can be seen that can significantly improve the TP values of through hole using plating agent provided by the invention.
Claims (9)
1. a kind of plating agent for electro-coppering, it is characterised in that described to plate agent to be one or more kinds of containing first kind work
Property functional group or the organic matter of the second class active function groups；Material containing first kind active function groups containing the second class with living
Property functional group material conjugation, reduction potential of the organic matter containing active function groups under electrochemical system be not higher than copper
Electro-deposition reduction potential.
2. a kind of plating agent for electro-coppering according to claim 1, it is characterised in that described to contain first kind activity
The chemical general formula of the material of functional group is as shown in formula I：
Separate between R1, R2, R3, R4 or any bonding in formula I；
The chemical general formula of the material containing the second class active function groups is as shown in formula II：
Separate between R1 ', R2 ', R3 ', R4 ' or any bonding in formula II.
3. a kind of plating agent for electro-coppering according to claim 2, it is characterised in that described to contain first kind activity
Phenyl ring is formed respectively between R1 and R2 and between R3 and R4 in functional group, obtains 9,10- anthraquinone derivatives, its chemical general formula
As shown in formula III：
X1, X2, X3, X4, X5, X6, X7, X8 are independently of each other or any cyclic in formula III；
Phenyl ring is formed between R1 ' and R2 ' and between R3 ' and R4 ' respectively in the material containing the second class active function groups,
Its chemical general formula is as shown in formula IV：
X1 ', X2 ', X3 ', X4 ', X5 ', X6 ', X7 ', X8 ' are independently of each other or any cyclic in formula IV.
4. a kind of plating agent for electro-coppering according to claim 2, it is characterised in that described to contain first kind activity
Naphthalene nucleus is formed between R3 and R4 in the material of functional group, obtains Isosorbide-5-Nitrae-anthraquinone derivatives, its chemical general formula is as shown in formula V：
Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 are independently of each other or any cyclic in formula V.
Naphthalene nucleus is formed between R3 ' and R4 ' in the material containing the second class active function groups, its chemical general formula such as institute of formula VI
Show：
Y1 ', Y2 ', Y3 ', Y4 ', Y5 ', Y6 ', Y7 ', Y8 ' are independently of each other or any cyclic in formula VI.
5. a kind of plating agent for electro-coppering according to claim 1, it is characterised in that the plating agent contains miaow
Any one in azoles, pyridine, pyrimidine, pyrazoles or two kinds of groups and/or contain polyether compound, polyethylene glycol and poly- the third two
Alcohol block polymer, polypropylene glycol or the free polyvinyl alcohol of hydroxylmethyl cellulose.
6. a kind of plating metal copper combination agent, including copper source, it is characterised in that also include plating agent, it is described to plate agent as one kind
Either a variety of organic matters containing first kind active function groups or the second class active function groups；Contain first kind active function groups
Material with containing the second class active function groups material be conjugated, the organic matter containing active function groups is in electrochemical system
Under reduction potential be not higher than copper electro-deposition reduction potential.
7. a kind of plating metal copper combination agent according to claim 6, it is characterised in that also include adding in the electroplate liquid
Any one in fast agent, leveling agent and inhibitor or any a variety of combination.
8. a kind of plating metal copper combination agent according to claim 6, it is characterised in that described to contain first kind activity official
The chemical general formula for the material that can be rolled into a ball is as shown in formula I：
Separate between R1, R2, R3, R4 or any bonding in formula I；
The chemical general formula of the material containing the second class active function groups is as shown in formula II：
Separate between R1 ', R2 ', R3 ', R4 ' or any bonding in formula II.
A kind of 9. plating metal copper combination agent according to claim 7, it is characterised in that it is described plating agent contain imidazoles,
Any one in pyridine, pyrimidine, pyrazoles or two kinds of groups and/or contain polyether compound, polyethylene glycol and polypropylene glycol
Block polymer, polypropylene glycol or the free polyvinyl alcohol of hydroxylmethyl cellulose.
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| CN109853006A (en) * | 2019-01-24 | 2019-06-07 | 电子科技大学 | The additive formulations and electro-plating method of electro-coppering under the conditions of a kind of high temperature and high speed |
| CN110158124A (en) * | 2019-05-24 | 2019-08-23 | 广东工业大学 | A kind of electro-coppering leveling agent and its electroplate liquid of application |
| CN110791784A (en) * | 2019-12-19 | 2020-02-14 | 奎克化学（中国）有限公司 | Additive for tin electroplating process by using methanesulfonic acid method |
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| CN110158124A (en) * | 2019-05-24 | 2019-08-23 | 广东工业大学 | A kind of electro-coppering leveling agent and its electroplate liquid of application |
| CN110791784A (en) * | 2019-12-19 | 2020-02-14 | 奎克化学（中国）有限公司 | Additive for tin electroplating process by using methanesulfonic acid method |
| CN112725850A (en) * | 2020-12-21 | 2021-04-30 | 上海新阳半导体材料股份有限公司 | Chip copper interconnection electroplating additive, preparation method and application thereof |
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| CN112760683A (en) * | 2020-12-21 | 2021-05-07 | 上海新阳半导体材料股份有限公司 | Chip copper interconnection electroplating additive, preparation method and application thereof |
| CN112795960A (en) * | 2020-12-21 | 2021-05-14 | 上海新阳半导体材料股份有限公司 | Chip copper interconnection electroplating additive, preparation method and application thereof |
| CN115417808A (en) * | 2022-08-12 | 2022-12-02 | 华东理工大学 | Anthraquinone quaternary ammonium salt compound and preparation method and application thereof |
| CN115417808B (en) * | 2022-08-12 | 2024-01-30 | 华东理工大学 | Anthraquinone quaternary ammonium salt compound and preparation method and application thereof |
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