CN108834309A - A kind of graphene metallization solution and the preparation method and application thereof - Google Patents
A kind of graphene metallization solution and the preparation method and application thereof Download PDFInfo
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- CN108834309A CN108834309A CN201811009256.3A CN201811009256A CN108834309A CN 108834309 A CN108834309 A CN 108834309A CN 201811009256 A CN201811009256 A CN 201811009256A CN 108834309 A CN108834309 A CN 108834309A
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention discloses a kind of graphene metallization solution and the preparation method and application thereof, and the graphene metallization solution is made of following raw materials according according to mass percent：Graphene or graphene oxide 0.5-5.0%；Film forming agent 1-3%；Dispersing agent 1-6%；Anionic surfactant 0.01-0.2%；Alkaline solution adjusts pH value to 4-14；Surplus is water.The present invention is using the graphene or suboxides degree graphene oxide composite material of low concentration as basic conductive material, pass through the pretreatment being simple and efficient, graphene metallization solution can be realized in effective absorption of non-metallic substrate surface or hole wall, by being simply dried, it can form that one layer of binding force is reliable, for electric conductivity close to the very thin film layer of even more than metallic copper, film layer only has the thickness of a few to tens of nanometers, can be used as bottoming conductive layer, it is subsequent can direct electro-coppering.
Description
Technical field
The present invention relates to new material synthesis and field of surface treatment more particularly to a kind of graphene metallization solution and its systems
Preparation Method and application.
Background technique
With the fast development of electronic information technology, wiring board and all kinds of metalized article demands are increasing.In electronics
On wiring board, in order to realize that interlayer interconnects, need to drill on substrate, and realize metalized to hole wall, that is, insulating
One layer of metal of deposited on substrates or conductive material, can be used as the bottoming coating of subsequent plating.Hole metallization is wiring board system
One of critical process of work.Currently used hole metallization technology mainly includes following：
1, chemical copper technology：Most common chemical copper uses acidic group or alkali activating solution, makees accelerator using fluoboric acid,
Chemical copper is used as primary raw material using copper sulphate, formaldehyde, sodium potassium tartrate tetrahydrate, edta and its sodium salt, sodium hydroxide etc.,
Cyanide generally is mostly used, for the dangerous material such as mercury chloride as stabilizer, pretreatment process is very long, needs by six processing liquid medicine
Slot, the road 10-14 ejected wash water, needs heat treatment mostly, and there are major fire hazards, and almost every circuit board plant all occurred not
With the fire incident of degree；Entire technical process generates a large amount of waste liquids and cleaning waste water, waste water treatmentntrol difficult and complexity, main useless
The hypertoxic stabilizer environmental pollution contained in the heavy copper liquid of liquid is serious, and extremely difficult decomposition in the natural environment, easy accumulation cause
Long-term hazards.In addition, a variety of hazardous chemicals (fluoboric acid, hydrochloric acid, sodium hydroxide) is used in entire technical process, oxidant
(concentrated sulfuric acid, persulfate), it is serious to atmosphere and indoor environmental pollution, and high risks, first that such as can be carcinogenic are generated to human body
Aldehyde, activator such as precious metal palladium etc., entire process costs are relatively high, and environment and cost of sewage disposal are very high.In addition, chemical
Copper tank liquor stability itself is poor, and in addition for handled substrate material such as resin type, glass fibre model etc. also compares
More sensitive, chemical layers of copper mechanical performance is poor compared with electroplated layer, and chemical copper process flow is long, and Operation and Maintenance is extremely inconvenient, quality control
Relatively difficult, operating cost is higher.
2, black holes/conductive black technology：Using the black holes technology of graphite or carbon black, subtract significantly although chemicals uses
Few, flow time greatly shortens, but the electric conductivity of carbon black or graphite itself is too poor, compared with traditional chemical plating copper layer,
It much can not meet the technical standard and performance requirement of Related product, can only make on part low side hardboard product or soft board
With, and generally require to repeat a process, production efficiency is greatly reduced, additional manpower and material resources time and space is increased
Cost；
3, Organic Conductive Films/superconductor technology：Organic Conductive Films electric conductivity itself forms black film conductive layer also compared with black holes technology
Want poor, there are the potential risks of aging cracking and Pintsch process, either properties of product requirement and technology for organic conductive polymer
It is required that or subsequent product service life and reliability, all there is performance deficiency or quality hidden danger, so at present can only be
Part low side hardboard product uses.
Other metallization process are difficult to be adapted to industrialization large-scale production again, therefore, find a kind of environment-friendly high-efficiency and
It is suitble to the metallization process technology of large-scale industrial production, requires increasingly strict situation in current environmental requirement and science and technology
Under, it appears it is especially urgent.Current many metallization technologies are not there are expensive, and it is many and diverse exactly to there is technology, technique stream
The problems such as journey complexity or unsuitable large-scale industrial production, technology controlling and process is difficult.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of graphene metallization solution and its systems
Preparation Method and application, it is intended to solve existing metallization technology, not be there are expensive, it is many and diverse exactly to there is technology, technique stream
The problems such as journey complexity or unsuitable large-scale industrial production, technology controlling and process is difficult.
Technical scheme is as follows：
A kind of graphene metallization solution, wherein be made of following raw materials according according to mass percent：
The graphene metallization solution, wherein the number of plies of the graphene or graphene oxide is 1-3.
The graphene metallization solution, wherein the piece diameter of the graphene or graphene oxide is at 10nm-5 μm.
The graphene metallization solution, wherein the film forming agent is one of JZ, PVP, PVA, CCMS or several
Kind.
The graphene metallization solution, wherein the dispersing agent is PVP, dimethylformamide, N- crassitude
One or more of ketone, methyl Cellosolve.
The graphene metallization solution, wherein the anionic surfactant is TxP-10, dodecyl sulphate
One or more of sodium, dodecyl sodium sulfate, carboxylate, sulfuric acid, sulfonate, phosphate ester salt.
The graphene metallization solution, wherein the alkaline solution is sodium hydroxide solution.
A kind of preparation method of graphene metallization solution of the present invention, wherein including step：According to above-mentioned quality
Percentage mixes graphene or graphene oxide, film forming agent, dispersing agent, anionic surface inorganic agent, alkaline solution with water
Uniformly, stable dispersion is formed to get the graphene metallization solution is arrived.
A kind of application of graphene metallization solution of the present invention, wherein metallize for nonmetallic surface.
The application, wherein the method for the nonmetallic surface metallization includes step：It metallizes in the graphene
The nonmetallic surface is handled in solution, and the nonmetallic surface is made to metallize.
Beneficial effect：The present invention is using the graphene or suboxides degree graphene oxide composite material of extremely low concentration as base
Effective suction of non-metallic substrate surface or hole wall can be realized by simple pre-treatment in plinth conductive material, non-metallic substrate
It is attached, by being simply dried, it can form that one layer of binding force is reliable, very thin film of the electric conductivity close to even more than metallic copper
Layer, and the film layer only has the thickness of a few to tens of nanometers, can be used as bottoming conductive layer, it is subsequent can direct electro-coppering.
Specific embodiment
The present invention provides a kind of graphene metallization solution and the preparation method and application thereof, to make the purpose of the present invention, skill
Art scheme and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that tool described herein
Body embodiment is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of graphene metallization solution, wherein is made of following raw materials according according to mass percent：
Grapheme material itself has excellent electric conductivity, is much superior to common metal material, and the present invention also can be used
The graphene oxide of suboxides degree, electric conductivity are equivalent to copper and silver, and part even surmounts the conductive capability of copper silver, therefore
A thin layer of continuous whole graphene film is only needed, that is, can reach bottoming and desired conductive effect is electroplated.
The present invention is using the graphene or suboxides degree graphene oxide composite material of extremely low concentration as basic conduction material
By simple pre-treatment effective absorption of non-metallic substrate surface or hole wall can be realized, by letter in material, non-metallic substrate
It is single to be dried, can form that one layer of binding force is reliable, electric conductivity close to even more than metallic copper very thin film layer, and it is described
Film layer only has the thickness (3-100nm) of a few to tens of nanometers, can be used as bottoming conductive layer, it is subsequent can direct electro-coppering.
The present invention is using graphene or suboxides degree graphene oxide composite material as basic conductive material.Preferably,
The number of plies of the graphene or graphene oxide is 1-3, i.e., based on single layer or few layer graphene, few layer graphene is 3 layers
And 3 layers or less.Preferably, the piece diameter of the graphene or graphene oxide is at 5 microns hereinafter, it is preferred that 10nm-5 μm, specifically
Its suitable piece diameter size is determined according to the minimum process size of processing object.
Preferably, the film forming agent be JZ (aliphatic alcohol polyoxyvinethene phosphate), PVP (polyvinylpyrrolidone),
PVA (polyvinyl alcohol), CCMS (polyethyleneglycol hard fatty acid ester), etc. one or more of.
Preferably, the dispersing agent is PVP (polyvinylpyrrolidone), dimethylformamide, N-Methyl pyrrolidone, first
One or more of base Cellosolve etc..
Preferably, the anionic surfactant is TXP-10 (phenolic ether phosphate kalium salt), lauryl sodium sulfate, ten
One or more of dialkyl sulfonates, carboxylate, sulfuric acid, sulfonate, phosphate ester salt etc..
Preferably, the alkaline solution is that sodium hydroxide solution etc. is without being limited thereto.
Preferably, the water is pure water or deionized water.
The present invention also provides the preparation methods of the graphene metallization solution described in one kind, wherein including step：According to upper
State mass percent, by graphene or graphene oxide, film forming agent, dispersing agent, anionic surface inorganic agent, alkaline solution with
Water is uniformly mixed, and forms stable dispersion to get the graphene metallization solution is arrived.
Specifically, first by ultrasonic wave and physical mechanicalness crushing technology, by graphene or graphene oxide root
Become piece diameter in the graphene sheet class solution of more than ten nanometer to 5 micron according to actual needs, then with dispersing agent, film forming
Agent, anionic surface inorganic agent, alkaline solution, water etc. mix together, form stable dispersion.
The present invention also provides the applications of the graphene metallization solution described in one kind, wherein is used for nonmetallic surface metal
Change.Wherein, it is described it is nonmetallic can be nonmetallic for wiring board, ceramics, plastics plastic cement, glass etc..
The present invention can be rectilinear dipping below using rectilinear dipping and horizontal dipping in production practical application
With the introduction of horizontal dipping：
Rectilinear dipping is relatively suitble to medium-sized and small enterprises and laboratory simulation production.Without adding equipment, directly using production
Producer's existing equipment adds microetch to complete with dipping drying two-step method or three-step approach.Production efficiency is not high, cannot play this hair
Bright odds for effectiveness.
Horizontal dipping：Using special corollary equipment, large and medium-sized enterprise's scale is suitble to produce in enormous quantities, it can be shorter
Metalized is realized in time, greatly improves production capacity and product quality.
In view of production efficiency and quality stability, preferred levels formula impregnates in present invention process.Horizontal dipping needs
Cooperate horizontal production equipment.Technique is illustrated by primary template of wiring board.Specific manufacturer can be according to certainly
Body conditional decision selects any production method.It is present invention process process and its process conditions below：
Process flow：Cleaning/adjustment → second level countercurrent rinsing → processing of graphene metallization solution → air-dried → drying →
Microetch → second level countercurrent rinsing → air-dry → drying → electro-coppering/pattern transfer route production.
Cleaning/adjustment：Contain surface treating agent, solvent, auxiliary agent, organic base, inorganic base in solution for cleaning/adjusting
Equal ingredients.Surface treating agent is cationic surfactant, nonionic surfactant, zwitterion amphoteric surfactant etc.
One or more of mixed dissolution object, nonmetal basal body surface can effectively be moistened by surface treating agent,
Cleaning (except pollutants such as degreasing, rust staining, finger-marks, dust, oxides), guarantees the cleannes on nonmetal basal body surface；Together
When the adjustment of polarity charge can be carried out to nonmetal basal body surface, make on nonmetal basal body adsorption one layer of uniform sun from
Sub- surfactant is convenient for subsequent graphene metalized.
Second level countercurrent rinsing：Nonmetal basal body degreaser remained on surface can be effectively removed, it is non-after guarantee cleaning/adjustment
The washing of metal base surface is abundant, and washes extra residual component.
The processing of graphene metallization solution：The nonmetallic surface is handled in the graphene metallization solution, makes institute
State nonmetallic surface metallization.Specifically, by the nonmetallic graphene metallization solution for being immersed in temperature and being 20-50 DEG C
Interior, soaking time is 30-300 seconds, and preferred soaking time is 60-120 seconds.It, can be in processing section in order to guarantee effect of perforating
Circulating filtration, high-pressure spraying and ultrasonic equipment are installed additional as auxiliary, improves solution to the processing capacity of deep hole aperture hole wall
With actually pass through effect.
By the above treatment process, the Brownian movement of microparticle and graphene film layer component in graphene metallization solution
Three-dimensional effect carries out effective absorption with nonmetal basal body surface and is combined, and passes through the cationic positive electricity on nonmetal basal body surface
The negative electrical charge of lotus effect and graphene surface forms charges of different polarity absorption, finally fine and closely woven equal at one layer of the formation of nonmetal basal body surface
Even film layer.
Microetch：Nonmetal basal body is handled using micro-corrosion liquid, the processing time is 20-40 seconds.The micro-corrosion liquid is generally over cure
Hydrochlorate-sulfuric acid system micro-corrosion liquid, wherein the concentration of the persulfate is 60-100g/L, the concentration of the sulfuric acid is 3-5%
(volume basis).
It air-dries and dries：It is all to be carried out by physical method, convenient for quickly forming conductive film layer.
Microetch and its subsequent technique processing step are suitable for electronic circuit board, this technique is suitable for electronic circuit board still not
It is limited to electronic circuit board plated through-hole field.
In above-mentioned operation, it should be noted that：
1, graphene metallization solution processing solution tank configures circulation stirring filter device, on a horizontal proposed arrangement ultrasound
Wave device；
2, the higher the better (preferably 80-100 DEG C) for drying section temperature, not only contributes to graphene drying film forming, is also beneficial to
The raising of membranous layer binding force；
3, graphene metallization solution opens cylinder using stoste, is not necessarily to analysis and regulation, stoste can be used, liquid level is replenished in time；
4, the circulation stirring for suggesting keeping graphene metallization solution processing solution tank when not producing, is conducive to the stabilization of tank liquor
Property；
5, graphene metallization solution of the present invention is for different substrate materials such as polyimides PI, polyester resin BT, polytetrafluoroethyl-ne
Alkene PTFE resin etc. can effectively deal with, without especially or additionally increasing treatment process；
6, the product testing of production process can use the backlight detection method and tabula rasa copper-plating method of traditional chemical copper.
In conclusion a kind of graphene metallization solution provided by the invention and the preparation method and application thereof, the present invention is adopted
The graphene or suboxides degree graphene oxide composite material for using low concentration are pre- by what is be simple and efficient as basic conductive material
Graphene metallization solution can be realized in effective absorption of non-metallic substrate surface or hole wall, by simply dry in processing
Processing, can form that one layer of binding force is reliable, and for electric conductivity close to the very thin film layer of even more than metallic copper, film layer only has several arrive
The thickness (3-100nm) of tens nanometers, can be used as bottoming conductive layer, it is subsequent can direct electro-coppering.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of graphene metallization solution, which is characterized in that be made of following raw materials according according to mass percent：
2. graphene metallization solution according to claim 1, which is characterized in that the graphene or graphene oxide
The number of plies be 1-3.
3. graphene metallization solution according to claim 1, which is characterized in that the graphene or graphene oxide
Piece diameter at 10nm-5 μm.
4. graphene metallization solution according to claim 1, which is characterized in that the film forming agent be JZ, PVP, PVA,
One or more of CCMS.
5. graphene metallization solution according to claim 1, which is characterized in that the dispersing agent is PVP, dimethyl methyl
One or more of amide, N-Methyl pyrrolidone, methyl Cellosolve.
6. graphene metallization solution according to claim 1, which is characterized in that the anionic surfactant is
TxOne of P-10, lauryl sodium sulfate, dodecyl sodium sulfate, carboxylate, sulfuric acid, sulfonate, phosphate ester salt
Or it is several.
7. graphene metallization solution according to claim 1, which is characterized in that the alkaline solution is that sodium hydroxide is molten
Liquid.
8. a kind of preparation method of the described in any item graphene metallization solutions of claim 1-7, which is characterized in that including step
Suddenly：According to above-mentioned mass percent, by graphene or graphene oxide, film forming agent, dispersing agent, anionic surface inorganic agent,
Alkaline solution is uniformly mixed with water, forms stable dispersion to get the graphene metallization solution is arrived.
9. a kind of application of the described in any item graphene metallization solutions of claim 1-7, which is characterized in that for nonmetallic
Surface metalation.
10. application according to claim 9, which is characterized in that the method for the nonmetallic surface metallization includes step：
The nonmetallic surface is handled in the graphene metallization solution, the nonmetallic surface is made to metallize.
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| CN109811380A (en) * | 2019-03-21 | 2019-05-28 | 华侨大学 | A kind of conducting surface treatment method before ABS plastic plating |
| CN111058078A (en) * | 2019-12-30 | 2020-04-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| EP3656894A1 (en) * | 2018-11-25 | 2020-05-27 | Nanjing Graphene Research Institute Corporation | Method for electroplating copper on non-metallic surfaces using graphene-based ink |
| CN112795965A (en) * | 2020-12-29 | 2021-05-14 | 中国科学院过程工程研究所 | Graphene oxide electroplating solution and preparation method and application thereof |
| CN113207243A (en) * | 2021-05-08 | 2021-08-03 | 电子科技大学中山学院 | Preparation and application method of black hole liquid |
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| EP3656894A1 (en) * | 2018-11-25 | 2020-05-27 | Nanjing Graphene Research Institute Corporation | Method for electroplating copper on non-metallic surfaces using graphene-based ink |
| CN109811380A (en) * | 2019-03-21 | 2019-05-28 | 华侨大学 | A kind of conducting surface treatment method before ABS plastic plating |
| CN109811380B (en) * | 2019-03-21 | 2022-06-10 | 华侨大学 | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic |
| CN111058078A (en) * | 2019-12-30 | 2020-04-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN111058078B (en) * | 2019-12-30 | 2021-09-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN112795965A (en) * | 2020-12-29 | 2021-05-14 | 中国科学院过程工程研究所 | Graphene oxide electroplating solution and preparation method and application thereof |
| CN112795965B (en) * | 2020-12-29 | 2022-04-01 | 中国科学院过程工程研究所 | Graphene oxide electroplating solution and preparation method and application thereof |
| CN113207243A (en) * | 2021-05-08 | 2021-08-03 | 电子科技大学中山学院 | Preparation and application method of black hole liquid |
| CN114016010A (en) * | 2021-11-05 | 2022-02-08 | 深圳市天熙科技开发有限公司 | Acidic pore-finishing agent and surface metallization treatment process method of inorganic non-metallic base material |
| CN114016010B (en) * | 2021-11-05 | 2024-05-24 | 深圳市天熙科技开发有限公司 | Acidic pore-forming agent and surface metallization treatment process method of inorganic nonmetallic substrate |
| CN114845480A (en) * | 2022-03-31 | 2022-08-02 | 厦门大学 | Flexible copper-clad plate graphene oxide hole metallization method |
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