CN103103590A - Direct-electroplating conductive liquid and preparation method thereof - Google Patents
Direct-electroplating conductive liquid and preparation method thereof Download PDFInfo
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- CN103103590A CN103103590A CN2013100055724A CN201310005572A CN103103590A CN 103103590 A CN103103590 A CN 103103590A CN 2013100055724 A CN2013100055724 A CN 2013100055724A CN 201310005572 A CN201310005572 A CN 201310005572A CN 103103590 A CN103103590 A CN 103103590A
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Abstract
The invention discloses a direct-electroplating conductive liquid and a preparation method thereof. The method comprises the following steps of adding graphene of 0.5-2.0g/L and a stabilizer of 0.2-0.6g/L into the deionized water of 500mL, dispersing by ultrasonic with frequency of 45KHz and power of 100W at 60-80 DEG C for 1-3 hours, then adding 200mL of 1-3% of an organic or inorganic stabilizer, regulating the pH value to 9-11 with a pH value modifier of 10%, replenishing the deionized water to 1000mL, dispersing by the ultrasonic continuously for 1 hour, and obtaining 1L of the direct-electroplating conductive liquid. The stabilizer comprises one or more agents among polyacrylic acid, carboxymethylcellulose, and sodium silicate. Being used for hole metallization, the conductive liquid provided by the invention has the advantages that the grain size is small, the use level is small, the adsorption capacity is strong, the formed grain layer is compact, the conductivity is strong, and the electroplating efficiency is high; furthermore, the conductive liquid is convenient and simple to use and maintain, and environment contamination is avoided.
Description
Technical field
The invention belongs to the electronic industrial technology field, relate to a kind of conductive liquid that makes printed circuit board (PCB) (PCB) Direct Electroplating.The present invention also further relates to a kind of conductive liquid that makes the non-conductor Direct Electroplating.
Background technology
Along with developing rapidly of electronic industrial technology, the demand of PCB increases severely day by day.On tellite, in order to make circuit, interconnect, need on substrate, wear through hole, and the hole inwall is plated to conductive metal, be i.e. hole metallization.Hole metallization is one of critical process of PCB manufacturing processed, and the main colloidal pd activation solution that adopts carries out electroless copper as catalyzer to PCB at present; Adopt graphite and one or both particles of carbon black to carry out Direct Electroplating copper as conducting particles.Colloidal pd activation solution is divided into two kinds of acidic group and alkali, the active high and good stability of acidic group, but because acidity is strong, easily produce " variable color ring " phenomenon in the copper facing process, and hydrochloric acid mist causes severe contamination to environment, although alkali has overcome the shortcoming of acidic group, acidity dies down, but activity and less stable, the content of palladium is higher simultaneously, has increased process costs.One or both particles of graphite and carbon black carry out Direct Electroplating as conducting particles, and because particle diameter ratio is larger, adsorptive power is poor, and a little less than electroconductibility, electroplating efficiency is low.Therefore, the preparation method who finds the Direct Electroplating conductive liquid of a kind of not only environmental protection but also highly effective seems particularly urgent.
U.S. Pat .Pat.No3099608 adopts graphite particle to have the shortcomings such as the metal property separated out of electroplating is low as the Direct Electroplating conductive layer; US.Pat.No3163588 carries out electric plating method after having disclosed particles such as adhering to silver, copper, graphite at through-hole wall and having given electroconductibility, when peeling off the plating excess electron excess fraction, due to the defects such as electrolytic coating generation pin hole of through-hole wall, need to carry out second time electroplating; US.Pat.No4619174, US.Pat.No4684560, US.Pat.No4724005 have introduced absorption carbon black suspension on the PCB hole wall, obtain the conductive carbon black layer after dry, then carry out Direct Electroplating, this technique can be cancelled the operations such as pre-activation, the activation of Pd/Sn colloid and electroless copper; But for adsorptivity and the electroconductibility of improving carbon black, US.Pat.No4622108 adopts alkaline hydrated oxide to flatten in advance solution-treated PCB hole wall, US.Pat.No5015339 adopts alkaline permanganate solution and neutralizing agent/leveling agent solution-treated PCB hole wall, improves the adsorptivity of carbon black suspension at the PCB hole wall surface; US.Pat.No4718993 adopts alkaline silicate solution to process the PCB hole wall, and US.Pat.No4964959 adds electric conductive polymer in carbon black suspension, in the US.Pat.No5290442 graphite suspension, adds silver powder, improves the electroconductibility of silica aerogel layer; US.Pat.No5139642, RE37765 be the depositing electrically conductive graphite linings on silica aerogel layer, has promoted the monolithic conductive of carbon black/graphite linings; Chinese patent CN1109924A adopts the suspension of two kinds, carbon black/graphite or a kind of particle as the Direct Electroplating conductive liquid; The graphite suspension that CN1733980A employing median size is 0.2um is as the Direct Electroplating conductive liquid; US.Pat.No6037020 adopts ultrasonic stirring before PCB immerses the suspension that contains two kinds, carbon black/graphite or a kind of particle, and US.Pat.No7128820 adopts specific surface area to be greater than 150m
2/ g carbon black particle, US.Pat.No7214304 adopts two kinds, carbon black/graphite or wherein a kind of as conducting particles, and, by multiple dispersing mode, its purpose is all adsorptivity and the electroconductibility in order to improve conductive layer.The specific surface area of Graphene is greater than the specific surface area of carbon black and graphite, and resistivity is less than the resistivity of carbon black and graphite, adopts the conducting particles of Graphene as the Direct Electroplating conductive liquid, and the adsorptivity of conductive layer and electroconductibility will further be improved.
Graphene (Graphene) is the novel material of the individual layer sheet structure that consists of carbon atom, be a kind of by carbon atom with SP
2hybridized orbital forms the flat film that hexangle type is the honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.After being found by the scientist of Univ Manchester UK from 2004, the structure that Graphene is unique with regard to it and excellent performance become the focus of scientific circles and industry member concern.Wherein Graphene has high electronic mobility (2 * 10
5cm
2(v ﹒ s)
-1), higher 100 times than the electronic mobility of silicon semiconductor, higher 20 times than the electronic mobility of gallium arsenide, and resistivity only has an appointment 10
-6Ω ﹒ cm, lower than copper and Yin Geng, be the current material of resistivity minimum in the world; The electric conductivity of graphite is 8-13 * 10
-6Ω ﹒ cm.The specific surface area of Graphene can reach 2630 ㎡/g, and the specific surface area of carbon black is 1500 ㎡/g, and the specific surface area of graphite is 1-20 ㎡/g.Therefore better as the conducting particles effect of Direct Electroplating conductive liquid with Graphene.
Ultrasonic wave, through liquid medium the time, can produce strong cavitation and vibration effect, and the high temperature that cavatition produces and a large amount of micro-bubbles that produce at solid surface have reduced the specific surface free energy of tiny crystal grains, has suppressed crystal grain and has assembled and grow up; The strong shock wave that ultrasonic cavitation produces and microjet have reduced the Van der Waals force between molecule effectively to shearing and the crushing effect of particle, thereby effectively stop the reunion of molecule; Ultrasonic wave can form again the turbulence of fluid in liquid, is conducive to the dispersion of molecule and stablizing of suspension.
Summary of the invention
In order to overcome, the adsorptive power existed in prior art is poor, a little less than electroconductibility and the low deficiency of electroplating efficiency, the present invention proposes a kind of Direct Electroplating conductive liquid and preparation method thereof.
Direct Electroplating conductive liquid of the present invention is that the Graphene of 0.5～2.0g/L and 0.2～0.6g/L stablizer are added in the 500mL deionized water and be prepared from.Described stablizer is one or more in polyacrylic acid, carboxymethyl cellulose, water glass.
The invention allows for a kind of method for preparing described Direct Electroplating conductive liquid, detailed process is:
Step 1, the preparation graphene dispersing solution; The 500mL deionized water is heated to 60～80 ℃; 0.5～2.0g/L Graphene is added in this deionized water, and disperse 1h by ultrasonic wave, obtain graphene dispersing solution;
Step 2, the preparation stabiliser solution; Separately get the 200mL deionized water, 0.2～0.6g/L stablizer is joined in described 200mL deionized water and dissolves, obtain stabiliser solution;
Step 3, add stabiliser solution; The stabiliser solution obtained is joined in the graphene dispersing solution in dispersion, and disperse the solution of added stablizer by ultrasonic wave;
Step 4, add the pH value conditioning agent; The pH value conditioning agent that is 10% by concentration is adjusted to 9-11 by the pH value of stabiliser solution and graphene dispersing solution; Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.Described pH value conditioning agent is ammoniacal liquor and sodium hydroxide.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
The conductive liquid that utilizes the present invention to propose carries out the technique of hole metallization, has a particle diameter little, and consumption is few, and adsorptive power is strong, the particle layer densification of formation, and electroconductibility is strong, and electroplating efficiency is high; Simultaneously, use and maintenance is simple and easy to do, has avoided environmental pollution.
In the present invention, the 0.5-2.0g Graphene is added in the 500mL deionized water, under 60-80 ℃, disperse 1-3h by the ultrasonic wave of frequency 45KHz, power 100W, add again 200mL1-3% organic or inorganic stablizer, with 10% pH value conditioning agent, pH value is adjusted to 9-11, supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
The present invention adopts Ultrasonic Radiation to disperse, and cavatition and vibration effect have weakened Graphene Van der Waals force between layers, have suppressed the reunion between graphite flake layer, is conducive to the dispersion of Graphene and stablizing of suspension.
Compared with prior art, beneficial effect of the present invention is:
With colloidal pd activation solution, compare, use and maintenance is simple and easy to do, avoids environmental pollution.Belong to physical adsorption between described Direct Electroplating conductive liquid and PCB, chemical reaction does not occur, without the component of analyzing and adjust conductive liquid, only need add this conductive liquid according to consumption integral body and get final product; The not hydrochloric acidic substance that wait of described Direct Electroplating conductive liquid, the adsorption process no hydrogen produces, and guarantees the inter-level interconnects quality of PCB, does not also have acid mist simultaneously and produces, and environment keeps the scene intact.
With carbon black, graphite suspension, compare, described Direct Electroplating conductive liquid particle diameter is little, and consumption is few, and adsorptive power is strong, the particle layer densification, and electroconductibility is strong, and electroplating efficiency is high.
Described Direct Electroplating conductive liquid adopts Graphene as conducting particles, its size of particles is thickness≤1.0nm, size≤200nm, usually in carbon black used, graphite suspension conductive liquid the median size graphite particle 2um of particle following, below carbon black particle 1um, the minimum 200nm that also reaches; From micro-structure diagram, can find out, the Graphene surface folding is laminar, graphite surface is smooth is irregular slab-like, the specific surface area of Graphene can reach 2630 ㎡/g, the specific surface area of carbon black is 1500 ㎡/g, the specific surface area of graphite is 1-20 ㎡/g, so the adsorptive power of Graphene and PCB is the strongest, particle layer is the finest and close, and consumption is minimum.The structure of Graphene is highly stable, up to now, the investigator does not find in Graphene to have the situation of carbon atom disappearance yet, connection in Graphene between each carbon atom is very pliable and tough, when applying external mechanical force, the carbon atom face is with regard to flexural deformation, thereby carbon atom needn't rearrange to adapt to external force, also just kept Stability Analysis of Structures, this stable crystalline network makes carbon atom have outstanding electroconductibility, when the electronics in Graphene moves in track, can or not introduce foreign atom because of lattice imperfection scattering occurs, because reactive force between atom is very strong, at normal temperatures, even carbon atom telescopes on every side, the interference that in Graphene, electronics is subject to is also very little, therefore Graphene has high electronic mobility (2 * 10
5cm2 (v ﹒ s)
-1), higher 100 times than the electronic mobility of silicon semiconductor, higher 20 times than the electronic mobility of gallium arsenide, and resistivity only has an appointment 10
-6Ω ﹒ cm, lower than copper and Yin Geng, be the current material of resistivity minimum in the world, the electric conductivity of graphite is 8-13 * 10
-6Ω ﹒ cm, so better as the conducting particles effect of Direct Electroplating conductive liquid with Graphene.
Ultrasonic wave, through liquid medium the time, can produce strong cavitation and vibration effect, and the high temperature that cavatition produces and a large amount of micro-bubbles that produce at solid surface have reduced the specific surface free energy of tiny crystal grains, has suppressed crystal grain and has assembled and grow up; The strong shock wave that ultrasonic cavitation produces and microjet have reduced the Van der Waals force between molecule effectively to shearing and the crushing effect of particle, thereby effectively stop the reunion of molecule; Ultrasonic wave can form again the turbulence of fluid in liquid, is conducive to the dispersion of molecule and stablizing of suspension.Described Direct Electroplating conductive liquid adopts ultrasonic wave to disperse, the strong shock wave produced by cavatition and microjet have weakened Graphene Van der Waals force between layers, suppressed the reunion of graphene film interlayer, the stable condition that provides for described Direct Electroplating conductive liquid, by adding stablizer, guaranteed that the stability of described Direct Electroplating conductive liquid is greater than 90 days again.
Adopt described Direct Electroplating conductive liquid to carry out the electro-coppering of PCB hole metallization, with experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
The accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of natural flake graphite;
Fig. 2 is scanning electron microscope (SEM) figure of Graphene;
Fig. 3 is transmission electron microscope (TEM) figure of graphite suspension;
Fig. 4 is graphene suspension (Direct Electroplating conductive liquid) transmission electron microscope (TEM) figure;
Fig. 5 is schema of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of Graphene, the 0.2g/L polyacrylic acid stablizer of 0.5g/L, usings ammoniacal liquor as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 60 ℃.The 0.5g/L Graphene is added in this deionized water, and disperse 1h by ultrasonic wave, obtain graphene dispersing solution.
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, the Powdered polyacrylic acid stablizer of 0.2g/L is joined in described 200mL deionized water and dissolves, obtain stabiliser solution.
Step 3, add stabiliser solution.The polyacrylic acid stabiliser solution obtained is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses the solution of added polyacrylic acid stablizer by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the ammoniacal liquor that is 10% by concentration will be added with the deionized water of polyacrylic acid stablizer and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 60 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization electro-coppering test, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Embodiment 2
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of Graphene, the 0.4g/L polyacrylic acid stablizer of 1.0g/L, usings ammoniacal liquor as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 70 ℃.The 1.0g/L Graphene is added in this deionized water, and disperse 2h by ultrasonic wave, obtain graphene dispersing solution.
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, the Powdered polyacrylic acid stablizer of 0.4g/L is joined in described 200mL deionized water and dissolves, obtain stabiliser solution.
Step 3, add stabiliser solution.The polyacrylic acid stabiliser solution obtained is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses the solution of added polyacrylic acid stablizer by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the ammoniacal liquor that is 10% by concentration will be added with the deionized water of polyacrylic acid stablizer and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 70 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization test electro-coppering, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Implement 3
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of Graphene, the 0.6g/L polyacrylic acid stablizer of 2.0g/L, usings ammoniacal liquor as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 80 ℃.The 2.0g/L Graphene is added in this deionized water, and disperse 3h by ultrasonic wave, obtain graphene dispersing solution.
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, the Powdered polyacrylic acid stablizer of 0.6g/L is joined in described 200mL deionized water and dissolves, obtain stabiliser solution.
Step 3, add stabiliser solution.The polyacrylic acid stabiliser solution obtained is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses the solution of added polyacrylic acid stablizer by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the ammoniacal liquor that is 10% by concentration will be added with the deionized water of polyacrylic acid stablizer and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 80 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization test electro-coppering, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Implement 4
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of Graphene, the 0.4g/L carboxymethyl cellulose stablizer of 1.0g/L, usings ammoniacal liquor as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 70 ℃.The 1.0g/L Graphene is added in this deionized water, and disperse 2h by ultrasonic wave, obtain graphene dispersing solution; .
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, the Powdered carboxymethyl cellulose stablizer of 0.4g/L is joined in described 200mL deionized water and dissolves, obtain stabiliser solution.
Step 3, add stabiliser solution.The carboxymethyl cellulose stabiliser solution obtained is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses the solution of added carboxymethyl cellulose stablizer by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the ammoniacal liquor that is 10% by concentration will be added with the deionized water of carboxymethyl cellulose stablizer and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 70 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization test electro-coppering, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Implement 5
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of the Graphene of 1.0g/L, polyacrylic acid stablizer and the 0.2g/L carboxymethyl cellulose stablizer of 0.2g/L, usings ammoniacal liquor as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 70 ℃.The 1.0g/L Graphene is added in this deionized water, and disperse 2h by ultrasonic wave, obtain graphene dispersing solution.
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, the Powdered polyacrylic acid stablizer of 0.2g/L and the Powdered carboxymethyl cellulose stablizer of 0.2g/L are joined in described 200mL deionized water simultaneously and dissolve, obtain stabiliser solution.
Step 3, add stabiliser solution.The solution of the polyacrylic acid that obtains and carboxymethyl cellulose stablizer is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses the solution of added polyacrylic acid and carboxymethyl cellulose stablizer by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the ammoniacal liquor that is 10% by concentration will be added with the deionized water of polyacrylic acid and carboxymethyl cellulose stabiliser solution and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 70 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization test electro-coppering, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Implement 6
The present embodiment is a kind of Direct Electroplating conductive liquid.Described conductive liquid is comprised of the Graphene of 1.0g/L, the water glass stablizer of 0.4g/L, usings aqueous sodium hydroxide solution as the pH value conditioning agent, adopts deionized water to be prepared from.
Thickness≤the 1.0nm of described Graphene, particle diameter≤200nm
The process for preparing described Direct Electroplating conductive liquid is:
Step 1, the preparation graphene dispersing solution.The 500mL deionized water is heated to 70 ℃.The 1.0g/L Graphene is added in this deionized water, and disperse 2h by ultrasonic wave, obtain graphene dispersing solution.
Step 2, the preparation stabiliser solution.Separately get the 200mL deionized water, 0.4g/L water glass stablizer is joined in described 200mL deionized water and dissolves, obtain stabiliser solution.
Step 3, add stabiliser solution.The water glass stabiliser solution obtained is joined to adding in dispersion to be had in the deionized water of Graphene, and disperses added water glass stabiliser solution by ultrasonic wave.
Step 4, add the pH value conditioning agent.The pH value that the aqueous sodium hydroxide solution that is 10% by concentration will be added with the deionized water of water glass stabiliser solution and Graphene is adjusted to 9-11.Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
In the process of preparation Direct Electroplating conductive liquid, system temperature is 70 ℃.
In the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
By standing 60 days of the Direct Electroplating conductive liquid obtained, described Direct Electroplating conductive liquid, without condensing and Precipitation, showed stable system.
Adopt described Direct Electroplating conductive liquid to carry out PCB hole metallization test electro-coppering, by experimental examination test specimen backlight, find that hole wall is all covered by the copper of uniform thickness, and, in conjunction with tight, tight produces.
Claims (5)
1. a Direct Electroplating conductive liquid, is characterized in that, the Graphene of 0.5～2.0g/L and 0.2～0.6g/L stablizer are added in the 500mL deionized water and be prepared from;
Described stablizer is one or more in polyacrylic acid, carboxymethyl cellulose, water glass.
2. a method for preparing the described Direct Electroplating conductive liquid of claim 1, is characterized in that, detailed process is:
Step 1, the preparation graphene dispersing solution; The 500mL deionized water is heated to 60～80 ℃; 0.5～2.0g/L Graphene is added in this deionized water, and disperse 1h by ultrasonic wave, obtain graphene dispersing solution;
Step 2, the preparation stabiliser solution; Separately get the 200mL deionized water, 0.2～0.6g/L stablizer is joined in described 200mL deionized water and dissolves, obtain stabiliser solution;
Step 3, add stabiliser solution; The stabiliser solution obtained is joined in the graphene dispersing solution in dispersion, and disperse the solution of added stablizer by ultrasonic wave;
Step 4, add the pH value conditioning agent; The pH value conditioning agent that is 10% by concentration is adjusted to 9-11 by the pH value of stabiliser solution and graphene dispersing solution; Supplement deionized water to 1000mL, continue ultrasonic dispersion 1h, obtain 1L Direct Electroplating conductive liquid.
3. prepare as claimed in claim 2 the method for Direct Electroplating conductive liquid, it is characterized in that, described pH value conditioning agent is ammoniacal liquor and sodium hydroxide.
4. prepare as claimed in claim 2 the method for Direct Electroplating conductive liquid, it is characterized in that, in the process of preparation Direct Electroplating conductive liquid, the ultrasonic wave of proportion 45KHz, power 100W is disperseed.
5. the method for Direct Electroplating conductive liquid as claimed in claim 2, is characterized in that, at the system temperature of preparation Direct Electroplating conductive liquid, is 60～80 ℃.
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| CN107723764A (en) * | 2017-10-31 | 2018-02-23 | 电子科技大学 | A kind of method of the Direct Electroplating on insulating substrate |
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| CN103450830A (en) * | 2013-09-02 | 2013-12-18 | 西北工业大学 | Preparation of high-performance magnetic conductive pressure-sensitive adhesive |
| CN103450830B (en) * | 2013-09-02 | 2015-05-13 | 西北工业大学 | Preparation of high-performance magnetic conductive pressure-sensitive adhesive |
| CN105714360A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof |
| CN105714360B (en) * | 2014-12-04 | 2017-12-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene nickel plating solution, its preparation method and application |
| CN105968929A (en) * | 2016-07-01 | 2016-09-28 | 天津普兰能源科技有限公司 | Preparation method of thin-film coating |
| CN106559961A (en) * | 2016-08-31 | 2017-04-05 | 广州市天承化工有限公司 | A kind of conduction liquid and preparation method thereof and conductive processing method |
| CN106559961B (en) * | 2016-08-31 | 2021-10-08 | 广东天承科技股份有限公司 | Conductive liquid, preparation method thereof and conductive treatment method |
| CN107723764A (en) * | 2017-10-31 | 2018-02-23 | 电子科技大学 | A kind of method of the Direct Electroplating on insulating substrate |
| CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
| CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
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