CN114845480A - Flexible copper-clad plate graphene oxide hole metallization method - Google Patents
Flexible copper-clad plate graphene oxide hole metallization method Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
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Abstract
The invention provides a method for metallizing graphene oxide holes of a flexible copper-clad plate. The hole wall produced by the hole metallization method is smooth and flat, has no flaws, and does not have the problem of plating leakage.
Description
Technical Field
The invention relates to a method for metallizing graphene oxide holes of a flexible copper-clad plate, and belongs to the technical field of flexible circuit boards.
Background
A Flexible Printed Circuit (FPC) is a highly reliable and excellent Flexible Printed Circuit board made of polyimide or polyester film as a base material. The thin-film transistor has the characteristics of high wiring density, light weight, thin thickness and good bending property, and is widely applied to flat-panel displays such as liquid crystal displays and plasma displays in the fields of electronics and communication.
The flexible circuit board is prepared on a flexible copper clad laminate by a certain process, and can be generally divided into a single-sided board, a double-sided board and a multilayer circuit board. The double-sided board and the multilayer circuit board are respectively provided with two layers of copper plates and a plurality of layers of copper plates, and the copper plates are separated by non-conductive base materials. Vias are therefore required between different copper layers to conduct the lines between layers. Since the base material is a non-conductive material, copper cannot be plated on the base material in the electroless plating. Therefore, it is necessary to perform metallization (hole metallization) on the hole wall of the through hole to make it conductive, thereby facilitating electroless copper plating.
Currently, there are three main processes for hole metallization: the first is to form a conductive layer from graphite or carbon black; the second step is to use a layer of metal palladium plated on the seed layer; the third is to use pyrrole, thiophene, furan, aniline, etc. to polymerize on the pore wall to form a conductive polymer layer. However, the conductive layer formed of graphite or carbon black has poor conductivity and is difficult to adhere when the size of the through-hole is small because of large particles; the metal palladium is difficult to be used in mass production due to higher cost; the polymer conductive layer is a most applied hole metallization process at present, but a potassium permanganate solution is required for oxidation treatment in the polymerization process, so that the environment is polluted to a certain degree, and the formed polymer conductive layer has limited conductive capability. When the traditional hole metallization processes are applied to some complex high-frequency circuit boards, the phenomenon of plating missing of the conductive layer often occurs on the hole wall of the circuit board, and the subsequent chemical plating is seriously influenced to cause waste products. There is still a great deal of room for improvement in the hole metallization process.
Disclosure of Invention
The invention provides a method for metallizing graphene oxide holes of a flexible copper-clad plate, which can effectively solve the problems.
The invention is realized by the following steps:
a method for metallizing graphene oxide holes of a flexible copper-clad plate comprises the steps of soaking the flexible copper-clad plate with through holes in a graphene oxide aqueous solution, and then carrying out chemical copper plating.
As a further improvement, the concentration of the graphene oxide aqueous solution is 18-24 wt%, and the treatment time is 2-10 min.
As a further improvement, ultrasonic treatment is also carried out in the soaking treatment process.
As a further improvement, the ultrasonic frequency range of the ultrasonic treatment is 20-60 kHz.
As a further improvement, before soaking treatment, the through holes of the flexible copper-clad plate are subjected to hole arrangement treatment by using a hole arrangement agent.
As a further improvement, after soaking treatment, microetching solution is used for carrying out microetching treatment on the through hole of the flexible copper-clad plate.
As a further improvement, the through hole is formed by drilling the surface of the flexible copper clad plate by using an ultraviolet laser drilling machine.
As a further improvement, the power of the ultraviolet laser drilling machine is 4.5W, the scanning speed is 50mm/s, and the repeated drilling times are 4 times.
As a further improvement, the graphene oxide is formed by carrying out sufficient oxidation reaction of potassium permanganate and graphite powder in concentrated sulfuric acid.
A flexible copper clad laminate prepared by the method.
The invention has the beneficial effects that:
according to the invention, the graphene oxide solution is adopted for hole metallization treatment, the microstructure of the graphene oxide is flaky, when the graphene oxide is dispersed in the solution, the flaky graphene oxide is very easy to adsorb on the surface of the copper hole wall, and at the moment, the graphene oxide has strong electrostatic adsorption force, and can completely adsorb the whole hole wall. Along with the increase of the hole metallization processing time, namely the black hole time of the flexible copper-clad plate in the graphene oxide solution is increased, the carboxyl in the graphene oxide molecules and copper are subjected to a complex reaction to form an intermetallic complex, the hole wall and the graphene oxide layer directly form a molecular bond force with strong binding force, the hole wall cannot fall off in the subsequent copper plating process, the hole wall is smooth and flat after copper is deposited on the inner wall of the through hole, the defect is avoided, and the problem of plating leakage cannot occur. In addition, compared with other hole metallization processes, the graphene oxide hole metallization has thinner conductive layer thickness and is more suitable for manufacturing high-frequency circuit boards.
According to the hole metallization method, due to the fact that the hole metallization method does not contain formaldehyde carcinogens and chemical liquid medicine which is harmful to the ecological environment, the whole production process flow is harmless to people, the graphene oxide wastewater can be recycled, and waste and environment pollution are avoided. Meanwhile, the process flow is simple, the efficiency is improved, the human resource cost can be saved, and higher economic benefit can be obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a microscopic image of a section of an electroplated copper layer after a graphene oxide black hole of a flexible copper clad laminate provided in embodiment 1 of the present invention is processed for 2 minutes.
FIG. 2 is a microscopic image of a section of an electroplated copper layer after a flexible copper clad laminate graphene oxide black hole provided in embodiment 2 of the invention is processed for 4 minutes.
FIG. 3 is a microscopic image of a section of an electroplated copper layer after a flexible copper clad laminate graphene oxide black hole provided in embodiment 3 of the present invention is processed for 6 minutes.
FIG. 4 is a microscopic image of a section of the electroplated copper layer after the black hole of graphene oxide of the flexible copper clad laminate provided in embodiment 4 of the present invention is processed for 8 minutes.
FIG. 5 is a microscopic image of a section of an electroplated copper layer 4 minutes after the carbon black hole treatment of the flexible copper-clad plate provided in comparative example 1 of the present invention.
FIG. 6 is a microscopic image of the section of the electroplated copper layer of the flexible copper clad laminate provided in comparative example 2 of the present invention.
FIG. 7 is a microscopic image of the section of the electroplated copper layer of the flexible copper clad laminate provided in comparative example 3 of the present invention.
FIG. 8 is a microscopic image of the section of the electroplated copper layer of the flexible copper clad laminate provided in comparative example 4 of the present invention.
FIG. 9 is a microscopic image of the section of the electroplated copper layer of the flexible copper clad laminate provided in comparative example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a method for metallizing graphene oxide holes of a flexible copper-clad plate.
As a further improvement, the concentration of the graphene oxide aqueous solution is 18-24 wt%, and the treatment time is 2-10 min. The graphene oxide is formed by performing a sufficient oxidation reaction between potassium permanganate and graphite powder in concentrated sulfuric acid. Further, the preparation of the graphene oxide is that graphite solid powder is added into concentrated sulfuric acid with the concentration of 98%, the mixture is stirred uniformly, potassium permanganate is slowly added for 5 times after the mixed liquid is cooled, and after the mixed liquid is cooled to room temperature, the graphene oxide sheet is obtained through centrifugal precipitation. Wherein the proportion of the concentrated sulfuric acid, the graphite solid powder and the potassium permanganate is 180-220mL:1.5-2.5g:8-12g, preferably 200mL:2g:10 g. The graphene oxide solution prepared by the method has good dispersibility, can be uniformly dispersed in an aqueous solution, does not agglomerate after being placed for a long time, has a flaky microstructure, is very easy to adsorb on the surface of a copper pore wall, and is beneficial to smooth pore metallization. Meanwhile, the potassium permanganate is added for 5 times, and the adding amount is firstly small, then gradually increased and finally reduced. The addition mode ensures that the graphene oxide molecules have rich carboxyl groups while the carbon ring edge has the carboxylic acid group and the carbon layer plane has the phenolic hydroxyl group and the epoxy group, the carboxyl group and the copper generate a complex reaction to produce an intermetallic complex, and at the moment, the hole wall and the graphene oxide layer directly form a molecular bond force with strong bonding force and cannot fall off in the subsequent copper plating process.
As a further improvement, ultrasonic treatment is also performed in the soaking treatment process, so that graphene oxide is more uniformly dispersed in the solution, and graphene oxide sheets are more uniformly adsorbed on the pore walls. Preferably, the ultrasonic wave of the ultrasonic treatment has the frequency range of 20-60kHz, preferably 40kHz, and is most beneficial to the dispersion of the graphene oxide.
As a further improvement, before soaking treatment, the through holes of the flexible copper-clad plate are subjected to hole arrangement treatment by using a hole arrangement agent. The whole hole is also called as oil removal, and aims to remove oil stains or other impurities on the surface of the copper clad laminate and enable the through hole of the flexible copper clad laminate to have electronegativity; the flexible copper clad laminate subjected to whole-hole treatment is easy to adhere to a conducting layer, the copper clad laminate is soaked in graphene oxide suspension with ultrasonic vibration, and hole metallization can be completed after a certain time. The hole-shaping step is provided with an ultrasonic generator, so that the hole wall is charged more uniformly. Further, the frequency range of the ultrasonic wave is 40-60 kHz. Preferably, the dispersion of the graphene oxide is most facilitated when the frequency of the ultrasonic wave is 45 kHz.
The pore-forming agent is an anionic surfactant such as polyacrylamide as a main component. Due to the fact that polyacrylamide hydrogen bonds are combined with oxygen-containing functional groups in the graphene oxide to form Van der Waals bonds, the adhesion force of the graphene oxide on the hole walls is further improved. The pore-forming agent is used at a concentration in the range of 15-30 wt% and a pH in the range of 9-12, at which hydrogen bonds are most readily formed in the polyacrylamide surfactant, and at a temperature in the range of 30-40 deg.C, which is conducive to the bonding of hydrogen bonds with oxygen-containing functional groups.
As a further improvement, after soaking treatment, microetching solution is used for carrying out microetching treatment on the through hole of the flexible copper-clad plate. The microetching solution is a mixed solution of 60-90g/L sulfuric acid and 30-50g/L sodium persulfate. The microetching solution has the microetching action temperature of 30-35 ℃ and the microetching time of 40-90 s. The microetching solution has good compatibility with graphene oxide, and cannot damage a GO adhesion layer; this temperature and time are based on considerations of the protection of the GO adhesion layer.
As a further improvement, the through hole is formed by drilling the surface of the flexible copper clad plate by using an ultraviolet laser drilling machine. The ultraviolet laser drilling machine is a 355nm picosecond ultraviolet laser drilling machine, the drilling power is 4.5W, the scanning speed is 50mm/s, and the repeated drilling times are 4 times. Under the condition of drilling, the hole wall has special textures, and graphene oxide is favorably attached.
As a further improvement, the temperature of the electroless copper plating is 30-42 ℃, and the copper plating time is 5-15 min. The chemical copper plating process can accurately control the thickness of copper plating, and the situation of hole wall plating leakage rarely occurs. The thickness of the copper plating is 15 to 20 μm, preferably 18 μm.
The embodiment of the invention also provides the flexible copper clad laminate prepared by the method. The flexible copper-clad plate can be a double-sided copper-clad plate or a multilayer copper-clad plate, and after copper is deposited on the inner wall of the through hole, the hole wall is smooth and flat without flaws, and the problem of plating leakage is avoided; meanwhile, compared with other hole metallization processes, the graphene oxide hole metallization has the advantage that the thickness of the conducting layer is smaller, so that the method is very suitable for manufacturing a flexible circuit board, and is particularly suitable for manufacturing a high-frequency circuit board.
Example 1
The specific process steps for metallizing the graphene oxide holes by adopting the flexible copper-clad plate disclosed by the invention are as follows:
firstly, drilling a plurality of through holes on a flexible copper-clad plate by utilizing ultraviolet laser drilling; a355 nm picosecond ultraviolet laser drilling machine is adopted, the power of the ultraviolet laser drilling machine is 4.5W, the scanning speed is 50mm/s, and the repeated drilling times are 4 times.
And secondly, circularly washing the punched flexible copper clad laminate, and then, carrying out hole-finishing treatment on the through hole of the flexible copper clad laminate by using a hole-finishing agent polyacrylamide. The pore-forming agent concentration range was 20 wt%, the pH range was 10, and the set temperature was 35 ℃. The whole hole treatment process is carried out by ultrasonic treatment, and the frequency is 45 kHz.
And step three, adding 2g of graphite solid powder into 200ml of 98% sulfuric acid, uniformly stirring, slowly adding 10g of potassium permanganate (1.5 g for the 1 st time, 2g for the 2 nd time, 3g for the 3 rd time, 2g for the 4 th time and 1.5g for the 5 th time) for 5 times after the mixed liquid is cooled, performing centrifugal precipitation after the mixed liquid is cooled to room temperature to obtain a graphene oxide sheet, and adding pure water to form a 20 wt% graphene oxide solution.
And fourthly, soaking the flexible copper clad laminate in the graphene oxide suspension for black hole treatment for 2 minutes. The soaking process is carried out by ultrasonic treatment with frequency of 40 kHz.
And fifthly, soaking the flexible copper clad laminate after the black hole in a mixed solution of 80g/L sulfuric acid and 40g/L sodium persulfate to achieve the aim of micro-etching. The temperature of the microetching solution is 32 ℃, and the microetching time of the copper-clad plate is 60 s.
And sixthly, carrying out chemical copper plating on the washed flexible copper-clad plate. The temperature of the electroless copper plating is 36 ℃, and the copper plating time is 10 min.
The graphene oxide carries out black hole treatment on the hole wall of the flexible copper-clad plate for two minutes, the hole wall is electroplated with a copper layer as shown in figure 1, the hole bottom is circular and complete, no black spot exists, the thickness of the hole copper is uniform, a small amount of defects exist at the hole opening, and no cavity or layering exists.
Example 2
The difference from example 1 was that the black hole treatment time was 4 minutes, and the other operations were the same as example 1.
The graphene oxide is used for carrying out black hole treatment on the hole wall of the flexible copper-clad plate for 4 minutes, the hole wall is electroplated with a copper layer as shown in figure 2, the hole bottom is circular and complete, no black spots exist, the thickness of the hole copper is uniform, no holes exist, no layering exists, and the hole copper is a group with the best black hole effect.
Example 3
The difference from example 1 was that the black hole treatment time was 6 minutes, and the other operations were the same as example 1.
The graphene oxide carries out black hole treatment on the hole wall of the flexible copper-clad plate for 6 minutes, the hole wall is electroplated with a copper layer as shown in figure 3, the hole bottom is circular and complete, a small number of black spots exist, the hole copper is uniform in thickness, no cavity exists, no layering exists, and the hole opening has partial defects.
Example 4
The difference from example 1 was that the black hole treatment time was 8 minutes, and the other operations were the same as example 1.
The graphene oxide carries out black hole treatment on the hole wall of the flexible copper-clad plate for 8 minutes, the hole wall is electroplated with a copper layer as shown in figure 4, the hole bottom is circular and complete, black spots exist, the thickness of the hole copper is uniform, no cavity exists, no layering exists, and the hole opening has partial defects.
Comparative example 1
The conventional carbon black suspension was used for via metallization of flexible circuit boards, and the other operations were performed simultaneously with example 1.
The carbon black suspension is prepared by adding carbon black powder and dispersant sodium tripolyphosphate into DI water, wherein the mass fraction of the carbon black powder is 3% and the mass fraction of the dispersant is 4%, and fully dispersing the carbon black powder and the dispersant by ultrasonic vibration to prepare the carbon black suspension.
The carbon black suspension liquid carries out black hole treatment on the hole wall of the flexible copper-clad plate for four minutes, the hole wall electroplated copper layer is shown in figure 5, the hole wall plated layer is more than 6 microns, residual copper in the hole is accumulated to the hole opening, and the hole bottom plated layer and base copper are layered.
Comparative example 2
The power of the UV laser drilling machine was 10W, the scanning speed was 60mm/s, the number of repeated drilling was 1, and the other operations were the same as in example 1.
As shown in fig. 6, the copper layer electroplated on the hole wall has more residues in the drilled hole due to the fact that laser drilling parameters are not preferred parameters, and copper is attached to the residues during copper plating to deposit, so that copper nodules appear in the hole.
Comparative example 3
The pore-adjusting agent is ethylene oxide-propylene oxide copolymer, and the other operations are the same as example 1.
Pore wall copper electroplating layer as shown in fig. 7, because ethylene oxide propylene oxide copolymer and GO have poor adsorptivity, hydrogen bonds cannot be provided to bond with GO, GO cannot be uniformly attached to the pore wall, GO is deposited in the pore, and thus, the copper electroplating layer deposits thick copper in the pore.
Comparative example 4
The potassium permanganate is added at one time in the preparation of the graphene oxide, and other operations are the same as those in example 1.
As shown in figure 8, the pore wall electroplated copper layer is formed by adding potassium permanganate at one time, so that GO cannot form enough carboxyl, the carboxyl and copper are subjected to a complex reaction and reduced, GO is deposited at the bottom of a pore, and a copper plating layer at the bottom is too thick.
Comparative example 5
The microetching solution was 40g/L sulfuric acid and 80g/L sodium persulfate, otherwise the same as in example 1.
As shown in fig. 9, the copper layer plated on the hole wall has poor compatibility with GO in the microetching solution at the above concentration, and part of GO is brought out of the hole wall by the microetching solution, so that the hole wall has poor electrification property and poor copper plating effect, and the hole wall is plated with copper too thinly.
As can be seen from examples 1 to 4 and comparative examples 1 to 5, the method for metallizing a graphene oxide hole of a flexible copper clad laminate according to the embodiments of the present invention mainly performs a hole metallization treatment on the flexible copper clad laminate by using a graphene oxide solution, and simultaneously, by adjusting a drilling process, a selection and use process of a hole-finishing agent, a preparation and use process of graphene oxide, a microetching process, and a copper plating process, each process interacts with graphene oxide to exert a synergistic effect, so as to promote graphene oxide to adhere to a hole wall and form a copper plating layer, thereby forming a uniform, fine and firmly-combined conductive layer, wherein the reliability of the copper plating layer is higher, the hole wall is smooth and flat after copper deposition on the inner wall of a through hole, and the problem of missing plating is not caused.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for metallizing graphene oxide holes of a flexible copper-clad plate is characterized in that the flexible copper-clad plate with through holes is immersed in a graphene oxide aqueous solution and then subjected to electroless copper plating.
2. The flexible copper clad laminate graphene oxide hole metallization method according to claim 1, wherein the concentration of the graphene oxide aqueous solution is 18-24 wt%, and the treatment time is 2-10 min.
3. The flexible copper clad laminate graphene oxide hole metallization method according to claim 1, wherein ultrasonic treatment is further performed in the soaking treatment process.
4. The flexible copper clad laminate graphene oxide hole metallization method according to claim 3, wherein the frequency range of the ultrasonic wave of the ultrasonic treatment is 20-60 kHz.
5. The method for metallizing graphene oxide holes on a flexible copper clad laminate according to claim 1, wherein the through holes of the flexible copper clad laminate are further subjected to hole arrangement treatment by using a hole arrangement agent before the soaking treatment.
6. The method for metallizing graphene oxide holes on a flexible copper clad laminate according to claim 1, wherein after the soaking treatment, the through holes on the flexible copper clad laminate are further microetched with a microetching solution.
7. The method for metallizing graphene oxide holes on a flexible copper clad laminate according to claim 1, wherein the through holes are formed by drilling the surface of the flexible copper clad laminate by using an ultraviolet laser drilling machine.
8. The flexible copper clad laminate graphene oxide hole metallization method according to claim 7, wherein the power of the ultraviolet laser drilling machine is 4.5W, the scanning speed is 50mm/s, and the number of repeated drilling is 4.
9. The flexible copper clad laminate graphene oxide hole metallization method according to claim 1, wherein the graphene oxide is formed by sufficient oxidation reaction of potassium permanganate and graphite powder in concentrated sulfuric acid.
10. A flexible copper clad laminate prepared by the method of any one of claims 1 to 9.
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