CN114845480A - Flexible copper-clad plate graphene oxide hole metallization method - Google Patents
Flexible copper-clad plate graphene oxide hole metallization method Download PDFInfo
- Publication number
- CN114845480A CN114845480A CN202210331517.3A CN202210331517A CN114845480A CN 114845480 A CN114845480 A CN 114845480A CN 202210331517 A CN202210331517 A CN 202210331517A CN 114845480 A CN114845480 A CN 114845480A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- flexible copper
- hole
- clad laminate
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000001465 metallisation Methods 0.000 title claims abstract description 26
- 238000007747 plating Methods 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 97
- 229910052802 copper Inorganic materials 0.000 claims description 97
- 239000010949 copper Substances 0.000 claims description 97
- 238000005553 drilling Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000006872 improvement Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210331517.3A CN114845480A (en) | 2022-03-31 | 2022-03-31 | Flexible copper-clad plate graphene oxide hole metallization method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210331517.3A CN114845480A (en) | 2022-03-31 | 2022-03-31 | Flexible copper-clad plate graphene oxide hole metallization method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114845480A true CN114845480A (en) | 2022-08-02 |
Family
ID=82564241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210331517.3A Pending CN114845480A (en) | 2022-03-31 | 2022-03-31 | Flexible copper-clad plate graphene oxide hole metallization method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114845480A (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130299217A1 (en) * | 2012-05-14 | 2013-11-14 | The Hong Kong University Of Science And Technology | Electrical and thermal conductive thin film with double layer structure provided as a one-dimensional nanomaterial network with graphene/graphene oxide coating |
CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
CN104582324A (en) * | 2015-01-07 | 2015-04-29 | 台山市精诚达电路有限公司 | Hole metallization method for flexible printed circuit board |
CN108712830A (en) * | 2018-05-30 | 2018-10-26 | 广东天承科技有限公司 | A kind of circuit board without palladium chemical-copper-plating process |
CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
CN109811382A (en) * | 2019-03-28 | 2019-05-28 | 烟台恒诺新材料有限公司 | A kind of application of graphene oxide conductive paste in black holesization is directly electroplated |
WO2021118108A1 (en) * | 2019-12-13 | 2021-06-17 | 한국전자기술연구원 | Surface treatment method for through-holes of printed circuit board and manufacturing method therefor |
-
2022
- 2022-03-31 CN CN202210331517.3A patent/CN114845480A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130299217A1 (en) * | 2012-05-14 | 2013-11-14 | The Hong Kong University Of Science And Technology | Electrical and thermal conductive thin film with double layer structure provided as a one-dimensional nanomaterial network with graphene/graphene oxide coating |
CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
CN104582324A (en) * | 2015-01-07 | 2015-04-29 | 台山市精诚达电路有限公司 | Hole metallization method for flexible printed circuit board |
CN108712830A (en) * | 2018-05-30 | 2018-10-26 | 广东天承科技有限公司 | A kind of circuit board without palladium chemical-copper-plating process |
CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
CN109811382A (en) * | 2019-03-28 | 2019-05-28 | 烟台恒诺新材料有限公司 | A kind of application of graphene oxide conductive paste in black holesization is directly electroplated |
WO2021118108A1 (en) * | 2019-12-13 | 2021-06-17 | 한국전자기술연구원 | Surface treatment method for through-holes of printed circuit board and manufacturing method therefor |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI499690B (en) | Paste metal laminates | |
KR102032624B1 (en) | Preparation method of polyamide glue free flexible printed circuit board | |
JP4927963B2 (en) | Surface-treated copper foil, method for producing the same, and copper-clad laminate | |
TW442395B (en) | Composite copper foil, process for preparing the same, and copper-clad laminate and printed wiring board using the same | |
TWI578871B (en) | The manufacturing method of laminates | |
TWI609779B (en) | Copper foil containing adhesive layer,copper clad laminate and printed wiring board | |
US10448506B2 (en) | Wiring substrate and process for producing it | |
TWI664323B (en) | Method of forming a metal layer and method of manufacturing a substrate having such metal layer | |
JPH1036997A (en) | Electroplating method | |
CN113163623B (en) | Method for manufacturing blind hole buried hole filling packaging substrate of multilayer board | |
CN104284527A (en) | Printed circuit board and manufacturing method thereof | |
JP5023732B2 (en) | Laminated board | |
JP2008108791A (en) | Multilayer printed wiring board and method of manufacturing the same | |
CN114845480A (en) | Flexible copper-clad plate graphene oxide hole metallization method | |
CN112194815A (en) | Double-sided copper-plated polyimide film and preparation method thereof | |
JP5133724B2 (en) | Method for producing polyimide resin laminate and method for producing metal-clad laminate | |
JP2008063560A (en) | Method for surface modification of polyimide resin layer and manufacturing process for metal-clad laminate | |
CN115028868B (en) | Multilayer bonding material and preparation method and application thereof | |
JP4722954B2 (en) | Adhesive for printed wiring board and method for producing adhesive layer for printed wiring board | |
CN113292938B (en) | Non-photosensitive masking film for laser processing electronic circuit board and preparation method thereof | |
CN113543523B (en) | Substrate hole processing method and application thereof | |
TW200930201A (en) | Printed circuit board and method for manufacturing the same | |
CN111424272A (en) | Browning liquid for printed circuit board | |
WO2015101135A1 (en) | Polyimide film, flexible circuit board, and method of preparing the same | |
CN114574116B (en) | Carrier resin film and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |