CN116489893A - Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof - Google Patents
Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof Download PDFInfo
- Publication number
- CN116489893A CN116489893A CN202310436688.7A CN202310436688A CN116489893A CN 116489893 A CN116489893 A CN 116489893A CN 202310436688 A CN202310436688 A CN 202310436688A CN 116489893 A CN116489893 A CN 116489893A
- Authority
- CN
- China
- Prior art keywords
- copper
- silver
- layer
- circuit board
- side wall
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 claims abstract description 53
- 239000004332 silver Substances 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 41
- 238000005530 etching Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- 239000011241 protective layer Substances 0.000 claims description 28
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 238000005219 brazing Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000011161 development Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000003631 wet chemical etching Methods 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 9
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000005476 soldering Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 229910000679 solder Inorganic materials 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000012858 packaging process Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000004021 metal welding Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention relates to the technical field of semiconductors, in particular to a copper-clad ceramic circuit board with a silver-free groove side wall and a preparation method thereof. According to the invention, the silver is chemically deposited firstly, then the pattern transfer and silver layer protection in the copper circuit etching and solder layer etching processes are realized by utilizing the ink protection layer, and then the ink protection layer is removed, so that the problem of silver on the side wall of the groove in the silver formation process of the copper-clad ceramic circuit board is solved, and finally the preparation of the copper-clad ceramic circuit board with no silver on the side wall of the groove is realized. The invention can avoid silver-packaging adhesive layering and silver migration in the downstream packaging process, thereby ensuring the reliability of the packaged device. The invention is not affected by the thickness of the copper layer and the solder layer, namely the depth of the groove, and has universality, and the ink protection layer in the invention can be cleanly removed by organic reagents such as dimethylbenzene in the preparation stage of the circuit board, so that the ink protection layer is prevented from influencing high temperature processes such as vacuum reflow soldering in the downstream packaging stage due to high temperature pyrolysis.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a copper-clad ceramic circuit board with a silver-free groove side wall and a preparation method thereof.
Background
The copper-clad ceramic circuit board is a core component of the high-power electronic packaging module, and has good heat conductivity, insulativity and high mechanical strength. Like the printed circuit board, the copper-clad ceramic circuit board can be etched into a circuit diagram according to the requirement, so that the application range of the copper-clad ceramic circuit board in the packaging field of high-power electronic devices is greatly improved, and the copper-clad ceramic circuit board is a preferred material in hot industries such as electric automobiles, high-speed rails and aerospace. The high integration of electronic components places more stringent requirements on the heat dissipation performance of the electronic package, the choice of circuit board materials, and the fabrication process.
The preparation method of the copper-clad ceramic circuit board can be divided into a surface copper plating technology, a direct copper plating technology and an active metal welding technology. The surface copper plating technology is simple in process and suitable for a miniaturized electronic packaging system; the direct copper-clad technology directly connects the copper foil and the ceramic substrate, and has low thermal resistance, strong heat dissipation capacity and low bonding strength. The active metal welding technology is an improvement on the direct copper coating technology, and the material with high heat conduction and high insulation performance can be prepared through selective surface silver treatment, so that the active metal welding technology is widely applied to the packaging of semiconductor devices with high power and high heat dissipation requirements. In the silver melting process, the silver on the side wall of the groove is inevitably generated due to the weak filling property of the dry film, and the problems of silver ion migration and layering of packaging adhesive and silver on the side wall are also brought, so that the reliability of a packaged device is seriously affected.
The patent CN113354449 provides a preparation method of a copper-clad ceramic circuit board with silver-free side walls, which is characterized in that after copper layer etching and brazing layer etching are completed, the protective groove is pre-filled with printing ink which has good filling property and can resist silver chemical liquid after secondary exposure, so that the technical effect that the side walls of the groove are not coated with silver is realized, and finally the printing ink is reserved on a product. But in general, this solution has the following limitations: firstly, the scheme is only suitable for the thin copper-clad ceramic circuit board, and has no universality. To realize that the side wall is not coated with silver, the ink needs to be completely filled in the groove, for example, when the ink is used for a thick copper product, the thicker the copper layer is, the deeper the groove is, the thicker the ink is, and the lower the ink solidification at the bottom of the groove is in secondary exposure; this solution is repeated several times for complete curing of the ink at the bottom of the trench, which is costly. Secondly, the ink in the groove remains in the product regardless of the thick copper product or the thin copper product, and when the downstream is packaged by vacuum reflow soldering, the ink can be layered or even cracked to fail due to high temperature. Therefore, it is very necessary to invent a preparation method of a copper-clad ceramic circuit board with no silver on the side wall of the groove.
Disclosure of Invention
The invention aims to provide a copper-clad ceramic circuit board with silver-free groove side walls and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a copper-clad ceramic circuit board with a silver-free groove side wall and a preparation method thereof comprise the following steps:
step 1: taking a copper-clad plate, wherein a copper layer, a brazing layer and a ceramic substrate are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film is attached to one side or two sides of the copper-clad plate, drying and curing are carried out, and ultraviolet light is adopted for carrying out primary exposure and development; forming a silver layer by chemical silver precipitation;
step 2: removing residual photosensitive dry film on the surface of the copper-clad plate by adopting a stripping solution;
step 3: coating or printing ink on the silver melting layer to form a printing ink protective layer and pre-baking;
step 4: performing secondary exposure by adopting an exposure negative film; curing the printing ink protective layer with the pattern on the surface of the copper layer and the silver layer of the copper-clad plate through exposure and development;
step 5: post-baking the ink protective layer;
step 6: etching the copper layer exposed out of the copper-clad plate by wet chemical etching; etching the brazing layer; and cleaning the printing ink protective layer by using organic reagents such as dimethylbenzene and the like to obtain the copper-clad ceramic circuit board with the silver-free side wall of the groove.
Further, in the step 1, the developing solution is sodium carbonate or potassium carbonate solution, the etching temperature is 30+/-2 ℃ and the etching time is 60 seconds; the exposure energy of the one-time exposure is 100-1500 mJ/cm 2 The exposure time is 1-2 min, and the wavelength is 360-410 nm.
In step 2, the stripping solution is sodium hydroxide solution or organic stripping solution.
Further, in the step 3, the ink is acid and alkali resistant ink and can be removed by an aromatic hydrocarbon solvent; the pre-baking temperature is 70-90 ℃ and the pre-baking time is 10-30 min.
Further, in the step 4, the exposure energy of the secondary exposure is 100-1500 mJ/cm 2 The time is 1-2 min, and the wavelength is 360-410 nm; the development time is 1-2 min.
In step 5, the post-baking temperature is 120 ℃ and the time is 5-30 min.
Further, in step 6, the etching solution for etching the copper layer is composed of nitric acid and hydrogen peroxide, wherein the volume ratio of nitric acid to hydrogen peroxide is 0.3-2: 0.8-1.5, wherein the mass concentration of nitric acid is 65-70%, and the mass concentration of hydrogen peroxide is 20-40%; the etching solution for etching the brazing layer consists of sodium hydroxide, hydrogen peroxide, water, magnesium sulfate and sodium silicate, wherein 5-15% of hydrogen peroxide, 3-5% of sodium hydroxide, 1-3% of magnesium sulfate and 3-5% of sodium silicate are calculated by volume, and the balance is water; the aromatic hydrocarbon solvent is preferably xylene or trimethylbenzene.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, through the process arrangement of firstly chemically depositing silver and then etching the copper layer and etching the groove, the problem of silver on the side wall of the groove is creatively avoided structurally, thereby avoiding the layering of silver-packaging adhesive and the occurrence of silver migration in the downstream packaging stage and ensuring the reliability of a packaged device; the printing ink protective layer for pattern transfer and silver layer protection is the hopeful LPR-805, can be cleanly removed through organic reagents such as dimethylbenzene, and the like, avoids the thermal decomposition of printing ink which is reserved in the groove and cannot withstand high temperature, and meets the high-temperature processing requirements such as downstream vacuum reflow soldering and the like; the scheme has universality and is applicable to both thin copper and thick copper products.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic illustration of a conformable photosensitive dry film of the present invention;
FIG. 3 is a schematic view of the one-shot exposure and development effect of the present invention;
FIG. 4 is a schematic representation of electroless silver plating of the present invention;
FIG. 5 is a schematic view of the invention for removing a photosensitive dry film;
FIG. 6 is a schematic view of a protective layer of printing ink according to the present invention;
FIG. 7 is a schematic view of the secondary exposure and development effects of the present invention;
FIG. 8 is a schematic view of the post-baking effect of the ink protective layer of the present invention;
FIG. 9 is a schematic diagram of copper layer etching in accordance with the present invention;
FIG. 10 is a schematic representation of a braze layer etch in accordance with the present invention;
fig. 11 is a schematic diagram of the finished product of the present invention.
Wherein, 1 is copper layer, 2 is the braze layer, 3 is ceramic substrate, 4 is photosensitive dry film, 5 is silver layer, 6 is printing ink protective layer.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The main materials and sources thereof in the following examples are as follows:
sodium carbonate (CAS number 497-19-8) was purchased from Ala-dine; sodium hydroxide (CAS number 1310-73-2) was purchased from Michelin; ink is purchased from Corrugation, model LPR-805; nitric acid (CAS number 7697-37-2) was purchased from Michelin; sulfuric acid (CAS number 7664-93-9) is purchased from Guozhong; hydrogen peroxide (CAS number 7722-84-1) was purchased from Guozhong; xylene (CAS number 1330-20-7) was purchased from Ala-dine; magnesium sulfate (CAS number 7487-88-9) is purchased from Guozhong; sodium silicate (CAS number 6834-92-0) was purchased from Ala-dine.
Examples
Step 1: taking a 40-mu m copper-clad plate, wherein a copper layer 1, a brazing layer 2 and a ceramic substrate 3 are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film 4 is attached to one side or two sides of the copper-clad plate, drying and solidifying are carried out, ultraviolet light is adopted for carrying out one-time exposure, and the exposure energy is 100mJ/cm 2 The exposure time is 1min, and the wavelength is 365nm; developing and etching by using sodium carbonate solution, wherein the etching temperature is 30+/-2 ℃ and the etching time is 60 seconds; forming a silver layer 5 by chemical silver precipitation;
step 2: removing the residual photosensitive dry film 4 on the surface of the copper-clad plate by adopting sodium hydroxide solution;
step 3: coating printing ink on the silver melting layer 5 to form a printing ink protective layer 6, and pre-baking at 70 ℃ for 20min;
step 4: performing secondary exposure with exposure film with exposure energy of 1000mJ/cm 2 The exposure time is 1min, and the wavelength is 365nm; exposing and developing to enable the printing ink protective layer 6 with patterns to be solidified on the surfaces of the copper layer 1 and the silver layer 5 of the copper-clad plate;
step 5: post-baking the ink protective layer 6 at 120 ℃ for 5min;
step 6: adopting a wet chemical etching method, and mixing 65% nitric acid and 20% hydrogen peroxide by volume ratio of 0.3:0.8, etching the copper layer 1 exposed on the copper-clad plate; the brazing layer 2 was etched by mixing 5% hydrogen peroxide, 3% sodium hydroxide, 1% magnesium sulfate, 3% sodium silicate and 88% water by volume; and removing the printing ink protective layer 6 by using dimethylbenzene to obtain the silver-free copper-clad ceramic circuit board on the side wall of the groove.
Examples
Step 1: taking a 127 mu m copper-clad plate, wherein a copper layer 1, a brazing layer 2 and a ceramic substrate 3 are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film 4 is attached to one side or two sides of the copper-clad plate, drying and solidifying are carried out, ultraviolet light is adopted for carrying out one-time exposure, and the exposure energy is 100mJ/cm 2 The exposure time is 1min, and the wavelength is 385nm; developing and etching by using sodium carbonate solution, wherein the etching temperature is 30+/-2 ℃ and the etching time is 60 seconds; forming a silver layer 5 by chemical silver precipitation;
step 2: removing the residual photosensitive dry film 4 on the surface of the copper-clad plate by adopting sodium hydroxide solution;
step 3: coating printing ink on the silver melting layer 5 to form a printing ink protective layer 6, and pre-baking at 70 ℃ for 20min;
step 4: performing secondary exposure with exposure film with exposure energy of 1000mJ/cm 2 The exposure time is 1min, and the wavelength is 385nm; exposing and developing to enable the printing ink protective layer 6 with patterns to be solidified on the surfaces of the copper layer 1 and the silver layer 5 of the copper-clad plate;
step 5: post-baking the ink protective layer 6 at 120 ℃ for 10min;
step 6: adopting a wet chemical etching method, and mixing 65% nitric acid and 20% hydrogen peroxide by volume ratio of 0.3:0.8, etching the copper layer 1 exposed on the copper-clad plate; the brazing layer 2 was etched by mixing 5% hydrogen peroxide, 3% sodium hydroxide, 1% magnesium sulfate, 3% sodium silicate and 88% water by volume; and removing the printing ink protective layer 6 by using dimethylbenzene to obtain the silver-free copper-clad ceramic circuit board on the side wall of the groove.
Examples
Step 1: taking a 300 mu m copper-clad plate, wherein a copper layer 1, a brazing layer 2 and a ceramic substrate 3 are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film 4 is attached to one side or two sides of the copper-clad plate, drying and solidifying are carried out, ultraviolet light is adopted for carrying out one-time exposure, and the exposure energy is 100mJ/cm 2 The exposure time is 1min, and the wavelength is 405nm; developing and etching by using sodium carbonate solution, wherein the etching temperature is 30+/-2 ℃ and the etching time is 60 seconds; forming a silver layer 5 by chemical silver precipitation;
step 2: removing the residual photosensitive dry film 4 on the surface of the copper-clad plate by adopting sodium hydroxide solution;
step 3: coating printing ink on the silver melting layer 5 to form a printing ink protective layer 6, and pre-baking at 70 ℃ for 20min;
step 4: performing secondary exposure with exposure film with exposure energy of 1000mJ/cm 2 The exposure time is 1min, and the wavelength is 405nm; the ink protective layer 6 with patterns is solidified on the copper layer 1 of the copper-clad plate and silver is converted by exposure and developmentA layer 5 surface;
step 5: post-baking the ink protective layer 6 at 120 ℃ for 15min;
step 6: adopting a wet chemical etching method, and mixing 65% nitric acid and 20% hydrogen peroxide by volume ratio of 0.3:0.8, etching the copper layer 1 exposed on the copper-clad plate; the brazing layer 2 was etched by mixing 5% hydrogen peroxide, 3% sodium hydroxide, 1% magnesium sulfate, 3% sodium silicate and 88% water by volume; and removing the printing ink protective layer 6 by using dimethylbenzene to obtain the silver-free copper-clad ceramic circuit board on the side wall of the groove.
Examples
Step 1: taking an 800-mu m copper-clad plate, wherein a copper layer 1, a brazing layer 2 and a ceramic substrate 3 are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film 4 is attached to one side or two sides of the copper-clad plate, drying and solidifying are carried out, ultraviolet light is adopted for carrying out one-time exposure, and the exposure energy is 100mJ/cm 2 The exposure time is 1min, and the wavelength is 365nm; developing and etching by using sodium carbonate solution, wherein the etching temperature is 30+/-2 ℃ and the etching time is 60 seconds; forming a silver layer 5 by chemical silver precipitation;
step 2: removing the residual photosensitive dry film 4 on the surface of the copper-clad plate by adopting sodium hydroxide solution;
step 3: coating printing ink on the silver melting layer 5 to form a printing ink protective layer 6, and pre-baking at 70 ℃ for 20min;
step 4: performing secondary exposure with exposure film with exposure energy of 1000mJ/cm 2 The exposure time is 1min, and the wavelength is 365nm; exposing and developing to enable the printing ink protective layer 6 with patterns to be solidified on the surfaces of the copper layer 1 and the silver layer 5 of the copper-clad plate;
step 5: post-baking the ink protective layer 6 at 120 ℃ for 20min;
step 6: adopting a wet chemical etching method, and mixing 65% nitric acid and 20% hydrogen peroxide by volume ratio of 0.3:0.8, etching the copper layer 1 exposed on the copper-clad plate; the brazing layer 2 was etched by mixing 5% hydrogen peroxide, 3% sodium hydroxide, 1% magnesium sulfate, 3% sodium silicate and 88% water by volume; and removing the printing ink protective layer 6 by using dimethylbenzene to obtain the silver-free copper-clad ceramic circuit board on the side wall of the groove.
AMB copper-clad ceramic substrates having a copper thickness of 800 μm were subjected to electroless silver deposition using the method provided in patent CN 113354449.
Conclusion: comparing examples 1-4 with comparative example 1, comparative example 1 has the problem of incomplete photo-curing of the ink in the grooves of the thick copper product, indicating that the method provided by patent CN113354449 is not applicable to the thick copper product; the invention is applicable to both thin copper and thick copper products, and the ink protection layer 6 can be cleanly removed by an organic reagent, so that the high-temperature processing requirements of downstream vacuum reflow soldering and the like can be met.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a copper-clad ceramic circuit board with a silver-free groove side wall is characterized by comprising the following steps: the method comprises the following steps:
step 1: taking a copper-clad plate, wherein a copper layer (1), a brazing layer (2) and a ceramic substrate (3) are sequentially arranged on one side of the copper-clad plate from top to bottom, a photosensitive dry film (4) is attached to one side or two sides of the copper-clad plate, and the copper-clad plate is dried and solidified, and is subjected to one-time exposure and development by ultraviolet light; forming a silver layer (5) by electroless silver deposition;
step 2: removing residual photosensitive dry film (4) on the surface of the copper-clad plate by adopting a stripping liquid;
step 3: coating or printing ink on the silver layer (5) to form a printing ink protective layer (6); pre-baking the printing ink protective layer (6);
step 4: performing secondary exposure by adopting an exposure negative film; the ink protective layer (6) with the patterns is solidified on the surfaces of the copper layer (1) and the silver layer (5) of the copper-clad plate through exposure and development;
step 5: post-baking the ink protective layer (6);
step 6: etching the copper layer (1) exposed on the copper-clad plate by wet chemical etching; etching the brazing layer (2); and cleaning the ink to obtain the copper-clad ceramic circuit board with the silver-free side wall of the groove.
2. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 1, the ultraviolet exposure energy is 100-1500 mJ/cm 2 The exposure time is 1-2 min, and the wavelength is 360-410 nm; the developing solution is sodium carbonate or potassium carbonate solution, the etching temperature is 30+/-2 ℃, and the etching time is 60 seconds.
3. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 2, the membrane removing liquid is sodium hydroxide solution.
4. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 3, the ink is acid and alkali resistant ink; the pre-baking temperature is 70-90 ℃ and the pre-baking time is 10-30 min.
5. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 4, the secondary exposure time is 1-2 min; the development time is 1-2 min.
6. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 5, the post-baking temperature is 120 ℃ and the time is 5-15 min.
7. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in the step 6, the etching solution for etching the copper layer (1) consists of nitric acid and hydrogen peroxide, wherein the volume ratio of the nitric acid to the hydrogen peroxide is 0.3-2: 0.8-1.5, wherein the mass concentration of nitric acid is 65-70%, and the mass concentration of hydrogen peroxide is 20-40%; the etching solution for etching the brazing layer (2) consists of sodium hydroxide, hydrogen peroxide, water, magnesium sulfate and sodium silicate, wherein the hydrogen peroxide accounts for 5-15% by volume, the sodium hydroxide accounts for 3-5% by volume, the magnesium sulfate accounts for 1-3% by volume, the sodium silicate accounts for 3-5% by volume, and the balance is water.
8. The method for manufacturing the copper-clad ceramic circuit board with no silver on the side wall of the groove, as claimed in claim 1, is characterized in that: in step 6, the stripping solution is an aromatic hydrocarbon solvent.
9. The copper-clad ceramic circuit board prepared by the method for preparing the copper-clad ceramic circuit board with no silver on the side wall of the groove according to any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310436688.7A CN116489893A (en) | 2023-04-23 | 2023-04-23 | Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310436688.7A CN116489893A (en) | 2023-04-23 | 2023-04-23 | Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116489893A true CN116489893A (en) | 2023-07-25 |
Family
ID=87224620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310436688.7A Pending CN116489893A (en) | 2023-04-23 | 2023-04-23 | Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116489893A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117769145A (en) * | 2024-02-22 | 2024-03-26 | 深圳市盛鸿运科技有限公司 | Circuit board etching method and circuit board |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781169A (en) * | 2012-07-24 | 2012-11-14 | 广东达进电子科技有限公司 | Method for producing silver-plated ceramic circuit boards |
| JP2015195309A (en) * | 2014-03-31 | 2015-11-05 | Ｄｏｗａメタルテック株式会社 | Manufacturing method of metal-ceramics circuit board |
| US20160192503A1 (en) * | 2013-08-29 | 2016-06-30 | Hitachi Metals, Ltd. | Method for producing ceramic circuit board |
| KR20170017708A (en) * | 2016-05-17 | 2017-02-15 | 주식회사 써키트 플렉스 | Manufacturing method for LED package type FPCB using Copper plate, and LED package produced thereby |
| CN111621787A (en) * | 2020-04-27 | 2020-09-04 | 江苏富乐德半导体科技有限公司 | Etching liquid system and method for etching aluminum nitride substrate |
| CN113241338A (en) * | 2021-07-09 | 2021-08-10 | 东莞市春瑞电子科技有限公司 | Leadless pre-plastic-packaged semiconductor packaging support and preparation method thereof |
| WO2022210507A1 (en) * | 2021-03-30 | 2022-10-06 | 株式会社 東芝 | Method for producing ceramic circuit board |
-
2023
- 2023-04-23 CN CN202310436688.7A patent/CN116489893A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781169A (en) * | 2012-07-24 | 2012-11-14 | 广东达进电子科技有限公司 | Method for producing silver-plated ceramic circuit boards |
| US20160192503A1 (en) * | 2013-08-29 | 2016-06-30 | Hitachi Metals, Ltd. | Method for producing ceramic circuit board |
| JP2015195309A (en) * | 2014-03-31 | 2015-11-05 | Ｄｏｗａメタルテック株式会社 | Manufacturing method of metal-ceramics circuit board |
| KR20170017708A (en) * | 2016-05-17 | 2017-02-15 | 주식회사 써키트 플렉스 | Manufacturing method for LED package type FPCB using Copper plate, and LED package produced thereby |
| CN111621787A (en) * | 2020-04-27 | 2020-09-04 | 江苏富乐德半导体科技有限公司 | Etching liquid system and method for etching aluminum nitride substrate |
| WO2022210507A1 (en) * | 2021-03-30 | 2022-10-06 | 株式会社 東芝 | Method for producing ceramic circuit board |
| CN113241338A (en) * | 2021-07-09 | 2021-08-10 | 东莞市春瑞电子科技有限公司 | Leadless pre-plastic-packaged semiconductor packaging support and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钱军浩: "《油墨配方设计与印刷手册》", pages: 412 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117769145A (en) * | 2024-02-22 | 2024-03-26 | 深圳市盛鸿运科技有限公司 | Circuit board etching method and circuit board |
| CN117769145B (en) * | 2024-02-22 | 2024-04-19 | 深圳市盛鸿运科技有限公司 | Circuit board etching method and circuit board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7462555B2 (en) | Ball grid array substrate having window and method of fabricating same | |
| CN110012597B (en) | Ceramic copper-clad circuit board and preparation method thereof | |
| CN116489893A (en) | Copper-clad ceramic circuit board with silver-free groove side wall and preparation method thereof | |
| CN108040435A (en) | A kind of aluminum nitride ceramic substrate circuit lithographic method | |
| CN113396241A (en) | Wiring substrate and method for manufacturing same | |
| CN107809855A (en) | The preparation method of one species support plate | |
| CN111212528A (en) | Method for manufacturing multilayer printed circuit board | |
| CN107708332B (en) | Processing method of conductive metal substrate | |
| TWI471073B (en) | Circuit substrate and manufacturing method thereof | |
| US8409461B2 (en) | Method of manufacturing printed wiring board with component mounting pin | |
| JP3596374B2 (en) | Manufacturing method of multilayer printed wiring board | |
| CN111403362A (en) | Chip on film packaging method, packaging structure, display device and electronic equipment | |
| CN102731170A (en) | Technology for coating film on surface of ceramic substrate | |
| JP3236812B2 (en) | Multilayer wiring board | |
| CN117279218B (en) | Preparation method of multilayer copper-clad ceramic substrate | |
| WO2024185566A1 (en) | Method for producing circuit pattern, method for producing circuit board, and circuit pattern | |
| CN114980535B (en) | Manufacturing method of metal-clad shielding microwave circuit board | |
| JPS58128791A (en) | Method of producing printed circuit board and printed circuit board | |
| CN114206024B (en) | Manufacturing method of MEMS (micro-electromechanical systems) packaging carrier plate | |
| TWI849559B (en) | Circuit board component and its manufacturing method therefore, packaging structure | |
| CN216752200U (en) | Circuit board | |
| TWI394246B (en) | Package substrate and method of forming same | |
| JP7263710B2 (en) | Wiring board manufacturing method | |
| JP7439384B2 (en) | wiring board | |
| CN113130407B (en) | Packaging cover plate and preparation method 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 |