CN113079646A - Surface metallization method of DPC copper-clad ceramic substrate - Google Patents
Surface metallization method of DPC copper-clad ceramic substrate Download PDFInfo
- Publication number
- CN113079646A CN113079646A CN202110308168.9A CN202110308168A CN113079646A CN 113079646 A CN113079646 A CN 113079646A CN 202110308168 A CN202110308168 A CN 202110308168A CN 113079646 A CN113079646 A CN 113079646A
- Authority
- CN
- China
- Prior art keywords
- substrate
- copper
- dpc
- ceramic substrate
- sulfuric acid
- 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
- 239000000758 substrate Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000000919 ceramic Substances 0.000 title claims abstract description 50
- 238000001465 metallisation Methods 0.000 title claims abstract description 15
- 238000007747 plating Methods 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- 238000003466 welding Methods 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 11
- ZQOMKIOQTCAGCM-UHFFFAOYSA-L [Na+].[Na+].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Na+].[Na+].OS(O)(=O)=O.[O-]S([O-])(=O)=O ZQOMKIOQTCAGCM-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000007602 hot air drying Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims abstract description 4
- 230000020477 pH reduction Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 29
- 238000004544 sputter deposition Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims 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 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- -1 polydithiodipropyl Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000005238 degreasing Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- SWPMTVXRLXPNDP-UHFFFAOYSA-N 4-hydroxy-2,6,6-trimethylcyclohexene-1-carbaldehyde Chemical compound CC1=C(C=O)C(C)(C)CC(O)C1 SWPMTVXRLXPNDP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film 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
- H05K3/02—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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a DPC copper-clad ceramic substrate surface metallization method, which comprises the following steps: carrying out oil removal cleaning, acid microetching and hot air drying on the ceramic substrate; B. friction welding of the surface of the substrate: the method is carried out on a rotary friction welding machine, and titanium alloy is coated and welded on the surface of a substrate by adopting a titanium alloy high-temperature stirring head through high-speed rotation in an inert gas atmosphere. Wherein the diameter of a shaft shoulder in the rotary friction welding machine is 10-20mm, the diameter of a rotary needle is 3-8mm, the diameter of the rotary needle is a tapered pin with threads, the welding speed of the rotary friction welding machine is 600-; C. surface chemical copper plating: sequentially carrying out corrosion of a sodium sulfate-sulfuric acid corrosion system and acidification of sulfuric acid and hydrochloric acid on a substrate, then carrying out surface copper plating in a copper sulfate-sulfuric acid system chemical plating solution, and ultrasonically washing the substrate with pure water; D. ultrasonic cleaning and drying.
Description
Technical Field
The invention belongs to the technical field of semiconductor substrate preparation, relates to a copper-clad ceramic substrate preparation technology, and particularly relates to a DPC copper-clad ceramic substrate surface metallization method.
Background
The DPC (direct Plated coater) ceramic substrate is also called a direct copper-Plated ceramic substrate, and is a novel ceramic substrate combining thin film circuit and electroplating process technology. The LED packaging structure is not only used in the fields of traditional illumination such as stages, landscapes, automobile headlamps and the like, but also used in the fields of packaging of high-power elements such as vertical cavity surface emitting lasers (vcsels) and the like, and in addition, the LED packaging structure also comprises ultraviolet light emitting diodes (UV LEDs) and the like. Compared with the traditional LTCC, HTCC, DBC and other thick film processes, the DPC ceramic substrate has the characteristics of high thermal conductivity, no material deformation, stable process, controllable metal layer thickness, high line resolution and the like.
The preparation process of the DPC ceramic substrate comprises the following steps: firstly, ceramic substrates are pretreated and cleaned, a Ti/Cu layer is deposited on the surfaces of the substrates in a vacuum sputtering mode to serve as a seed layer, then circuit manufacturing is completed through photoetching, developing and etching processes, finally the thickness of the circuit is increased in an electroplating/chemical plating mode, and the substrate manufacturing is completed after photoresist is removed.
In DPC production, ceramic surface metallization is an extremely important process, and the prior art adopts a vacuum sputtering process to carry out titanium alloy plating and copper plating treatment on the surface of a ceramic substrate in sequence. However, the sputtering process has high cost and low yield, and the binding force of the copper and the porcelain is difficult to ensure.
The friction welding is a method for welding by using heat generated by friction of a contact surface of a workpiece as a heat source to enable the workpiece to generate plastic deformation under the action of pressure, and a metal surface coating layer with certain performance, controllable thickness and strong interface bonding force can be prepared on the surface of the ceramic chip by a solid-state bonding method. The prior art does not have a report about the application of the friction welding process to the surface metallization process of the DPC copper-clad ceramic substrate.
Disclosure of Invention
Aiming at solving the defects, the friction welding process is introduced in the preparation process of the DPC copper-clad ceramic substrate to solve the problems of high cost and low copper-ceramic bonding force of the existing sputtering process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a surface metallization method of a DPC copper-clad ceramic substrate, which comprises the following steps:
A. pretreatment of a substrate: after the ceramic substrate is subjected to oil removal cleaning and acid microetching, hot air drying is carried out to remove oily impurities on the surface of the substrate;
B. friction welding of substrate surface
The method is carried out on a rotary friction welding machine, a titanium alloy high-temperature stirring head is adopted, and titanium alloy is coated and welded on the surface of a substrate through high-speed rotation in an inert gas atmosphere, so that the arrangement of a Ti layer is realized. Wherein the diameter of a shaft shoulder in the rotary friction welding machine is 10-20mm, the diameter of a rotary needle is 3-8mm, the diameter of the rotary needle is a tapered pin with threads, the welding speed of the rotary friction welding machine is 600-;
C. chemical copper plating of surface
B, sequentially corroding the substrate by a sodium sulfate-sulfuric acid corrosion system, acidifying by sulfuric acid and acidifying by hydrochloric acid, then pasting a film on the substrate, then carrying out surface copper plating in a copper sulfate-sulfuric acid system chemical plating solution at 22-28 ℃, and after the copper plating is finished, ultrasonically washing by pure water;
D. ultrasonic cleaning and drying
And C, carrying out ultrasonic cleaning on the substrate treated in the step C and carrying out hot air drying.
The principle of the method of the invention is as follows: when friction welding is carried out on the surface of the substrate, the friction force and the heat generated by friction on the contact surface of the workpiece change the microcrystalline state of the surface of the substrate, so that the solid-state bonding force between the surface of the titanium alloy and the surface of the silicon crystal is enhanced. Because the titanium alloy layer is used as the intermediate connecting layer for realizing the combination between the copper layer and the surface of the substrate, the solid-state combination force between the surface of the titanium alloy and the surface of the silicon crystal is enhanced, and the combination force between copper and ceramic is inevitably enhanced.
Preferably, the step B further comprises a vacuum sputtering process, wherein after the seed layer is sputtered on the ceramic substrate in vacuum, the rotary friction welding is carried out, and titanium tungsten plating of 0.05-0.1 μm and copper plating of 0.5-1 μm are sequentially carried out on the surface of the substrate through the vacuum sputtering process.
The processing conditions of the vacuum sputtering process are as follows: degree of vacuum 1X 10-8Substrate temperature 150-- 3torr, bias voltage of-200V, time 30-40 min.
Experiments prove that an extremely thin seed layer is formed on the surface of a substrate by adopting a vacuum sputtering process, then a titanium alloy layer is coated by rotary friction welding and a surface chemical copper plating layer is carried out, so that the bonding force between copper and porcelain can be further enhanced, but the process is too complex, the investment cost is too high, the method is only suitable for small-batch production of the surface metallization treatment of the DPC copper-coated ceramic substrate, and is not suitable for industrial expanded production.
Preferably, the specific processing steps of step a are as follows: ultrasonic treating in one or more of anhydrous alcohol, isopropanol and acetone at normal temperature for 5-30 min, micro-etching in HF solution for 1-3min, ultrasonic washing for 1-3min, overflow washing, water absorbing roller, and drying with 80-100 deg.C hot air for 3-5 min.
Preferably, in step B, the inert gas is high-purity argon, and the oxygen content in the argon is less than 500 ppm.
Preferably, in step C, the step of chemically plating copper on the surface is as follows:
corrosion of C1 sodium sulfate-sulfuric acid corrosion system: putting the substrate into a corrosive liquid, acidifying and corroding at room temperature for 20-40s, and ultrasonically washing with pure water for 1-5 min; wherein, each 1L of the corrosive liquid comprises 250g of sodium persulfate, 30-50mL of sulfuric acid and the balance of water;
acidifying C2 with sulfuric acid and hydrochloric acid: putting the substrate into a sulfuric acid solution with the volume fraction of 10-30, acidifying for 60-120s at room temperature, taking out the substrate, putting the substrate into a hydrochloric acid solution with the volume fraction of 10-30, carrying out secondary acidification for 60-120s at room temperature, and then carrying out immersion washing for 1-5min by pure water;
c3 substrate film: carrying out substrate film pasting under the conditions of temperature of 105-;
c4 copper plating on bottom: placing the substrate obtained from C3 in a plating solution, reacting at 22-28 deg.C for 15-25min, and controlling the film thickness to 3-5 μm;
c5 copper plating of circuit: placing the substrate obtained in C4 in a plating solution, carrying out copper plating at the temperature of 22-28 ℃, controlling the thickness of a copper layer to be 15-100 mu m, and carrying out ultrasonic immersion washing for 1-5min by pure water after the copper plating is finished;
wherein, in the C4 and C5, each 1L of plating solution contains 60-110g of copper sulfate, 200g of sulfuric acid 160-. The leveling agent mainly comprises an ethyl acrylate polymer, the brightening agent mainly comprises sodium polydithiodipropyl sulfonate, and the leveling agent and the brightening agent are both commercially available products and can be obtained by purchasing the products.
Preferably, the specific processing steps of step D are as follows: ultrasonic cleaning with pure water for 3-10min, and drying with 80-100 deg.C hot air for 3-5 min.
The invention has the following beneficial effects:
firstly, compared with the mode of realizing basic surface metallization by the currently used vacuum sputtering process, the method adopts the mode of friction welding a Ti layer on the surface of the substrate and then plating copper, can realize operation under the normal pressure condition and does not need to meet the requirement of vacuum degree; meanwhile, compared with the existing vacuum sputtering process which needs two steps of electroplating operation, the equipment investment of the rotary friction and surface chemical copper plating is also lower. Therefore, the method of the present invention contributes to a reduction in the investment cost of equipment, and also contributes to an increase in the product yield due to the simplicity of operation.
Secondly, after the surface metallization operation is finished by adopting the method and the existing vacuum sputtering process, the tensile test is carried out on the substrate processed by the two modes under the same tensile test condition, and the result shows that the bonding force of the substrate copper ceramic substrate obtained by adopting the method is larger and is improved by about 15-20%.
Drawings
FIG. 1 is a flow chart of a method for metallizing a surface of a DPC copper-clad ceramic substrate in example 1 of the present invention;
fig. 2 is a flowchart of a DPC copper-clad ceramic substrate surface metallization method in embodiment 2 of the present invention.
Detailed Description
The following embodiments are implemented on the premise of the technical scheme of the present invention, and give detailed implementation modes and specific operation procedures, but the protection scope of the present invention is not limited to the following embodiments.
The reagents and starting materials used in the present invention are commercially available or can be prepared according to literature procedures. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Example 1
According to fig. 1, the DPC copper-clad ceramic substrate surface metallization method provided in this embodiment includes the following steps:
A. substrate pretreatment
And (3) after the ceramic substrate is subjected to oil removal cleaning and acid microetching, hot air drying is carried out, and oily impurities on the surface of the substrate are removed. The specific process comprises the following steps: ultrasonic treating in one or more of anhydrous alcohol, isopropanol and acetone at normal temperature for 5-30 min, micro-etching in HF solution for 1-3min, ultrasonic washing for 1-3min, overflow washing, water absorbing roller, and drying with 80-100 deg.C hot air for 3-5 min.
B. Friction welding of substrate surface
The method is carried out on a rotary friction welding machine, a titanium alloy high-temperature stirring head is adopted, and titanium alloy is coated and welded on the surface of a substrate through high-speed rotation in an argon gas atmosphere, so that the arrangement of a Ti layer is realized. Wherein, the diameter of a shaft shoulder in the rotary friction welding machine is 10-20mm, a rotary needle is a taper pin with a thread with the diameter of 3-8mm, the welding speed of the rotary friction welding machine is 600-900mm/min, the rotation speed of a stirring head is 800-1200r/min, the inclination angle of a rotating head is 1.5-5 degrees, the flow rate of argon gas is 200-2000 mL/min, the argon gas is high-purity argon, and the oxygen content is less than 500 ppm.
C. Chemical copper plating of surface
And B, sequentially corroding the substrate by a sodium sulfate-sulfuric acid corrosion system, acidifying by sulfuric acid and acidifying by hydrochloric acid, then pasting a film on the substrate, then carrying out surface copper plating in a copper sulfate-sulfuric acid system chemical plating solution at 22-28 ℃, and after the copper plating is finished, ultrasonically washing by pure water. The method comprises the following specific steps:
corrosion of C1 sodium sulfate-sulfuric acid corrosion system: putting the substrate into a corrosive liquid, acidifying and corroding at room temperature for 20-40s, and ultrasonically washing with pure water for 1-5 min; wherein, each 1L of the corrosive liquid comprises 250g of sodium persulfate, 30-50mL of sulfuric acid and the balance of water;
acidifying C2 with sulfuric acid and hydrochloric acid: putting the substrate into a sulfuric acid solution with the volume fraction of 10-30, acidifying for 60-120s at room temperature, taking out the substrate, putting the substrate into a hydrochloric acid solution with the volume fraction of 10-30, carrying out secondary acidification for 60-120s at room temperature, and then carrying out immersion washing for 1-5min by pure water;
c3 substrate film: carrying out substrate film pasting under the conditions of temperature of 105-;
c4 copper plating on bottom: placing the substrate obtained from C3 in a plating solution, reacting at 22-28 deg.C for 15-25min, and controlling the film thickness to 3-5 μm;
c5 copper plating of circuit: placing the substrate obtained from C4 in a plating solution, carrying out copper plating at the temperature of 22-28 ℃, controlling the thickness of a copper layer to be 15-100 mu m, and carrying out ultrasonic immersion washing for 1-5min by pure water after the copper plating is finished;
wherein, in the C4 and C5, each 1L of plating solution contains 60-110g of copper sulfate, 200g of sulfuric acid 160-. The leveling agent mainly comprises an ethyl acrylate polymer, the brightening agent mainly comprises sodium polydithiodipropyl sulfonate, and the leveling agent and the brightening agent are both commercially available products and can be obtained by purchasing the products.
D. Ultrasonic cleaning and drying
C, carrying out ultrasonic cleaning on the substrate treated in the step C and carrying out hot air drying, wherein the specific treatment steps are as follows: ultrasonic cleaning with pure water for 3-10min, and drying with 80-100 deg.C hot air for 3-5 min.
Comparative example 1
The friction welding of the tile surface in example 1 was replaced by the conventional method in the prior art: vacuum sputtering: carrying out titanium-tungsten plating and copper plating treatment (firstly titanium-tungsten plating and then copper plating) on the surface of the ceramic substrate in sequence, wherein the treatment conditions are as follows: degree of vacuum 1X 10-8Substrate temperature 150--3torr, bias-200V, time 30min, film thickness: titanium tungsten 0.05-0.1 μm, copper 0.5-1 μm. The rest of the process was identical to example 1.
Example 2
According to fig. 2, before step B) in example 1, the DPC copper-clad ceramic substrate surface metallization method provided in this embodiment adds a vacuum sputtering process: carrying out titanium-tungsten plating and copper plating treatment (firstly titanium-tungsten plating and then copper plating) on the surface of the ceramic substrate in sequence, wherein the treatment conditions are as follows: degree of vacuum 1X 10-8Substrate temperature 150--3torr, bias-200V, time 30min, film thickness: titanium tungsten 0.05-0.1 μm, copper 0.5-1 μm. Vacuum sputtering was followed by spin friction welding, and the remaining process was the same as in example 1. The method in the embodiment comprises the steps of substrate pretreatment, vacuum sputtering process, substrate surface friction welding, surface chemical copper plating, ultrasonic cleaning and drying.
The DPC copper-clad ceramic substrate obtained in the above example was subjected to a tensile test, which was in accordance with the american society for electronics and electronics industry standard, and the test results are shown in table 1:
table 1 results of tensile test of ceramic substrates of examples 1 and 2 and comparative example 1
| Numbering | tension/Kg. mm-2 |
| Example 1 | 2.80 |
| Comparative example 1 | 2.41 |
| Example 2 | 3.45 |
As can be seen from Table 1, the tensile forces of the examples and comparative examples are greater than 1.5 Kg. mm-2And the quality requirements of the DPC copper-clad substrate can be met.
In the embodiment 1, the bonding force of the DPC copper-clad ceramic substrate copper porcelain prepared by the friction welding method is obviously improved compared with that in the embodiment 1. The reason may be that the friction force and the heat generated by friction at the contact surface of the workpiece change the microcrystalline state of the substrate surface when the substrate surface is friction welded, thereby enhancing the solid-state bonding force between the titanium alloy surface and the silicon crystal surface. Because the titanium alloy layer is used as the intermediate connecting layer for realizing the combination between the copper layer and the surface of the substrate, the solid-state combination force between the surface of the titanium alloy and the surface of the silicon crystal is enhanced, and the combination force between copper and ceramic is inevitably enhanced.
In example 2, an extremely thin seed layer is formed on the surface of the substrate by a vacuum sputtering process, and then the titanium alloy layer is coated by spin friction welding and the copper layer is chemically electroplated on the surface, so that the bonding force between copper and ceramics can be further enhanced, and thus the copper-clad ceramic substrate prepared by the method has the maximum bonding force between copper and ceramics. However, the process is too complex, the investment cost is too high, and the method is only suitable for small-batch production of the surface metallization treatment of the DPC copper-clad ceramic substrate with special requirements and is not suitable for industrial expanded production.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (9)
1. A DPC copper-clad ceramic substrate surface metallization method is characterized by comprising the following steps:
A. substrate pretreatment
After degreasing, cleaning and acid microetching are carried out on the ceramic substrate, hot air drying is carried out;
B. friction welding of substrate surface
The method is carried out on a rotary friction welding machine, a titanium alloy high-temperature stirring head is adopted, the titanium alloy is coated and welded on the surface of a substrate through high-speed rotation in an inert gas atmosphere,
wherein the diameter of a shaft shoulder in the rotary friction welding machine is 10-20mm, the diameter of a rotary needle is 3-8mm, the diameter of the rotary needle is a tapered pin with threads, the welding speed of the rotary friction welding machine is 600-;
C. chemical copper plating of surface
B, sequentially corroding the substrate by a sodium sulfate-sulfuric acid corrosion system, acidifying by sulfuric acid and acidifying by hydrochloric acid, then pasting a film on the substrate, then carrying out surface copper plating in a copper sulfate-sulfuric acid system chemical plating solution at 22-28 ℃, and after the copper plating is finished, ultrasonically washing by pure water;
D. ultrasonic cleaning and drying
And C, carrying out ultrasonic cleaning on the substrate treated in the step C and carrying out hot air drying.
2. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 1, wherein:
wherein, the step B also comprises a vacuum sputtering process, the seed layer is sputtered on the ceramic substrate in vacuum, and then the rotary friction welding is carried out,
by the vacuum sputtering process, the titanium-tungsten plating is carried out on the surface of the substrate by 0.05-0.1 mu m and the copper plating is carried out by 0.5-1 mu m in sequence.
3. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 2, wherein:
wherein, the processing conditions of the vacuum sputtering process are as follows: degree of vacuum 1X 10-8Substrate temperature 150--3torr, bias voltage of-200V, time 30-40 min.
4. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 1, wherein:
the specific processing steps of the step A are as follows: ultrasonic treating in one or more of anhydrous alcohol, isopropanol and acetone at normal temperature for 5-30 min, micro-etching in HF solution for 1-3min, ultrasonic washing for 1-3min, overflow washing, water absorbing roller, and drying with 80-100 deg.C hot air for 3-5 min.
5. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 1, wherein:
in the step B, the inert gas is argon, and the oxygen content in the argon is less than 500 ppm.
6. The method for metalizing the surface of the DPC copper-clad ceramic substrate in the claim 1 is characterized in that:
wherein, in the step C, the step of surface chemical copper plating is as follows:
corrosion of C1 sodium sulfate-sulfuric acid corrosion system: putting the substrate into a corrosive liquid, acidifying and corroding at room temperature for 20-40s, and ultrasonically washing with pure water for 1-5 min; wherein, each 1L of the corrosive liquid comprises 250g of sodium persulfate, 30-50mL of sulfuric acid and the balance of water;
acidifying C2 with sulfuric acid and hydrochloric acid: putting the substrate into a sulfuric acid solution with the volume fraction of 10-30, acidifying for 60-120s at room temperature, taking out the substrate, putting the substrate into a hydrochloric acid solution with the volume fraction of 10-30, carrying out secondary acidification for 60-120s at room temperature, and then carrying out immersion washing for 1-5min by pure water;
c3 substrate film: carrying out substrate film pasting under the conditions of temperature of 105-;
c4 copper plating on bottom: placing the substrate obtained from C3 in a plating solution, reacting at 22-28 deg.C for 15-25min, and controlling the film thickness to 3-5 μm;
c5 copper plating of circuit: placing the substrate obtained in C4 in a plating solution, carrying out copper plating at the temperature of 22-28 ℃, controlling the thickness of a copper layer to be 15-100 mu m, and carrying out ultrasonic immersion washing for 1-5min by pure water after the copper plating is finished;
wherein, in the C4 and C5, each 1L of plating solution contains 60-110g of copper sulfate, 200g of sulfuric acid 160-.
7. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 6, wherein:
wherein, in the step C3, after the film pasting is finished, natural wind is adopted for cooling for 30 min.
8. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 6, wherein:
in C4 and C5, the leveling agent mainly comprises an ethyl acrylate polymer, and the brightening agent mainly comprises sodium polydithiodipropyl sulfonate.
9. The method for metallizing a surface of a DPC copper-clad ceramic substrate according to claim 1, wherein:
the specific processing steps of the step D are as follows: ultrasonic cleaning with pure water for 3-10min, and drying with 80-100 deg.C hot air for 3-5 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110308168.9A CN113079646A (en) | 2021-03-23 | 2021-03-23 | Surface metallization method of DPC copper-clad ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110308168.9A CN113079646A (en) | 2021-03-23 | 2021-03-23 | Surface metallization method of DPC copper-clad ceramic substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113079646A true CN113079646A (en) | 2021-07-06 |
Family
ID=76613433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110308168.9A Pending CN113079646A (en) | 2021-03-23 | 2021-03-23 | Surface metallization method of DPC copper-clad ceramic substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113079646A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789513A (en) * | 2021-08-19 | 2021-12-14 | 上海富乐华半导体科技有限公司 | Ceramic substrate surface copper plating method based on positive and negative pulses |
| CN114921825A (en) * | 2022-04-24 | 2022-08-19 | 江苏富乐华功率半导体研究院有限公司 | DPC ceramic substrate copper plating pretreatment method |
| CN115279042A (en) * | 2022-07-26 | 2022-11-01 | 江苏富乐华半导体科技股份有限公司 | Preparation method of chemically nickel-plated gold DPC ceramic substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014084077A1 (en) * | 2012-11-28 | 2014-06-05 | ニッコー株式会社 | Ceramic copper-metallized wiring board and process for producing same |
| US20160212846A1 (en) * | 2015-01-16 | 2016-07-21 | Jx Nippon Mining & Metals Corporation | Copper foil provided with carrier, laminate, printed wiring board, electronic device, and method for fabricating printed wiring board |
| CN106888551A (en) * | 2017-04-17 | 2017-06-23 | 深圳市环基实业有限公司 | A kind of ceramic base copper-clad plate and its preparation technology |
| CN109112495A (en) * | 2018-09-12 | 2019-01-01 | 山东司莱美克新材料科技有限公司 | Ceramic substrate vacuum magnetic-control sputtering copper-plating technique |
-
2021
- 2021-03-23 CN CN202110308168.9A patent/CN113079646A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014084077A1 (en) * | 2012-11-28 | 2014-06-05 | ニッコー株式会社 | Ceramic copper-metallized wiring board and process for producing same |
| US20160212846A1 (en) * | 2015-01-16 | 2016-07-21 | Jx Nippon Mining & Metals Corporation | Copper foil provided with carrier, laminate, printed wiring board, electronic device, and method for fabricating printed wiring board |
| CN106888551A (en) * | 2017-04-17 | 2017-06-23 | 深圳市环基实业有限公司 | A kind of ceramic base copper-clad plate and its preparation technology |
| CN109112495A (en) * | 2018-09-12 | 2019-01-01 | 山东司莱美克新材料科技有限公司 | Ceramic substrate vacuum magnetic-control sputtering copper-plating technique |
Non-Patent Citations (1)
| Title |
|---|
| T.CHMIELEWSKI 等: "utilizing the energy of kinetic friction for the metallization of ceramics", 《BULLETIN OF THE POLISH ACADEMY OF SCIENCES-TECHNICAL SCIENCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789513A (en) * | 2021-08-19 | 2021-12-14 | 上海富乐华半导体科技有限公司 | Ceramic substrate surface copper plating method based on positive and negative pulses |
| CN114921825A (en) * | 2022-04-24 | 2022-08-19 | 江苏富乐华功率半导体研究院有限公司 | DPC ceramic substrate copper plating pretreatment method |
| CN114921825B (en) * | 2022-04-24 | 2023-04-07 | 江苏富乐华功率半导体研究院有限公司 | DPC ceramic substrate copper plating pretreatment method |
| CN115279042A (en) * | 2022-07-26 | 2022-11-01 | 江苏富乐华半导体科技股份有限公司 | Preparation method of chemically nickel-plated gold DPC ceramic substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113079646A (en) | Surface metallization method of DPC copper-clad ceramic substrate | |
| US5308463A (en) | Preparation of a firm bond between copper layers and aluminum oxide ceramic without use of coupling agents | |
| CN109608221A (en) | A kind of preparation method of aluminium nitride ceramic copper-clad substrate | |
| CN110743913B (en) | Production process of copper-aluminum composite decorative material | |
| CN114309955B (en) | Ceramic copper-clad substrate and laser processing technology thereof | |
| JP2001130986A (en) | Copper plated ceramic board, peltier element using the same and method for producing copper plated ceramic board | |
| US4964923A (en) | Method of forming a copper film on a ceramic body | |
| CN113789513A (en) | Ceramic substrate surface copper plating method based on positive and negative pulses | |
| NO20072917L (en) | Autocatalytic Process | |
| CN112779501A (en) | Gold-tin alloy heat sink film, preparation method thereof, heat sink substrate and LED device | |
| CN109661121B (en) | Method for chemically plating metal on copper substrate and printed circuit board and wafer prepared by method | |
| CN112458542B (en) | Surface treating agent and method for p-type bismuth telluride-based material applied to thermoelectric device | |
| US11499233B2 (en) | Plated laminate and printed circuit board | |
| Franke et al. | Investigations in the optimization of power electronics packaging through additive plasma technology | |
| CN109951947B (en) | Reflective ceramic circuit board and processing method thereof | |
| US20040154929A1 (en) | Electroless copper plating of electronic device components | |
| JPH05160551A (en) | Method of manufacturing electronic part mounting aluminum nitride board | |
| CN209949533U (en) | Reflective ceramic circuit board | |
| CN108091632A (en) | The compound bonding wire of electrum and its manufacturing method | |
| JP2001185836A (en) | Wiring board, method and device for producing wiring board | |
| CN114990473A (en) | Stainless steel base surface treatment method, copper-clad plate and preparation method | |
| JPH01301866A (en) | Formation of metallic layer on aluminum nitride surface | |
| RU2153784C1 (en) | Process of metal coating of holes in printed-circuit boards | |
| CN117702214A (en) | Direct copper plating process for seed layer surface of ceramic substrate | |
| JPH0360185A (en) | Manufacture of ceramic substrate with copper wiring |
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 | ||
| CB02 | Change of applicant information |
Address after: 224200 No. 18 Hongda Road, Chengdong New District, Dongtai City, Yancheng City, Jiangsu Province Applicant after: Jiangsu fulehua Semiconductor Technology Co.,Ltd. Address before: 224200 No. 18 Hongda Road, Chengdong New District, Dongtai City, Yancheng City, Jiangsu Province Applicant before: JIANGSU FULEDE SEMICONDUCTOR TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210706 |
|
| RJ01 | Rejection of invention patent application after publication |