CN102060573B - Manufacture method for copper-coated ceramic substrate on basis of electronic paste - Google Patents
Manufacture method for copper-coated ceramic substrate on basis of electronic paste Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 title claims description 47
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyoxyethylene Polymers 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- 239000013008 thixotropic agent Substances 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- 238000007772 electroless plating Methods 0.000 claims description 5
- 235000021323 fish oil Nutrition 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- 235000019439 ethyl acetate Nutrition 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 4
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
The invention relates to a manufacture method for a copper-coated ceramic wafer on the basis of electronic paste, belonging to the technical field of micro-electronic packaging. The manufacture method comprises the following steps of: coating oily or aqueous electronic paste prepared from cuprous oxide powder as a raw material on the surface of the ceramic wafer to form a coating with the thickness of 80-120mum; sintering at high temperature, reducing and obtaining a copper layer on the surface of alumina ceramic; processing in the mode of electrofacing or chemical plating to obtain the wafer; and then obtaining the copper-coated ceramic wafer with compact interface and smooth surface. The manufacture method has simple process, cheap raw material, low cost and yield rate up to above 90% and does not need large equipment. The interface oxygen content can be adjusted according to the content of the cuprous oxide powder and sintering atmosphere. Metal imaging is easy to realize, and surface finish is high. Especially, the wafer interface copper layer is compact and continuous and has controllable thickness, and thus the power electronic device works more stably.
Description
Technical field
The present invention relates to a kind of deposited copper ceramic substrate manufacture method based on electric slurry, belong to the microelectronic packaging technology field.
Background technology
In field of power electronics, the exemplary power circuit application mainly comprises power semiconductor modular, DC/DC umformer, light barretter, motor drive controller, automotive control system etc.The load current value of various power circuits does not wait, rangeability can from several amperes to hundreds of ampere and even thousands of ampere, this has just caused varying of all kinds of power circuit functional requirements.Modern microelectronics Packaging is nearly all carried out or relevant with substrate at substrate.Along with the appearance of novel high-density packing forms, many functions of Electronic Packaging, as be electrically connected, physical protection, stress relax, heat radiation protection against the tide, size transition, normalization and stdn etc. are just progressively partly or entirely born by substrate.Substrate has played most important effect in the heat radiation process, if the heat dispersion of substrate is bad, will cause the components and parts on the printed circuit board (PCB) overheated, thereby whole aircraft reliability is descended, even loses efficacy.Except bearing heat dissipation, the thermal expansivity (CTE) that substrate also must have and Si, GaAs are complementary is to reduce the thermal stresses between chip and the substrate, and electrical insulating property and lower specific inductivity reduce time lag in order to be applicable to high frequency circuit preferably.Under this background, the PCB substrate that always is in dominant position obviously can not satisfy above-mentioned requirements, on heat radiation requires, must select the high baseplate material of thermal conductivity for use, so ceramic substrate just enters first-selected ranks especially.
In the ceramic substrate material of practicality, price of aluminium oxide is lower, consider that from aspects such as physical strength, insulativity, thermal conductivity, thermotolerance, resistance to sudden heating, chemical stabilities its over-all properties is best, use at most as baseplate material that its processing technology is compared also most advanced with other materials.Companies such as U.S. Lamina Ceramics, German Curmilk have been applied to ceramic substrate among the high-power LED chip encapsulation; because integrated eutectic layer, electrostatic discharge protective circuit, driving circuit and control compensating circuit on this substrate; not only simple in structure; and because the material thermal conductivity height; hot interface is few; improved heat dispersion greatly, for the high-power LED array encapsulation has proposed solution.
Method at industrial realization metal and ceramic bonding mainly contains thick film and molybdenum manganese method at present.Thick film is that the particulate of noble metal is formed by being crimped on together, and the glass by fusion adheres on the pottery again, so the conductivity of thick film is than metallic copper difference.Molybdenum manganese method technology is ripe, some metallic particles in the molybdenum manganese slurry are by the moisture oxidation in the wet hydrogen, manganese as activator is oxidized to manganese oxide, a part is diffused into the internal surface of pottery and some oxide compound in the pottery forms glassy phase, a part forms the middle layer, pottery and metal layer mutually mutual diffusion realize ceramic and the good sticking power of metal layer.But the formed middle layer of this method is thicker, thermal resistance is bigger, is unfavorable for rapid heat radiation in fields such as high-power circuit, power model, and the metal layer thickness that forms by molybdenum manganese method is often very thin, less than 25 μ m, this has just limited the anti-surge capacity of high power module assembly.Aluminum oxide direct copper (DBC) substrate of Chu Xianing combines the excellent properties of copper and alumina-ceramic in recent years, and is applied in the high power device.The deposited principle that connects of DBC substrate is to introduce an amount of oxygen element before applying termination process or in the process between copper and pottery, and in ° C scope of 1065 ° of C ~ 1083, copper and oxygen form Cu-O eutectic liquid.The DBC technology is utilized this eutectic liquid, generates intermediate phase (CuAlO with ceramic chemical reaction on the one hand
2Or CuAl
2O
4), soak into the combination that Copper Foil is realized aluminium oxide ceramic substrate and copper coin on the other hand.Therefore key factor is the introducing of oxygen element in its preparation process, but directly the control oxygen level is difficult to accomplish in industrial production.
Summary of the invention
In order to overcome the existing existing above-mentioned deficiency of direct copper technology, the technical problem to be solved in the present invention provides a kind of interface oxygen level, metal patternization can controlled indirectly and applies copper ceramic substrate production method conveniently, cheaply.
A kind of deposited copper ceramic substrate manufacture method based on electric slurry is characterized in that may further comprise the steps:
(1), prepares Red copper oxide oil series electron slurry: after 75.75 ~ 83.9 weight part function phases, 15.1 ~ 22.73 weight part organic carriers, 0.5 ~ 0.76 weight part thixotropic agent, 0.5 ~ 0.76 weight part wetting agent are mixed, through ball milling, make slurry, viscosity is 45Pas ~ 100Pas;
Preparation Red copper oxide water system electric slurry: 48.7 ~ 65.5 weight part function phases, 33.2 ~ 49.4 weight part organic carriers, 0.65 ~ 0.95 weight part thixotropic agent, 0.65 ~ 0.95 weight part wetting agent are mixed by ball milling, make slurry, viscosity is 0.1Pas ~ 10Pas;
(2), get Red copper oxide oil system or the water system electric slurry of step (1) preparation, apply or the mode of silk screen printing by rotation, forming thickness at ceramic base plate surface is the coating of 50 ~ 120 μ m, coating thickness can be adjusted according to speed of rotation and web plate thickness;
(3), get the ceramic substrate of step (2) preparation, through high temperature sintering, reduction processing, at alumina-ceramic surface acquisition copper layer;
(4), prepare electroplate liquid: standby after 15 ~ 16 weight part Salzburg vitriols, 5 ~ 6 weight part vitriol oils, 0.4 weight part glucose, 77.6 ~ 79.6 weight part distilled water are mixed;
Prepare chemical plating fluid: standby after 1.5 weight part Salzburg vitriols, 1.5 weight parts, 36% formaldehyde solution, 1.4 weight part sodium hydroxide, 1.2 weight part Seignette salts, 2 weight part EDTA-2Na, 0.015 weight part yellow prussiate of potash, 0.05 weight part polyoxyethylene glycol, 92.34 weight part distilled water are mixed;
(5), get the ceramic substrate of step (3) preparation, adopt the electroplate liquid of step (4) preparation to electroplate or adopt chemical plating fluid to carry out electroless plating, can obtain the interface densification, ganoid deposited copper ceramic substrate.
Aforesaid deposited copper ceramic substrate manufacture method based on electric slurry is characterized in that the function that Red copper oxide oil series electron slurry adopts is cuprous oxide powder mutually; Organic carrier is the mixed solution of 57 weight part Terpineol 350s, 28.5 weight part diethylene glycol monobutyl ether acetic esters, 9.5 weight part dibutyl phthalates and 5 weight part ethyl cellulose; Thixotropic agent is hydrogenated castor oil, oleic acid, fish oil; Wetting agent is polyoxyethylene glycol;
The function that Red copper oxide water system electric slurry adopts is cuprous oxide powder mutually; Organic carrier is the mixed solution of 5 weight parts, 5% polyvinyl alcohol water solution, 1.32 weight part dibutyl phthalates and 93.68 weight part distilled water; Thixotropic agent is hydrogenated castor oil, oleic acid, fish oil; Wetting agent is polyoxyethylene glycol;
Aforesaid deposited copper ceramic substrate manufacture method based on electric slurry is characterized in that the cuprous oxide powder particle diameter is 6 ~ 10 μ m.
Aforesaid deposited copper ceramic substrate manufacture method based on electric slurry, the material that it is characterized in that described ceramic substrate is aluminum oxide, silicon oxide, silicon nitride, aluminium nitride, glass.
Aforesaid deposited copper ceramic substrate manufacture method based on electric slurry, it is characterized in that: the concrete technology of step (3) is: substrate is put into electric tube furnace, be heated to 1150 ° of C under air, sintering 2 hours and furnace cooling are realized the effective combination between coat and the pottery.After sample to be sintered is cooled to room temperature, the tubular type furnace chamber is evacuated, and is heated to 600 ° of C, at H
2+ N
2Reductase 12 hour under (throughput ratio is 1:2) atmosphere.
Adopt and electroplate or chemical plating method, the end properties difference of preparation is: adopt the electro-coppering technology, coating is thicker, the highest copper layer of realizing 150 μ m; Adopt the electroless copper technology, coating is thinner, the surface finish height.Compare with at present used DBC forming technology, the present invention need not main equipment, technology is simple, cost of material is low, reduce cost, yield rate reaches more than 99%, the interface oxygen level is effectively controlled, metal patternization is convenient, and surface smoothness height, particularly substrate interface copper layer are continuously fine and close, and controllable thickness makes the power electronic device more stable work.
Description of drawings
Fig. 1 is example 1 preparation high-temperature sample sintering rear interface material phase analysis of the present invention
Fig. 2 is example 1 preparation sample surfaces microscopic appearance of the present invention;
Fig. 3 is example 1 preparation example interface microscopic appearance of the present invention;
Fig. 4 is example 2 preparation sample surfaces line patterns of the present invention.
Embodiment
Following cuprous oxide powder that embodiment adopts, Terpineol 350, diethylene glycol monobutyl ether acetic ester, ethyl cellulose, hydrogenated castor oil, polyoxyethylene glycol, dibutyl phthalate, polyvinyl alcohol, Salzburg vitriol, the vitriol oil, glucose, formaldehyde, sodium hydroxide, Seignette salt, the yellow prussiate of potash of the present invention all is to obtain by market.
Embodiment 1
Step 1: preparation Red copper oxide water system electric slurry: be that cuprous oxide powder (analytical pure) 53.6 weight parts, 5% polyvinyl alcohol water solution, 44.3 weight parts, dibutyl phthalate 0.5 weight part, hydrogenated castor oil 0.8 weight part and polyoxyethylene glycol 0.8 weight part of 6 μ m mixes with particle diameter, and on planetary ball mill ball milling 2 hours, obtain Red copper oxide water system electric slurry, viscosity is 1Pas.
Step 2: 96 alumina ceramic plates are put into ethanolic soln, and ultrasonic cleaning 30 minutes in ultrasonic cleaner, taking-up is dried; The Red copper oxide water system electric slurry that applies step 1 preparation by rotation on coating machine evenly is coated with on the alumina-ceramic surface subsequently, and spin speed is 500 rev/mins, and obtaining coat-thickness is 50 μ m.
Step 3: step 2 coatings prepared substrate is put into electric tube furnace, under air, be heated to 1150 ° of C, sintering 2 hours and furnace cooling, thus generate the CuAlO that a layer thickness is 10 ~ 20 μ m in coating and ceramic interface
2Transition layer, as shown in Figure 1, this process is similar to the DBC technology, and it is not by extraneous atmosphere that oxygen level is only at the interface introduced, but introduces by the oxygen element in the Red copper oxide, thereby has realized the effective combination between coating and the pottery.After sample to be sintered is cooled to room temperature, the tubular type furnace chamber is evacuated, and is heated to 600 ° of C, at H
2+ N
2Reductase 12 hour under (throughput ratio is 1:2) atmosphere.
Step 4: Salzburg vitriol 15.6 weight parts, the vitriol oil 5.9 weight parts, glucose 0.4 weight part are joined in distilled water 78.1 weight parts, stir, the preparation acid copper sulfate solution.As anode, the prepared substrate sample of step 3 is as negative electrode with the fine copper sheet, and it is 5A/dm that direct supply is set
2, and plating 30 minutes in heat collecting type thermostatically heating magnetic stirring apparatus, envrionment temperature is 40 ° of C.The deposited copper ceramic substrate interface that makes as shown in Figure 3, interface copper layer densification, thickness reaches 80 μ m, its surface topography as shown in Figure 2, surfacing is smooth, imperforate existence, yield rate reaches 90%.
Embodiment 2
Step 1: preparation Red copper oxide oil series electron slurry: be that cuprous oxide powder 81.3 weight parts of 10 μ m fully mix, stir with diethylene glycol monobutyl ether acetic ester 4.63 weight parts, Terpineol 350 9.27 weight parts, dibutyl phthalate 1.54 weight parts, ethyl cellulose 0.81 weight part, hydrogenated castor oil 1.22 weight parts, polyoxyethylene glycol 1.22 weight parts and particle diameter, obtain Red copper oxide oil series electron slurry, ball milling, make slurry, viscosity is 60Pas.
Step 2: by 300 order silk screens, utilize the Red copper oxide slurry of step 1 preparation to print out circuitous pattern on 96 alumina-ceramic surfaces, print thickness can be adjusted according to web plate thickness.
Step 3: the printed base plate that step 2 is prepared carries out sintering and reducing, and is identical with the step 3 of example 1, and circuitous pattern as shown in Figure 4.
Step 4: the made substrate of step 3 is carried out electroplating processes, and identical with the step 4 of example 1, the gained copper layer thickness reaches 120 μ m.
Embodiment 3
Step 1: preparation Red copper oxide oil series electron slurry, the step 1 of preparation process and example 2 is identical.
Step 2: at silicon oxide ceramics circuit forming surface figure, the step 2 of printing process and example 2 is identical by silk screen printing.
Step 3: the printed base plate that step 2 is prepared carries out sintering and reducing, and is identical with the step 3 of example 1.
Step 4: Salzburg vitriol 1.5 weight parts, 36% formaldehyde solution, 1.5 weight parts, sodium hydroxide 1.4 weight parts, Seignette salt 1.2 weight parts, EDTA-2Na 2 weight parts, yellow prussiate of potash 0.015 weight part, polyoxyethylene glycol 0.05 weight part are joined in the 92.34 weight part distilled water, stir the preparation chemical plating fluid.The substrate sample that step 3 is made is suspended in the plating bath subsequently, and plating is 1 hour in heat collecting type thermostatically heating magnetic stirring apparatus, constantly blasts air in the plating process, 50 ° of C of control temperature.The deposited copper ceramic substrate interface copper layer densification that makes, thickness reaches 90 μ m, and surfacing is smooth.
The material that embodiment 4 to 6 adopts and preparation method such as following table, except the content of table 1, all the other contents are identical with the content of embodiment 1.
| ? | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Ceramic base material | Aluminium nitride | Silicon nitride | Glass |
| The mode of plating | Electroplate | Electroless plating | Electroless plating |
| Slurry | Water system | Oil system | Water system |
| Thixotropic agent | Hydrogenated castor oil | Oleic acid | Fish oil |
| Wetting agent is | Polyoxyethylene glycol | Polyoxyethylene glycol | Polyoxyethylene glycol |
| Coating method | Rotation applies | Silk screen printing | Rotation applies |
| Copper layer thickness | 70μm | 80μm | 60μm |
Above-mentionedly enumerated six way of example of the present invention, but above-mentioned embodiment of the present invention can only think all can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention.Therefore; under the situation of not violating basic thought of the present invention; apply at metal and to connect in the production process of ceramic substrate; as long as having adopted cuprous oxide powder is raw material; and it is identical with additive of the present invention; and by using any processing technology in plating and the electroless plating, all should think to belong to protection scope of the present invention.
Claims (5)
1. deposited copper ceramic substrate manufacture method based on electric slurry is characterized in that may further comprise the steps:
(1), prepares Red copper oxide oil series electron slurry: after 75.75 ~ 83.9 weight part function phases, 15.1 ~ 22.73 weight part organic carriers, 0.5 ~ 0.76 weight part thixotropic agent, 0.5 ~ 0.76 weight part wetting agent are mixed, through ball milling, make slurry, viscosity is 45Pas ~ 100Pas; The function that Red copper oxide oil series electron slurry adopts is cuprous oxide powder mutually; Organic carrier is the mixed solution of 57 weight part Terpineol 350s, 28.5 weight part diethylene glycol monobutyl ether acetic esters, 9.5 weight part dibutyl phthalates and 5 weight part ethyl cellulose; Thixotropic agent is hydrogenated castor oil, oleic acid, fish oil; Wetting agent is polyoxyethylene glycol;
Preparation Red copper oxide water system electric slurry: 48.7 ~ 65.5 weight part function phases, 33.2 ~ 49.4 weight part organic carriers, 0.65 ~ 0.95 weight part thixotropic agent, 0.65 ~ 0.95 weight part wetting agent are mixed by ball milling, make slurry, viscosity is 0.1Pas ~ 10Pas; The function that Red copper oxide water system electric slurry adopts is cuprous oxide powder mutually; Organic carrier is the mixed solution of 5 weight parts, 5% polyvinyl alcohol water solution, 1.32 weight part dibutyl phthalates and 93.68 weight part distilled water; Thixotropic agent is hydrogenated castor oil, oleic acid, fish oil; Wetting agent is polyoxyethylene glycol;
(2), get Red copper oxide oil system or the water system electric slurry of step (1) preparation, apply or the mode of silk screen printing by rotation, forming thickness at ceramic base plate surface is the coating of 50 ~ 120 μ m, coating thickness can be adjusted according to speed of rotation and web plate thickness;
(3), get the ceramic substrate of step (2) preparation, through high temperature sintering, reduction processing, at alumina-ceramic surface acquisition copper layer;
(4), prepare electroplate liquid: standby after 15 ~ 16 weight part Salzburg vitriols, 5 ~ 6 weight part vitriol oils, 0.4 weight part glucose, 77.6 ~ 79.6 weight part distilled water are mixed;
Prepare chemical plating fluid: standby after 1.5 weight part Salzburg vitriols, 1.5 weight parts, 36% formaldehyde solution, 1.4 weight part sodium hydroxide, 1.2 weight part Seignette salts, 2 weight part EDTA-2Na, 0.015 weight part yellow prussiate of potash, 0.05 weight part polyoxyethylene glycol, 92.34 weight part distilled water are mixed;
(5), get the ceramic substrate of step (3) preparation, adopt the electroplate liquid of step (4) preparation to electroplate or adopt chemical plating fluid to carry out electroless plating, can obtain the interface densification, ganoid deposited copper ceramic substrate.
2. the deposited copper ceramic substrate manufacture method based on electric slurry according to claim 1 is characterized in that the cuprous oxide powder particle diameter is 6 ~ 10 μ m.
3. the deposited copper ceramic substrate manufacture method based on electric slurry according to claim 1, the material that it is characterized in that described ceramic substrate is aluminum oxide, silicon oxide, silicon nitride, aluminium nitride, glass.
4. the deposited copper ceramic substrate manufacture method based on electric slurry according to claim 1, the concrete technology that it is characterized in that step (3) is: substrate is put into electric tube furnace, under air, be heated to 1150 ° of C, sintering 2 hours and furnace cooling, realize the effective combination between coat and the pottery, after sample to be sintered is cooled to room temperature, the tubular type furnace chamber is evacuated, and be heated to 600 ° of C, at H
2And N
2Reductase 12 hour under the atmosphere.
5. the deposited copper ceramic substrate manufacture method based on electric slurry according to claim 4 is characterized in that H
2And N
2Throughput ratio be 1:2.
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| CN103274700A (en) * | 2013-04-23 | 2013-09-04 | 云南银峰新材料有限公司 | Method for preparing ceramic medium slurry for screen printing |
| CN104064478B (en) * | 2014-06-24 | 2016-08-31 | 南京航空航天大学 | A kind of manufacture method of copper/aluminium nitride ceramics composite heat-conducting substrate |
| CN107639237B (en) * | 2017-09-18 | 2020-08-11 | 广东工业大学 | Cu/SiO2Composite material, preparation method thereof and preparation method of copper-ceramic substrate |
| CN108658627B (en) * | 2018-06-01 | 2020-06-02 | 中国工程物理研究院流体物理研究所 | Metallization method of aluminum nitride ceramic |
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