CN114394750B - Low-temperature cofiring dielectric ceramic material and wiring structure - Google Patents
Low-temperature cofiring dielectric ceramic material and wiring structure Download PDFInfo
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- CN114394750B CN114394750B CN202210068231.0A CN202210068231A CN114394750B CN 114394750 B CN114394750 B CN 114394750B CN 202210068231 A CN202210068231 A CN 202210068231A CN 114394750 B CN114394750 B CN 114394750B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a low-temperature co-fired dielectric ceramic material and a wiring structure based on the material. The low-temperature co-fired dielectric ceramic material comprises 75-85% of calcium borosilicate crystal glass and 15-20% of borosilicate modified glass by mass. The wiring structure was wired using the following aluminum conductor paste: comprises, by mass, 0-20% of silver powder, 55-75% of aluminum powder, 0.1-2.0% of a first inorganic modifier, 0-8% of a first glass powder and 13.0-24.9% of an organic carrier. The material can be used for obtaining low-temperature co-fired ceramic electronic devices for multilayer wiring, not only can be used for a large amount of metal aluminum, but also has clear wiring and stable quality, and meets the application requirements of domestic low-temperature co-fired ceramic products.
Description
Technical Field
The invention relates to a ceramic dielectric material and an electronic component comprising the same.
Background
The low temperature co-fired ceramic (LTCC) technology is widely used for miniaturization and chip formation of discrete components such as capacitors, resistors, inductors, transformers, and the like, and is also used for multi-layer interconnection integration and multi-layer interconnection packaging of radio frequency, microwave, millimeter wave passive components and circuits such as LEDs and Surface Acoustic Wave (SAW) devices, si, gaAs, inP, and the like, including system SIP (System in Package) packaging from conventional packaging forms to PGA, BGA, LCC, MCM-C, MCM-C/D, MEMS devices, module packaging, and the like. Various products based on the low-temperature co-fired ceramic technology are widely applied to the fields of computers, communication, automobiles, aerospace, biomedical science, illumination, internet of things and the like. Is an important supporting technology for the high-speed development of the numerous fields of the army and the civilian at present.
In the low-temperature co-firing ceramic technology, the co-firing compatibility of the low-temperature co-firing low-dielectric constant dielectric ceramic material with wiring and interconnection conductors plays a key role in the yield and reliability of low-temperature co-firing ceramic products. At present, the domestic LTCC low dielectric constant ceramic materials are still mainly imported, wherein LTCC materials such as Ferro A6M, ferro A6S, ferro L8, dupont951, dupont9K7 and the like monopolize most of the markets in China. Murata, kyocera, NEC, NGK, tektronix, westinghouse, IBM, fujitsu et al have their unique LTCC porcelain systems. Numerous scientific research institutions and enterprises in China conduct long-term research and development, but mature and reliable commercial products are not yet promoted, an electronic paste system matched with the commercial products starts later, researches are fewer, and in actual production, the electronic paste system of Dupont, ferro, heraus, ESL monopoly the Chinese market for a long time.
At present, the low-temperature cofiring dielectric ceramic and the mixed conductor slurry system of all gold, silver, palladium and the like realize cofiring at 850-900 ℃. The compatibility and the matching performance of the material are embodied in physical and chemical compatibility in the cofiring process. Effective measures are needed to be taken to control the shrinkage behavior of the metal conductor paste, adjust the expansion and other characteristics of a conductor paste system, reduce the system stress, and otherwise, the defects of deformation, foaming, cracking, peeling and the like can occur. Noble metal gold is expensive, and the current LTCC cofiring temperature is 850-900 ℃, the energy consumption is still higher, and only high-end fields such as military industry and the like can bear the cost pressure. Although the cost of silver is lower than that of gold, oxidation-reduction reaction can occur in the sintering, storage and use processes of Ag, and the Ag and a ceramic dielectric material can also have physical and chemical effects, so that silver is diffused and migrated, a hole and a pore are formed in a conductor silver wire or a silver conductor interconnection passage, the cross section is changed, the density is reduced, the conductivity is reduced, even the circuit is blurred due to silver diffusion, and the phenomena of disappearance of a silver layer, disconnection or reduction of insulation performance of adjacent wires, short circuit and the like occur; meanwhile, silver enters the substrate material in a silver atom or silver ion state (silver absorption or silver penetration) to cause local yellowing phenomenon of the low-temperature co-fired ceramic, and even the transformation and crystallization behaviors of glass in the low-temperature co-fired ceramic are seriously influenced, so that the dielectric property of the low-temperature co-fired ceramic is further influenced. The cost of gold or silver is still high in the civil field, so that LTCC cannot be widely used in the related field.
The excellent cofiring conductor paste must meet the following requirements: firstly, the resistivity of the interlayer metal wire and the interconnection metal conductor is low, and the interlayer metal wire and the interconnection metal conductor can form an excellent bonding matching structure with the cofired ceramic, and the interlayer metal wire and the interconnection metal conductor are required to have excellent weldability and welding resistance for the surface layer conductor; secondly, the long-term reliability under various severe conditions is fully ensured; thirdly, silver diffusion is restrained and eliminated in the preparation process of the low-temperature cofiring ceramic for a silver-containing system, the problems of disconnection, short circuit, insulation resistance reduction and the like of in-layer wiring and interlayer interconnection are avoided, and the adverse problems of power loss, signal crosstalk and the like in the signal transmission process are eliminated; fourth, performance degradation of the low temperature co-fired ceramic product during storage and use is eliminated.
From practical application, the low-temperature co-fired ceramic green tape system of Dupont, ferro, heraus or ESL has unique all-gold-series, all-silver-series or gold-silver mixed-series electronic paste matched with the low-temperature co-fired ceramic green tape system, and the electronic paste with the same purpose and the same function comprises the conductor paste for multilayer wiring, and the conductor paste is not universal and interchangeable. At present, a plurality of domestic low-temperature co-fired ceramic products mainly adopt Dupont, ferro ceramic green belts and matched slurry. The domestic practical products in the related fields do not form a system of the domestic practical products, and are in research and development stages. In terms of electronic paste, published Chinese patent, application number: 201610411085.1 "a method for preparing a silicon dioxide coated copper electronic paste for LTCC substrates", the sintering of which requires nitrogen protection, is not currently the dominant technique in the art; application number: 20181150300. X 'hole-filling conductor paste for low-temperature multilayer cofired ceramic LTCC' is characterized in that the conductor filling of the low-temperature cofired ceramic is realized by using an environment-friendly plasticizer, and is not suitable for multilayer wiring conductors. Application number: 201010186567.4 "leadless solder-resistant silver conductor paste" is mainly used for thick film network resistors and is not suitable for low-temperature co-firing ceramic process requirements. Application number: 201910312643.2A conductive silver paste for low-temperature sintering LTCC solves the problem that Du Bangjiang material is not matched with self-made LTCC porcelain in sintering, the sintering temperature is 600-650 ℃, and the conductive silver paste is mainly matched with capacitor porcelain.
Said invention adopts 850-900 deg.C and noble metal cofiring system as main current LTCC technology, represented by Ferro, dupont; IBM, fujitsu, murata, kyocera adopts copper cofiring technology under nitrogen atmosphere, but must be matched with a reduction-resistant LTCC porcelain system; there are few enterprises that use low-temperature silver paste and special-purpose porcelain co-firing technology, and the method has few application scenes and is not used for fundamentally improving and eliminating the problems of silver diffusion and migration.
CN06904970A 'tungsten-based ultralow-temperature co-fired microwave dielectric ceramic material and preparation method thereof', wherein the sintering temperature of porcelain in the material is 580-630 ℃; CN108911746A 'a low-loss ultralow-temperature sintered microwave dielectric ceramic material, and a preparation method and application thereof', wherein the sintering temperature of the porcelain material is 560-740 ℃; CN 103951413A' ultra-low temperature sintered microwave dielectric ceramic Li 3 V 2 PO 9 The sintering temperature of the porcelain in the preparation method is 600-630 ℃; CN 101805186A' ultra-low sintering temperature microwave dielectric ceramic material and preparation thereofMethod ", the material can be sintered at 500-850 ℃; CN104876568A 'vanadium-based temperature stable ultralow temperature sintering microwave dielectric ceramic material and preparation method thereof', wherein the sintering temperature of the material is 575-650 ℃; TW201200489A1 'ultra-low temperature sintered microwave dielectric ceramic' uses Te 2 (Mo1-xWx)O 7 Is a main crystal phase, can be sintered at 480-540 ℃, but Te is a high toxic substance. The possibility of co-firing with base metal aluminum paste in a certain temperature range (580-750 ℃) is provided in the range of 480-750 ℃ from the sintering temperature alone, but to truly achieve the aim, conductor paste is also required to be matched with a porcelain system, and the invention does not truly develop related tests, and further has no sintering test cases and results; in addition, ULTCC (ultra low temperature co-fired ceramic) systems using phosphate, molybdate, tungstate and the like as main crystal phases are all compounds with strong water absorption, and have great problems in weather resistance and chemical stability, and have great distance from actual practical application. And Te-containing systems are very toxic and do not meet current industry development policies.
In summary, the present invention of low-cost high-performance aluminum paste for LTCC and aluminum-containing low-silver conductor cofiring system has not been reported. The invention adopts a unique technical path to prepare 580-680 ℃ low-temperature sintered aluminum paste and 640-750 ℃ medium-temperature sintered aluminum silver paste, which can be used for multilayer wiring of LTCC; an outer solderable and gold-plated silver paste is prepared to match the paste. Meanwhile, a LTCC dielectric ceramic system which can be co-fired with low-cost high-performance aluminum paste and aluminum-containing low-silver conductors at the temperature below 720 ℃ is developed successfully.
Disclosure of Invention
The invention aims to provide a low-temperature co-fired dielectric ceramic material which can be used for wiring by using one or more of aluminum paste, aluminum silver paste and silver paste to prepare a wiring structure, wherein the wiring structure can realize co-firing formation below 720 ℃, and a conductor and a porcelain system have excellent matching performance. The wiring structure manufactured by the method inhibits and eliminates the silver diffusion phenomenon of the all-silver system. The conductor system partially or completely realizes the replacement of noble base materials, the porcelain system overcomes the problem of poor weather resistance and chemical stability of ULTCC (ultra low temperature co-fired ceramic) systems taking phosphate, molybdate, tungstate and the like as main crystal phases, and simultaneously greatly reduces the sintering temperature of LTCC (low temperature co-fired ceramic) systems such as boron silicon calcium crystallized glass systems and the like. The competitiveness of LTCC is improved through the reduction of material cost and energy consumption.
The low-temperature co-fired dielectric ceramic material comprises the following components in percentage by mass: 75-85% of calcium borosilicate crystal glass and 15-20% of borosilicate modified glass.
In one embodiment, the calcium borosilicate crystalline glass consists essentially of SiO by mass 2 25-32％，BO 3 15-25%, caO 28-42%, calcium phosphate 2-7%, zrO 2 1-5%.
In one embodiment, the borosilicate modified glass consists essentially of, by mass, B 2 O 3 、SiO 2 And Al 2 O 3 The preferable mass percentage of the composition is B 2 O 3 38-50％、SiO 2 45-56％、Al 2 O 3 0.5-2％。
In one embodiment, the composition further comprises Li in an amount of not more than 10% 2 O 3 、Na 2 O、K 2 O, znO, preferably comprising Li 2 O 3 1.0-2.0％、Na 2 O0.5-1.5％、K 2 1.0-2.5% of O and 0.5-1.5% of ZnO.
In a second aspect of the present invention, there is provided a wiring structure including a low-temperature co-fired ceramic and a wiring structure, wherein the low-temperature co-fired ceramic is made of the above-described low-temperature co-fired dielectric ceramic material, and at least a part of the metal wire is formed of an aluminum conductor paste including, by mass: 0-20% of silver powder, 55-75% of aluminum powder, 0.1-2.0% of first inorganic modifier, 0-8% of first glass powder and 13.0-24.9% of organic carrier, wherein the first inorganic modifier is selected from one or more of Cu, mg, zn, al, fe, ti, V, W and Mo oxides, silicides, borides or metal organic compounds, the first glass powder is zinc-boron-silicon-aluminum glass, and the main preparation raw materials of the glass are ZnO and B 2 O 3 、SiO 2 And Al 2 O 3 Preferred proportion45-55wt% of ZnO and B 2 O 3 30-40wt％、SiO 2 10-18wt％、Al 2 O 3 0.5-5wt％。
In one embodiment, D of the first glass frit 50 The softening point is preferably 580 to 640℃in the range of 1 to 3. Mu.m.
In a specific embodiment, the organic carrier is a compound of ethyl cellulose resin, acrylic resin, terpineol and dodecyl ester, and the preferable proportion is that the mass ratio of the ethyl cellulose resin to the acrylic resin to the terpineol to the dodecyl ester is 5-15:1-6:50-80:5-10.
In one embodiment, a portion of the metal wire is formed from a conductive silver paste comprising, in mass percent: 78-83% of silver powder, 0.1-0.5% of second inorganic modifier, 0-5% of second glass powder and 11.5-21.9% of organic carrier.
In a specific embodiment, the second inorganic modifier is one or more of oxides, silicides, borides or metal organic compounds of Cu, ti, V, preferably Cu 2 O、CuO、TiO 2 、V 2 O 5 One or more of (a) and (b).
In one specific embodiment, the main preparation raw material of the second glass powder is Bi 2 O 3 、B 2 O 3 、SiO 2 And Al 2 O 3 The preferable proportion is Bi 2 O 3 60-80wt％、B 2 O 3 15-25wt％、SiO 2 5-12wt％、Al 2 O 3 0.5-5wt%, preferably D 50 The softening point is preferably 580 to 640 ℃, more preferably 560 to 620 ℃ in the range of 1 to 3 μm.
According to the wiring structure obtained by the invention, the conductor takes aluminum as a main material, and an aluminum-silver conductor containing a small amount of silver is adopted when the sintering temperature is higher, so that the pattern is clear, the porcelain body is free from yellowing, the bad silver diffusion phenomenon is inhibited and eliminated, and the conductor is free from defects such as short circuit, open circuit and the like; no failure modes such as cracking, warping, foaming, delamination and the like occur. The wiring structure of the present invention is particularly suitable for making multilayer wiring structures, and different layers can be wired with different metal pastes as described above. The slurry system for multilayer wiring can meet the application requirements of domestic low-dielectric constant low-temperature co-fired ceramics, and promotes the autonomous and domestic processes in the field of domestic low-temperature co-fired ceramic products.
Detailed Description
The following is a description of the embodiments of the present invention using specific examples.
In the following examples, viscosity measurements were made using noble metal paste testing methods in accordance with GB/T17473.5-1998 thick film microelectronics; the sheet resistance measurement is carried out according to a precious metal slurry test method for a GB/T17473.3-2008 microelectronic technology; fineness measurement the noble metal slurry test method for microelectronic technology is according to GB/T17473.2-2008.
The preparation of the LTCC dielectric ceramic system is carried out by maintaining the melting temperature of calcium-boron-silicon crystallized glass at 1450 ℃ for 1 hour, quenching in deionized water, ball milling and drying for later use. Softening point 850 ℃, D 50 1-4 μm, preferably 2-3 μm; borosilicate modified glass is used, and the melting temperature of the glass is 1500 ℃ and the temperature is kept for 1 hour. Quenching in deionized water, ball milling with absolute ethyl alcohol, and oven drying, wherein the softening point of the glass is 480-550deg.C; and (3) carrying out tape casting molding according to the proportion to obtain the low-temperature cofired ceramic green tape capable of meeting the requirement of screen printing.
And (3) testing qualified metallic aluminum and aluminum silver conductor paste, and printing multilayer wiring patterns and interconnection through holes of the LTCC low-temperature co-fired ceramic green tape. The outer layer solderable and gildable silver conductor paste which is qualified in test is used for manufacturing surface layer and bottom layer sheet resistance test patterns, and the sheet resistance test patterns are printed by a precise screen printer and connected with the interlayer multilayer wiring patterns through vertical interconnection conductors. Laminating, cutting, and co-firing at 580-720 ℃. The co-fired multilayer ceramic is used for testing the sheet resistance of the surface and bottom silver layers and the on-off test of the multilayer interconnection. The test sample has a four-layer structure.
The low temperature cofired ceramic green tape thickness was 125 μm, the top layer, bottom layer test patterns and the inner layer wiring patterns were printed with 325 mesh stainless steel mesh (photoresist film thickness 25 μm), and the interlayer interconnection gap was printed with 325 mesh stainless steel mesh (photoresist film thickness 35 μm) on a printer with a negative pressure hole filling device to fill the through holes.
Example 1
The material is prepared from the following components in percentage by mass: 70wt% of spherical aluminum powder, 2wt% of silver powder and 6wt% of zinc-boron-silicon aluminum glass powder (50 wt% of ZnO and 35wt% of B are contained in the glass powder 2 O 3 、13wt％SiO 2 And 2wt% Al 2 O 3 ) Inorganic modifier TiO 2 0.5wt％、MoSi 2 0.2wt% and 21.3wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin, terpineol: the mass ratio of the dodecanol ester is 10:2:80:8. the viscosity of the slurry prepared by the processes of proportioning, wet stirring and dispersing, rolling by a three-roller mill, viscosity adjustment and the like is 260+/-50 dPa.S, the fineness of the slurry is less than or equal to 8 mu m, and the solid content is 78.7%. The test results for the inner conductor used in the four-layer cofiring test specimens are shown in table 1.
Example 2
The material is prepared from the following components in percentage by mass: 75wt% of spherical aluminum powder, 8wt% of zinc-boron-silicon aluminum glass powder (same as in example 1) and inorganic modifier TiB 2 0.3wt％、V 2 O 5 0.1wt% and 16.6wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin, terpineol: the mass ratio of the dodecanol ester is 8:2:82:8. the slurry preparation method is as described above. The viscosity of the slurry is 280+/-50 dPa.S, the fineness of the slurry is less than or equal to 7 mu m, and the solid content is 83.4%. The test results for the inner conductor used in the four-layer cofiring test specimens are shown in table 1.
Example 3
80wt% of spherical silver powder, 0.2wt% of inorganic modifier CuO and 0.2wt% of TiO 2 0.5wt% of bismuth borosilicate glass powder 2.0wt% (70 wt% Bi is contained) 2 O 3 、20wt％B 2 O 3 、8wt％SiO 2 And 2wt% Al 2 O 3 ) 17.3wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin, terpineol: the mass ratio of the dodecanol ester is 12:4:64:20, the slurry preparation method is as described above.
The preparation method is as described above. The viscosity of the slurry is 300+/-50 dPa.S, the fineness of the slurry is less than or equal to 10 mu m, and the solid content is 82.7%. The outer conductor used in the four-layer cofiring test specimens was prepared and the test results are shown in table 1.
Table 1 test results for examples 1 to 3
Example 4
Calcium borosilicate crystalline glass (comprising SiO) 2 28％，B 2 O 3 20%, caO 34%, calcium phosphate 5%, zrO2 3%) and heat-preserving at 1450 ℃ for 1 hour, quenching in deionized water, drying, heat-treating at 750 ℃ for 15 minutes, ball-milling and drying for later use, and softening point of 850 ℃ and D 50 2.1 μm; borosilicate modified glass (containing B) 2 O 3 43.0％、SiO 2 51.0％、Al 2 O 3 1.0％、Li 2 O 1.5％、Na 2 O 1.0％、K 2 O1.5% and ZnO 1.0%), the glass melting temperature is kept at 1500 ℃ for 1 hour, after quenching in deionized water, ball milling and drying are carried out for standby, the softening point is 480-550 ℃, and D 50 2.0 μm; in order to detect the dielectric property of the porcelain, 80 weight percent of calcium borosilicate crystal glass and 20 weight percent of borosilicate modified glass are weighed to obtain LTCC dielectric ceramic powder, and the LTCC dielectric ceramic powder is subjected to ball milling, granulation and dry pressing to obtain a ceramic green body phi 16 multiplied by 3, and the ceramic green body is sintered at 720 ℃ and is kept for 30 minutes. And printing silver paste on the sintered ceramic body, and performing infiltration heat preservation at 530 ℃ for 10 minutes to obtain a test sample. The dielectric properties were tested with an AV2782LCR tester. The dielectric constant is 6.5 at 1MHz, and the dielectric loss is 2.56×10 -4 The detection result shows that the porcelain can be transferred to the casting forming stage. Casting and forming dielectric ceramic powder according to the mass ratio: casting binder = 52:48 a casting binder is added. Ball milling, mixing, removing bubbles, and casting to obtain the low-temperature co-fired ceramic green tape. Can be used as a ceramic dielectric layer for LTCC screen printing. The porcelain test results are shown in Table 2.
Example 5
The calcium-boron-silicon crystallized glass (same as in example 4) used was heat-preserved for 1 hour at 1450℃and quenched in deionized waterDrying, heat treating at 750deg.C for 5 min, ball milling, drying at 850 deg.C, and D 50 2.1 μm. Borosilicate modified glass (same as in example 4) was used, and the glass melting temperature was kept at 1500℃for 1 hour. Quenching in deionized water, ball milling and drying for standby, wherein the softening point is 480-550 ℃. In order to detect the dielectric property of the porcelain, 70 weight percent of calcium-boron-silicon crystallized glass and 30 weight percent of borosilicate modified glass are weighed to obtain LTCC dielectric ceramic powder, and the LTCC dielectric ceramic powder is subjected to ball milling, granulation and dry pressing to obtain a ceramic green body phi 16 multiplied by 3, and the ceramic green body is sintered at 660 ℃ and is kept for 30 minutes. And printing silver paste on the sintered ceramic body, and performing infiltration heat preservation at 530 ℃ for 10 minutes to obtain a test sample. The dielectric properties were tested with an AV2782LCR tester. The dielectric constant is 6.0 at 1MHz, and the dielectric loss is 5.20X10 -4 . The detection result shows that the porcelain can be transferred to the casting forming stage. Casting and forming dielectric ceramic powder according to the mass ratio: casting binder = 52:48 a casting binder is added. Ball milling, mixing, removing bubbles, and casting to obtain the low-temperature co-fired ceramic green tape. A ceramic dielectric layer of LTCC screen printing may be used. The porcelain test results are shown in Table 2.
TABLE 2 test results of the porcelain products prepared in examples 5 and 6
Example 6
Printing an inner layer pattern and first to fourth layer interconnection through holes on the second and third layer green tapes by using the low-temperature co-fired ceramic green tapes prepared in the embodiment 4 as a dielectric layer and using the aluminum paste prepared in the embodiment 1 by adopting a standard multilayer ceramic production process; the silver paste prepared in example 3 was used to print the patterns on the top (first layer) and bottom (fourth layer). Laminating, and then sintering at 700 ℃ peak temperature, and keeping the temperature for 30 minutes. The results of the final test are shown in Table 3.
Example 7
Using standard multilayer ceramic production process, using low temperature co-fired ceramic green tape prepared in example 4 as dielectric layer, using aluminum paste prepared in example 2 to print inner layer pattern and interconnection via holes on the second and third layers green tape, and via holes on the first and second layers; the silver paste prepared in example 3 was used to print the patterns on the top (first layer) and bottom (fourth layer). Laminating, and then sintering at 650 ℃ peak temperature, and keeping the temperature for 30 minutes. The results of the final test are shown in Table 3.
Table 3 test results for example 6 and 7
The invention adopts a unique preparation method of metal aluminum, aluminum silver conductors and low-temperature co-fired ceramics, realizes co-firing at 580-720 ℃, realizes that the internal conductors are replaced by base materials, has excellent matching performance, ensures that the sintering temperature of a porcelain system is 100 ℃ lower than that of the current LTCC porcelain, can meet the use requirement of the civil field on LTCC (low-temperature co-fired ceramics) substrates and devices, and greatly reduces the manufacturing and use cost of products.
The invention is not described in detail in the prior art.
The embodiments selected herein for the purposes of the present invention should be construed as illustrative, and not limiting the scope of the invention, which is defined in the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made to the present invention without departing from its spirit or scope.
Claims (9)
1. The low-temperature co-fired dielectric ceramic material comprises the following components in percentage by mass: 75-85% of calcium borosilicate crystal glass and 15-20% of borosilicate modified glass, wherein the calcium borosilicate crystal glass mainly comprises SiO (silicon dioxide) by mass 2 25-32%，B 2 O 3 15-25%, caO 28-42%, calcium phosphate 2-7%, zrO 2 1-5% by mass of a borosilicate modified glass consisting essentially of B 2 O 3 、SiO 2 And Al 2 O 3 The composition is as follows in percentage by mass 2 O 3 38-50%、SiO 2 45-56%、Al 2 O 3 0.5-2%, the borosilicate modified glass further comprising a total of no more than 10% Li 2 O 、Na 2 O 、K 2 O, znO.
2. The low temperature co-fired ceramic dielectric material of claim 1, wherein the borosilicate modified glass comprises Li 2 O 1.0-2.0%、Na 2 O 0.5-1.5%、K 2 1.0-2.5% of O and 0.5-1.5% of ZnO.
3. A wiring structure comprising a low-temperature co-fired ceramic made of the low-temperature co-fired dielectric ceramic material according to claim 1 or 2 and a metal wire, at least a part of the metal wire being formed of an aluminum conductor paste comprising, by mass: 0-20% of silver powder, 55-75% of aluminum powder, 0.1-2.0% of first inorganic modifier, 0-8% of first glass powder and 13.0-24.9% of organic carrier, wherein the first inorganic modifier is selected from one or more of Cu, mg, zn, al, fe, ti, V, W and Mo oxides, silicides, borides or metal organic compounds, the first glass powder is zinc-boron-silicon-aluminum glass, and the main preparation raw materials of the glass are ZnO and B 2 O 3 、SiO 2 And Al 2 O 3 。
4. The wiring structure according to claim 3, wherein D of the first glass frit 50 1-3 μm, and softening point of 580-640 ℃.
5. The wiring structure according to claim 3, wherein the organic carrier is a composite of ethyl cellulose resin, acrylic resin, terpineol, and dodecanol ester.
6. The wiring structure according to claim 3, wherein a part of the metal wire is formed of a conductive silver paste including, in mass fraction: 78-83% of silver powder, 0.1-0.5% of second inorganic modifier, 2-5% of second glass powder and 11.5-21.9% of organic carrier.
7. The wiring structure according to claim 6, wherein the second inorganic modifier is one or a combination of more of oxides, silicides, borides, or metal-organic compounds of Cu, ti, V.
8. The wiring structure according to claim 7, wherein the second inorganic modifier is Cu 2 O、CuO、TiO 2 、V 2 O 5 One or more of (a) and (b).
9. The wiring structure according to claim 6, wherein the main material of the second glass frit is Bi 2 O 3 、B 2 O 3 、SiO 2 And Al 2 O 3 The proportion is Bi 2 O 3 60-80wt%、B 2 O 3 15-25wt%、SiO 2 5-12wt%、Al 2 O 3 0.5-5wt%。
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| CN202011622190.2A CN112786234B (en) | 2020-12-16 | 2020-12-31 | Metallic aluminum conductor paste, conductor paste and low-temperature co-fired dielectric ceramic material matched with same |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016096A1 (en) * | 1991-02-27 | 1992-09-17 | David Sarnoff Research Center, Inc. | Low temperature co-fired multilayer ceramic circuit boards with silver conductors |
| KR20030094774A (en) * | 2002-06-07 | 2003-12-18 | 한국과학기술연구원 | Dielectric ceramic composition and method for preparing dielectric ceramic for low temperature co-fired ceramic |
| TW575535B (en) * | 2003-01-28 | 2004-02-11 | Ruei-Ju Rau | Method for producing high precision multilayered ceramic component |
| CN102030477A (en) * | 2009-10-07 | 2011-04-27 | 旭硝子株式会社 | Ceramic material composition |
| CN102030471A (en) * | 2010-10-18 | 2011-04-27 | 南京工业大学 | Low-temperature cofiring glass and ceramic multilayer microcircuit substrate and preparation method thereof |
| CN102531392A (en) * | 2012-02-01 | 2012-07-04 | 云南云天化股份有限公司 | Low-temperature co-fired ceramic material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789456A (en) * | 2010-03-05 | 2010-07-28 | 西安宏星电子浆料科技有限责任公司 | Lead-free aluminum paste for solar battery |
| CN106328250A (en) * | 2015-06-29 | 2017-01-11 | 江苏正能电子科技有限公司 | Back-passivation solar cell aluminium paste |
| CN111312427B (en) * | 2020-04-17 | 2021-08-31 | 洛阳理工学院 | Silver paste for multilayer wiring for low-temperature co-fired low-dielectric-constant dielectric ceramic |
-
2020
- 2020-12-31 CN CN202210068231.0A patent/CN114394750B/en active Active
- 2020-12-31 CN CN202011622190.2A patent/CN112786234B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016096A1 (en) * | 1991-02-27 | 1992-09-17 | David Sarnoff Research Center, Inc. | Low temperature co-fired multilayer ceramic circuit boards with silver conductors |
| KR20030094774A (en) * | 2002-06-07 | 2003-12-18 | 한국과학기술연구원 | Dielectric ceramic composition and method for preparing dielectric ceramic for low temperature co-fired ceramic |
| TW575535B (en) * | 2003-01-28 | 2004-02-11 | Ruei-Ju Rau | Method for producing high precision multilayered ceramic component |
| CN102030477A (en) * | 2009-10-07 | 2011-04-27 | 旭硝子株式会社 | Ceramic material composition |
| CN102030471A (en) * | 2010-10-18 | 2011-04-27 | 南京工业大学 | Low-temperature cofiring glass and ceramic multilayer microcircuit substrate and preparation method thereof |
| CN102531392A (en) * | 2012-02-01 | 2012-07-04 | 云南云天化股份有限公司 | Low-temperature co-fired ceramic material and preparation method thereof |
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| CN112786234B (en) | 2022-01-07 |
| CN112786234A (en) | 2021-05-11 |
| CN114394750A (en) | 2022-04-26 |
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