CN112786234A - Metallic aluminum conductor paste, conductor paste and low-temperature co-fired dielectric ceramic material matched with same - Google Patents

Metallic aluminum conductor paste, conductor paste and low-temperature co-fired dielectric ceramic material matched with same Download PDF

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CN112786234A
CN112786234A CN202011622190.2A CN202011622190A CN112786234A CN 112786234 A CN112786234 A CN 112786234A CN 202011622190 A CN202011622190 A CN 202011622190A CN 112786234 A CN112786234 A CN 112786234A
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glass
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paste
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CN112786234B (en
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周世平
周纪平
温俊磊
马丹丹
李武
裴广斌
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Luoyang Zhongchao New Material Shares Co ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Glass Compositions (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a metallic aluminum conductor paste, a conductor silver paste matched with the paste and a low-temperature co-fired dielectric ceramic material. Wherein the metallic aluminum conductor paste comprises 0-20% of silver powder, 55-75% of aluminum powder, 0.1-2.0% of inorganic modifier, 0-8% of glass powder and 13.0-24.9% of organic carrier. The low-temperature co-fired dielectric ceramic material comprises 75-85% of calcium borosilicate crystalline glass and 15-20% of borosilicate modified glass. The low-temperature co-fired ceramic electronic device for multilayer wiring can be obtained by using the material of the invention, not only can a large amount of metal aluminum be used, but also the wiring is clear, the quality is stable, and the application requirements of the domestic low-temperature co-fired ceramic product are met.

Description

Metallic aluminum conductor paste, conductor paste and low-temperature co-fired dielectric ceramic material matched with same
Technical Field
The invention belongs to the technical field of materials, relates to a preparation method of metallic aluminum and aluminum silver conductor slurry and low-temperature co-fired ceramic, and belongs to the technical field of materials.
Background
The low temperature co-fired ceramic (LTCC) technology is widely applied to the miniaturization and chip-type of discrete components such as capacitors, resistors, inductors and transformers, and is also applied to the multilayer interconnection integration and multilayer interconnection packaging of LED and Surface Acoustic Wave (SAW) devices, rf, microwave and millimeter wave passive components such as Si, GaAs and InP, and circuits, and includes the system sip (system in package) packaging from the traditional packaging form to PGA, BGA, LCC, MCM-C, MCM-C/D, MEMS devices and module packaging. Various products based on the low-temperature co-fired ceramic technology are widely applied to the fields of computers, communication, automobiles, aerospace, biomedical treatment, illumination, Internet of things and the like. Is an important supporting technology for the rapid development of a plurality of fields of military and civilian nowadays.
In the low-temperature co-fired ceramic technology, the co-firing compatibility of the low-temperature co-fired low-dielectric-constant dielectric ceramic material with the wiring and the interconnection conductor plays a key role in the yield and reliability of the low-temperature co-fired ceramic product. At present, 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 markets in China. Murata, Kyocera, NEC, NGK, Tektronix, Westinghouse, IBM, Fujitsu, etc. all have their own unique LTCC porcelain systems. Numerous scientific research institutes and enterprises in China have been researched for a long time, but no mature and reliable commercialized product is provided yet, and the matched electronic paste system starts later and is researched less, and in actual production, the electronic paste systems of Dupont, Ferro, Heraus and ESL monopolize the Chinese market for a long time.
At present, the low-temperature co-fired dielectric ceramic and mixed conductor slurry systems of all gold, silver, palladium and the like are co-fired at 850-900 ℃. The compatibility and matching are realized by physical and chemical compatibility in the co-firing process. Effective measures need to be taken to control the shrinkage behavior of the metal conductor paste, adjust the expansion and other characteristics of the conductor paste system and reduce the system stress, otherwise, the defects of deformation, foaming, cracking, peeling and the like can occur. The noble metal gold is expensive, the co-firing temperature of the conventional LTCC is 850-900 ℃, the energy consumption is still high, and the cost pressure can be borne only in high-end fields such as military industry and the like. Although the cost of silver is lower than that of gold, Ag can generate oxidation-reduction reaction in the sintering, storage and use processes, and can also generate physical and chemical action with ceramic dielectric materials, so that the diffusion and migration of silver are caused, and holes and pores are formed on silver wires or silver conductor interconnection passages, so that the cross section is changed, the density is reduced, the conductivity is reduced, and even the phenomena of circuit blurring, disappearance of silver layers, wire breakage or reduction of the insulating property of adjacent wires, so that short circuit and the like are caused; meanwhile, silver enters the substrate material in a silver atom or silver ion state (silver absorption or silver impregnation) to cause the local yellowing phenomenon of the low-temperature co-fired ceramic, and even seriously affects the transformation and crystallization behaviors of glass in the low-temperature co-fired ceramic, thereby further affecting the dielectric property of the low-temperature co-fired ceramic. Whether gold or silver, the cost of the LTCC is still high for the civil field, so that the LTCC cannot be widely used in the related fields.
An excellent co-fired conductor paste must meet the following requirements: firstly, the electrical resistivity of the interlayer metal wire and the interconnection metal conductor is low, an excellent bonding matching structure can be formed with co-fired ceramic, and the surface layer conductor is required to have excellent weldability and welding resistance; secondly, the long-term reliability under various severe conditions is fully guaranteed; thirdly, silver diffusion of a silver-containing system in the preparation process of the low-temperature co-fired ceramic is inhibited and eliminated, the problems of open circuit, short circuit, reduction of insulation resistance and the like of wiring in a layer and interconnection between layers are avoided, and the problems of power loss, signal crosstalk and the like in the signal transmission process are eliminated; and fourthly, the performance degradation of the low-temperature co-fired ceramic product during storage and use is eliminated.
From the practical application, no matter Dupont, Ferro, Heraus or ESL low-temperature co-fired ceramic green tape systems, the low-temperature co-fired ceramic green tape systems have unique all-gold series, all-silver series or gold-silver mixed series electronic paste matched with the low-temperature co-fired ceramic green tape systems, and electronic paste with the same function and the same application, including conductor paste for multilayer wiring, is not universal or interchangeable. At present, Dupont and Ferro ceramic green tapes and matched slurry are mainly adopted in many domestic low-temperature co-fired ceramic products. The domestic practical products in the related fields do not form a system of the products, and are mostly in the research and development stage. In the aspect of electronic paste, published chinese patent, application No.: 201610411085.1 'preparation method of silicon dioxide coated copper electronic paste for LTCC substrate', sintering of which needs nitrogen protection and is not the mainstream technology in the field at present; application No.: 201811505300.X 'hole-filling conductor slurry for low-temperature multilayer co-fired ceramic LTCC', which is characterized in that conductor filling of low-temperature co-fired ceramic is realized by using an environment-friendly plasticizer, and is not suitable for multilayer wiring conductors. Application No.: 201010186567.4 'leadless solder-resistant all-silver conductor paste' is mainly used for thick film network resistors and is not suitable for the process requirement of low temperature co-fired ceramics. Application No.: 201910312643.2A conductive silver paste for low temperature sintering LTCC solves the problem that DuPont slurry is not matched with self-made LTCC ceramic in sintering, the sintering temperature is 600-650 ℃, and the conductive silver paste is mainly matched with capacitor ceramic in use.
In the invention, a 850- -; IBM, Fujitsu, Murata, Kyocera adopt a copper co-firing technology under a nitrogen atmosphere, but must be matched with an anti-reduction LTCC ceramic material system; few enterprises adopt a low-temperature silver paste and special-purpose porcelain co-firing technology, the application scenes of the method are few, and the problems of silver diffusion and migration are not fundamentally improved and eliminated.
CN06904970A W-based ultralow temperature co-fired microwave dielectric ceramic material and the preparation method thereof, the sintering temperature of the ceramic material in the preparation method is 580-630 ℃; CN108911746A 'A low-loss ultralow-temperature sintered microwave dielectric ceramic material, and the preparation method and application thereof' the sintering temperature of the ceramic material is 560-; CN 103951413A' ultralow temperature sintered microwave dielectric ceramic Li3V2PO9The sintering temperature of the porcelain in the preparation method is 600-630 ℃; CN101805186A 'an ultra-low sintering temperature microwave dielectric ceramic material and a preparation method thereof', the material can be sintered at 500-850 ℃; CN104876568A vanadium-based temperature-stable ultralow-temperature sintering microwave dielectric ceramic material and the preparation method thereof, wherein the material sintering temperature in the preparation method is 575-650 ℃; TW201200489A1 "ultra-low temperature sintered microwave dielectric ceramic" with Te2(Mo1-xWx)O7Is a main crystal phase and can be sintered at 480-540 ℃, but Te is a highly toxic substance. The possibility of realizing co-firing with base metal aluminum paste within a certain temperature range (580-; in addition, these ultra low temperature co-fired ceramic (ULTCC) systems using phosphates, molybdates, tungstates, etc. as main crystalline phases are compounds having strong water absorption, and have great problems in weather resistance and chemical stability, and have a great distance from practical use. And the Te-containing system has high toxicity and does not accord with the current industrial development policy.
In summary, the invention of the low-cost high-performance aluminum paste for LTCC and the aluminum-containing low-silver conductor co-firing system has not been reported in the prior art. The invention adopts a unique technical path to prepare 580-680 ℃ low-temperature sintered aluminum paste and 640-750 ℃ medium-temperature sintered aluminum paste, and can be used for multilayer wiring of LTCC; silver pastes are prepared that match the outer solderable and gold platable layers. At the same time, an 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 of below 720 ℃ is successfully developed.
Disclosure of Invention
In order to meet the application requirements and future development of domestic low-dielectric-constant low-temperature co-fired ceramic, the invention aims to provide aluminum paste, aluminum paste and outer weldable and gildable silver paste for multilayer wiring of low-temperature co-fired low-dielectric-constant dielectric ceramic, wherein a conductor system can be co-fired with a microcrystalline glass and glass ceramic composite system low-temperature co-fired ceramic green tape at the temperature below 720 ℃, and the conductor and a ceramic material system have excellent matching performance. The multilayer wiring structure manufactured by the method inhibits and eliminates the silver diffusion phenomenon of an all-silver system. The conductor system partially or completely realizes the base cost, the porcelain material system overcomes the problems of poor weather resistance and chemical stability of an ULTCC (ultra-low temperature co-fired ceramic) system which takes phosphate, molybdate, tungstate and the like as main crystal phases, and simultaneously greatly reduces the sintering temperature of LTCC (low temperature co-fired ceramic) such as a boron-calcium crystallized glass system and the like. Through the reduction of material cost and energy consumption, the competitiveness of the LTCC is improved.
In order to achieve the purpose, the invention adopts the specific scheme that:
a metallic aluminum, aluminum silver conductor paste, comprising by mass: 0 to 20 percent of silver powder, 55 to 75 percent of aluminum powder, 0.1 to 2.0 percent of inorganic modifier, 0 to 8 percent of glass powder and 13.0 to 24.9 percent of organic carrier.
In the invention, the silver powder can be optionally added according to the requirement to adapt to the adjustment of the sintering temperature, the sintering temperature is increased, and the using amount of the silver powder can be correspondingly increased. The silver powder is preferably used in an amount of 1 to 15%, more preferably 1 to 10%. Preferably spherical silver powder, D thereof50Is 0.5 to 5 μm, more preferably 2 to 4 μm. The aluminum powder is preferably spherical aluminum powder, D thereof50Preferably 3-5 μm.
D of the inorganic modifier50Typically between 0.5 and 4 μm, preferably 1 to 3 μm; it is selected from one or more of the oxides, silicides, borides or metal organic compounds of Cu, Mg, Zn, Al, Fe, Ti, V, W and Mo, with oxides being preferred. The same effect can be achieved by decomposing the metal organic compound into oxide in the co-firing process. In the invention, the inorganic modifier plays an important role, can reduce the shrinkage rate of the conductor slurry and adjust the shrinkage rate of the conductor slurry in the co-firing process, promotes the sintering densification of the conductor slurry, and ensures that the thermodynamic and kinetic properties of the conductor slurry are consistent with those of a low-temperature co-fired low-dielectric-constant dielectric ceramic material in the sintering process; simultaneously, the glass can flow and permeate in the low-temperature co-firing processThe diffusion plays a role in stopping; the diffusion of silver may also be inhibited or eliminated.
In the specific embodiment of the invention, the zinc-boron-silicon-aluminum glass powder prepared by the applicant is used, and the main preparation raw materials of the glass are ZnO and B2O3、SiO2And Al2O3. In a typical embodiment of the present invention, the ratio of each component is 45 to 55 wt% ZnO, B2O3 30-40wt％、SiO2 10-18wt％、Al2O30.5-5 wt%. A typical embodiment of the invention uses 50 wt% ZnO, 35 wt% B2O313 wt% and SiO2 2wt％Al2O3The proportion of (A) and (B). The conductor paste can be well bonded to the ceramic material using a lead-free and alkali-free glass. Glass powder of D50Is 0.5 to 10 μm, preferably 1 to 3 μm, and the softening point is preferably 580-640 ℃. However, the glass frit that can be used in the present invention is not limited thereto, and those skilled in the art can select other kinds of glass frits.
In a typical embodiment of the present invention, an organic vehicle, which is self-made by the applicant, is used. The organic carrier provides good controllability of solvent evaporation rate and thixotropy. The organic carrier adopts a composite system of ethyl cellulose resin, acrylic resin, terpineol and decaglycol ester, and the preferable mixture ratio is that the mass ratio of the ethyl cellulose resin to the acrylic resin to the terpineol to the decaglycol ester is 5-15: 1-6: 50-80: 5-10. Other suitable organic carriers can also be found by those skilled in the art.
In a second aspect of the present invention, there is provided a solderable and gold-platable outer silver paste comprising, in mass percent: 78-83% of silver powder, 0.1-0.5% of inorganic modifier, 0-5% of glass powder and 11.5-21.9% of organic carrier.
In a specific embodiment, the silver powder is a spherical silver powder, D thereof50Is 1-4 μm, preferably 2-3 μm. D of the inorganic modifier50Is 0.5 to 4 μm, preferably 1 to 3 μm. The inorganic modifier is one or the combination of more of Cu, Ti and V oxide, silicide, boride or metal organic compound. Typical oxides include Cu2O、CuO、TiO2、V2O5。
In the specific embodiment of the invention, the bismuth borosilicate glass powder manufactured by the applicant is used, and the main preparation raw material of the glass is Bi2O3、B2O3、SiO2And Al2O3. In a typical embodiment of the present invention, the ratio of each component is Bi2O3 60-80wt％、B2O3 15-25wt％、SiO2 5-12wt％、Al2O30.5-5 wt%. A typical embodiment of the present invention uses 70 wt% Bi2O3、20wt％B2O3、8wt％SiO2And 2 wt% Al2O3The proportion of (A) and (B). The lead-free and alkali-free glass can be used for well bonding the conductor paste and the ceramic material. Glass powder of D500.5-4 μm, preferably 1-3 μm, and a softening point of preferably 580-640 ℃, preferably 560-620 ℃. However, the glass frit that can be used in the present invention is not limited thereto, and those skilled in the art can select other kinds of glass frits.
In a typical embodiment of the present invention, an organic vehicle, which is self-made by the applicant, is used. The organic carrier provides good controllability of solvent evaporation rate and thixotropy. The organic carrier adopts a composite system of ethyl cellulose resin, acrylic resin, terpineol and decaglycol ester, and the preferable mixture ratio is that the mass ratio of the ethyl cellulose resin to the acrylic resin to the terpineol to the decaglycol ester is 5-15: 1-6: 50-80: 5-10. Other suitable organic carriers can also be found by those skilled in the art.
The third aspect of the invention provides a low-temperature co-fired dielectric ceramic material, which comprises the following components in percentage by mass: 75-85% of calcium borosilicate crystal glass and 15-20% of borosilicate modified glass.
In an exemplary embodiment of the present invention, the calcium borosilicate crystalline glass is composed mainly of SiO by mass225-32％，B2O315-25%, CaO 28-42%, calcium phosphate 2-7%, ZrO21-5 percent of the composition. The formulation used in the exemplary embodiment of the present invention is SiO2 28％，B2O3 20％，CaO 34％5% of calcium phosphate, ZrO2 3％。
In an exemplary embodiment of the invention, the borosilicate-modified glass consists essentially of B by mass2O3、SiO2And Al2O3And (4) forming. The percentage composition of which is usually in the range of B2O3 38-50％、SiO2 45-56％、Al2O30.5 to 2 percent. As a further optimization, Li may be added in an amount not exceeding 10% in total2O、Na2O、K2O, ZnO, respectively. Preferably comprising Li2O 1.0-2.0％、Na2O 0.5-1.5％、K2O1.0-2.5% and ZnO 0.5-1.5%. One embodiment of the present invention uses composition B2O3 43.0％、SiO2 51.0％、Al2O3 1.0％、Li2O 1.5％、Na2O 1.0％、K2O1.5% and ZnO 1.0%.
In one embodiment, the calcium borosilicate crystalline glass has a softening point at 850 ℃ D501-4 μm, preferably 2-3 μm; the glass melting temperature is 1450 ℃, and the temperature is kept for 1 hour.
The low-temperature co-fired ceramic dielectric material green tape obtained by the composition can be co-fired with various conductor pastes at 580-720 ℃ to form a multilayer wiring structure, has excellent matching performance, has clear conductor patterns, can meet the use requirements of the civil field on LTCC (low-temperature co-fired ceramic) substrates and devices, and greatly reduces the manufacturing and use cost of products.
According to the multilayer wiring structure obtained by the invention, the conductor takes aluminum as a main material, and the 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 does not turn yellow, the bad silver diffusion phenomenon is inhibited and eliminated, and the conductor does not have the defects of short circuit, open circuit and the like; no failure modes such as cracking, warping, foaming, delamination and the like occur. The slurry system for multilayer wiring can meet the application requirements of domestic low-dielectric-constant low-temperature co-fired ceramics, and promotes the autonomy and the domestic process of the field of low-temperature co-fired ceramic products in China.
Detailed Description
The following examples are given to illustrate the embodiments of the present invention.
In the examples below, the viscosity measurements were carried out according to the test method for noble metal pastes for GB/T17473.5-1998 thick-film microelectronics; the sheet resistance is determined according to a method for testing noble metal slurry used in GB/T17473.3-2008 microelectronic technology; the fineness measurement is carried out according to a method for testing the noble metal slurry used in the GB/T17473.2-2008 microelectronic technology.
In the preparation of the LTCC dielectric ceramic system, the used calcium borosilicate crystalline glass is subjected to heat preservation for 1 hour at the melting temperature of 1450 ℃, and is quenched in deionized water, ball-milled and dried for later use. Softening point 850 ℃, D501-4 μm, preferably 2-3 μm; the borosilicate modified glass is subjected to heat preservation for 1 hour at the glass melting temperature of 1500 ℃. Quenching in deionized water, and then ball-milling and drying by using absolute ethyl alcohol for later use, wherein the softening point of the glass is 480-550 ℃; the low-temperature co-fired ceramic green tape which can meet the screen printing is obtained by casting molding according to the proportion.
The qualified metal aluminum and aluminum silver conductor paste is used for printing LTCC low-temperature co-fired ceramic green tape multilayer wiring patterns and interconnection through holes. The qualified silver conductor paste of the outer layer which can be welded and plated with gold is used for manufacturing the sheet resistance test patterns of the surface layer and the bottom layer, and the sheet resistance test patterns are printed by a precise screen printer and connected with the multilayer wiring patterns between layers through vertical interconnection conductors. After lamination, lamination and cutting, the materials are co-fired at 580-720 ℃. The co-fired multilayer ceramic is used for testing the sheet resistance of the surface and the bottom silver layer and the on-off test of multilayer interconnection. The test sample was a four-layer structure.
The thickness of the low-temperature co-fired ceramic green tape is 125 mu m, the test patterns of the top layer and the bottom layer and the wiring patterns of the inner layer are printed by 325-mesh stainless steel nets (the thickness of the photosensitive glue film is 25 mu m), and the interlayer interconnection filling is printed by 325-mesh stainless steel nets (the thickness of the photosensitive film is 35 mu m) on a printer with a negative pressure hole filling device to fill the through holes.
Example 1
The materials are prepared according to the following mass percentages: 70 wt% of spherical aluminum powder, 2 wt% of silver powder and 6 wt% of zinc-boron-silicon-aluminum glass powder (containing 50 wt% of ZnO and 35 wt% of B)2O3、13wt％SiO2And 2 wt% Al2O3) Inorganic modifier TiO2 0.5wt％、MoSi20.2 wt% and 21.3 wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin terpineol: the mass ratio of the decaglycol ester is 10: 2: 80: 8. the viscosity of the slurry prepared by the processes of material preparation, wet stirring dispersion, three-roll mill rolling, 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 percent. The inner conductor used in the four-layer co-fired test sample was prepared, and the test results are shown in table 1.
Example 2
The materials are prepared according to the following mass percentages: 75 wt% of spherical aluminum powder, 8 wt% of zinc-boron-silicon-aluminum glass powder (same as example 1) and inorganic modifier TiB2 0.3wt％、V2O50.1 wt% and 16.6 wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin terpineol: the mass ratio of the decaglycol ester is 8: 2: 82: 8. the slurry preparation method is as described above. The viscosity of the prepared 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 inner conductor used in the four-layer co-fired test sample was prepared, and the test results are shown in table 1.
Example 3
According to 80 wt% of spherical silver powder, 0.2 wt% of inorganic modifier CuO and TiO20.5 wt% and 2.0 wt% of a bismuth-boron-silicon glass frit (containing 70 wt% of Bi)2O3、20wt％B2O3、8wt％SiO2And 2 wt% Al2O3) 17.3 wt% of organic carrier. The proportion of the organic carrier is ethyl cellulose resin: acrylic resin terpineol: the mass ratio of the decaglycol 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 prepared 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 co-fired test sample was prepared, and the test results are shown in table 1.
Table 1 test results of examples 1 to 3
Figure BDA0002878562650000071
Example 4
The calcium borosilicate crystal glass (containing SiO)2 28％，B2O320%, CaO 34%, calcium phosphate 5%, ZrO 23%), smelting at 1450 deg.C for 1 hr, quenching in deionized water, oven drying, heat treating at 750 deg.C for 15 min, ball milling, oven drying, softening point at 850 deg.C, and D502.1 μm; borosilicate-modified glass (containing B)2O3 43.0％、SiO2 51.0％、Al2O3 1.0％、Li2O 1.5％、Na2O 1.0％、K21.5 percent of O and 1.0 percent of ZnO), the glass melting temperature is 1500 ℃, the temperature is kept for 1 hour, the glass is ball milled and dried for standby after being quenched in deionized water, the softening point is 480-502.0 μm; in order to detect the dielectric property of the ceramic material, LTCC dielectric ceramic powder is obtained by weighing 80 wt% of calcium borosilicate crystal glass and 20 wt% of borosilicate modified glass, and the LTCC dielectric ceramic powder is subjected to ball milling, granulation and dry pressing to obtain a phi 16 multiplied by 3 ceramic green body, and the ceramic green body is sintered at 720 ℃ for 30 minutes. And printing silver paste on the sintered porcelain body, and sintering, infiltrating and preserving heat at 530 ℃ for 10 minutes to obtain a test sample. The dielectric properties were tested with an AV2782LCR tester. The dielectric constant at 1MHz was 6.5 and the dielectric loss was 2.56X 10-4And the detection result shows that the porcelain can be transferred to the tape casting stage. Tape casting to form dielectric ceramic powder according to mass ratio: casting binder 52: 48 adding a casting binder. Ball milling, mixing, defoaming and tape casting to obtain the low temperature co-fired ceramic green tape. The ceramic dielectric layer 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 borosilicate crystal glass (same as example 4) is melted at 1450 ℃ and is preserved for 1 hour, quenched in deionized water and then dried, then is thermally treated at 750 ℃ for 5 minutes, and then is ball-milled and dried for standby, the softening point is 850 ℃, and D502.1 μm. The borosilicate-modified glass used (same as in example 4) was incubated at a glass melting temperature of 1500 ℃ for 1 hour. Quenching in deionized water, ball milling, drying, and softeningThe point is 480-550 ℃. In order to detect the dielectric property of the ceramic material, LTCC dielectric ceramic powder is obtained by weighing 70 wt% of calcium borosilicate crystalline glass and 30 wt% of borosilicate modified glass, and the LTCC dielectric ceramic powder is subjected to ball milling, granulation and dry pressing forming to obtain a ceramic green body with phi 16 multiplied by 3, and the ceramic green body is sintered at the temperature of 660 ℃ and the heat preservation time is 30 minutes. And printing silver paste on the sintered porcelain body, and sintering, infiltrating and preserving heat at 530 ℃ for 10 minutes to obtain a test sample. The dielectric properties were tested with an AV2782LCR tester. The dielectric constant at 1MHz was 6.0 and the dielectric loss was 5.20X 10-4. The detection result shows that the porcelain can be transferred to the tape casting stage. Tape casting to form dielectric ceramic powder according to mass ratio: casting binder 52: 48 adding a casting binder. Ball milling, mixing, defoaming and tape casting to obtain the low temperature co-fired ceramic green tape. LTCC screen printed ceramic dielectric layers may be used. The porcelain test results are shown in table 2.
TABLE 2 test results for the porcelain made in examples 5 and 6
Figure BDA0002878562650000081
Example 6
By adopting a standard multilayer ceramic production process, taking the low-temperature co-fired ceramic green tape prepared in the embodiment 4 as a dielectric layer, and printing inner layer patterns and first to fourth layers of interconnection through holes on the second and third layers of green tapes by using the aluminum paste prepared in the embodiment 1; the silver paste prepared in example 3 was used to print a pattern on the top surface (first layer) and the bottom layer (fourth layer). Laminating, sintering at 700 deg.C peak temperature, and holding for 30 min. The results of the finished product testing are shown in table 3.
Example 7
By adopting a standard multilayer ceramic production process, taking the low-temperature co-fired ceramic green tape manufactured in the embodiment 4 as a dielectric layer, and printing inner layer patterns and interconnection through holes as well as the through holes of the first layer and the second layer on the second layer green tape and the third layer green tape by using the aluminum paste manufactured in the embodiment 2; the silver paste prepared in example 3 was used to print a pattern on the top surface (first layer) and the bottom layer (fourth layer). The layers were laminated, then fired at a peak temperature of 650 ℃ for 30 minutes. The results of the finished product testing are shown in table 3.
Table 3 examples 6 and 7 test results
Figure BDA0002878562650000091
The invention adopts the unique preparation method of the metallic aluminum and aluminum silver conductors and the low-temperature co-fired ceramic, realizes the co-firing at 580-one-step temperature of 720 ℃, realizes that the inner conductor is cheap and has excellent matching performance, the sintering temperature of the ceramic material system is lower than that of the current LTCC ceramic material by more than 100 ℃, can meet the use requirements of the civil field on LTCC (low temperature co-fired ceramic) substrates and devices, and greatly reduces the manufacturing and using cost of the product.
The present invention is not described in detail in the prior art.
The embodiments chosen for the purpose of this invention are to be considered as illustrative and not restrictive, the scope of the invention being indicated by the claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.

Claims (12)

1. A metallic aluminum conductor paste comprising, by mass: 0 to 20 percent of silver powder, preferably 1 to 10 percent of aluminum powder, 55 to 75 percent of aluminum powder, 0.1 to 2.0 percent of inorganic modifier, 0 to 8 percent of glass powder and 13.0 to 24.9 percent of organic carrier.
2. The metallic aluminum conductor paste of claim 1, the inorganic modifier selected from one or more of oxides, silicides, borides, or metal-organic compounds of Cu, Mg, Zn, Al, Fe, Ti, V, W, and Mo.
3. The metallic aluminum conductor paste as claimed in claim 1, wherein the glass powder is a zinc-boron-silicon-aluminum glass, and the glass is prepared from ZnO and B as main raw materials2O3、SiO2And Al2O3Preferred ratio of componentsZnO45-55 wt%, B2O330-40wt％、SiO210-18wt％、Al2O30.5-5wt％。
4. The metallic aluminum conductor paste as set forth in claim 1, D of the glass frit501-3 μm, and the softening point is preferably 580-640 ℃.
5. The metallic aluminum conductor paste as claimed in claim 1, wherein the organic vehicle is a composite of ethyl cellulose resin, acrylic resin, terpineol and decaglycol ester, and the preferred mixture ratio is that the mass ratio of the ethyl cellulose resin to the acrylic resin to the terpineol to the decaglycol ester is 5-15: 1-6: 50-80: 5-10.
6. An outer layer weldable and gold-plated conductor silver paste comprises the following components in percentage by mass: 78-83% of silver powder, 0.1-0.5% of inorganic modifier, 0-5% of glass powder and 11.5-21.9% of organic carrier.
7. The conductor silver paste of claim 6, wherein the inorganic modifier is one or more of an oxide, silicide, boride or organometallic compound of Cu, Ti, V, preferably Cu2O、CuO、TiO2、V2O5One or more of (a).
8. The conductor silver paste of claim 6, wherein the main preparation raw material of the glass powder is Bi2O3、B2O3、SiO2And Al2O3The preferred proportion is Bi2O360-80wt％、B2O315-25wt％、SiO25-12wt％、Al2O30.5-5 wt.%, preferably D501-3 μm, and the softening point is preferably 580-640 ℃, more preferably 560-620 ℃.
9. A low-temperature co-fired dielectric ceramic material comprises the following components in percentage by mass: 75-85% of calcium borosilicate crystalline glass and 15-20% of borosilicate modified glass.
10. The low temperature co-fired dielectric ceramic material of claim 9, wherein the calcium borosilicate crystallized glass consists essentially of SiO by mass225-32％，BO315-25%, CaO 28-42%, calcium phosphate 2-7%, ZrO21-5 percent of the composition.
11. The low temperature co-fired dielectric ceramic material of claim 9, wherein the borosilicate-modified glass consists essentially of B by mass2O3SiO and Al2O3Composition, preferably in mass percent B2O338-50％、SiO245-56％、Al2O30.5-2％。
12. The low temperature co-fired dielectric ceramic material of claim 11, further comprising up to 10% total Li2O3、Na2O、K2O, ZnO, preferably containing Li2O31.0-2.0％、Na2O0.5-1.5％、K2O1.0-2.5% and ZnO 0.5-1.5%.
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