CN114783652A - Gold conductor wiring slurry co-fired with microwave dielectric ceramic at low temperature and preparation method thereof - Google Patents

Gold conductor wiring slurry co-fired with microwave dielectric ceramic at low temperature and preparation method thereof Download PDF

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CN114783652A
CN114783652A CN202210476507.9A CN202210476507A CN114783652A CN 114783652 A CN114783652 A CN 114783652A CN 202210476507 A CN202210476507 A CN 202210476507A CN 114783652 A CN114783652 A CN 114783652A
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gold
fired
conductor wiring
temperature
slurry
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CN114783652B (en
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代胜强
周世平
裴广斌
周纪平
温俊磊
马丹丹
孙闯
赵岩
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Luoyang Zhongchao New Material Shares Co ltd
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Luoyang Zhongchao New Material Shares Co ltd
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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
    • 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
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

The invention discloses a gold conductor wiring paste co-fired with microwave dielectric ceramic at a low temperature and a preparation method thereof, belonging to the technical field of electronic paste. The gold conductor wiring slurry consists of 70-83 wt% of gold powder, 1-5 wt% of glass powder, 0.5-1 wt% of inorganic modifier and 15-24.5 wt% of organic carrier, is co-fired with the calcium-boron-silicon microcrystalline glass at the low temperature of 830-870 ℃, can present good resolution, conductivity and bonding strength, and can meet the requirements of industrialization of low-temperature dielectric ceramics.

Description

Gold conductor wiring slurry co-fired with microwave dielectric ceramic at low temperature and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic paste, and particularly relates to gold conductor wiring paste co-fired with microwave dielectric ceramic at a low temperature and a preparation method thereof.
Background
With the rapid development of microelectronics and nanoelectronics, miniaturization, weight reduction, integration and multilayering of components and circuits have become a great trend. The development of electronic paste technology adapted to the above is more and more advanced, and at present, there are metallic pastes of aluminum, copper, nickel, molybdenum, tungsten, ruthenium, silver, gold, etc., and some composite metallic pastes. Gold conductor pastes are increasingly used in the field of electronics, in particular in the field of military electronics, and especially in the field of highly reliable and high-frequency LTCC (low temperature co-fired ceramic) applications. However, the development of LTCC product technology in China is at least 20 years later than that of developed countries abroad, and the gap is larger particularly in the aspects of LTCC materials and matched slurry thereof.
The conductor metal used in the electronic paste has the highest conductivity of silver, and the second conductivity of copper, and the second conductivity of gold, but the gold has much higher chemical corrosion resistance and discoloration resistance than silver and copper in the normal condition, and does not melt, discolor, oxidize or ablate at the high temperature of 1000 ℃; therefore, the gold paste has higher chemical stability and the capability of working in a harsh environment. At present, the problem of mismatch of co-firing still exists between the slurry and the substrate in China, in the co-firing process of the slurry and the green tape, the matching between the substrate and the slurry is mutually influenced, but the former has stronger selectivity to the latter, and for the surface solderable gold conductor slurry, if the initial shrinkage temperature and the shrinkage rate of the slurry and the green tape are obviously different from those of the green tape, the problems of warping, layering, curling and the like occur in the sintering process of the printed substrate, and the electrical property of the conductive gold slurry is influenced; particularly, the resolution of the current commercialized conductive gold paste is about 100 μm, which cannot meet the development requirement of the LTCC field. Therefore, high printing resolution, high co-firing matching and high wiring density are inevitable trends in the development of gold paste.
At present, the research on gold paste in China, patent CN 112735631A, the paste viscosity of low-viscosity organic gold paste which can be sintered on the surface of a circuit board substrate at low temperature is too low to be suitable for multilayer wiring conductors. Patent CN 110322983a, "a sintered electronic conductive gold paste and its preparation method" is only suitable for post-firing conductor process of sintered ceramic such as HIC, thermistor, silicon oxide, silicon nitride ceramic, and is not suitable for low-temperature co-fired ceramic, patent CN 104157326a "a paste applied to low-temperature co-fired ceramic inner electrode conductive gold paste and its preparation method" is suitable for inner conductor not suitable for wiring conductor, patent CN109087723A "a gold conductive paste and its preparation method" is only suitable for "Al gold paste2O3+CaZrO3The paste viscosity in the lead borosilicate glass ceramic system patent CN 113314252A, a resin gold conductor paste, is low and is only suitable for the use requirement of partial thick film printing process, and the patent CN104200865A, a surface conductive gold paste applied to low-temperature co-fired ceramic and a preparation method thereof, whether SrCaO exists or not3This compound is problematic and the printing resolution of the paste is low.
Although the printing resolution of the LTCC thick film process reaches 100/100 micrometers (line width/space), even 70/70 micrometers, the printing resolution is difficult to reach 40/40 micrometers or less, and the advantages of high conductivity, high adhesive force and good matching performance are not appeared.
Therefore, in order to meet the requirement of matching the low-temperature co-firing development of microwave dielectric ceramics, the development of gold conductor wiring slurry which has good co-firing matching property with a self-made green tape, high conductivity, high adhesive force and high resolution is urgently needed.
Disclosure of Invention
The invention aims to provide gold conductor wiring slurry co-fired with microwave dielectric ceramic at a low temperature, which consists of 70-83 wt% of gold powder, 1-5 wt% of glass powder, 0.5-1 wt% of inorganic modifier and 15-24.5 wt% of organic carrier; the microwave dielectric ceramic is a calcium-boron-silicon microcrystalline glass system, and the low-temperature co-firing temperature is 830-870 ℃.
In some embodiments, the glass frit component is a calcium magnesium boro-alumino-silicate glass comprising an alkali metal oxide and a rare earth oxide; the glass powder comprises CaO and B2O3、SiO2、Al2O3、MgO、SrO、ZnO、Bi2O3、Li2O、Na2O、K2O and rare earth oxide, wherein CaO and B2O3、SiO2The calcium-boron-silicon glass is a main component of a calcium-boron-silicon glass system, and other components are used for improving and adjusting various performance parameters of the whole glass system; wherein, Al2O3The ZnO acts as a stabilizing system, the ZnO acts as a nucleating function, and the components with different contents can adjust the transition point temperature, the crystallization degree and the like of the glass; the rare earth oxide comprises La2O3、CeO2And Y2O3One or more of the above;
in some preferred embodiments, the glass powder comprises 10-15 wt% of CaO and B2O3 20～30wt％、Al2O35～15wt％、MgO 1～2wt％、SrO 0.1～1wt％、ZnO 0.5～2wt％、Bi2O30.1～1wt％、Li2O 1～2wt％、Na2O 1～4wt％、K21-2 wt% of O, 0.1-1 wt% of rare earth oxide and the balance of SiO2。
In some preferred embodiments, D of the glass frit50Between 1 to 3 μm; the transition temperature of the glass powder is 650-750 ℃, and the softening point is 700-800 ℃.
In some embodiments, the gold powder is spherical gold powder with a particle size selection D100.1 to 1.0 μm, D500.8 to 1.5 μm, D90Between 1.2 to 2.5 μm and D100Gold powder with a particle size of less than or equal to 5 mu m.
In some embodiments, the organic vehicle comprises the following ingredients: 40-60 wt% of terpineol, 20-50 wt% of butyl carbitol, 5-15 wt% of ethyl cellulose resin, 1-5 wt% of acrylic resin and 1-5 wt% of auxiliary agent. The formula of the adopted organic carrier is easy to regulate and control, and has good thixotropy.
In some embodiments, the adjuvants include dispersants, defoamers, rheology adjuvants, leveling agents, solubilizing plasticizers;
in some preferred embodiments, wherein the dispersant comprises: hindered alkanolamine compounds with open chain NOR comprising: one or more of piperazinone NOR, piperazine NOR, seven-membered heterocyclic NOR, Tego Dispery-650, Tego Dispery-651, Tego Dispery-652, BYK-102, OP-8018 and OP-8146;
the defoaming agent comprises: OP-8150, BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-065, XP-1273, n-hexanol and/or n-butanol;
the rheological aid comprises: hamming Nuosperse FA196, hydrogenated castor oil, soybean lecithin, vaseline, fish oil, span 80, span 85, BYK410, or mixture thereof;
the solubilizing plasticizer comprises: one or more of dibasic ester (DBE), tributyl citrate and tributyl phosphate;
the leveling agent comprises: 1, 4-gamma butyrolactone and/or BYK-163.
In some preferred embodiments, the content of the auxiliary in the organic carrier is as follows:
0.5 wt% Tego Dispery-650, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
0.5 wt% Tego Dispery-651, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
or
0.5 wt% seven membered heterocyclic NOR, 1 wt% dibasic ester (DBE), 1 wt% Hamming Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone.
In some preferred embodiments, the inorganic modifier is a solid oxide of a metal or nonmetal, including: CoO, Co2O3、Co3O4、SiO2、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、MgO、CuO、Cu2O、ZrO2Any one or more of the above; the average particle size of the inorganic modifier is 1-3 mu m. The inorganic modifier is added to reduce the shrinkage rate of the conductor slurry during sintering, the shrinkage rate is controlled and regulated through the control of the addition amount, the types of the added substances and the interaction, so that the low-temperature co-fired dielectric ceramic material is subjected to matching co-firing, and the conductor slurry is more densified after sintering.
The invention also provides a preparation method of the gold conductor wiring slurry co-fired with the microwave dielectric ceramic at the low temperature, which comprises the following steps:
1) screening gold powder raw materials with required particle size distribution by particle size classification;
2) mixing the organic carrier according to the component proportion, heating and stirring until the organic carrier is completely dissolved, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s;
3) preparing glass powder according to the proportion, uniformly mixing, smelting at 1400-1550 ℃ for 1h, quenching with deionized water, drying, and crushing with ethanol as a solvent to obtain a particle size D50Glass powder within the range of 1-3 mu m;
4) mixing and grinding the intermediate material obtained in the steps 1), 2) and 3) and an inorganic modifier in proportion for 10-30 min, and then rolling for 1-2 h by using a three-roll mill to obtain gold conductor wiring slurry;
the dispersion fineness of the slurry is less than or equal to 5 mu m, and the viscosity is between 100 and 200 Pa.s.
In addition, the invention relates to a method for preparing gold conductor wiring slurry on microwave dielectric ceramic by low-temperature co-firing, which comprises the steps of printing the gold conductor slurry on the surface of a ceramic green tape, and co-firing at 830-870 ℃ after lamination, lamination and cutting; and before the co-firing operation, cleaning and pretreating the printed gold conductor paste film layer by using ethanol or acetone.
Has the beneficial effects that:
the invention provides a preparation method of a wiring gold paste for low-temperature co-firing of microwave dielectric ceramics, which meets the requirements of gold conductor wiring paste matched with domestic microwave dielectric ceramics and solves the problems of low printing resolution and low yield.
Drawings
FIG. 1 is a paste print image;
FIG. 2 is a screen printed image of the gold paste prepared in example 1 with a resolution of 40 μm/40 μm;
FIG. 3 is a screen printed image of the gold paste prepared in example 2, with a resolution of 40 μm/80 μm;
FIG. 4 is a screen printed image of the gold paste prepared in comparative example 1, with a resolution of 100 μm/100 μm;
FIG. 5 is a screen printed image of gold paste prepared in comparative example 2 with a resolution of 200 μm/200 μm;
FIGS. 6 and 7 are screen-printed images of comparative example 2 printed with a high resolution of 40 μm/40 μm.
Detailed Description
The percentages mentioned in the following are all percentages by mass unless otherwise specified.
The gold conductor wiring paste is co-fired with microwave dielectric ceramic at a low temperature, and consists of 70-83 wt% of gold powder, 1-5 wt% of glass powder, 0.5-1 wt% of inorganic modifier and 15-24.5 wt% of organic carrier;
the ceramic is calcium-boron-silicon microcrystalline glass, and the low-temperature co-firing temperature is 830-870 ℃.
In one embodiment, the glass powder component is calcium-magnesium-boron-silicon-aluminum series glass containing alkali metal oxide and rare earth oxide; the glass powder comprises CaO and B2O3、SiO2、Al2O3、MgO、SrO、ZnO、Bi2O3、Li2O、Na2O、K2O and rare earth oxides; the rare earth oxide comprises La2O3、CeO2And Y2O3One or more of the above;
specifically, the glass powder comprises 10-15 wt% of CaO and B2O320～30wt％、Al2O3 5～15wt％、MgO 1～2wt％、SrO 0.1～1wt％、ZnO 0.5～2wt％、Bi2O30.1～1wt％、Li2O 1～2wt％、Na2O 1～4wt％、K21-2 wt% of O, 0.1-1 wt% of rare earth oxide, and the balance of SiO2. By adding a small amount of rare earth metal oxide into the glass powder, the performance between the gold conductor wiring slurry and the adaptive ceramic is regulated and controlled, the adhesive force between the gold conductor wiring slurry and the adaptive ceramic is enhanced, the conductive resistance is reduced, and the conductivity after co-firing is improved.
Preferably, the glass powder comprises 12% of CaO and 23% of B2O3、42％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% La2O3；
11％CaO、23％B2O3、43％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% CeO2；
10％CaO、23％B2O3、44％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% Y2O3；
18％CaO、23％B2O3、36％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O and 2% K2O and 1% La2O3。
In one embodiment, D of the glass frit50Between 1 to 3 μm; the transition temperature of the glass powder is 650-750 ℃, and the softening point is 700-800 ℃.
In one embodiment, the gold powder is spherical gold powder with a particle size D10Between 0.1 and 1.0 μm, D50Between 0.8 and 1.5 mum、D90Between 1.2 to 2.5 μm and D100Gold powder with the diameter less than or equal to 5 mu m.
The organic carrier comprises the following components in percentage by weight: 40-60 wt% of terpineol, 20-50 wt% of butyl carbitol, 5-15 wt% of ethyl cellulose resin, 1-5 wt% of acrylic resin and 1-5 wt% of auxiliary agent. The formula of the adopted organic carrier is easy to regulate and control, so that the gold conductor wiring slurry has good thixotropy. By adding a small amount of auxiliary agent, the thixotropic property of the paste can be greatly improved, and the good thixotropic property is shown in that the printed pattern can have higher resolution, and the printed pattern is clear and complete and has no phenomena of protrusion, bending and the like.
Preferably, the organic carrier comprises the following components in percentage by weight: 48% of terpineol, 38% of butyl carbitol, 8% of ethyl cellulose, 2% of acrylic resin and 4% of auxiliary agent;
48.5 percent of terpineol, 38.5 percent of butyl carbitol, 7 percent of ethyl cellulose resin, 2 percent of acrylic resin and 4 percent of auxiliary agent;
or
47.5 percent of terpineol, 37.5 percent of butyl carbitol, 9 percent of ethyl cellulose, 2 percent of acrylic resin and 4 percent of auxiliary agent;
in one embodiment, the auxiliary agent comprises a dispersing agent, a defoaming agent, a rheological auxiliary agent, a leveling agent and a dissolving-assisting plasticizer;
wherein the dispersant comprises: hindered alkanolamine compounds with open chain NOR comprising: one or more of piperazinone NOR, piperazine NOR, seven-membered heterocyclic NOR, Tego Dispery-650, Tego Dispery-651, Tego Dispery-652, BYK-102, OP-8018 and OP-8146;
the defoaming agent comprises: OP-8150, BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-065, XP-1273, n-hexanol and/or n-butanol;
the rheological aid comprises: hamming Nuosperse FA196, hydrogenated castor oil, soybean lecithin, vaseline, fish oil, span 80, span 85, BYK410, or mixture thereof;
the solubilizing plasticizer comprises: one or more of dibasic ester (DBE), tributyl citrate and tributyl phosphate;
the leveling agent comprises: 1, 4-gamma butyrolactone and/or BYK-163.
Preferably, in the organic carrier, the content of the auxiliary agent is as follows:
0.5 wt% Tego Dispery-650, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
0.5 wt% Tego Dispery-651, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
or 0.5 wt% seven membered heterocyclic NOR, 1 wt% dibasic ester (DBE), 1 wt% Hamming Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone.
The inorganic modifier is a metal or nonmetal solid oxide, wherein the inorganic modifier comprises: CoO, Co2O3、Co3O4、SiO2、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、MgO、CuO、Cu2O、ZrO2And the like. The average particle size is 1 to 3 μm. The inorganic modifier is added to reduce the shrinkage rate of the conductor paste during sintering, the shrinkage rate is controlled and regulated through the control of the addition amount, the types of the added substances and the interaction, so that the low-temperature co-fired dielectric ceramic material is subjected to matching co-firing, and the conductor paste is more densified after sintering.
A preparation method of gold conductor wiring slurry co-fired with microwave dielectric ceramic at low temperature comprises the following steps:
1) screening gold powder raw materials with required particle size distribution by particle size classification;
2) preparing the organic carrier according to the component proportion, heating and stirring until the organic carrier is completely dissolved, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s;
3) preparing glass powder according to the proportion, uniformly mixing, smelting at 1400-1550 ℃ for 1h, quenching with deionized water, drying, and crushing with ethanol as a solvent to obtain a particle size D50Glass powder within the range of 1-3 mu m;
4) mixing and grinding the intermediate material obtained in the steps 1), 2) and 3) and an inorganic modifier for 10-30 min in proportion, and then rolling for 1-2 h by using a three-high mill to obtain gold conductor wiring slurry; the dispersion fineness of the slurry is less than or equal to 5 mu m, and the viscosity is 100-200 Pa.s.
A method for preparing gold conductor wiring slurry on microwave dielectric ceramic by low-temperature co-firing comprises the steps of printing the gold conductor slurry on the surface of a ceramic green tape, cleaning and pretreating a printed gold conductor slurry film layer by using ethanol or acetone, and then co-firing at 830-870 ℃ after laminating, laminating and cutting. The material is cleaned and treated by ethanol or acetone, so that the conductivity of the material and the bonding strength of the material can be improved, and the conductive resistance is less than 3m omega/sq/mil; preferably less than 1.6m Ω/sq/mil. The bonding strength with a 1mil aluminum wire is more than 29 g; more preferably, the bonding strength is 35g or more.
The gold conductor wiring paste prepared by the preparation method shows good resolution. After the microwave dielectric ceramic is co-fired at a low temperature, the film layer is printed on the ceramic material, the printed pattern is clear and complete, the printed film is uniform in thickness, the co-fired matching property with a self-made low-temperature dielectric ceramic green tape is good, the green tape is tightly combined after sintering, the texture densification degree is high, the surface is flat, the measured conductive resistance is small, the conductivity is high, and the cracking, short circuit and warping are avoided.
The resolution (line width/line spacing (mum)) can be controlled to be 40μm/40μm-100μm/100μm; preferably 40 μm/40 μm to 40 μm/80 μm; more preferably 40 μm/40 μm.
The invention is further illustrated in detail in the following examples:
in the microwave dielectric ceramic material (LTCC) system, the used calcium borosilicate microcrystalline glass is melted at 1450-1550 ℃ and is kept warm for 1 hour, and then is quenched in deionized water, ball-milled and dried for later use. Softening point of 600-850 deg.C, D501-4 μm, preferably 2-3 μm; and (3) casting and forming according to the proportion to obtain the low-temperature co-fired ceramic green tape meeting the silk-screen printing.
Example 1
1) Size classification and screening D100.1 to 1.0 μm, D50Is between 0.8～1.5μm、D90Between 1.2 and 2.5 μm and D100Gold powder with the particle size less than or equal to 5 mu m;
2) preparing an organic carrier: weighing 48% of terpineol, 38% of butyl carbitol, 8% of ethyl cellulose resin, 2% of acrylic resin, 0.5% of Tego Dispery-650, 1% of dibasic ester (DBE), 1% of Haimines Nuosperse FA196, 0.5% of OP-8150 and 1% of 1, 4-gamma butyrolactone according to the mass percentage, then mixing the components, continuously stirring at 80 ℃ until the liquid is uniform and transparent, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s, thus obtaining the organic carrier;
3) preparing glass powder: weighing 12 percent of CaO and 23 percent of B according to the mass percentage2O3、42％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% La2O3Then mixing the components, smelting at 1500 deg.C for 1h, quenching with deionized water and oven drying, grinding with ethanol as solvent by planetary ball mill for 5h, and determining by particle size distribution instrument that the average particle diameter of glass powder is 2.361 μm and particle diameter D50In the range of 1 to 3 μm;
4) pulping: weighing 76% of the prepared gold powder, 2.5% of glass powder, 20% of organic carrier and mixed Co according to mass percentage2O31.5 percent, evenly mixing and grinding the mixture until the fineness is less than or equal to 5 mu m and the viscosity is 123-163 Pa.s, and obtaining the gold conductive slurry.
Evaluation and performance test of gold conductive paste
Printing the prepared gold conductor slurry on the surface of the low-temperature co-fired ceramic green tape with the thickness of 127 mu m by using a 325-mesh stainless steel net with a preset printing sheet resistance test pattern, cleaning and pretreating a printing film layer by using ethanol or acetone, co-firing at 850 +/-20 ℃ after laminating, laminating and cutting, and then testing.
Example 2
1) Size classification and screening D10Between 0.1 and 1.0 μm, D500.8 to 1.5 μm,D90Between 1.2 to 2.5 μm and D100Gold powder with the particle size less than or equal to 5 mu m;
2) preparing an organic carrier: weighing 48.5% of terpineol, 38.5% of butyl carbitol, 7% of ethyl cellulose resin, 2% of acrylic resin, 0.5% of Tego Dispery-651, 1% of dibasic ester (DBE), 1% of Hamming Nuosperse FA196, 0.5% of OP-8150 and 1% of 1, 4-gamma butyrolactone, mixing the components, continuously stirring at 80 ℃ until the liquid is uniform and transparent, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s to obtain the organic carrier;
3) preparing glass powder: weighing 11 percent of CaO and 23 percent of B according to the mass percentage2O3、43％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% CeO2Then mixing the components, smelting at 1500 ℃ for 1h, quenching with deionized water, drying, and grinding with ethanol as a solvent for 5h by a ball mill to obtain glass powder;
4) pulping: weighing 76% of gold powder, 2.5% of glass powder, 20% of organic carrier and mixing inorganic modifier Fe3O41.5 percent, uniformly mixing and grinding the components until the fineness is less than or equal to 5 mu m and the viscosity is 115-155 Pa.s to obtain the gold conductive slurry.
Evaluation and performance test of gold conductive paste
Printing the prepared gold conductor slurry on the surface of a self-made low-temperature co-fired ceramic green tape with the thickness of 127 mu m by using a 325-mesh stainless steel net with a preset printing sheet resistance test pattern, cleaning and pretreating a printing film layer by using ethanol or acetone, co-firing at 850 +/-20 ℃ after laminating, laminating and cutting, and then testing.
Comparative example 1
1) Size classification and screening D10Between 0.1 and 1.0 μm, D500.8 to 1.5 μm, D90Between 1.2 and 2.5 μm and D100Gold powder with the particle size less than or equal to 5 mu m;
2) preparing an organic carrier: weighing 47.5% of terpineol, 37.5% of butyl carbitol, 9% of ethyl cellulose, 2% of acrylic resin, 0.5% of seven-membered heterocyclic NOR, 1% of dibasic ester (DBE), 1% of Haimines Nuosperse FA196, 0.5% of OP-8150 and 1% of 1, 4-gamma butyrolactone according to the mass percentage, then mixing the components, continuously stirring at 80 ℃ until the liquid is uniform and transparent, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s, thus obtaining the organic carrier;
3) preparing glass powder: weighing 10 percent of CaO and 23 percent of B according to mass percentage2O3、44％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O、2％K2O and 1% Y2O3Then mixing the components, smelting at 1500 ℃ for 1h, quenching with deionized water, drying, using water as a solvent, and grinding for 5h by a ball mill to obtain the glass powder.
4) Pulping: weighing 76% of gold powder, 2.5% of glass powder, 20% of organic carrier and mixed inorganic modifier Cu according to mass percentage2And after 1.5 percent of O, uniformly mixing and grinding the components until the fineness is less than or equal to 5 mu m and the viscosity is 130-170 Pa.s, thus obtaining the gold conductive slurry.
And printing the prepared gold conductor slurry on the surface of a self-made low-temperature co-fired ceramic green tape with the thickness of 127 mu m by using a 325-mesh stainless steel net with a preset printing sheet resistance test pattern, co-firing the tape at 850 +/-20 ℃ after laminating, laminating and cutting, and then testing.
Comparative example 2
1) Size grading and screening D10Between 0.1 and 1.0 μm, D500.8 to 1.5 μm, D90Between 1.2 to 2.5 μm and D100Gold powder with the particle size less than or equal to 5 mu m;
2) preparing an organic carrier: weighing 46% of terpineol, 36% of butyl carbitol, 13% of ethyl cellulose, 3% of acrylic resin, 1% of hydrogenated castor oil and 1% of n-butyl alcohol according to the mass percentage, mixing the components, and continuously stirring at 80 ℃ until the liquid is uniform and transparent to obtain the organic carrier;
3) preparing glass powder: weighing 18 percent of CaO and 23 percent of B according to mass percentage2O3、37％SiO2、10％Al2O3、2％MgO、1％SrO、2％ZnO、1％Bi2O3、2％Li2O、2％Na2O and 2% K2Mixing the components after O, then smelting at 1500 ℃ for 1h, quenching with deionized water, then drying, using water as a solvent, and grinding for 5h by using a ball mill to obtain glass powder;
4) pulping: weighing 76% of gold powder prepared in the steps, 2.5% of glass powder, 20% of organic carrier and mixed inorganic modifier Ni according to mass percentage2After the content of O is 1.5 percent, the components are uniformly mixed and ground until the fineness is less than or equal to 6 mu m and the viscosity is 180Pa.s, thus obtaining the gold conductive slurry.
And printing the prepared gold conductor slurry on the surface of a self-made low-temperature co-fired ceramic green tape with the thickness of 127 mu m by using a 325-mesh stainless steel net with a preset printing sheet resistance test pattern, co-firing the tape at 850 +/-20 ℃ after laminating, laminating and cutting, and then testing.
Characterization of Properties
The results of the above examples and comparative tests are shown in tables 1 to 3.
Table 1 test results of printing and sintering matching of pastes of examples and comparative examples
Figure BDA0003625798450000111
Figure BDA0003625798450000121
Viscosity measurements the noble metal pastes were tested according to GB/T17473.5-1998 thick film microelectronics technologies.
And the fineness is determined according to a method for testing the noble metal slurry used in the GB/T17473.2-2008 microelectronic technology.
As can be seen from table 1, examples 1 and 2 both showed good resolution using the gold conductor wiring paste formulation of the present application. In the range of the optimal implementation scheme of the examples 1 and 2, from the test results of gold paste printing and sintering at 850 ℃/15min, the wiring gold paste co-fired with the microwave dielectric ceramic at low temperature is prepared, and from the test results and the attached drawings 1-7, the film layers of the examples 1 and 2 are printed, the resolution is high and reaches 40 μm/40 μm, the printed patterns are clear and complete, the printed film thickness is uniform, the performances are not separated from good thixotropy, the co-firing matching performance of the paste and a self-made low-temperature dielectric ceramic green tape is good, the bonding with the green tape after sintering is tight, the texture densification degree is high, the surface is smooth, no crack, short circuit and warpage are caused, and the conductive resistance is small and the conductivity is high. The paste of the formula of comparative example 2, which is not used, shows a great reduction in resolution, and when a pattern with a resolution of 40 μm/40 μm is printed, missing printing and breaking printing frequently occur, the pattern is blurred, and the printed film is uneven in thickness, which proves that the paste of the formula of comparative example 2 cannot achieve a high resolution of 40 μm/40 μm.
The invention can meet the domestic use requirements of LTCC (low temperature co-fired ceramic) substrates and devices, has high resolution and stable products, and greatly reduces the manufacturing and use cost of domestic products.
The adhesion of the sintered film to the substrate is an important factor affecting the conductivity, weldability and service life of the sintered film, and the results of the adhesion test of the sintered film to the substrate are shown in tables 2 and 3.
Table 2 test results of adhesion of examples and comparative examples
Examples/comparative examples Example 1 Example 2 Comparative example 1 Comparative example 2
Adhesion force 35g 29g 19g 16g
Adhesion determination a noble metal paste test method was used according to GB/T17473.4-2008 microelectronics technology.
According to the test results, in the embodiments 1 and 2, the glass powder is obtained by grinding for 5 hours through the ball mill, so that the glass powder is finer and has better dispersibility, the gold conductor slurry is printed on the surface of the low-temperature co-fired ceramic green tape, the printed film layer is cleaned by ethanol or acetone for pretreatment, the solvent and the auxiliary agent in the film layer slurry are reduced, the gold powder is burnt, the conductivity of the sintered film layer is improved, and the conductive resistance of the film layer is further reduced. The conductivity of the products of examples 1 and 2 is therefore much better than that of comparative examples 1 and 2 without pretreatment with ethanol or acetone.
Table 3 test results of conductivity of examples and comparative examples
Figure BDA0003625798450000131
Sheet resistance measurement A noble metal slurry test method (sheet resistance measurement) was used according to GB/T17473.3-2008 microelectronic technology.
It can be seen from the test results that in examples 1 and 2, after treating the printed film layer and washing it with ethanol/acetone solution, the conductive resistance of the film layer becomes small and the conductivity is more excellent than that of comparative examples 1 and 2 which have not been pretreated, and also that the adhesion of example 1 is higher than that of example 2, so that the conductivity of example 1 is higher than that of example 2.
In summary, the formula gold conductor wiring slurry obtained by the method can show good resolution after being co-fired with the calcium-boron-silicon microcrystalline glass at the low temperature of 830-870 ℃. And the gold conductor paste printed on the surface of the low-temperature co-fired ceramic green tape is prepared by cleaning with ethanol or acetone for pretreatment, so that the solvent and the auxiliary agent in the film layer paste can be reduced, the sintering of gold powder is realized, and the conductivity and the adhesive force of the sintered film layer are improved.
All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. The present invention is not limited to the above embodiments, and any modification and modification made by those skilled in the art within the technical scope of the present invention are intended to be covered by the present invention. The protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The gold conductor wiring paste co-fired with the microwave dielectric ceramic at a low temperature is characterized by comprising 70-83 wt% of gold powder, 1-5 wt% of glass powder, 0.5-1 wt% of an inorganic modifier and 15-24.5 wt% of an organic carrier; the ceramic is calcium-boron-silicon microcrystalline glass, and the low-temperature co-firing temperature is 830-870 ℃.
2. The gold conductor wiring paste low-temperature co-fired with a microwave dielectric ceramic according to claim 1, wherein the glass powder component is calcium-magnesium-boron-silicon-aluminum series glass containing alkali metal oxide and rare earth oxide; the glass powder comprises CaO and B2O3、SiO2、Al2O3、MgO、SrO、ZnO、Bi2O3、Li2O、Na2O、K2O and rare earth oxides; the rare earth oxide comprises La2O3、CeO2And Y2O3One or more of the above;
the glass powder comprises 10-15 wt% of CaO and B2O3 20～30wt％、Al2O3 5～15wt％、MgO 1～2wt％、SrO 0.1～1wt％、ZnO 0.5～2wt％、Bi2O3 0.1～1wt％、Li2O 1～2wt％、Na2O 1～4wt％、K21-2 wt% of O, 0.1-1 wt% of rare earth oxide and the balance of SiO2。
3. The gold conductor wiring paste low-temperature co-fired with microwave dielectric ceramic as claimed in claim 1, wherein D of the glass frit is50Between 1 to 3 μm; the transition temperature of the glass powder is 650-750 ℃, and the softening point is 700-800 ℃.
4. The gold conductor wiring paste as claimed in claim 1, wherein the gold powder is spherical gold powder, and the particle size D is selected100.1 to 1.0 μm, D50Between 0.8 and 1.5 μm, D90Between 1.2 and 2.5 μm and D100Gold powder with the diameter less than or equal to 5 mu m.
5. The gold conductor wiring paste co-fired with a microwave dielectric ceramic at a low temperature as claimed in claim 1, wherein the organic vehicle comprises the following components: 40-60 wt% of terpineol, 20-50 wt% of butyl carbitol, 5-15 wt% of ethyl cellulose resin, 1-5 wt% of acrylic resin and 1-5 wt% of auxiliary agent.
6. The gold conductor wiring paste co-fired with the microwave dielectric ceramic at the low temperature according to claim 5, wherein the auxiliary agents comprise a dispersing agent, a defoaming agent, a rheological auxiliary agent, a leveling agent and a dissolution assisting plasticizer;
wherein the dispersant comprises: sterically hindered alkanolamine compounds with open chain NOR comprising: one or more of piperazinone NOR, piperazine NOR, seven-membered heterocycle NOR and Tego Dispery-650, Tego Dispery-651, Tego Dispery-652, BYK-102, OP-8018 and OP-8146;
the defoaming agent comprises: OP-8150, BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-065, XP-1273, n-hexanol and/or n-butanol;
the rheological aid comprises: HAIMINUS NUosperse FA196, hydrogenated castor oil, soybean lecithin, vaseline, fish oil, span 80, span 85, BYK410, or a mixture thereof;
the solubilizing plasticizer comprises: one or more of dibasic ester (DBE), tributyl citrate and tributyl phosphate;
the leveling agent comprises: 1, 4-gamma butyrolactone and/or BYK-163.
7. The gold conductor wiring paste co-fired with microwave dielectric ceramic at low temperature as claimed in claim 6, wherein the organic vehicle contains the following components:
0.5 wt% Tego Dispery-650, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
0.5 wt% Tego Dispery-651, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone;
or
0.5 wt% seven-membered heterocyclic NOR, 1 wt% dibasic ester (DBE), 1 wt% Haimines Nuosperse FA196, 0.5 wt% OP-8150 and 1 wt% 1, 4-gamma butyrolactone.
8. The gold conductor wiring paste low-temperature Co-fired with a microwave dielectric ceramic as claimed in claim 1, wherein the inorganic modifier is a solid oxide of metal or nonmetal including CoO, Co2O3、Co3O4、SiO2、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、MgO、CuO、Cu2O、ZrO2Any one or more of the above; the inorganic modifier has an average particle diameter of 1 to 3 μm.
9. A preparation method of gold conductor wiring slurry co-fired with microwave dielectric ceramic at low temperature is characterized by comprising the following steps:
1) screening the gold powder raw material with the required particle size distribution by particle size classification;
2) preparing the organic carrier according to the component proportion, heating and stirring until the organic carrier is completely dissolved, and cooling at room temperature until the viscosity is controlled within the range of 6-10 Pa.s;
3) preparing glass powder according to the proportion, uniformly mixing, smelting at 1400-1550 ℃ for 1h, quenching with deionized water, drying, and crushing with ethanol as a solvent to obtain a particle size D50Glass powder within the range of 1-3 mu m;
4) mixing and grinding the intermediate material obtained in the steps 1), 2) and 3) and an inorganic modifier in proportion for 10-30 min, and then rolling for 1-2 h by using a three-roll mill to obtain gold conductor wiring slurry;
the dispersion fineness of the slurry is less than or equal to 5 mu m, and the viscosity is 100-200 Pa.s.
10. A method for preparing gold conductor wiring slurry on microwave dielectric ceramic by low-temperature co-firing is characterized in that the gold conductor slurry of any one of claims 1-8 is printed on the surface of a ceramic green tape, and is co-fired at 830-870 ℃ after lamination, lamination and cutting; the method is characterized in that before the co-firing operation, the printed gold conductor paste film layer is cleaned and pretreated by ethanol or acetone.
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CN115894002A (en) * 2022-12-06 2023-04-04 中国科学院合肥物质科学研究院 Dual-phase ceramic reinforced low-temperature co-fired ceramic material and preparation method and application thereof

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CN107799197A (en) * 2017-09-07 2018-03-13 天津大学 Realize LTCC conductive copper films of air dumping and preparation method thereof
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