Gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate, preparation method and application

Abstract

The present invention provides a gold inner electrode conductor slurry for matching LTCF / LTCC composite structure substrate, a preparation method and application. In terms of mass percentage, the gold inner electrode conductor slurry includes: 75-88wt% of gold powder, 2-6wt% of inorganic glass ceramic additives and 10-20wt% of organic carriers; the preparation method is to mix the above raw materials evenly, place them for 1-2 hours to complete the infiltration, and then add them to a three-roller machine for rolling 6-10 times to obtain the gold inner electrode conductive slurry; and it is used to prepare LTCF / LTCC composite structure substrates. The present invention adopts the combination of gold powders of different morphologies, inorganic glass ceramic additives and organic carriers to adjust the sintering shrinkage rate of the gold inner electrode conductor slurry and the bonding strength with LTCC and LTCF, so as to obtain a gold inner conductor slurry with good printing performance, dense sintering, and can be matched with LTCC raw tape materials and LTCF raw tape materials for co-firing.

Description

Technical Field

[0001] The invention relates to the field of low temperature co-fired ceramic co-fired matching metal slurry and its preparation, and in particular to a gold inner electrode conductor slurry for matching LTCF / LTCC composite structure substrate, a preparation method and application. Background Art

[0002] LTCF (Low Temperature Co-fired Ferrite) material refers to low-temperature co-fired ferrite material. The magnetic properties of ferrite can be used to realize the integrated design of components such as inductors and transformers; while LTCC (Low Temperature Co-fired Ceramics) material refers to low-temperature co-fired ceramic material. The dielectric properties of microwave dielectric ceramics can be used to prepare components such as LTCC components, LTCC functional devices, LTCC packaging substrates and LTCC module substrates.

[0003] LTCF / LTCC composite structure substrate refers to the composite of LTCF material and LTCC material, which has both magnetic and microwave properties.

[0004] Both LTCC materials and LTCF materials have their own advantages. In order to realize LTCF / LTCC composite structure substrate, metal conductor paste is necessary to interconnect them. Especially in the military, aerospace and aviation fields, the metal conductor is required to have very good chemical stability and not be easily oxidized, so as to ensure the stability of communication devices. In addition, the metal conductor paste is required to have good co-firing matching with LTCF materials and LTCC materials.

[0005] Gold conductor electronic paste becomes a gold conductor after sintering and has very good chemical stability. Therefore, it is widely used in the field of LTCC / LTCF matching and co-firing. In addition, there are gold conductor pastes on the market that can be matched and co-fired with LTCF materials alone, and there are also gold conductor pastes that can be matched and co-fired with LTCC materials alone. However, there is no gold conductor electronic paste that can be co-fired with both materials at the same time.

[0006] Therefore, it is necessary to provide a technical solution to address the above-mentioned deficiencies in the prior art. Summary of the invention

[0007] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a gold inner electrode conductor paste, a preparation method and an application for matching LTCF / LTCC composite structure substrates, so as to solve the problem in the prior art that the gold conductor paste cannot be matched with both LTCF materials and LTCC materials for co-firing.

[0008] To achieve the above-mentioned purpose and other related purposes, the present invention provides a gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate. Calculated by the mass percentage of the gold inner electrode conductor paste, the gold inner electrode conductor paste comprises: 75-88wt% of gold powder, 2-6wt% of inorganic glass ceramic additives and 10-20wt% of organic carrier.

[0009] Preferably, the gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3;

[0010] The D50 particle size of the spherical gold powder is 1 to 3 μm; the D50 particle size of the flaky gold powder is 5 to 12 μm.

[0011] Preferably, the inorganic glass ceramic additive is a mixture of LTCC powder material and LTCF powder material, and the mass ratio of the LTCC powder material to the LTCF powder material is 4:6 to 6:4;

[0012] Wherein, the LTCC powder material is Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass, ZnO-B 2 O 3 -SiO 2 glass; the LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 Glass mixed.

[0013] Preferably, the organic carrier comprises, in terms of mass percentage, 70-90 wt % of a solvent, 10-30 wt % of an organic binder and 0.5-1 wt % of an organic auxiliary agent;

[0014] The solvent is one or a combination of butyl carbitol and terpineol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic auxiliary agent is a dispersant.

[0015] The present invention also provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate, the preparation method comprising the following steps:

[0016] S1. By mass percentage, 75-88 wt% of gold powder, 2-6 wt% of inorganic glass ceramic additives and 10-20 wt% of organic carrier are mixed evenly, and allowed to stand for 1-2 hours to complete the infiltration, to obtain a mixture;

[0017] S2, adding the mixed material into a three-roll mill and rolling it for 6 to 10 times to obtain a gold inner electrode conductive slurry.

[0018] Preferably, the gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3;

[0019] The D50 particle size of the spherical gold powder is 1 to 3 μm; the D50 particle size of the flaky gold powder is 5 to 12 μm.

[0020] Preferably, the inorganic glass ceramic additive is a mixture of LTCC powder material and LTCF powder material, and the mass ratio of the LTCC powder material to the LTCF powder material is 4:6 to 6:4;

[0021] Wherein, the LTCC powder material is Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass, ZnO-B 2 O 3 -SiO 2 glass; the LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 Glass mixed.

[0022] Preferably, the organic carrier comprises, in terms of mass percentage, 70-90 wt % of a solvent, 10-30 wt % of an organic binder and 0.5-1 wt % of an organic auxiliary agent;

[0023] The solvent is one or a combination of butyl carbitol and terpineol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic auxiliary agent is a dispersant.

[0024] Preferably, the fineness of the gold inner electrode conductive paste is not higher than 8 μm; the viscosity of the gold inner electrode conductive paste is 80-140 kcps; and the sheet resistance of the gold inner electrode conductive paste is 2.0-3.5 mΩ / □ / mil.

[0025] The present invention also provides an application of a gold inner electrode conductive paste, wherein the gold inner electrode conductive paste is prepared by the above-mentioned preparation method, and the gold inner electrode conductive paste is used for preparing an LTCF / LTCC composite structure substrate.

[0026] As described above, the gold inner electrode conductor slurry for matching LTCF / LTCC composite structure substrate, preparation method and application of the present invention have the following beneficial effects:

[0027] The present invention provides a gold inner electrode conductor paste for matching an LTCF / LTCC composite structure substrate. The paste adopts a combination of gold powders with different morphologies, an inorganic glass ceramic additive and an organic carrier, so as to adjust the sintering shrinkage rate of the gold inner electrode conductor paste and the bonding strength with the LTCC raw tape and the LTCF raw tape, thereby obtaining a gold inner electrode conductor paste with good printing performance, dense sintering, and the ability to be matched and co-fired with the LTCC raw tape material and the LTCF raw tape material.

[0028] The gold inner electrode conductor paste prepared in the present invention is used to match the LTCF / LTCC composite structure substrate. The gold inner electrode conductor paste is printed on the LTCF material and the LTCC material respectively, which are stacked and co-fired at low temperature to form a device module of the three materials of LTCF / LTCC / Au heterogeneous co-fired, and the warpage of the device module is less than 0.7%. At the same time, the prepared LTCF / LTCC composite structure substrate can make full use of the electrical and magnetic properties of the LTCC material and the LTCF material respectively, so that high-frequency circuits such as capacitors, filters, power dividers, and couplings are integrated with magnetic components such as inductors and transformers and other low-frequency circuits in the circuit substrate, and cavities are made on the substrate and IC bare chips are assembled, thereby realizing the integrated miniaturization of the circuit module. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram showing the structure of the LTCF / LTCC composite structure substrate in a specific embodiment of the present invention.

[0030] Figure 2It shows a cross-sectional microscope image of a LTCF / LTCC composite structure substrate formed by co-firing a gold inner electrode conductor paste and a LTCF / LTCC material in a specific embodiment of the present invention.

[0031] Component number description

[0032] 100 Gold inner electrode conductor paste layer

[0033] 200 LTCF material layers

[0034] 300 LTCC material layers DETAILED DESCRIPTION

[0035] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0036] See also Figures 1-2 It should be noted that the illustrations provided in this embodiment are only used to illustrate the basic concept of the present invention in a schematic manner, and the drawings only show components related to the present invention rather than being drawn according to the number, shape and size of components in actual implementation. In actual implementation, the type, quantity and proportion of each component may be changed arbitrarily, and the component layout may also be more complicated.

[0037] The present invention provides a gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrates, which adopts the combination of gold powders with different morphologies, inorganic glass ceramic additives and organic carriers, so as to adjust the sintering shrinkage rate of the gold inner electrode conductor paste and the bonding strength with LTCC raw tape and LTCF raw tape, so as to obtain the gold inner electrode conductor paste with good printing performance, dense sintering, and can be matched and co-fired with LTCC raw tape materials and can also be matched and co-fired with LTCF raw tape materials at the same time; the gold inner electrode conductor paste prepared in the present invention is used for matching LTCF / LTCC composite structure substrates, and the gold inner electrode conductor paste is matched and co-fired with LTCC raw tape materials. The inner electrode conductor paste is printed on the LTCF material and the LTCC material respectively, which are stacked and co-fired at low temperature to form a device module of the three materials LTCF / LTCC / Au, and the warpage of the device module is less than 0.7%. At the same time, the LTCF / LTCC composite structure substrate can make full use of the electrical and magnetic properties of the LTCC material and the LTCF material respectively, so that high-frequency circuits such as capacitors, filters, power dividers, couplings, and magnetic components such as inductors and transformers and other low-frequency circuits are integrated into the circuit substrate, and cavities are made on the substrate and IC bare chips are assembled, thereby realizing the integrated miniaturization of the circuit module.

[0038] The invention provides a gold inner electrode conductor slurry for matching LTCF / LTCC composite structure substrate. Calculated by mass percentage of the gold inner electrode conductor slurry, the gold inner electrode conductor slurry comprises: 75-88wt% of gold powder, 2-6wt% of inorganic glass ceramic additive and 10-20wt% of organic carrier.

[0039] Specifically, gold powder may include a value within any range of 75wt%, 77wt%, 79wt%, 81wt%, 83wt%, 85wt%, 87wt%, 88wt%, etc.; the inorganic glass ceramic additive may include a value within any range of 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, etc.; the organic carrier may include a value within any range of 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, etc., and the specific amount can be adjusted as needed.

[0040] As an example, the gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3; wherein the D50 particle size of the spherical gold powder is 1 to 3 μm; and the D50 particle size of the flaky gold powder is 5 to 12 μm.

[0041] Specifically, the mass ratio of spherical gold powder to flaky gold powder is any value within the range of 3:7, 4:6, 5:5, 6:4, 7:3, etc.; wherein the D50 particle size of the spherical gold powder may include any value within the range of 1μm, 1.5μm, 2μm, 2.5μm, 3μm, etc., and the D50 particle size of the flaky gold powder may include any value within the range of 5μm, 7μm, 9μm, 11μm, 12μm, etc., and can be adjusted as needed.

[0042] As an example, the inorganic glass ceramic additive is a mixture of LTCC powder material and LTCF powder material, and the mass ratio of LTCC powder material to LTCF powder material is 4:6 to 6:4; wherein the LTCC powder material is Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass, ZnO-B 2 O 3 -SiO 2 glass; LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 Glass mixed.

[0043] Specifically, the mass ratio of the LTCC powder material to the LTCF powder material includes values ​​within any range such as 4:6, 5:5, and 6:4; the Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 Glass is mixed in a certain ratio. There is no restriction on the ratio. 2 O 3 -ZnO-SiO 2 Glass is CaO, B 2 O 3 , ZnO and SiO 2 According to a certain ratio, ZnO-B 2 O 3 -SiO 2 Glass is ZnO, B 2 O 3 and SiO 2 The mixture is mixed in a certain proportion, but there is no excessive restriction on the above proportion, and it can be adjusted according to specific needs.

[0044] In addition, LTCF powder materials (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 The ratio of glass is not limited here. In the embodiment, ZnO-B 2 O 3 -SiO 2 The glass is a low melting point glass, also ZnO, B 2 O 3 and SiO 2It is mixed in a certain proportion, but there is no excessive restriction on the ratio, and it can be adjusted according to specific needs.

[0045] As an example, the organic carrier includes, in terms of mass percentage, 70-90wt% of a solvent, 10-30wt% of an organic binder and 0.5-1wt% of an organic additive; wherein the solvent is one or a combination of butyl carbitol and pinene alcohol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic additive is a dispersant.

[0046] Specifically, in terms of the mass percentage of the organic carrier, in the organic carrier, the solvent may include a value within any range such as 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, etc., the organic binder may include a value within any range such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, etc., and the organic solvent may include a value within any range such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, etc.; in addition, the organic additive is preferably BYK-111, whose chemical composition is a copolymer containing an acidic group, which can effectively reduce the viscosity of the mixture.

[0047] Specifically, the preparation method of the organic carrier includes: weighing a certain amount of solvent, organic binder and organic auxiliary agent according to mass percentage, placing them in a constant temperature water bath stirring kettle and stirring for 8 to 16 hours, and taking them out for use after stirring evenly. The stirring time may include any range of values ​​such as 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, etc., and is adjusted according to specific needs.

[0048] The present invention also provides a method for preparing a gold inner electrode conductor slurry for matching a LTCF / LTCC composite structure substrate. The method uses the above-mentioned gold inner electrode conductor slurry, but the above-mentioned gold inner electrode conductor slurry is not limited thereto, and specifically may include the following steps:

[0049] S1. By mass percentage, 75-88 wt% of gold powder, 2-6 wt% of inorganic glass ceramic additives and 10-20 wt% of organic carrier are stirred and mixed uniformly, and allowed to stand for 1-2 hours to complete the infiltration, to obtain a mixture;

[0050] S2. Add the mixed material into a three-roll mill and roll it 6 to 10 times to obtain a gold inner electrode conductive slurry.

[0051] Specifically, gold powder may include a value within any range of 75wt%, 77wt%, 79wt%, 81wt%, 83wt%, 85wt%, 87wt%, 88wt%, etc.; the inorganic glass ceramic additive may include a value within any range of 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, etc.; the organic carrier may include a value within any range of 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, etc., and the specific amount can be adjusted as needed.

[0052] In step S1, the gold powder, inorganic glass ceramic additive and organic carrier are added to a rapid mixer and mixed for 1 to 2 hours, and then placed for 1 to 2 hours to be completely infiltrated; the number of rolling in step S2 can include 6, 7, 8, 9, 10 times.

[0053] As an example, the gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3; wherein the D50 particle size of the spherical gold powder is 1 to 3 μm; and the D50 particle size of the flaky gold powder is 5 to 12 μm.

[0054] Specifically, the mass ratio of spherical gold powder to flaky gold powder is any value within the range of 3:7, 4:6, 5:5, 6:4, 7:3, etc.; wherein the D50 particle size of the spherical gold powder may include any value within the range of 1μm, 1.5μm, 2μm, 2.5μm, 3μm, etc., and the D50 particle size of the flaky gold powder may include any value within the range of 5μm, 7μm, 9μm, 11μm, 12μm, etc., and can be adjusted as needed.

[0055] The volume resistivity of flake gold powder of the same quality is smaller than that of spherical gold powder. This is mainly because the contact of spherical gold powder in the slurry is point-to-point contact, while the flake gold powder has both point-to-point contact and surface-to-surface contact, which can reduce the contact resistance of the overall slurry. Moreover, the sintering shrinkage rates of the two morphologies of gold powder are also quite different. Therefore, the combination of the two morphologies of gold powder can effectively adjust the matching of the gold conductor slurry and LTCF / LTCC materials when they are co-fired.

[0056] As an example, the inorganic glass ceramic additive is a mixture of LTCC powder material and LTCF powder material. In terms of the mass percentage of the inorganic glass ceramic additive, the mass ratio of LTCC powder material to LTCF powder material is 4:6 to 6:4; wherein the LTCC powder material is Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3-ZnO-SiO 2 Glass, ZnO-B 2 O 3 -SiO 2 glass; LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 Glass mixed.

[0057] Specifically, the mass ratio of the LTCC powder material to the LTCF powder material includes values ​​within any range such as 4:6, 5:5, and 6:4; the Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn 0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 Glass is mixed in a certain ratio. There is no restriction on the ratio. 2 O 3 -ZnO-SiO 2 Glass is CaO, B 2 O 3 , ZnO and SiO 2 According to a certain ratio, ZnO-B 2 O 3 -SiO 2 Glass is ZnO, B 2 O 3 and SiO 2 The mixture is mixed in a certain proportion, but there is no excessive restriction on the above proportion, and it can be adjusted according to specific needs.

[0058] In addition, LTCF powder materials (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3-SiO 2 The ratio of glass is not limited here. In the embodiment, ZnO-B 2 O 3 -SiO 2 The glass is a low melting point glass, also ZnO, B 2 O 3 and SiO 2 It is mixed in a certain proportion, but there is no excessive restriction on the ratio, and it can be adjusted according to specific needs.

[0059] As an example, the organic carrier includes, in terms of mass percentage, 70-90wt% of a solvent, 10-30wt% of an organic binder and 0.5-1wt% of an organic additive; wherein the solvent is one or a combination of butyl carbitol and pinene alcohol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic additive is a dispersant.

[0060] Specifically, in terms of the mass percentage of the organic carrier, in the organic carrier, the solvent may include a value within any range such as 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, etc., the organic binder may include a value within any range such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, etc., and the organic solvent may include a value within any range such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, etc.; in addition, the organic additive is preferably BYK-111, whose chemical composition is a copolymer containing an acidic group, which can effectively reduce the viscosity of the mixture.

[0061] As an example, the fineness of the gold inner electrode conductive paste is not higher than 8 μm; the viscosity of the gold inner electrode conductive paste is 80-140 kcps, and the square resistance of the gold inner electrode conductive paste is 2.0-3.5 mΩ / □ / mil.

[0062] Specifically, the fineness of the gold inner electrode conductive paste may include values ​​within any range such as 1μm, 2μm, 4μm, 6μm, 8μm, etc.; the viscosity of the gold inner electrode conductive paste may include slurries within any range such as 80kcps, 90kcps, 100kcps, 110kcps, 120kcps, 130kcps, 140kcps, etc.; the square resistance of the gold inner electrode conductive paste includes slurries within any range such as 2.0Ω / □ / mil, 2.5Ω / □ / mil, 3.0Ω / □ / mil, 3.5Ω / □ / mil, etc.; the specific adjustment shall be made according to the needs.

[0063] The viscosity of the gold inner electrode conductive paste is tested according to GB / T 17473.5-2008; the square resistance of the gold inner electrode conductive paste is tested according to the requirements of GB / T 17473.3-2008. In order to better understand the gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate in the present invention, the present invention also provides an application of the gold inner electrode conductive paste, and the gold inner electrode conductive paste prepared in the above preparation method is used to prepare LTCF / LTCC composite structure substrate.

[0064] For details, see Figure 1 The preparation method of the LTCF / LTCC composite structure substrate includes: printing the gold inner electrode conductor paste prepared above on the LTCF material layer 200 and the LTCC material layer 300, respectively, to obtain the LTCF raw tape and the LTCC raw tape printed with the gold inner electrode conductor paste layer 100, respectively; then, stacking the LTCF raw tape printed with the gold inner electrode conductor paste layer 100 and the LTCC raw tape printed with the gold inner electrode conductor paste layer 100, according to the upper-middle-lower structure of LTCF material layer 200-LTCC material layer 300-LTCF material layer 200, or according to the upper-middle-lower structure of LTCC material layer 300-LTCF material layer 200-LTCC material layer 300, pressing, cutting, and sintering at 890°C for 4h to prepare the LTCF / LTCC composite structure substrate.

[0065] The present invention adopts the combination of gold powders of different morphologies, inorganic glass ceramic additives, and organic carriers to adjust the sintering shrinkage rate of the gold inner electrode conductor paste and the bonding strength with LTCC / LTCF, thereby obtaining a gold inner conductor paste with good printing performance, dense sintering, and can be matched and co-fired with LTCC materials and can also be matched and co-fired with LTCF materials. In order to better understand the gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrates, the preparation method and application in the present invention, the present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0066] In the following Examples 1 to 9, the formula of the organic carrier used is shown in Table 1 below. The formula of the organic carrier in Table 1 is only a partial formula, that is, the formula of the organic carrier is not limited to this;

[0067] In addition, the D50 particle size of the spherical gold powder used in the following Examples 1 to 9 is 1 to 3 μm; the D50 particle size of the flake gold powder is 5 to 12 μm; and the LTCC powder material is Li 2 Mg 0.3 Zn 0.7 SiO 4 Ceramic, Zn0.8 Mg 0.2 TiO 3 Ceramics, CaO-B 2 O 3 -ZnO-SiO 2 Glass, ZnO-B 2 O 3 -SiO 2 glass; LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe 2 O 3 ) 0.98 Ferrite ceramics and ZnO-B 2 O 3 -SiO 2 and the spherical gold powder and flaky gold powder used in each embodiment are the same, and the LTCC powder material and the LTCF powder material are the same.

[0068] Table 1: Formulation of organic carrier

[0069]

[0070] The specific method for preparing the organic carrier is as follows: adding the raw materials according to the ratio into a constant temperature water bath stirring kettle and stirring for 8 to 16 hours, and after stirring evenly, taking out and setting aside.

[0071] Example 1

[0072] This embodiment provides a method for preparing a gold inner electrode conductor paste for matching an LTCF / LTCC composite structure substrate, the preparation method comprising the following steps:

[0073] S1. In terms of mass percentage, 32wt% of spherical gold powder, 48wt% of flake gold powder, 1.5wt% of LTCC powder material, 1.5wt% of LTCF powder material and 17wt% of organic carrier with serial number ZT-1 are added into a rapid mixer and stirred and mixed, and allowed to stand for 1 to 2 hours to complete the infiltration, to obtain a mixture;

[0074] S2. Add the mixed material into a three-roll mill and roll it 6 to 10 times to obtain a gold inner electrode conductive slurry.

[0075] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is applied to the preparation of an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is specifically as follows: the gold inner electrode conductor paste prepared in this embodiment is printed on an LTCF raw tape and an LTCC raw tape, respectively, to obtain an LTCF raw tape and an LTCC raw tape printed with the gold inner electrode conductor paste, respectively; then, the LTCF raw tape printed with the gold inner electrode conductor paste and the LTCC raw tape printed with the gold inner electrode conductor paste are stacked, pressed, cut into pieces, and sintered at 890°C for 4 hours to obtain an LTCF / LTCC composite structure substrate.

[0076] See also Figure 1 The figure shows a schematic diagram of the structure of the LTCF / LTCC composite structure substrate prepared after co-firing, wherein a gold inner electrode conductor paste layer 100 is printed on the LTCF material layer 200, and a gold inner electrode conductor paste layer 100 is printed on the LTCC material layer 300, and then they are stacked and sintered according to the top-middle-bottom structure of 5LTCF-2LTCC-5LTCF.

[0077] Figure 2 The figure shows a microscope picture of the cross section of the LTCF / LTCC composite structure substrate. The interface between the LTCC material and the LTCF material is clear on the cross section, and the LTCC material is not diffused and dyed by the LTCF material. This also reflects that the sintering shrinkage rate of the gold inner electrode conductor slurry and the bonding strength with the LTCC material and LTCF material are good. The LTCF / LTCC composite structure substrate has a tight co-firing bond and good co-firing matching.

[0078] Performance test: The viscosity of the gold inner electrode conductive paste in this embodiment is tested according to GB / T 17473.5-2008; the square resistance of the gold inner electrode conductive paste in this embodiment is tested according to the requirements of GB / T17473.3-2008; the warpage of the co-fired matching LTCF / LTCC composite structure substrate is tested; the test results are shown in Table 2 below.

[0079] Example 2

[0080] The present embodiment provides a method for preparing a gold inner electrode conductor paste for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 40wt% of spherical gold powder, 40wt% of flaky gold powder, 1.5wt% of LTCC powder material, 1.5wt% of LTCF powder material and 17wt% of an organic carrier with the serial number ZT-2 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and are not repeated here.

[0081] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0082] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0083] Example 3

[0084] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 48wt% of spherical gold powder, 32wt% of flaky gold powder, 1.5wt% of LTCC powder material, 1.5wt% of LTCF powder material and 17wt% of an organic carrier with the serial number ZT-3 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and will not be repeated here.

[0085] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0086] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0087] Example 4

[0088] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that the raw material ratio in step S1 is different. In the present embodiment, 32 wt% of spherical gold powder, 48 wt% of flaky gold powder, 2 wt% of LTCC powder material, 2 wt% of LTCF powder material and 16 wt% of an organic carrier with the serial number ZT-2 are added to a rapid mixer and stirred and mixed. The other steps and methods are the same as those in Example 1 and will not be repeated here.

[0089] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0090] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0091] Example 5

[0092] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that the raw material ratio in step S1 is different. In the present embodiment, 40 wt% of spherical gold powder, 40 wt% of flaky gold powder, 2 wt% of LTCC powder material, 2 wt% of LTCF powder material and 16 wt% of an organic carrier with the serial number ZT-2 are added to a rapid mixer and stirred and mixed. The other steps and methods are the same as those in Example 1 and will not be repeated here.

[0093] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0094] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0095] Example 6

[0096] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 48wt% of spherical gold powder, 32wt% of flaky gold powder, 2wt% of LTCC powder material, 2wt% of LTCF powder material and 16wt% of an organic carrier with the serial number ZT-3 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and will not be repeated here.

[0097] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0098] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0099] Example 7

[0100] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 32wt% of spherical gold powder, 48wt% of flaky gold powder, 2.5wt% of LTCC powder material, 2.5wt% of LTCF powder material and 15wt% of an organic carrier with the serial number ZT-2 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and will not be repeated here.

[0101] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0102] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0103] Example 8

[0104] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 40 wt% of spherical gold powder, 40 wt% of flaky gold powder, 2.5 wt% of LTCC powder material, 2.5 wt% of LTCF powder material and 15 wt% of an organic carrier with the serial number ZT-2 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and will not be repeated here.

[0105] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0106] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0107] Example 9

[0108] The present embodiment provides a method for preparing a gold inner electrode conductor slurry for matching an LTCF / LTCC composite structure substrate. The preparation method is different from that in Example 1 in that: the raw material ratio in step S1 is different. In the present embodiment, by mass percentage, 48wt% of spherical gold powder, 32wt% of flaky gold powder, 2.5wt% of LTCC powder material, 2.5wt% of LTCF powder material and 15wt% of an organic carrier with the serial number ZT-3 are added to a rapid mixer and stirred and mixed; the other steps and methods are the same as those in Example 1 and will not be repeated here.

[0109] In addition, this embodiment also provides an application of a gold inner electrode conductive paste. The gold inner electrode conductive paste prepared in this embodiment is used to prepare an LTCF / LTCC composite structure substrate. The preparation method of the LTCF / LTCC composite structure substrate is the same as that in Example 1 and will not be repeated here.

[0110] The performance test is the same as the test method in Example 1, which will not be repeated here. The test results are shown in Table 2 below.

[0111] Table 2: Viscosity and resistance of the gold inner electrode conductor paste prepared in Examples 1 to 9 and the warpage of the prepared LTCF / LTCC composite structure substrate.

[0112]

[0113]

[0114] In summary, the present invention provides a gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrates, which adopts the combination of gold powders with different morphologies, inorganic glass ceramic additives and organic carriers, so as to adjust the sintering shrinkage rate of the gold inner electrode conductor paste and the bonding strength with LTCC raw tape and LTCF raw tape, so as to obtain a gold inner conductor paste with good printing performance, dense sintering, and can be matched and co-fired with LTCC raw tape materials, and can also be matched and co-fired with LTCF raw tape materials at the same time; the gold inner electrode conductor paste prepared in the present invention is used for matching LTCF / LTCC composite structure substrates , the gold inner electrode conductor paste is printed on the LTCF material and the LTCC material respectively, and the three materials are stacked and co-fired at low temperature to form a device module of LTCF / LTCC / Au heterogeneous co-fired, and the warpage of the device module is less than 0.7%; at the same time, the LTCF / LTCC composite structure substrate made can make full use of the electrical and magnetic properties of the LTCC material and the LTCF material, so that high-frequency circuits such as capacitors, filters, power dividers, couplings, and magnetic components such as inductors and transformers and other low-frequency circuits are integrated into the circuit substrate, and cavities are made on the substrate and IC bare chips are assembled, so as to realize the integrated miniaturization of the circuit module. Therefore, the present invention effectively overcomes the various shortcomings of the prior art and has a high industrial utilization value.

[0115] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate, characterized in that: In terms of the mass percentage of the gold inner electrode conductor slurry, the gold inner electrode conductor slurry comprises: 75-88wt% of gold powder, 2-6wt% of inorganic glass ceramic additives and 10-20wt% of organic carriers; the inorganic glass ceramic additives are a mixture of LTCC powder material and LTCF powder material, and the mass ratio of the LTCC powder material to the LTCF powder material is 4:6-6:4; wherein the LTCC powder material is Li2Mg 0.3 Zn 0.7 SiO4 ceramics, Zn 0.8 Mg 0.2 TiO3 ceramic, CaO-B2O3-ZnO-SiO2 glass, ZnO-B2O3-SiO2 glass are mixed; the LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe2O3) 0.98 Ferrite ceramics are mixed with ZnO-B2O3-SiO2 glass.

2. The gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate according to claim 1, characterized in that: The gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3; The D50 particle size of the spherical gold powder is 1 to 3 μm; the D50 particle size of the flaky gold powder is 5 to 12 μm.

3. The gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate according to claim 1, characterized in that: Calculated by mass percentage of the organic carrier, the organic carrier comprises: 70-90wt% of a solvent, 10-30wt% of an organic binder and 0.5-1wt% of an organic auxiliary agent; The solvent is one or a combination of butyl carbitol and terpineol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic auxiliary agent is a dispersant.

4. A method for preparing a gold inner electrode conductor paste for matching LTCF / LTCC composite structure substrate, characterized in that: The preparation method comprises the following steps: S1. In terms of mass percentage, 75-88wt% of gold powder, 2-6wt% of inorganic glass ceramic additive and 10-20wt% of organic carrier are mixed evenly, and placed for 1-2h to complete infiltration to obtain a mixture; the inorganic glass ceramic additive is a mixture of LTCC powder material and LTCF powder material, and the mass ratio of the LTCC powder material to the LTCF powder material is 4:6-6:4; wherein the LTCC powder material is Li2Mg 0.3 Zn 0.7 SiO4 ceramics, Zn 0.8 Mg 0.2 TiO3 ceramic, CaO-B2O3-ZnO-SiO2 glass, ZnO-B2O3-SiO2 glass are mixed; the LTCF powder material is (Ni 0.5-x Cu x Zn 0.5 )(Fe2O3) 0.98 Ferrite ceramics are mixed with ZnO-B2O3-SiO2 glass; S2, adding the mixed material into a three-roll mill and rolling it for 6 to 10 times to obtain a gold inner electrode conductive slurry.

5. The preparation method according to claim 4, characterized in that: The gold powder is a mixture of spherical gold powder and flaky gold powder, wherein the mass ratio of the spherical gold powder to the flaky gold powder is 3:7 to 7:3; The D50 particle size of the spherical gold powder is 1 to 3 μm; the D50 particle size of the flaky gold powder is 5 to 12 μm.

6. The preparation method according to claim 4, characterized in that: Calculated by mass percentage of the organic carrier, the organic carrier comprises: 70-90wt% of a solvent, 10-30wt% of an organic binder and 0.5-1wt% of an organic auxiliary agent; The solvent is one or a combination of butyl carbitol and terpineol; the organic binder is one or a combination of ethyl cellulose, nitrocellulose and acrylic resin; and the organic auxiliary agent is a dispersant.

7. The preparation method according to claim 4, characterized in that: The fineness of the gold inner electrode conductive paste is not higher than 8 μm; the viscosity of the gold inner electrode conductive paste is 80-140 kcps; and the square resistance of the gold inner electrode conductive paste is 2.0-3.5 mΩ / □ / mil.

8. An application of a gold inner electrode conductor slurry, characterized in that: The gold inner electrode conductive paste is prepared by the preparation method according to any one of claims 4 to 7, and the gold inner electrode conductive paste is used to prepare LTCF / LTCC composite structure substrate.

Images