Conductive paste containing copper particles and its use for the manufacture of electronic components - Patents.com

Abstract

Provided herein is a conductive paste comprising copper particles, glass frit, and an organic vehicle. The conductive paste is useful as a precursor for electronic components such as dielectric filters. Provided herein is further a method for producing electronic components such as dielectric filters.

Description

[Technical field]

[0001] The present invention relates to the field of electronic components, and in particular to electrodes deposited on a substrate and components such as dielectric filters fabricated with such electrodes. [Background technology]

[0002] Several patents and publications are cited herein in order to more fully describe the state of the art to which this invention pertains, the entire disclosures of each of which are incorporated herein by reference.

[0003] Communication systems use radio waves at various frequencies, with specific ranges of frequencies allocated to different applications. A bandpass filter selects the frequency range for which it is designed and rejects the unselected frequencies. Several types of filters are known, including metal cavity filters and dielectric filters. Dielectric filters have the advantages of being small and lightweight, reliable, and relatively inexpensive to manufacture. Summary of the Invention [Problem to be solved by the invention]

[0004] A need exists for dielectric filters made from a variety of materials that provide manufacturing flexibility and potentially reduced costs. [Means for solving the problem]

[0005] In a first aspect, the present invention provides a conductive paste, comprising: (i) a 0.8 to 2.6 μm D 50 (ii) a glass frit, and (iii) an organic vehicle.

[0006] In a second aspect, the present invention provides a method for manufacturing an electronic component, the method comprising the steps of: (a) providing a ceramic substrate; and (b) applying a conductive paste onto the ceramic substrate, the conductive paste having (i) a D of 0.8 to 2.6 μm. 50 (ii) a glass frit, and (iii) an organic vehicle; and (c) firing the ceramic substrate and the applied conductive paste. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The inventors have surprisingly found that the D 50 It has been discovered that conductive pastes made with copper particles having the formula: when sintered onto a ceramic substrate provide good results, particularly as measured by quality factor.

[0008] In one embodiment, the present invention provides a conductive paste, the conductive paste comprising: (i) a conductive paste having a D 50 (ii) a glass frit, and (iii) an organic vehicle, wherein the sum of the weight percentages of the copper powder, the glass frit, and the organic vehicle is 100 wt%, based on the total weight of the conductive paste.

[0009] copper powder The copper powder is preferably pure copper powder. Also suitable are copper powders that are fully or partially coated with organic materials and copper powders that are fully or partially coated with copper oxide. Pure copper powders, whether coated, uncoated, or partially coated, preferably contain at least 99.0 wt%, at least 99.5 wt%, at least 99.9 wt%, or at least 99.99 wt% elemental copper.

[0010] D of 0.8 to 2.6 μm when measured by laser diffraction according to ASTM B822-20 method, using water as the suspending medium and calculated based on MIE theory. 50 Any copper powder is suitable for use in the present invention so long as it has

[0011] In a preferred embodiment, the copper powder has a D of 0.8 to 2.5 μm, more preferably 0.9 to 2.5 μm, more particularly preferably 1.0 to 2.4 μm, as measured by laser diffraction using water as the suspension medium. 50 has.

[0012] In a preferred embodiment, the copper powder has an average particle size of 1 to 2.6 μm as measured by laser diffraction using water as the suspension medium. 50 The above is the same as for determining

[0013] In another preferred embodiment, the copper powder has 2.9-39.8% of particles having a size less than 1 μm as measured by laser diffraction using water as the suspension medium. In another preferred embodiment, the copper powder has 36-98% of the particles having a size less than 2 μm as measured by laser diffraction using water as the suspension medium.

[0014] In a preferred embodiment, the copper powder has less than 50% of the particles having a size less than 1 μm. In another preferred embodiment, the copper powder has more than 32% of particles with a size less than 2 μm.

[0015] In another preferred embodiment, the copper powder has a D5 of 0.5 to 1.0 μm as measured by laser diffraction using water as the suspension medium. In another preferred embodiment, the copper powder has a D of 0.6 to 1.2 μm as measured by laser diffraction using water as the suspension medium. 10 has.

[0016] In another preferred embodiment, the copper powder has a D of 1.2 to 4.5 μm, preferably 1.5 to 4.3 μm, as measured by laser diffraction using water as the suspension medium. 90 has.

[0017] In another preferred embodiment, the copper powder has a D of 1.5 to 5.5 μm, preferably 1.7 to 5.1 μm, as measured by laser diffraction using water as the suspension medium. 95 has.

[0018] In another preferred embodiment, the copper powder has an average particle size of 1.0 to 2.6 μm. In a particularly preferred embodiment, the copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspension medium. 50 and has less than 50% of the particles having a size less than 1 μm.

[0019] In another particularly preferred embodiment, the copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspension medium. 50 and has more than 32% of particles with a size less than 2 μm.

[0020] In another particularly preferred embodiment, the copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspension medium. 50 having less than 50% of the particles having a size less than 1 μm and having more than 32% of the particles having a size less than 2 μm.

[0021] In a particularly preferred embodiment, the copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspension medium. 50 and D of 1.2 to 4.5 μm 90 has.

[0022] In another preferred embodiment, the copper powder has a D5 of 0.5-1.0 μm and a D of 1.0-2.4 μm as measured by laser diffraction using water as the suspending medium. 50 has.

[0023] In another preferred embodiment, the copper powder has a D of 0.6 to 1.2 μm as measured by laser diffraction using water as the suspension medium. 10and D of 1.0 to 2.4 μm 50 has.

[0024] In another preferred embodiment, the copper powder has a D of 1.5 to 4.3 μm as measured by laser diffraction using water as the suspension medium. 90 and D of 1.0 to 2.4 μm 50 has.

[0025] In another preferred embodiment, the copper powder has a D of 1.7 to 5.1 μm as measured by laser diffraction using water as the suspending medium. 95 and D of 1.0 to 2.4 μm 50 has.

[0026] In another preferred embodiment, the copper powder has a D of 0.5-1.0 μm, a D of 0.6-1.2 μm, as measured by laser diffraction using water as the suspending medium. 10 , and D of 1.0 to 2.4 μm 50 , 1.5 to 4.3 μm D 90 , D 1.7~5.1μm 95 and D of 1.0 to 2.4 μm 50 has.

[0027] The shape of the copper powder particles is not particularly limited, but spherical particles are preferred. By spherical, we mean particles that appear roughly isometric (i.e. have roughly the same dimensions in all axes) under a scanning electron microscope at a magnification of 400 to 5500 times, preferably 5000 times. Preferably, the particles also have an aspect ratio of 1 to 1.2, more preferably 1 to 1.1.

[0028] The specific surface area (SA) of the copper powder is preferably 0.1 to 8.0 m 2 / g, more preferably 0.3 to 4.0 m 2 / g, particularly preferably 0.5 to 2.0 m 2 The specific surface area can be measured by a BET method such as ASTM B922-22 using an apparatus such as Monosorb™ manufactured by Quantachrome Instruments Corporation.

[0029] If the copper particle size is too small, the sintering process will be too fast and cracks will easily occur. If the cracks are severe, the sintered copper film may peel off or the electrical conductivity may be significantly reduced. If the copper particle size is too large, the sintering may not be performed sufficiently, and the electrical conductivity of the sintered copper film may not be fully achieved, or voids may occur inside the sintered copper film, hindering electrical conductivity.

[0030] The copper powder is preferably used in an amount of 40 to 95 weight percent (wt%), more preferably 52 to 93 wt%, and particularly preferably 65 to 92 wt%, based on the weight of the conductive paste.

[0031] Suitable copper powders are commercially available from a number of well-known sources. Glass Frit The glass frit functions to enhance adhesion of the sintered conductive paste to the ceramic substrate. Any glass that performs this function is suitable for use in the conductive pastes described herein. Its chemical composition is not otherwise limited.

[0032] In one embodiment, the glass frit is made from a metal oxide selected from the group consisting of bismuth oxide (Bi2O3), boron oxide (BO3), zinc oxide (ZnO), aluminum oxide (Al2O3), silicon oxide (SiO2), and mixtures of two or more thereof.

[0033] In another embodiment, the glass frit is a Si-B-Zn glass, a Bi-B-Zn glass, or a mixture thereof. In one embodiment, no lead (Pb) or lead oxide is intentionally added to the glass frit, hi another embodiment, the glass frit contains less than 100 ppm, less than 50 ppm, less than 5 ppm, or less than 1 ppm of lead.

[0034] The softening point of the glass frit is preferably at least about 350° C., 400° C., 450° C., 500° C., or 550° C. Additionally, the softening point of the glass frit is preferably no greater than about 900° C., no greater than about 875° C., no greater than about 850° C., no greater than about 750° C., or no greater than about 700° C. In some preferred embodiments, the softening point of the glass frit is about 524° C.

[0035] In a preferred embodiment, the glass frit is prepared from a mixture including SiO2, B2O3, Al2O3, Bi2O3, CaO and ZnO. In a particularly preferred embodiment, the glass frit is prepared from a mixture containing 5-9 wt% SiO2, 5-12 wt% B2O3, 1-3 wt% Al2O3, 65-75 wt% Bi2O3, 0.1-1 wt% CaO, and 8-16 wt% ZnO, based on the total weight of the glass frit. In a more preferred embodiment, the glass frit is prepared from a mixture containing 7.1 wt% SiO2, 8.4 wt% B2O3, 2.1 wt% Al2O3, 69.8 wt% Bi2O3, 0.5 wt% CaO, and 12.0 wt% ZnO, based on the total weight of the glass frit. The sum of the weight percentages of the components making up the glass frit is 100 wt%.

[0036] Glass frit particle size (D 50 ) is preferably 0.1 to 15 μm, more preferably 0.5 to 11 μm, more particularly preferably 1.0 to 6.8 μm, and in another embodiment, 1.5 to 4.5 μm. 50 ) can be measured by laser scattering using, for example, a Microtrac model S-3500, with water as the suspending medium. The particle size measurement method is the D of copper powder. 50 The above is the same as for determining

[0037] The glass frit is preferably used in the conductive paste at a level of 0.5 to 2 wt%, more preferably 0.7 to 1.8 wt%, and most preferably 0.8 to 1.5 wt%, based on the total weight of the conductive paste.

[0038] Suitable glass frits can be prepared by methods well known in the art, such as those described in U.S. Patent No. 5,439,852 issued to Jacob Hormadaly. Some, but not all, of the glass frits described herein may be commercially available from known sources.

[0039] Organic Vehicle The conductive powder and glass frit are dispersed in an organic vehicle to form a conductive paste. Preferably, the conductive paste has a viscosity suitable for application to a substrate by conventional means such as, for example, screen printing, spraying, or dipping.

[0040] The organic vehicle preferably comprises an organic polymer and a solvent, or at least one organic polymer and at least one organic solvent. In certain embodiments, the organic polymer is selected from the group consisting of ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenolic resins, lower (C 1~6 ) polymethacrylates of alcohols, and mixtures of two or more thereof.

[0041] The organic polymer is preferably used at a level of from 0.1 to 50 wt%, 0.5 to 42 wt%, 1 to 35 wt%, 2 to 27 wt%, and particularly preferably 3 to 15 wt%, based on the weight of the organic vehicle.

[0042] The solvent is preferably selected from the group consisting of texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), ester alcohols, terpineol, kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, dibutyl carbitol, hexylene glycol, dibasic esters, and mixtures of two or more thereof. The solvent is selected such that the organic polymer is readily soluble therein.

[0043] The organic polymer is used at a level of 50-99.9 wt%, 48-99.5 wt%, 65-99 wt%, 73-98 wt%, preferably 75-95 wt%, more preferably 80-93 wt%, and more especially preferably 85-93 or 97 wt%, based on the weight of the organic vehicle.

[0044] In a preferred embodiment, the organic vehicle comprises a mixture of ethyl cellulose and texanol. Particularly preferred is that the organic vehicle comprises 3 to 15 wt. % ethyl cellulose and 85 to 93 or 97 wt. % texanol, based on the weight of the organic vehicle.

[0045] The organic vehicle may optionally include an organic additive. The organic additive may be one or more of a thickener, a stabilizer, a viscosity modifier, a surfactant, and a thixotropic agent in one embodiment. The amount of the organic additive depends on the desired properties of the resulting conductive paste.

[0046] When present, the optional organic additives are preferably used at a level of up to 25 wt%, up to 10 wt%, up to 5 wt%, up to 2 wt%, or up to 1 wt%, based on the total weight of the organic vehicle. The sum of the weight percentages of the organic polymer, the solvent, and the optional organic additives, if present, is 100 wt%, based on the total weight of the organic vehicle.

[0047] The organic vehicle is preferably used at a level of 5 to 30 wt %, more preferably 6 to 15 wt %, and especially preferably 7 to 10 wt %, based on the weight of the conductive paste. Other Ingredients The conductive paste may further include one or more other components. Suitable materials for use as the other components and suitable amounts of the other components are described in U.S. Patent No. 11,228,080 issued by Yusuke Tachibana. Briefly, the other components include organic materials and inorganic additives. Preferred organic materials include, but are not limited to, thickeners, stabilizers, viscosity modifiers, surfactants, and thixotropic agents. Preferred inorganic additives include, but are not limited to, metal oxides selected from the group consisting of copper oxide (CuO, Cu2O), iron oxide (FeO, Fe2O3), zinc oxide (ZnO), titanium oxide (TiO2), lithium ruthenium oxide (Li2RuO3), and combinations of two or more of these oxides. Also preferably, the metal oxide is a powder having a D50 of 0.1 to 10 μm.

[0048] Method for manufacturing conductive paste The conductive paste of the present invention is prepared by dispersing the copper powder, glass frit, and other ingredients, if present, in an organic vehicle in a mixer, such as a disperser, and homogenizing the mixture using, for example, a three-roll mill.

[0049] Electronic components and their manufacturing method The present invention also provides a method for producing an electronic component, the method comprising the steps of: (a) providing a ceramic substrate; and (b) applying a conductive paste onto the ceramic substrate, the conductive paste having (i) a D of 0.8 to 2.6 μm. 50 (ii) a copper powder having a formula (I) of 100; (iii) a glass frit; and (iv) an organic vehicle; and (c) firing the ceramic with the applied conductive paste.

[0050] The ceramic substrate has a dielectric constant, ε γThe dielectric constant of the ceramic substrate can be measured by known methods, for example, the method of ASTM standard D2520 (2013) at 5 GHz. Such a ceramic substrate is suitable for ceramic filters used in the radio frequency range, for example. More specifically, such a ceramic substrate is suitable for use in the range of 1 GHz to 10 GHz.

[0051] Preferred ceramic substrates include those made of certain metal oxide compositions. The metal component of the ceramic substrate may be selected from the group consisting of, for example, Al, Ba, Ca, La, Mg, Mn, Nb, Nd, Ni, Pb, Sm, Sn, Sr, Ta, Ti, Zn, Zr, and mixtures of two or more thereof. In some embodiments, the ceramic substrate comprises at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or 100 mol% of one or more metal components selected from this group. In one embodiment, the metal component of the ceramic substrate includes other metals.

[0052] The ceramic substrate is not particularly limited, but examples thereof include Al2O3, BaTi4O9, Ba2Ti9O 20 , BaSnO3, BaMgO3, BaTaO3, BaZrO3, Ba(ZrTi)O3, Ba(NiTa)O3, Ba(ZrZnTa)O3, Ba(Mg 1 / 3 Ta 2 / 3 )O3, Ba(Mg 1 / 3 Nb 2 / 3 )O3, Ba(Zn 1 / 3 Ta 2 / 3 )O3, Ba(Zn 1 / 3 Nb 2 / 3 )O3, Ba(Mn 1 / 3 Ta 2 / 3 )O3, CaTiO3, (CaSrBa)ZrO3, MgTiO3, (Mg 0.95 Ca 0.05 )TiO3, SrZrO3, Sr(Zn 1 / 3 Nb 2 / 3 )O3, Sr(Zn 1 / 3 Ta 2 / 3 )O3, ZrTiO2, (Zr0.8 Sn 0.2 )TiO4, and mixtures of two or more thereof. In a preferred embodiment, the ceramic substrate is selected from Al2O3, MgTiO3, (Mg 0.95 Ca 0.05 )TiO3, Ba(Mg 1 / 3 Ta 2 / 3 )O3, BaTi4O9, Ba2Ti9O 20 , Ba(Zn 1 / 3 Ta 2 / 3 )O3, and Ba(Zn 1 / 3 Nb 2 / 3 )O3, (Zr 0.8 Sn 0.2 ) TiO4.

[0053] The ceramic substrate may be surface treated, for example, smoothed or roughened. A primer layer may also be used. The primer layer may be formed, for example, by chemical vapor deposition or plating.

[0054] The conductive paste of the present invention is applied onto a ceramic substrate. The conductive paste can be applied, for example, by screen printing, spraying, or dipping. In another embodiment, the conductive paste is applied by screen printing.

[0055] The conductive paste may be applied to the entire surface of the ceramic substrate or to only a portion of the surface. The viscosity of the conductive paste can be adjusted to suit the selected application method. Suitable methods for adjusting the viscosity include adjusting the amount of organic vehicle in the conductive paste, adjusting the ratio of the solvent and organic polymer in the organic vehicle, adjusting the molecular weight of the organic polymer, selecting a different organic polymer, or selecting a different solvent. Two or more of these methods may be used in combination.

[0056] For application by printing, the preferred viscosity range is 200-450 Pa·s. For application by dipping, the preferred viscosity range is 4-10 Pa·s. For application by spraying, the preferred viscosity range is 0.5-4 Pa·s.

[0057] Preferably, the viscosity of the conductive paste is from 0.5 to 450 Pa·s, in another embodiment from 1 to 400 Pa·s, in another embodiment from 5 to 350 Pa·s, and in another embodiment from 10 to 300 Pa·s, as measured by a Brookfield HBT using spindle SC4-14 at 10 rpm, an RVT using spindle SC4-14 at 10 rpm, or an LVT using spindle SC4-14 at 10 rpm.

[0058] The conductive paste is typically applied at a thickness of 5-40 μm in one embodiment, 7-30 μm in another embodiment, 10-20 μm in another embodiment, or 7-16 μm in another embodiment. If the thickness is significantly less than 5 μm, the quality factor is reduced. If the thickness is significantly greater than 40 μm, delamination may become an issue.

[0059] After application to the ceramic substrate, the conductive paste may be optionally dried prior to the firing step. Typical drying conditions are 50-250°C, or 100-150°C for 3-30 minutes. Drying helps to remove volatile elements and improve the conductive layer. Firing without drying may result in blistering or the formation of voids.

[0060] The ceramic substrate with the conductive paste applied thereto is fired to sinter the paste onto the substrate. This process produces electronic components. During the firing process, the glass frit gradually softens with increasing temperature and eventually flows. At the same time, the glass frit promotes the sintering of the copper powder during the process, thereby forming a conductive layer. Furthermore, the molten glass reacts with the ceramic substrate. Thus, a glass layer is formed between the ceramic substrate and the copper metal-rich top layer of the sintered conductive paste.

[0061] The calcination peak temperature is preferably 600-1100° C., in another embodiment 650-1050° C., in another embodiment 800-1000° C. The calcination time at the peak temperature is preferably 3-30 minutes, 5-20 minutes, or 7-15 minutes. Calcination is preferably carried out under oxygen-deficient conditions, for example under a blanket of nitrogen or argon, or under vacuum.

[0062] The electronic component is for example used in the radio frequency range. More specifically, the electronic component is suitable for a filter used in the range of 1 GHz to 10 GHz. In a preferred embodiment, the electronic component is a dielectric filter.

[0063] When the ceramic substrate is Al2O3 and the quality factor is measured at 2.7 GHz according to the method used in the examples, the quality factor is preferably greater than 2,550, more preferably greater than 2,600, more particularly preferably greater than 2,750 or greater than 2,800.

[0064] The ceramic base is Mg 0.95 Ca 0.05 When TiO3 and the quality factor is measured at 2.6 GHz according to the method used in the examples, the quality factor is preferably greater than 2,200, more preferably greater than 2,300.

[0065] Particularly preferred embodiments 1. A conductive paste, comprising: (i) a thickness of 0.8 to 2.6 μm; 50 (ii) a Cu powder having the formula (I) above, (iii) a glass frit, and (iv) an organic vehicle. 2. A method of manufacturing an electronic component, comprising the steps of: (a) providing a ceramic substrate; and (b) applying a conductive paste onto the ceramic substrate, the conductive paste having (i) a D of 0.8 to 2.6 μm. 50 (ii) a Cu powder having a formula (I) of at least one of: (a) a glass frit; and (b) an organic vehicle; and (c) firing the applied conductive paste. 3. Embodiment 1 or 2, wherein the copper powder has less than 50% of particles with a size less than 1 μm. 4. Embodiment 1, 2 or 3, wherein the copper powder has more than 32% of particles having a size less than 2 μm. 5. Copper powder with D of 1.2 to 4.5 μm 90 Any one of the preceding embodiments. 6. Copper powder with D of 1.5 to 5.5 μm 95 Any one of the preceding embodiments. 7. Any one of the preceding embodiments, wherein the copper powder has an average particle size of 0.8 to 2.8 μm. 8. Copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspending medium. 50 and having less than 50% of particles with a size less than 1 μm. 9. Any one of the preceding embodiments, wherein the copper powder has a D5 of 0.5 to 1.0 μm as measured by laser diffraction using water as the suspending medium. 10. Copper powder has a D of 0.6 to 1.2 μm as measured by laser diffraction using water as the suspending medium. 10 Any one of the preceding embodiments. 11. The copper powder has a D of 1.2 to 4.5 μm, preferably 1.5 to 4.3 μm, as measured by laser diffraction using water as the suspending medium. 90 Any one of the preceding embodiments. 12. The copper powder has a D of 1.5 to 5.5 μm, preferably 1.7 to 5.1 μm, as measured by laser diffraction using water as the suspending medium. 95 Any one of the preceding embodiments. 9. Copper powder has a D5 of 0.5-1.0 μm and a D of 1.0-2.4 μm as measured by laser diffraction using water as the suspending medium. 50 Any one of the preceding embodiments. 10. Copper powder has a D of 0.6 to 1.2 μm as measured by laser diffraction using water as the suspending medium. 10and D of 1.0 to 2.4 μm 50 Any one of the preceding embodiments. 11. Copper powder has a D of 1.5 to 4.3 μm as measured by laser diffraction using water as the suspending medium. 90 and D of 1.0 to 2.4 μm 50 Any one of the preceding embodiments. 12. Copper powder has a D of 1.7 to 5.1 μm as measured by laser diffraction using water as the suspending medium. 95 and D of 1.0 to 2.4 μm 50 Any one of the preceding embodiments. 13. Copper powder has a D of 0.5-1.0 μm, D of 0.6-1.2 μm, as measured by laser diffraction using water as the suspending medium. 10 , and D of 1.0 to 2.4 μm 50 , 1.5 to 4.3 μm D 90 , D 1.7~5.1μm 95 and D of 1.0 to 2.4 μm 50 Any one of the preceding embodiments. 14. Any one of the preceding embodiments, wherein the copper powder has spherical particles. 15. Any one of the preceding embodiments, wherein the copper particles have an aspect ratio of 1 to 1.2, preferably 1 to 1.1. 16. The specific surface area of ​​copper powder is 0.1 to 8.0 m 2 / g, more preferably 0.3 to 4.0m 2 / g, particularly preferably 0.5 to 2.0 m 2 Any one of the preceding embodiments, wherein: 17. Any one of the preceding embodiments, wherein the copper powder is used in an amount of 40 to 95 weight percent (wt%), more preferably 52 to 93 wt%, and particularly preferably 65 to 92 wt%, based on the weight of the conductive paste. 18. Any one of the preceding embodiments, wherein the glass frit comprises a metal oxide selected from the group consisting of bismuth oxide (Bi2O3), boron oxide (B2O3), zinc oxide (ZnO), aluminum oxide (Al2O3), silicon oxide (SiO2), and mixtures thereof. 19. Any one of the preceding embodiments, wherein the glass frit is a Si-B-Zn glass, a Bi-B-Zn glass, or a mixture thereof. 20. Any one of the preceding embodiments, wherein the glass frit is lead-free. 21. Any one of the preceding embodiments, wherein the glass frit has a softening point of at least about 350° C., 400° C., 450° C., 500° C., or 550° C. Additionally, the softening point of the glass frit is preferably not greater than about 900° C., not greater than about 875° C., not greater than about 850° C., not greater than about 750° C., or not greater than about 700° C. In some preferred embodiments, the softening point of the glass frit is about 524° C. 22. Any one of the preceding embodiments, wherein the glass frit comprises SiO2, B2O3, Al2O3, Bi2O3, CaO, and ZnO. 23. Any one of the preceding embodiments, wherein the glass frit comprises 5-9 wt% SiO2, 5-12 wt% B2O3, 1-3 wt% Al2O3, 65-75 wt% Bi2O3, 0.1-1 wt% CaO, and 8-16 wt% ZnO. 24. Any one of the preceding embodiments, wherein the glass frit comprises 7.1 wt.% SiO2, 8.4 wt.% B2O3, 2.1 wt.% Al2O3, 69.8 wt.% Bi2O3, 0.5 wt.% CaO, and 12.0 wt.% ZnO. The glass frit has a softening point of 524°C. 28. Glass frit particle size (D 50 Any one of the preceding embodiments, wherein the average particle diameter is 0.1 to 15 μm, more preferably 0.5 to 11 μm, more particularly preferably 1.0 to 6.8 μm, and 1.5 to 4.5 μm. 29. Any one of the preceding embodiments, wherein the glass frit is used in the conductive paste at 0.5-2 wt%, more preferably 0.7-1.8 wt%, and particularly preferably 0.8-1.5 wt%, based on the total weight of the conductive paste. 30. The organic vehicle is ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenolic resin, low (C 1~6Any one of the preceding embodiments, comprising an organic polymer selected from the group consisting of polymethacrylates of alcohols, and mixtures thereof. 31. Embodiment 30, wherein the organic polymer is used in an amount of preferably 0.1 to 50 wt%, 0.5 to 42 wt%, 1 to 35 wt%, 2 to 27 wt%, and particularly preferably 3 to 15 wt%, based on the weight of the organic vehicle. 32. Any one of the preceding embodiments, wherein the organic vehicle comprises a solvent selected from the group consisting of texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), ester alcohol, terpineol, kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, dibutyl carbitol, hexylene glycol, dibasic esters, and mixtures thereof. 33. Embodiment 32, in which the solvent is used in an amount of 75 to 95 wt. %, more preferably 80 to 93 wt. %, more particularly preferably 85 to 93 wt. %, based on the weight of the organic vehicle. 34. Any one of the preceding embodiments, wherein the organic vehicle comprises a mixture of ethyl cellulose and texanol. 35. Any one of the preceding embodiments, wherein the organic vehicle comprises 3-15 wt.% ethyl cellulose and 85-93 wt.% texanol, based on the weight of the organic vehicle. 36. Any one of the preceding embodiments, wherein the organic vehicle is used in an amount of 5 to 30 wt%, more preferably 6 to 15 wt%, and particularly preferably 7 to 10 wt%, based on the weight of the conductive paste. 37. The ceramic substrate has a dielectric constant, ε γ Embodiment 2 and any preceding embodiment relating to embodiment 2, 38. The ceramic substrate is made of Al2O3, BaTi4O9, Ba2Ti9O 20 , BaSnO3, BaMgO3, BaTaO3, BaZrO3, Ba(ZrTi)O3, Ba(NiTa)O3, Ba(ZrZnTa)O3, Ba(Mg 1 / 3 Ta 2 / 3 )O3, Ba(Mg1 / 3 Nb 2 / 3 )O3, Ba(Zn 1 / 3 Ta 2 / 3 )O3, Ba(Zn 1 / 3 Nb 2 / 3 )O3, Ba(Mn 1 / 3 Ta 2 / 3 )O3, CaTiO3, (CaSrBa)ZrO3, MgTiO3, (Mg 0.95 Ca 0.05 )TiO3, SrZrO3, Sr(Zn 1 / 3 Nb 2 / 3 )O3, Sr(Zn 1 / 3 Ta 2 / 3 )O3, ZrTiO2, (Zr 0.8 Sn 0.2 ) TiO4, and mixtures thereof. 39. The ceramic substrate is made of Al2O3, MgTiO3, (Mg 0.95 Ca 0.05 )TiO3, Ba(Mg 1 / 3 Ta 2 / 3 )O3, BaTi4O9, Ba2Ti9O 20 , Ba(Zn 1 / 3 Ta 2 / 3 )O3, and Ba(Zn 1 / 3 Nb 2 / 3 )O3, (Zr 0.8 Sn 0.2 ) TiO4, and any one of the preceding embodiments relating to embodiment 2. 40. The embodiment 2 and any preceding embodiment related to embodiment 2, wherein the conductive paste is applied by screen printing, spraying, or dipping. 41. The embodiment 2 and any preceding embodiment related to embodiment 2, wherein the conductive paste is dried prior to the firing step. 42. The embodiment 2 and any preceding embodiment related to embodiment 2, wherein the calcination step is carried out at 600-1100°C, in another embodiment 650-1050°C, 800-1000°C. 43. Embodiment 2 and any preceding embodiment related to embodiment 2, wherein the calcination step is carried out under an oxygen-deficient atmosphere, such as nitrogen, argon, or under vacuum. 44. Embodiment 2 and any preceding embodiment related to embodiment 2, wherein baking is carried out for 3 to 30 minutes, 5 to 20 minutes, or 7 to 15 minutes. 45. The embodiment 2 and any preceding embodiment related to embodiment 2, wherein the electronic component is a dielectric filter. EXAMPLES

[0066] The following examples are provided to further illustrate the present invention, which set forth preferred modes presently contemplated for carrying out the invention and are intended to be illustrative, not limiting.

[0067] 100 parts by weight of Cu powder and 1.6 parts by weight of glass frit were dispersed in 10 parts by weight of organic vehicle in a mixer and homogenized on a three-roll mill. The particle size distribution of various Cu powders is shown in Table 1.

[0068] The glass frit was prepared by the method described in the above-referenced U.S. Patent No. 5,439,852. The composition of the mixture from which the glass frit was prepared was 7.1 wt% SiO2, 8.4 wt% B2O3, 2.1 wt% Al2O3, 69.8 wt% Bi2O3, 0.5 wt% CaO, and 12.0 wt% ZnO. The glass frit had a softening point of 524°C.

[0069] The organic vehicle was a mixture of 6 wt% organic polymer, 91 wt% solvent, and 34 wt% organic additives, based on the weight of the organic vehicle. The paste viscosity was approximately 250–400 Pa·s as measured by Brookfield HBT using spindle SC4-14 at 10 rpm.

[0070] The conductive paste is made of Al2O3 and Mg 0.95 Ca 0.05 A ring pattern (2.5 mm wide, 10 μm thick, circular length 80 mm) was screen printed on a TiO3 substrate (25 mm long, 25 mm wide, 0.6 mm thick).

[0071] The dielectric constant of the substrate is 9.6 for Al2O3 and 9.6 for Mg 0.95 Ca 0.05 For TiO3 it was 21. Electrodes were formed by firing the ring patterns at a peak temperature of 900 °C for 10 min under N2 after drying at 150 °C for 10 min.

[0072] The results are shown in Table 2. 50 Conductive pastes containing Cu powder with diameters between 0.8 and 2.6 μm exhibit higher quality factors Q. The quality factors Q were determined according to the method described in the above-cited U.S. Pat. No. 11,228,080. Briefly, the ring patterns formed on the fired substrates were connected to a network analyzer (Keysight, E5063A). The Q values ​​and their associated frequencies were measured and recorded.

[0073] Although certain preferred embodiments of the present invention have been described and specifically exemplified above, it is not intended that the present invention be limited to such embodiments. Various modifications can be made without departing from the scope and spirit of the present invention, as set forth in the following claims.

[0074] [Table 1]

[0075] [Table 2]

Claims

1. A conductive paste, comprising: (i) a D ５０ (ii) a glass frit, and (iii) an organic vehicle.

2. 2. The paste of claim 1, wherein the copper powder has less than 50% of the particles having a size less than 1 μm.

3. 3. The paste of claim 1 or 2, wherein the copper powder has more than 32% of particles with a size less than 2 μm.

4. The copper powder has a D of 1.2 to 4.5 μm. ９０ The paste of claim 1 having the formula:

5. The copper powder has a D of 1.5 to 5.5 μm. ９５ The paste of claim 1 having the formula:

6. The paste of claim 1, wherein the copper powder has an average particle size of 0.8 to 2.8 μm.

7. The copper powder has a D of 0.8 to 2.6 μm as measured by laser diffraction using water as the suspending medium. ５０ and having less than 50% of particles having a size less than 1 μm.

8. The paste of claim 1 , wherein the copper powder has spherical particles.

9. 9. The paste of claim 8, wherein the particles have an aspect ratio of 1 to 1.2, preferably 1 to 1.

1.

10. The specific surface area of ​​the copper powder is 0.1 to 8.0 m ２ / g, more preferably 0.3 to 4.0 m ２ / g, particularly preferably 0.5 to 2.0 m ２ The paste according to claim 1, wherein the viscosity is 100 MPa.

11. 2. The paste of claim 1, wherein the copper powder is used in an amount of 40 to 95 weight percent (wt%), more preferably 52 to 93 wt%, and particularly preferably 65 to 92 wt%, based on the weight of the conductive paste.

12. The glass frit is made of bismuth oxide (Bi ２ O ３ ), boron oxide (B ２ O ３ ), zinc oxide (ZnO), aluminum oxide (Al ２ O ３ ), silicon oxide (SiO ２ 2. The paste of claim 1, which is made from a metal oxide selected from the group consisting of:

13. The paste of claim 1 , wherein the glass frit is a Si—B—Zn glass, a Bi—B—Zn glass, or a mixture thereof.

14. The paste of claim 1 , wherein the glass frit is lead-free.

15. The glass frit has a softening point of at least about 350° C., 400° C., 450° C., 500° C., or 550° C., and the softening point of the glass frit is about 900° C. or less, about 875° C. or less.

2. The paste of claim 1, wherein the melting point is about 100° C. or less, about 850° C. or less, about 750° C. or less, or about 700° C. or less.

16. The glass frit is SiO ２ , B ２ O ３ , Al ２ O ３ , Bi ２ O ３ 2. The paste of claim 1, which is made from a mixture containing CaO and ZnO.

17. The glass frit is 5 to 9 wt % of SiO ２ , 5 to 12 wt% B ２ O ３ , 1-3 wt% Al ２ O ３ , 65 to 75 wt% Bi ２ O ３ %, 0.1-1 wt % CaO, and 8-16 wt % ZnO.

18. The glass frit is 7.1 wt % SiO ２ , 8.4 wt% B ２ O ３ , 2.1 wt% Al ２ O ３ , 69.8 wt% Bi ２ O ３ %, 0.5 wt.% CaO, and 12.0 wt.% ZnO.

19. The particle diameter of the glass frit (D ５０ 2. The paste according to claim 1, wherein the average particle diameter of the powder is 0.1 to 15 μm, more preferably 0.5 to 11 μm, more particularly preferably 1.0 to 6.8 μm, and 1.5 to 4.5 μm.

20. The paste of claim 1 , wherein the glass frit is used in the conductive paste at 0.5 to 2 wt %, based on the total weight of the conductive paste.

21. The paste of claim 1, wherein the glass frit is used in the conductive paste at 0.7 to 1.8 wt %, or 0.8 to 1.5 wt %, based on the total weight of the conductive paste.

22. The organic vehicle is selected from the group consisting of ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenolic resin, low-molecular-weight (C １～６ 2. The paste of claim 1, comprising an organic polymer selected from the group consisting of polymethacrylates of alcohols, and mixtures thereof.

23. 23. The paste according to claim 22, wherein the organic polymer is preferably used in an amount of 0.1 to 50 wt %, 0.5 to 42 wt %, 1 to 35 wt %, 2 to 27 wt %, and particularly preferably 3 to 15 wt %, based on the weight of the organic vehicle.

24. 2. The paste of claim 1, wherein the organic vehicle comprises a solvent selected from the group consisting of texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), ester alcohol, terpineol, kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, dibutyl carbitol, hexylene glycol, dibasic esters, and mixtures of two or more thereof.

25. 25. A paste according to claim 24, wherein the solvent is used in an amount of 75 to 95 wt. %, more preferably 80 to 93 wt. %, more particularly preferably 85 to 93 wt. %, based on the weight of the organic vehicle.

26. 2. The paste of claim 1, wherein the organic vehicle comprises a mixture of ethyl cellulose and texanol.

27. 10. The paste of claim 1, wherein the organic vehicle comprises 3-15 wt. % ethyl cellulose and 85-93 wt. % texanol, based on the weight of the organic vehicle.

28. 2. The paste according to claim 1, wherein the organic vehicle is used in an amount of 5 to 30 wt. %, more preferably 6 to 15 wt. %, particularly preferably 7 to 10 wt. %, based on the weight of the conductive paste.

29. 11. A method for manufacturing an electronic component, comprising the steps of: (a) preparing a ceramic substrate; (b) applying the conductive paste of claim 1 onto the ceramic substrate; and (c) firing the ceramic substrate together with the applied conductive paste.

30. The ceramic substrate has a dielectric constant ε of 9 to 50, more preferably 15 to 45, and particularly preferably 20 to 40. γ 30. The method of claim 29, having the following structure:

31. The ceramic substrate is made of Al ２ O ３ ,BaTi ４ O ９ , Ba ２ Ti ９ O ２０ , BaSnO ３ , BaMgO ３ , BaTaO ３ , BaZrO ３ , Ba(ZrTi)O ３ , Ba(NiTa)O ３ , Ba(ZrZnTa)O ３ , Ba(Mg １／３ T ２／３ ) O ３ , Ba(Mg １／３ Nb ２／３ ) O ３ , Ba(Zn １／３ T ２／３ ) O ３ , Ba(Zn １／３ Nb ２／３ ) O ３ , Ba(Mn １／３ T ２／３ ) O ３ , CaTiO ３ , (CaSrBa)ZrO ３ , MgTiO ３ , (Mg ０．９５ Ca ０．０５ ) TiO ３ , SrZrO ３ , Sr(Zn １／３ Nb ２／３ ) O ３ , Sr(Zn １／３ T ２／３ ) O ３ , ZrTiO ２ , (Zr ０．８ Sn ０．２ ) TiO ４ and mixtures of two or more thereof.

32. The ceramic substrate is made of Al ２ O ３ , MgTiO ３ , (Mg ０．９５ Ca ０．０５ ) TiO ３ , Ba(Mg １／３ T ２／３ ) O ３ ,BaTi ４ O ９ , Ba ２ Ti ９ O ２０ , Ba(Zn １／３ T ２／３ ) O ３ , and Ba(Zn １／３ Nb ２／３ ) O ３ , (Zr ０．８ Sn ０．２ ) TiO ４ 30. The method of claim 29, wherein the aryl group is selected from the group consisting of:

33. 30. The method of claim 29, wherein the conductive paste is applied by screen printing, spraying or dipping.

34. 30. The method of claim 29, wherein the conductive paste is dried prior to the firing step.

35. 30. The method of claim 29, wherein the calcination step is carried out at 600-1100°C, 650-1050°C, or 800-1000°C.

36. 30. The method of claim 29, wherein the calcination step is carried out under an oxygen-deficient atmosphere, such as nitrogen, argon or under vacuum.

37. 30. The method of claim 29, wherein the baking is carried out for 3 to 30 minutes, 5 to 20 minutes, or 7 to 15 minutes.

38. 30. The method of claim 29, wherein the electronic component is a dielectric filter.

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