WO2013089128A1 - Composition conductrice, substrat de céramique à couches multiples, et procédé de fabrication de ce substrat - Google Patents

Composition conductrice, substrat de céramique à couches multiples, et procédé de fabrication de ce substrat Download PDF

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Publication number
WO2013089128A1
WO2013089128A1 PCT/JP2012/082169 JP2012082169W WO2013089128A1 WO 2013089128 A1 WO2013089128 A1 WO 2013089128A1 JP 2012082169 W JP2012082169 W JP 2012082169W WO 2013089128 A1 WO2013089128 A1 WO 2013089128A1
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Prior art keywords
ceramic substrate
multilayer ceramic
hole conductor
component
powder
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PCT/JP2012/082169
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English (en)
Japanese (ja)
Inventor
正人 野宮
洋右 寺下
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株式会社村田製作所
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Publication of WO2013089128A1 publication Critical patent/WO2013089128A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
    • H05K3/4061—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in inorganic insulating substrates
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4629—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating inorganic sheets comprising printed circuits, e.g. green ceramic sheets

Definitions

  • the present invention relates to a conductive composition used for a via-hole conductor in a multilayer ceramic substrate, a multilayer ceramic substrate, and a method for manufacturing the same.
  • Patent Document 1 describes a multilayer ceramic substrate including a via-hole conductor.
  • This multilayer ceramic substrate defines the crystallite diameter of silver powder in the conductive paste used for the via-hole conductor.
  • a main object of the present invention is a multilayer ceramic substrate having a via-hole conductor filled with a conductive composition as a conductive paste, and the multilayer ceramic substrate is formed by, for example, a bulge of the via-hole conductor in the sintering process of the multilayer ceramic substrate. It is an object to provide a conductive composition, a multilayer ceramic substrate, and a method for producing the same, which can suppress warping and undulation.
  • the conductive composition according to the present invention is a conductive composition used for a via hole conductor filled in a via hole in a multilayer ceramic substrate including a plurality of laminated ceramic layers and a via hole formed through the ceramic layer.
  • An electrically conductive composition comprising an electrically conductive powder, a glass powder, a phosphorus-containing powder, and an organic vehicle.
  • glass powder contains more than phosphorus containing powder.
  • a multilayer ceramic substrate according to the present invention is a multilayer ceramic substrate having a via-hole conductor formed in a thickness direction with respect to the ceramic layer, comprising a ceramic layer that does not contain a phosphorus component when unfired, and containing phosphorus in the via-hole conductor
  • a multilayer ceramic substrate comprising a glass compound and a phosphorus component.
  • the phosphorus component is preferably diffused from the via-hole conductor into the ceramic layer.
  • the ceramic layer preferably contains Ba, Al, and Si oxide components as main components.
  • the ceramic layer includes a material obtained by adding a glass component to alumina or barium titanate. Furthermore, in the multilayer ceramic substrate according to the present invention, a constraining layer is preferably formed along the plurality of ceramic layers, and the main component of the constraining layer is preferably Al.
  • a method of manufacturing a multilayer ceramic substrate according to the present invention includes a step of forming a via hole in a ceramic green sheet, a step of filling a via hole with the conductive composition according to the present invention to form a via hole conductor, A plurality of ceramic layers including a step of forming a conductor pattern connected to a via-hole conductor, a step of stacking the obtained ceramic green sheets to prepare a temporary laminate, and a firing step of firing the temporary laminate.
  • a method for manufacturing a multilayer ceramic substrate comprising: a shrinkage behavior of a via-hole conductor follows a shrinkage behavior of a ceramic layer in a firing step.
  • the phosphorus-containing component prevents the glass component contained in the conductive composition from being cured at the time of firing and softens the conductive composition.
  • the electrically conductive composition which can adjust the softening behavior of the glass component at the time with a phosphorus component can be obtained.
  • the conductive composition according to the present invention contains more glass powder than the phosphorus-containing component, the phosphorus component does not diffuse excessively from the via-hole conductor into the ceramic layer. Therefore, since the degree of softening of the glass component in the via-hole conductor in the high temperature range can be promoted, a conductive composition that can suppress the protrusion of the via-hole conductor can be obtained.
  • the phosphorus component is not extremely diffused in the ceramic layer, it is possible to prevent the shrinkage suppressing effect from being exerted on the ceramic layer. Can further promote the softening behavior of the via-hole conductor in the stage where the ceramic layer contracts greatly. Therefore, it is possible to obtain a multilayer ceramic substrate in which the protrusion of the via-hole conductor is suppressed.
  • the phosphorus component is diffused from the via hole conductor to the ceramic layer, the softening behavior of the glass component at the interface between the via hole conductor and the ceramic layer can be adjusted stepwise.
  • the multilayer ceramic substrate according to the present invention contains Ba, Al, Si oxide components as the main component of the ceramic layer, or a glass component added to alumina or barium titanate as the main component of the ceramic layer.
  • the constraining layer is formed along the ceramic layer in the multilayer ceramic substrate according to the present invention, the shrinkage behavior in the thickness direction is particularly large, but it is also effective for the multilayer ceramic substrate including the constraining layer. Raising of the via-hole conductor can be suppressed.
  • the shrinkage behavior of the via-hole conductor can be made to follow the shrinkage behavior of the ceramic layer at the firing temperature at which the ceramic layer is greatly shrunk in the firing step. Therefore, for example, a multilayer ceramic substrate in which the bulge of via-hole conductors formed on the multilayer ceramic substrate is suppressed can be manufactured.
  • a multilayer ceramic substrate including a via-hole conductor filled with a conductive composition as a conductive paste, and warpage or undulation of the multilayer ceramic substrate due to a rise of the via-hole conductor in the sintering process of the multilayer ceramic substrate.
  • a conductive composition, a multilayer ceramic substrate, and a method for producing the same can be obtained.
  • thermomechanical analyzer of the volume change behavior with respect to the temperature change in the conductive paste which is the conductive composition according to the present invention and the conductive paste not including the phosphorus-containing powder is shown.
  • 1 is a schematic cross-sectional view of an embodiment of a multilayer ceramic substrate according to the present invention. It is a cross-sectional schematic diagram of other embodiment of the multilayer ceramic substrate concerning this invention. The shrinkage rate with respect to the firing temperature of the multilayer ceramic substrate used in Experimental Example 1 and the multilayer ceramic substrate used in Experimental Example 2 and the time-series change of the firing temperature are shown. The cross-sectional schematic diagram of the multilayer ceramic substrate used in Experimental example 1 is shown.
  • the example of the analysis result of the composition distribution in the multilayer ceramic substrate of this invention is shown, (a) shows the boundary vicinity of a ceramic layer and a via-hole conductor, (b) shows the copper (Cu) in a via-hole conductor. (C) shows the distribution of phosphorus (P) in the via-hole conductor, and (d) shows the distribution of glass (Si) in the via-hole conductor.
  • the cross-sectional schematic diagram of the multilayer ceramic substrate used in Experimental example 2 is shown.
  • the conductive composition according to the present invention is used for, for example, a via-hole conductor filled in a via-hole formed through a multilayer ceramic substrate.
  • the multilayer ceramic substrate is formed by laminating a plurality of ceramic layers.
  • This conductive composition is produced, for example, as a conductive paste.
  • the conductive paste includes a conductive powder, a glass powder, a phosphorus-containing powder, and an organic vehicle.
  • a metal having excellent electrical conductivity such as Ag, Au, Cu, Ni, an Ag—Pd alloy, or an Ag—Pt alloy is preferably used as a main component.
  • other conductive powders or conductive materials may be used as long as the addition amount is not reversed unless an unnecessary reaction is caused with the ceramic layer or dissolution during firing.
  • Oxide powder may be added.
  • the shape, average particle size, and particle size distribution of the conductive powder are not particularly limited, but the average particle size is preferably about 0.1 ⁇ m to 10 ⁇ m, and is preferably free of coarse powder or extremely agglomerated powder.
  • inorganic components components that are not sintered in the firing step of the ceramic green sheet to be used (hereinafter referred to as inorganic components) are arranged on the surface of the conductive powder with substantially no gap.
  • this inorganic component an oxide containing Al, Si, Zr, Ni, Ti, Nb, Mn, and Mg can be used.
  • These inorganic components need to be selected in consideration of the shrinkage conditions of the multilayer ceramic substrate and the affinity with the glass powder to be added, which will be described later, and the inorganic component materials in the present invention include Al, Si, and Zr. Particularly preferred.
  • these inorganic components need to be disposed on the surface of the conductive powder with substantially no gap.
  • the state in which the surface of the conductive powder in the present embodiment has substantially no gap refers to the conductivity. It is sufficient that the powder does not exhibit the sintering behavior by itself, and does not necessarily indicate that there is no gap at all.
  • the amount of the inorganic component added depends on the state of adhesion of the conductive powder to the surface, but is preferably about 0.5 to 8% by weight with respect to the conductive powder, and more desirably. Is from 1% to 7% by weight.
  • the conductive powder is coated with an organic aluminate such as an alkyl aluminate and then heat-treated, Alternatively, by immersing the conductive powder in an aluminum salt solution and then subjecting it to a dry heat treatment, or treating the fine alumina powder by the microcapsule method and placing the fine alumina powder on the surface of the conductive powder as it is It is possible to get.
  • an organic aluminate such as an alkyl aluminate
  • the conductive powder used for this conductive paste is not particularly dependent on these production methods, but it can realize the above-described sintering behavior suppressing effect with a small amount of coating component, or a coating component with a glass component described later.
  • the glass powder contained in the conductive paste is preferably a glass powder selected from Si—B, more preferably SiO 2 : 40 wt% to 55 wt%, B 2 O 3 : 10
  • a mixture containing 20% by weight to 20% by weight, BaO and / or SrO: 20% by weight to 30% by weight is melted at a predetermined temperature and then vitrified.
  • the glass powder does not show excessive reaction with the multilayer ceramic substrate, and any known one can be used as long as it has a softening point lower by about 150 ° C. to 300 ° C. than the sintering temperature of the ceramic layer. It is.
  • the addition amount of these components into the glass is adjusted in order to ensure the removability of the inorganic components by the glass components described later. It is desirable to keep it. This is because if the coating amount of the inorganic component exceeds the reaction limit with the addition amount of the glass powder, the target inorganic component may not be sufficiently removed.
  • the glass powder does not contain a phosphorus component in the glass state, but it is more desirable to have a composition that promotes a softening tendency in a desired temperature range by reaction with the phosphorus-containing component.
  • the particle size of the glass powder to be added is preferably selected according to the particle size of the conductive powder, but it has an average particle size of about 0.5 ⁇ m to 3 ⁇ m that gives good dispersibility and is coarse. Those without powder or extremely agglomerated powder are desirable.
  • the phosphorus-containing powder contained in the conductive paste is the same product as the conductive powder after decomposition because unnecessary reactions after decomposition can be suppressed.
  • the conductive powder is copper
  • use of copper pyrophosphate or the like is suitable, but it is not particularly limited thereto.
  • any phosphorus-containing component that can be supplied to the glass component can be used.
  • the particle size of the phosphorus-containing powder is preferably selected according to the particle size of the conductive powder, but it has an average particle size of about several ⁇ m, which can provide good dispersibility and decomposability. What does not have an agglomerated powder is desirable.
  • the organic vehicle contained in the conductive paste is a mixture of a binder resin and a solvent, and is not particularly limited.Although alcohols such as terpineol, isopropylene alcohol, butyl carbitol, butyl carbitol acetate, acrylic resin, It can be obtained by dissolving alkyd resin, butyral resin, ethyl cellulose, and the like, and various dispersants, plasticizers, and activators may be added as necessary.
  • alcohols such as terpineol, isopropylene alcohol, butyl carbitol, butyl carbitol acetate, acrylic resin, It can be obtained by dissolving alkyd resin, butyral resin, ethyl cellulose, and the like, and various dispersants, plasticizers, and activators may be added as necessary.
  • the conductive paste may contain a resin component that is insoluble in the solvent component in the organic vehicle.
  • resin components and the like may contain polypropylene, polyethylene, polystyrene, acrylic resin, cellulose resin and the like. These resin components and the like preferably have an average particle size of about 3 ⁇ m to 7 ⁇ m and are free of coarse powder or extremely agglomerated powder.
  • the addition ratio of each component is as follows: conductive powder having non-sintered component on the surface: 60% to 85% by weight, glass powder having a softening point of 700 ° C. or higher selected from Si—B system: 1% to 10% Wt%, phosphorus-containing powder: 0.1 wt% to 0.8 wt% (phosphorus component conversion 0.02 wt% to 0.16 wt%), copper oxide powder: 0 wt% to 40 wt%, organic vehicle: 10 wt% to 25 wt%, preferably resin components insoluble in the solvent component in the organic vehicle: 0 wt% to 7 wt%. That is, in the conductive composition according to the present invention, the glass powder is contained more than the phosphorus-containing powder.
  • the amount of glass powder added is 10% by weight or more, the conduction resistance of the via-hole conductor increases and the glass tends to float on the electrode surface, which can be an obstacle to plating deposition.
  • the lower limit of the amount of glass powder added depends on the amount of the resin component insoluble in the solvent component in the organic vehicle and the softening tendency of the glass component, but even if the maximum amount of resin component is added, the added glass When the added amount of the powder is 1% by weight or less, the amount is not sufficient to remove the non-sintered components on the surface of the particles of the conductive powder, and as a result, an unsintered portion may remain in the via-hole conductor. .
  • the softening point of the glass component glass powder having a softening point lower by 300 ° C. or more than the sintering temperature of the multilayer ceramic substrate starts to be sintered at an earlier stage than the sintering of the multilayer ceramic substrate. Therefore, the object of the present invention of matching the shrinkage behavior between the conductive paste and the ceramic layer of the multilayer ceramic substrate is not achieved, which is not preferable.
  • the difference between the sintering temperature of the ceramic layer of the multilayer ceramic substrate and the softening point of the glass component is less than 150 ° C., the glass component is not sufficiently softened, and as a result, the glass component is incorporated into the conductive paste. Insufficient diffusion may leave unsintered portions in the via-hole conductor.
  • the phosphorus-containing powder is preferably 0.02 wt% to 0.16 wt% in terms of phosphorus component. This is because an excessive addition tends to cause defects in the conductor structure, and the flatness of the ceramic layer itself is impaired by diffusion into the ceramic layer.
  • the addition amount of the phosphorus-containing powder is preferably adjusted to an appropriate amount in consideration of the glass components described above, but is preferably about 1/20 to 1/200 of the addition amount of the glass powder.
  • the resin component and the copper oxide component it is possible to select a relatively free addition amount within the range of the addition amount described above, but both additives can reduce the amount of bulge by increasing the addition amount.
  • the amount of voids inside the conductive layer is also increased, which adversely affects conductivity, reliability, and the like. Therefore, it is preferable to suppress the addition amount.
  • a desired conductive paste can be obtained by mixing the above materials and stirring and kneading them with a laika machine and three rolls. Note that the technique is not particularly limited as long as it can perform sufficient stirring and kneading.
  • the average particle diameter in the various powder mentioned above is a result measured using a micro track.
  • the glass powder and the phosphorus-containing powder are components made of different substances, so that in the firing step, the reaction with the glass component is first performed when the phosphorus-containing component is decomposed. As shown. That is, unlike the phosphorus-containing glass in which the phosphorus-containing component is contained in the glass from the beginning, the reaction can be started after the decomposition of the phosphorus-containing component occurs.
  • FIG. 1 is an example of the measurement result by the thermomechanical analyzer (TMA) of the volume change behavior with respect to the temperature change in the conductive paste which is the conductive composition according to the present invention and the conductive paste not including the phosphorus-containing powder. Indicates.
  • TMA thermomechanical analyzer
  • a ceramic layer particularly shrinks greatly by causing a phosphorus-containing component to act on a glass component in a firing step. It becomes possible to rapidly soften at a high temperature range of ⁇ 1000 ° C. That is, it becomes possible to promote the degree of softening of the glass component in a high temperature range by newly causing the phosphorus component to act on the glass component in a heated state. As a result, even in the multilayer ceramic substrate, the tendency to soften more than in the case of single glass at the stage of contraction of the ceramic layer, so that the removal of the inorganic components formed on the surface of the conductive powder is facilitated. Further, since the hardness of the via hole conductor as a whole is also reduced, the shrinkage of the via hole conductor itself connected to the ceramic layer is promoted by the shrinkage behavior of the ceramic layer, and the via hole conductor is further lowered.
  • the phosphorus-containing component reacts with the glass component, the phosphorus-containing component is not excessively diffused from the via-hole conductor to the ceramic layer side, and there is an adverse effect such as insufficient shrinkage on the ceramic layer around the via-hole conductor. Does not affect. That is, when a phosphorus-containing component is added to the via-hole conductor, the phosphorus-containing component diffuses to the ceramic layer side due to the diffusion behavior, but the phosphorus-containing component is captured by the glass component.
  • reaction with the phosphorus-containing component can be similarly applied to the glass component diffusing from the ceramic layer into the via-hole conductor. That is, since a phosphorus-containing component is separately added to the glass component, the same action can be applied to the inflow glass component in addition to the glass component added in the via-hole conductor.
  • the shrinkage behavior of the via-hole conductor can be adjusted so as to follow the shrinkage behavior of the ceramic layer during firing. Therefore, it is possible to obtain a conductive composition that can suppress the bulge on the surface of the via-hole conductor that occurs during sintering. Moreover, even if the ceramic layer has a large amount of shrinkage near the completion of sintering, or the ceramic layer has a different direction of shrinkage behavior, especially via-hole conductors where the periphery of the via hole is not surrounded by ceramic, the amount of bumps can be suppressed. it can. Therefore, the use of the conductive composition according to the present invention for the via-hole conductor enables planarization on the surface of the multilayer ceramic substrate.
  • FIG. 2 is a cross-sectional view of an embodiment of a multilayer ceramic substrate according to the present invention.
  • a multilayer ceramic substrate 10 includes a plurality of laminated ceramic layers 12 and via-hole conductors 14. Although not shown in FIG. 1, a conductive film is formed on the ceramic layer 12. This conductor film is formed as a surface conductor film on the front and back surfaces of the multilayer ceramic substrate 10 and is formed as an inner conductor film inside.
  • the material of the ceramic layer 12 preferably contains barium oxide, silicon oxide, and alumina as main components.
  • a material that acts as a ceramic filler such as alumina or barium titanate may be added with a glass component that acts as a sintering aid. Good.
  • borosilicate glass or silicon oxide may be added.
  • the via-hole conductor 14 is formed by filling a via hole 16 formed through the ceramic layer 12 with a conductive paste made of the conductive composition according to the present invention.
  • the surface layer conductor film and the inner conductor film are electrically connected to the via-hole conductor 14.
  • the phosphorus component is present at a position substantially close to the glass component, and the diffusion into the ceramic layer 12 is extremely small. That is, the phosphorus component can be retained in the via-hole conductor 14 by reacting the phosphorus-containing component with the glass component. Since the phosphorus-containing component is not diffused in the ceramic layer 12, it is possible to prevent the effect of suppressing shrinkage on the ceramic layer 12 even though the phosphorus-containing component is added in the via-hole conductor 14. It is said. Due to the reaction between the phosphorus-containing component and the glass component, the softening behavior can be further promoted at the stage where the ceramic layer 12 contracts particularly greatly. Since the phosphorus-containing component is added separately from the glass component, the same softening behavior can be promoted for the diffusion glass from the ceramic layer 12.
  • the multilayer ceramic substrate 10 according to the present invention is the multilayer ceramic substrate 10 in which the via-hole conductor 14 is formed of a conductive composition that can rapidly soften the degree of softening in a high temperature range in the firing process, It is possible to obtain the multilayer ceramic substrate 10 that can suppress the protrusion of the via-hole conductor 14.
  • the multilayer ceramic substrate 20 includes a plurality of laminated ceramic layers 12, constraining layers 18, and via-hole conductors 14. That is, in the multilayer ceramic substrate 20 according to this embodiment, the constraining layer 18 is further formed along each of the plurality of ceramic layers 12.
  • the material of the ceramic layer 12 is the same as the material of the ceramic layer 12 in the multilayer ceramic substrate 10.
  • a material of the constraining layer 18 for example, alumina, zirconia, or the like can be used as a main component.
  • a glass component may be added as a sintering aid as needed.
  • the main component of the material of the ceramic layer 12 is barium oxide, silicon oxide, or alumina
  • the main component of the constraining layer 18 is preferably composed mainly of alumina.
  • the multilayer ceramic substrate 20 including the constraining layer 18 according to this embodiment can suppress the shrinkage behavior in the planar direction in the firing process as compared to the multilayer ceramic substrate 10, but even in such a case, A multilayer ceramic substrate in which the bulge of the via-hole conductor 14 is suppressed can be obtained.
  • a ceramic green sheet that becomes the ceramic layer 12 after firing is prepared.
  • This ceramic green sheet can be sintered at a temperature of about 1000 ° C.
  • a ceramic material powder mainly composed of barium oxide, silicon oxide, alumina or the like is used.
  • an organic binder, an organic solvent, etc. are added to the ceramic material powder, and a ceramic slurry is produced.
  • a ceramic green sheet is obtained by forming the ceramic slurry into a sheet.
  • the ceramic green sheet it may replace with this and may use what added the glass component which acts as a sintering aid to the material which acts as a ceramic filler like alumina or barium titanate, for example.
  • the glass component for example, borosilicate glass or silicon oxide may be added.
  • the constraining layer 18 may be formed on the above-described ceramic green sheet. That is, in the present invention, an inorganic material that is not sintered at the firing temperature of the multilayer ceramic substrate 20 is used as the constraining layer 18 between the ceramic layer 12 that can be sintered at a temperature of about 1000 ° C. and each layer in the multilayer ceramic substrate 20. You may arrange.
  • the constraining layer 18 is manufactured as follows. First, an organic binder, an organic solvent, and the like are added to an inorganic material powder that is not substantially sintered at a sintering temperature at which the ceramic material powder contained in the ceramic green sheet can be sintered, and these are mixed together to form a slurry. Make it. The slurry is formed in a thin layer on a ceramic green sheet by a coater or the like.
  • an inorganic material used for the constraining layer 18 mainly alumina is preferably used, but other compositions such as zirconia can be used as long as the ceramic green sheet is not sintered.
  • the constraining layer 18 may be formed first, and then the ceramic layer 12 may be formed. Furthermore, if there is no problem in efficiency, these may be repeated as many times as necessary, and multiple coatings may be performed.
  • the ceramic layer 12 and the constraining layer 18 are separately formed into a sheet shape, and are subjected to pressure bonding in a later step. It does not matter if they are pasted together. Further, in the production of the multilayer ceramic substrate 20 including the ceramic layer 12 and the constraining layer 18, it may be formed by, for example, spray coating, dip coating, thick film printing, etc. without forming into a sheet shape.
  • the conductive paste described above is filled in the via hole 16 previously provided in the ceramic green sheet or the constraining layer 18, and a conductor film having a predetermined shape is screened on the main surface of the ceramic green sheet or the constraining layer 18 as necessary.
  • An unfired temporary laminate is obtained by forming, laminating, and pressure bonding by a printing method, a transfer method, or the like.
  • a desired multilayer ceramic substrate can be obtained by firing the temporary laminate under conditions according to the components of the conductor film and the ceramic layer 12.
  • the firing conditions in the firing step are not particularly limited, and any known method can be used as long as the ceramic green sheet and the conductor film are sufficiently sintered.
  • a temperature keeping region in a specific temperature range or a region in which the temperature rising rate is extremely reduced is provided under firing conditions. In some cases, it is necessary to pay attention to the selection of glass components.
  • a temperature keeping region is provided in the range of 750 ° C. to 900 ° C. and 950 to 990 ° C. according to various conditions, and the maximum temperature is set to 990 ° C.
  • a phosphorus-containing component is allowed to act on the glass component during firing, particularly in a high temperature range. It is possible to rapidly soften the degree of softening. That is, it becomes possible to promote the degree of softening of the glass component in a high temperature range by newly causing the phosphorus component to act on the glass component in a heated state. Therefore, since the shrinkage behavior of the via-hole conductor 14 can be followed in accordance with the shrinkage behavior of the ceramic layer 12, for example, it is possible to obtain the multilayer ceramic substrates 10 and 20 that do not cause the bumps on the surface of the via-hole conductor. .
  • FIG. 4 shows the shrinkage ratio of the multilayer ceramic substrates 30 and 40 used in Experimental Example 1 and Experimental Example 2 with respect to the firing temperature, and time-series changes in the firing temperature.
  • Example 1 In Experimental Example 1, a glass powder having a softening point in a temperature range lower than the sintering temperature of the ceramic green sheet by about 150 to 300 ° C. with respect to the conductive powder, a phosphorus-containing compound, an organic vehicle, and the organic vehicle A conductive paste in which a predetermined amount of a resin component insoluble in the solvent component was added was produced.
  • Example 1 in Examples 1 to 6, the following materials were used as materials contained in the conductive paste. That is, as the conductive powder, alumina-coated copper powder was used, and an average particle size of 0.1 ⁇ m to 10 ⁇ m was used. The conductive powder was used in the range of 60% to 85% by weight. As the glass powder, a glass powder having a softening point of 700 ° C. or higher selected from Si—B system was used, and it was used within a range of 1 wt% to 10 wt%. In addition, copper pyrophosphate was used as the phosphorus-containing compound, and was used within the range of 0.1% to 0.8% by weight (0.02% to 0.16% by weight in terms of phosphorus component).
  • organic vehicle a mixture of ethyl cellulose and terpineol was used and used in the range of 10 wt% to 25 wt%.
  • polypropylene beads were used as necessary as a resin component insoluble in the solvent component of the organic vehicle, and used within the range of 0 to 7% by weight.
  • copper oxide powder was contained as required, and was used within the range of 0 to 40% by weight. The above-mentioned materials were mixed, and the desired paste was obtained by stirring and kneading with a lykai machine and three rolls.
  • Example 1 and Example 2 produced a conductive paste containing glass powder having an addition amount of copper pyrophosphate of 0.1% by weight and glass softening points of 680 ° C. and 830 ° C., respectively.
  • Examples 3 and 4 produced conductive pastes containing glass powders with an addition amount of copper pyrophosphate of 0.4% by weight and glass softening points of 680 ° C. and 830 ° C., respectively.
  • Example 5 and Example 6 produced conductive pastes containing glass powders with an addition amount of copper pyrophosphate of 0.8 wt% and glass softening points of 680 ° C. and 830 ° C., respectively.
  • Comparative Example 3 and Comparative Example 4 produced conductive pastes containing glass powder having an addition amount of copper pyrophosphate of 0.4 wt% and glass softening points of 600 ° C. and 880 ° C., respectively.
  • Comparative Example 5 and Comparative Example 6 produced conductive paste containing glass powder having an addition amount of copper pyrophosphate of 1.2 wt% and glass softening points of 680 ° C. and 830 ° C., respectively.
  • the conductive paste produced in each example and each comparative example was filled in a via hole previously formed in a ceramic green sheet and laminated, pressure-bonded, etc. to obtain an unfired temporary laminated body.
  • the temporary laminate was fired at a maximum temperature of 1000 ° C. with a temperature keeping region.
  • FIG. 5 is a schematic cross-sectional view of the multilayer ceramic substrate 30 used in Experimental Example 1.
  • the serial via-hole conductor 14 ′ shown in (a) is formed in a columnar shape, and has a diameter of 200 ⁇ m and a thickness of 300 ⁇ m. Further, (b) is formed by dividing the via-hole conductor, and each divided via-hole conductor 14′a, 14′b is formed in a rectangular parallelepiped shape having a width of 200 ⁇ m, a depth of 600 ⁇ m, and a thickness of 300 ⁇ m. Is formed.
  • the ceramic material of the ceramic layer used for the multilayer ceramic substrate 30 is mainly composed of barium oxide, silicon oxide, alumina, boron oxide, calcium oxide, and can be sintered at a temperature of 1000 ° C. or less. Using.
  • Table 1 shows the amount of copper pyrophosphate contained in the conductive pastes in Examples 1 to 6 and Comparative Examples 1 to 6 according to Experimental Example 1, the glass softening point of the glass powder, and the via-hole conductor.
  • the experimental result of the amount of upheaval is shown.
  • the height of the protruding amount of the series via-hole conductor 14 'in FIG. 5A is indicated by H1
  • the height of the protruding amount of the divided via-hole conductors 14'a and 14'b in FIG. 5B is indicated by H2.
  • the raised amount of the divided via-hole conductors 14′a and 14′b was an average value of the raised amounts of the two divided divided via-hole conductors 14′a and the divided via-hole conductor 14′b.
  • the protruding amount of the series via-hole conductor 14 ′ was 40 ⁇ m or less, but the protruding amounts of the divided via-hole conductors 14 ′ a and 14 ′ b were, except for Comparative Example 3, It was larger than 40 ⁇ m.
  • the protruding amount of the divided via-hole conductors 14′a and 14′b was 22 ⁇ m and was 40 ⁇ m or less.
  • FIG. 6 shows an example of the analysis result of the composition distribution in the multilayer ceramic substrate of the present invention, (a) shows the vicinity of the boundary between the ceramic layer and the via-hole conductor, and (b) shows the via-hole conductor.
  • C) shows the distribution of phosphorus (P) in the via-hole conductor
  • Si shows the distribution of glass (Si) in the via-hole conductor.
  • the phosphorus component is present at a position substantially close to the glass component, and the diffusion of the phosphorus component into the ceramic layer is extremely small. I understand that.
  • the phosphorus component can be retained in the via-hole conductor by reacting the phosphorus component with the glass component.
  • the phosphorus component is not extremely diffused in the ceramic layer, it is possible to prevent the shrinkage suppression effect on the ceramic layer from being exhibited even though the phosphorus component is added in the via-hole conductor. ing.
  • the softening behavior of the via-hole conductor can be promoted at the stage where the ceramic layer is particularly contracted by the reaction between the phosphorus component and the glass component. Therefore, the experimental results in Experimental Example 1 revealed that the use of the conductive paste made of the conductive composition according to the present invention for the via-hole conductor suppresses the bulge of the via-hole conductor in the multilayer ceramic substrate. .
  • Example 2 Also in Experimental Example 2, as in Experimental Example 1, with respect to the conductive powder, a glass powder having a softening point in a temperature range lower by about 150 to 300 ° C. than the sintering temperature of the ceramic green sheet, a phosphorus-containing compound, an organic vehicle, And the electroconductive paste which added the predetermined amount of resin components insoluble in the solvent component in the said organic vehicle was produced.
  • the following materials were used as materials contained in the conductive paste. That is, as the conductive powder, alumina-coated copper powder was used, and an average particle size of 0.1 ⁇ m to 10 ⁇ m was used. The conductive powder was used in the range of 60% to 85% by weight. As the glass powder, a glass powder having a softening point of 700 ° C. or higher selected from Si—B system was used, and it was used within a range of 1% by weight to 15% by weight. In addition, copper pyrophosphate was used as the phosphorus-containing compound, and was used within the range of 0.1% to 0.8% by weight (0.02% to 0.16% by weight in terms of phosphorus component).
  • organic vehicle a mixture of ethylcellulose and terpineol was used and used in the range of 10 wt% to 20 wt%.
  • polypropylene beads were used as necessary as a resin component insoluble in the solvent component of the organic vehicle, and used within the range of 0 to 7% by weight.
  • copper oxide powder was contained as required, and was used within the range of 0 to 40% by weight. The above-mentioned materials were mixed, and the desired paste was obtained by stirring and kneading with a lykai machine and three rolls.
  • Example 7 and Example 8 produced conductive paste containing glass powder having an addition amount of copper pyrophosphate of 0.1% by weight and glass softening points of 680 ° C. and 830 ° C., respectively.
  • Examples 9 and 10 produced conductive pastes containing glass powders with an addition amount of copper pyrophosphate of 0.4% by weight and glass softening points of 680 ° C. and 830 ° C., respectively.
  • Example 11 and Example 12 produced conductive paste containing glass powder in which the amount of copper pyrophosphate added was 0.8% by weight and the glass softening points were 680 ° C. and 830 ° C., respectively.
  • Comparative Example 7 and Comparative Example 8 produced a conductive paste containing glass powder in which copper pyrophosphate was not added and the softening points of glass were 680 ° C. and 830 ° C., respectively.
  • Comparative Example 9 and Comparative Example 10 produced conductive paste containing glass powder having an addition amount of copper pyrophosphate of 0.4 wt% and glass softening points of 600 ° C. and 880 ° C., respectively.
  • Comparative Example 11 and Comparative Example 12 produced conductive paste containing glass powder having an addition amount of copper pyrophosphate of 1.2% by weight and glass softening points of 680 ° C. and 830 ° C., respectively.
  • the conductive paste produced in each Example and each comparative example is filled in the via hole previously formed in the ceramic green sheet or the constraining layer 18, and laminated
  • the temporary laminate was fired at a maximum temperature of 1000 ° C. with a temperature keeping region.
  • FIG. 7 is a schematic cross-sectional view of the multilayer ceramic substrate 40 used in Experimental Example 2.
  • the serial via-hole conductor 14 ′ shown in (a) is formed in a columnar shape, and has a diameter of 200 ⁇ m and a thickness of 300 ⁇ m. Further, (b) is formed by dividing the via-hole conductor, and each divided via-hole conductor 14′a, 14′b is formed in a rectangular parallelepiped shape having a width of 200 ⁇ m, a depth of 600 ⁇ m, and a thickness of 300 ⁇ m. Is formed.
  • the multilayer ceramic substrate 40 in Experimental Example 2 includes the constraining layer 18.
  • a ceramic material of the ceramic layer 12 used for the multilayer ceramic substrate 40 a material mainly composed of barium oxide, silicon oxide, alumina, boron oxide, and calcium oxide, which can be sintered at a temperature of 1000 ° C. or less. used.
  • Alumina was used as the material of the constraining layer 18.
  • the thickness ratio between the ceramic layer 12 and the constraining layer 18 was set to 2 ⁇ m for the constraining layer 18 with respect to 40 ⁇ m for the ceramic layer 12.
  • Table 2 shows the amount of copper pyrophosphate contained in the conductive pastes in Examples 7 to 12 and Comparative Examples 7 to 12 according to Experimental Example 2, the glass softening point of the glass powder, and the via-hole conductor.
  • the experimental result of the amount of upheaval is shown.
  • the height of the protruding amount of the serial via-hole conductor 14 ′ is indicated by H1
  • the height of the protruding amount of the divided via-hole conductors 14′a and 14′b in FIG. 7B is indicated by H2.
  • the raised amount of the divided via-hole conductors 14′a and 14′b was an average value of the raised amounts of the two divided divided via-hole conductors 14′a and the divided via-hole conductor 14′b.
  • the protruding amount of the series via-hole conductor 14 ′ was 40 ⁇ m or less except for Comparative Example 8, but the protruding amounts of the divided via-hole conductors 14′a and 14′b were compared with Comparative Example 9. The amount of protrusion was larger than 40 ⁇ m. In Comparative Example 9, the protruding amount of the divided via-hole conductors 14′a and 14′b was 36 ⁇ m and was 40 ⁇ m or less.
  • the shrinkage behavior in the thickness direction in the firing process becomes particularly steep. That is, as shown in FIG. 4, the multilayer ceramic substrate 40 of Experimental Example 2 shows a larger shrinkage behavior in the thickness direction than the multilayer ceramic substrate 30 of Experimental Example 1. Thus, it is difficult for the multilayer ceramic substrate including the constraining layer to suppress the protrusion of the via-hole conductor.
  • the conductive paste of the conductive composition according to the present invention is used for the via-hole conductor even in the multilayer ceramic substrate including the constraining layer as used in the experimental example 2. Thus, it was clarified that the bulge of the via-hole conductor in the multilayer ceramic substrate is suppressed.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

La présente invention concerne une composition conductrice qui permet de supprimer le gauchissement ou la boursouflure d'un substrat céramique à couches multiples, lequel est fourni avec un conducteur de trou d'interconnexion qui est obtenu par remplissage d'une composition conductrice qui sert de pâte conductrice, ce défaut étant dû à un renflement du conducteur de trou d'interconnexion, et à d'autres causes similaires, durant l'étape de frittage du substrat de céramique à couches multiples. L'invention concerne également un substrat de céramique à couches multiples, ainsi qu'un procédé de fabrication de substrat de céramique à couches multiples. Une composition conductrice selon la présente invention est utilisée pour un conducteur à trou d'interconnexion (14) qui est rempli dans un trou d'interconnexion (16) dans un substrat de céramique à couches multiples (10), qui comprend une pluralité de couches de céramique stratifiées (12) et le trou d'interconnexion (16) formé de façon à pénétrer les couche de céramique (12). Cette composition conductrice contient une poudre conductrice, une poudre de verre, une poudre contenant du phosphore, et un véhicule organique. L'utilisation de cette composition conductrice pour un conducteur à trou d'interconnexion (14) permet d'obtenir un substrat de céramique à couches multiples (10) dont le renflement du conducteur à trou d'interconnexion (14) est supprimé.
PCT/JP2012/082169 2011-12-16 2012-12-12 Composition conductrice, substrat de céramique à couches multiples, et procédé de fabrication de ce substrat WO2013089128A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI673726B (zh) * 2015-01-07 2019-10-01 日商則武股份有限公司 導電性組成物、半導體元件與太陽電池元件

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1116418A (ja) * 1997-06-25 1999-01-22 Kyocera Corp 銅メタライズ組成物及びそれを用いたガラスセラミック配線基板
WO2007032167A1 (fr) * 2005-09-16 2007-03-22 Murata Manufacturing Co., Ltd. Substrat multicouche céramique et procede de fabrication idoine
JP2007141978A (ja) * 2005-11-16 2007-06-07 Ngk Spark Plug Co Ltd 導電性ペーストの製造方法および配線基板の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1116418A (ja) * 1997-06-25 1999-01-22 Kyocera Corp 銅メタライズ組成物及びそれを用いたガラスセラミック配線基板
WO2007032167A1 (fr) * 2005-09-16 2007-03-22 Murata Manufacturing Co., Ltd. Substrat multicouche céramique et procede de fabrication idoine
JP2007141978A (ja) * 2005-11-16 2007-06-07 Ngk Spark Plug Co Ltd 導電性ペーストの製造方法および配線基板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI673726B (zh) * 2015-01-07 2019-10-01 日商則武股份有限公司 導電性組成物、半導體元件與太陽電池元件

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