CERAMIC SUBSTRATE AND METHOD FOR PRODUCTION THEREOF

Abstract

A ceramic substrate and a method for production thereof are provided, in which the ceramic substrate includes a composite of : a first ceramic layer including Sr anorthite and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3; and a second ceramic layer including Sr anorthite and cordierite and having a dielectric constant lower than that of the first ceramic layer.

Claims

1. A ceramic substrate comprising: a first ceramic layer comprising Sr anorthite and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3; and a second ceramic layer comprising Sr anorthite and cordierite and having a dielectric constant lower than that of the first ceramic layer.

2. The ceramic substrate according to claim 1, wherein the absolute value of a difference in thermal expansion coefficient between the first ceramic layer and the second ceramic layer is 1×10.sup.−6/° C. or less.

3. The ceramic substrate according to claim 1, wherein the first ceramic layer and the second ceramic layer contains 0.5% by mass or less of B in terms of B.sub.2O.sub.3.

4. The ceramic substrate according to claim 1, wherein the first ceramic layer has a dielectric constant of 7 or more, and the second ceramic layer has a dielectric constant of 6.5 or less.

5. The ceramic substrate according to claim 1, wherein the first ceramic layer contains 40 to 50% by mass of Al in terms of Al.sub.2O.sub.3, 30 to 40% by mass of Si in terms of SiO.sub.2, and 10 to 20% by mass of Sr in terms of SrCO.sub.3.

6. The ceramic substrate according to claim 1, wherein the first ceramic layer has a main phase of Al.sub.2O.sub.3 or the oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3, and the second ceramic layer has a main phase of Sr anorthite.

7. A method for producing a ceramic substrate, the method comprising the steps of: stacking a layer of a first insulating material and a layer of a second insulating material to form a laminate, wherein the first insulating material comprises a powder of a mixture of at least glass capable of forming Sr anorthite; and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3, and the second insulating material comprises a powder of a mixture of at least glass capable of forming Sr anorthite; and cordierite; and firing the laminate to form Sr anorthite.

8. The method according to claim 7, wherein the first insulating material is a calcined product obtained by calcining a mixture of oxides or carbonates of Al, Si, and Sr or a calcined product mixture obtained by mixing the calcined product and an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3, and the second insulating material is a calcined product mixture obtained by mixing a cordierite powder and a calcined product obtained by calcining a mixture of oxides or carbonates of Al, Si, and Sr.

9. The method according to claim 7, which produces a ceramic substrate comprising: a first ceramic layer comprising Sr anorthite and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3; and a second ceramic layer comprising Sr anorthite and cordierite and having a dielectric constant lower than that of the first ceramic layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] FIG. 1 is a cross-sectional view illustrating an embodiment of the ceramic substrate of the invention; and

[0031] FIG. 2 is a photograph showing an observed cross-section of a ceramic substrate according to Example 1 of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The ceramic substrate of the invention and the method for production thereof will be described with reference to the drawings. Note that components unnecessary for the description are omitted from some or all of the drawings and that some components are illustrated, for example, in an enlarged or reduced manner to facilitate the description. Terms indicating positional relationships, such as “upper” and“lower,” are used only to make the description easy to understand and are not intended to limit the features of the invention at all.

[0033] Hereinafter, the ceramic substrate of the invention will be described. As illustrated in FIG. 1, the ceramic substrate of the invention includes a first ceramic layer 1 and a second ceramic layer 2, in which a plurality of ceramic layers may be provided for each type. The first and second ceramic layers 1 and 2 have different dielectric constants. In general, each ceramic layer is provided with a wiring pattern 3 and optionally a via for electrical interlayer connection. In the illustrated example, wiring patterns 3 for electrodes are provided on both sides of the first ceramic layer 1 with a higher dielectric constant to form a capacitor C. In addition, wiring patterns are provided between the second ceramic layers 2 to form an interconnection line, an inductor L, and other components. In the ceramic substrate of the invention, the first and second ceramic layers 1 and 2 contain Sr anorthite as a common phase. The ceramic substrate also includes a stack of ceramic layers having different dielectric constants, in which the first ceramic layer 1 has a relatively high dielectric constant while the second ceramic layer 2 has a relatively low dielectric constant. The order of stacking the respective ceramic layers and the number of the stacked ceramic layers may be appropriately designed depending on the intended use of the ceramic substrate and taking into account the circuit to be formed on the substrate, the desired mechanical strength and other physical properties, and other factors.

[0034] The first ceramic layer can be formed by firing a first insulating material that includes a powder of a mixture of at least glass capable of forming Sr anorthite; and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3. Any oxides, carbonates, or other materials capable of forming, for example, Mg.sub.2SiO.sub.4, ZrO.sub.2, BaTiO.sub.3, or TiO.sub.2 upon firing as described below may be used as raw materials for the oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3. Such raw materials may be added simultaneously with raw materials capable of producing Sr anorthite-forming glass. In addition, TiO.sub.2 may also be used to control the temperature characteristic τf of the resonance frequency of the dielectric ceramic.

[0035] As used herein, the term “Sr anorthite” refers to a material typically represented by the composition SrAl.sub.2Si.sub.2O.sub.8. The term “Sr anorthite” is also intended to include materials in which the Sr atom is partially substituted with another atom. Sr anorthite can be identified, for example, by observing the X-ray diffraction peak of an SrAl.sub.2Si.sub.2O.sub.8 phase in X-ray diffractometry (XRD) as described below.

[0036] The glass capable of forming Sr anorthite can be obtained by calcining raw materials including oxides or carbonates of Al, Si, and Sr as described below. Oxides and carbonates may be interchangeably used as raw materials because CO.sub.2 is dissociated (decarbonized) by calcination even when carbonates are used. It will be understood that the Sr anorthite may contain impurities derived from raw materials (inevitable impurities).

[0037] The contents of Al, Si, and Sr in the first insulating material should be such that SrAl.sub.2Si.sub.2O.sub.8 can be formed by firing the first insulating material and the first insulating material can be sintered at a low temperature of 1,000° C. or less to form a product with a sufficient sintered density. From these points of view, the first insulating material preferably contains 40 to 50% by mass in terms of Al.sub.2O.sub.3, 30 to 40% by mass in terms of SiO.sub.2, and 10 to 20% by mass in terms of SrCO.sub.3, based on 100% by mass of the total amount of the first insulating material. The composition of the first insulating material used to form the first ceramic layer should be so designed that the content of Al.sub.2O.sub.3 as a raw material is higher than that in the stoichiometric composition of SrAl.sub.2Si.sub.2O.sub.8 (Al.sub.2O.sub.3 31.30% by mass, SiO.sub.2 36.89% by mass, SrO 31.81% by mass), so that the resulting first ceramic layer can contain Al.sub.2O.sub.3 and SrAl.sub.2Si.sub.2O.sub.8. When the first insulating material contains Ti, the content of Ti in terms of TiO.sub.2 is preferably 0 to 10% by mass based on 100% by mass of the total amount of the first insulating material in view of temperature characteristic τf.

[0038] In addition to the main components mentioned above, the first insulating material may also contain, for example, Bi, Na, K, Cu, or Mn as a sub-component.

[0039] In order to reduce the softening point of the glass and make sintering possible at lower temperature, the first insulating material may contain at least one selected from the group consisting of 10% by mass or less of Bi in terms of Bi.sub.2O.sub.3, 5% by mass or less of Na in terms of Na.sub.2O, and 5% by mass or less of K in terms of K.sub.2O, based on 100% by mass of the main components.

[0040] Cu or Mn is preferably added to the first insulating material so that the Sr anorthite crystal precipitation temperature can be lowered. For this purpose, the first insulating material may contain at least one of 5% by mass or less of Cu in terms of CuO and 5% by mass or less of Mn in terms of MnO.sub.2, based on 100% by mass of the main components.

[0041] In the invention, the raw materials for the low-temperature sintered material should be as free of B.sub.2O.sub.3 as possible, though B.sub.2O.sub.3 is used for some conventional LTCC substrates. For this purpose, the content of B in terms of B.sub.2O.sub.3 is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, based on 100% by mass of the total amount of the first insulating material. B.sub.2O.sub.3 is disadvantageous in that it can dissolve in water or an alcohol during the manufacturing process, segregate during drying, react with electrode materials during sintering, or react with the organic binder used so that it can degrade the performance of the binder. However, reducing the B content to the above range can prevent the problems with the manufacturing process.

[0042] The respective raw materials for the low-temperature sintered material may be provided in the form of, for example, oxides or carbonates, which may be combined freely in such a manner that the contents of the main components and the sub-components can fall within the above ranges.

[0043] In the invention, the first insulating material is preferably obtained by weighing each raw material, then mixing the raw materials, drying the mixture, and calcining the resulting dried powder. The raw materials may be mixed using any known mixing method. In view of uniformity, for example, the raw materials and ion-exchanged water are preferably added to a ball mill containing zirconia balls and mixed under wet conditions for 10 to 30 hours to form a slurry.

[0044] A water-soluble organic binder such as polyvinyl alcohol (PVA) may be added to the slurry, and then the mixture may be subjected to a known drying method. For example, the mixture may be spray-dried in a spray dryer so that the mixture of the raw materials can be obtained in the form of granules with a diameter of about 50 to about 100 μm.

[0045] The raw material granules obtained after the drying may be calcined to form the first insulating material. The calcination may be performed using a known firing method. For example, the calcination is preferably performed in such a manner that the granules are kept at 850° C. or lower for 1 to 3 hours in the air in a firing furnace under such conditions that SiO.sub.2 is partially converted into glass. The granules are preferably fired at a calcination temperature of 750 to 850° C. A ground powder is obtained by grinding the resulting calcined product. The resulting ground powder preferably has a BET specific surface area of 10 to 20 m.sup.2/g so that it allows the first ceramic layer to have a dense structure and improved dielectric characteristics during firing. The first insulating material obtained through the calcination in this way includes Al.sub.2O.sub.3 as amain phase. The first insulating material may contain an oxide with a dielectric constant higher than that of Al.sub.2O.sub.3, such as Mg.sub.2SiO.sub.4, ZrO.sub.2, BaTiO.sub.3, or TiO.sub.2. In such a case, such an oxide may form the main phase if its content is high. The first insulating material may be a calcined product obtained by calcining a mixture of oxides or carbonates of Al, Si, and Sr. Alternatively, the first insulating material may be a calcined product mixture obtained by mixing the calcined product and an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3.

[0046] The first ceramic layer obtained by firing (sintering) the first insulating material by the method described below includes Sr anorthite and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3. The oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3 preferably includes an oxide such as Mg.sub.2SiO.sub.4, ZrO.sub.2, BaTiO.sub.3, or TiO.sub.2.

[0047] The first ceramic layer preferably contains 40 to 50% by mass of Al in terms of Al.sub.2O.sub.3, 30 to 40% by mass of Si in terms of SiO.sub.2, and 10 to 20% by mass of Sr in terms of SrCO.sub.3. The first ceramic layer has an Al.sub.2O.sub.3 content higher than that in the stoichiometric composition of SrAl.sub.2Si.sub.2O.sub.8 (Al.sub.2O.sub.3 31.30% by mass, SiO.sub.2 36.89% by mass, SrO 31.81% by mass). Therefore, the first ceramic layer can contain an Al.sub.2O.sub.3 crystal phase and an SrAl.sub.2Si.sub.2O.sub.8 crystal phase, which can provide high dielectric constant and form strong interface bonding. The first ceramic layer preferably contains 0.5% by mass or less of B in terms of B.sub.2O.sub.3.

[0048] In order to prevent delamination and cracking, the first ceramic layer preferably has a thermal expansion coefficient of 4×10.sup.−6 to 8×10.sup.−6/° C.

[0049] To have a higher dielectric constant, the first ceramic layer preferably contains a main phase of Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3. In particular, Al.sub.2O.sub.3 is more preferred because it has high strength and thus can form a substrate with higher transverse strength.

[0050] Next, a second insulating material used to form the second ceramic layer will be described. The second insulating material used to from the second ceramic layer includes a powder of a mixture of at least glass capable of forming Sr anorthite; and cordierite. The glass capable of forming Sr anorthite can be obtained similarly to that in the first insulating material by calcining raw materials including, for example, oxides or carbonates of Al, Si, and Sr. Hereinafter, a repeated description of the same features as those of the first insulating material may be omitted as appropriate.

[0051] The second insulating material preferably contains 10 to 20% by mass of Al in terms of Al.sub.2O.sub.3, 50 to 65% by mass of Si in terms of SiO.sub.2, and 20 to 30% by mass of Sr in terms of SrCO.sub.3 so that SrAl.sub.2Si.sub.2O.sub.8 can be formed as a main phase by firing the second insulating material. The second insulating material should have an Al content lower than that of the first insulating material, so that a higher SrAl.sub.2Si.sub.2O.sub.8 phase content can be achieved to provide a lower dielectric constant.

[0052] In addition to the main components mentioned above, the second insulating material may contain, for example, Bi, Na, K, Cu, or Mn as a sub-component.

[0053] Similarly to the process for the first insulating material, a powder is calcined, which is obtained by weighing the respective raw materials, then mixing the raw materials, and drying the mixture. The resulting calcined product has a SiO.sub.2 crystal phase and an Al.sub.2O.sub.3 crystal phase, in which Al.sub.2O.sub.3 is the main phase. A silicate mineral cordierite represented by the composition 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 is added to the calcined product, and then the resulting mixture is ground. The 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material is not limited and may be any of a natural product and a synthetic product. A commercially available product produced by a known method may also be directly used as the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material. Before use, a commercially available product may also be ground to a median diameter D50 of, for example, 1 to 3 μm. Alternatively, the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material may be produced by mixing the respective raw material powders containing Si, Al, and Mg, respectively, in a stoichiometric ratio or other ratios, firing the mixture at 1, 300° C. to 1, 400° C. by a known method, and grinding the fired product to form a fine powder. As used herein, the term “median diameter D50” refers to the particle size corresponding to a cumulative volume fraction of 50% in the curve showing the relationship between the particle size and the cumulative volume (the value obtained by summing the volumes of particles with particle sizes equal to and lower than a specific particle size).

[0054] The calcined product and the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material are ground under wet conditions to form a mixture powder. The step of grinding the mixture may be performed using any grinding means capable of forming a mixture powder with a median diameter D50 of less than 1 μm. A ball mill is preferred as a machine suitable for wet grinding. For example, the calcined product, the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material, and an organic solvent such as ethanol or butanol may be added to a ball mill containing zirconia balls and ground under wet conditions for 15 to 20 hours, so that a mixture powder with a desiredparticle size can be obtained. The mixture powder preferably has a BET specific surface area of 10 to 20 m.sup.2/g so that it can form a dense structure and provide improved dielectric characteristics during sintering.

[0055] The mixture powder preferably contains 20 to 35% by mass of the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material and 65 to 80% by mass of the calcined product based on 100% by mass of the total amount of the calcined product and the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material. When the contents of the materials fall within these ranges, the resulting dielectric ceramic can have a desired level of dielectric characteristics such as dielectric constant at high frequencies in the microwave band. The second insulating material obtained through the calcination in this way can contain a main phase of Al.sub.2O.sub.3 or a main phase of 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 depending on the content of the 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material. The second insulating material may be a calcined product mixture of a cordierite powder and a calcined product obtained by calcining a mixture of oxides or carbonates of Al, Sr, and Sr.

[0056] The second ceramic layer obtained by firing (sintering) the second insulating material by the method described below includes Sr anorthite and cordierite and has a dielectric constant lower than that of the first ceramic layer. As used herein, the term “cordierite” refers to a silicate mineral typically represented by the composition 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2. The cordierite has the following chemical composition: SiO.sub.2 42-56% by mass, Al.sub.2O.sub.3 30-45% by mass, Mg0 12-16% by mass, in which MgO, Al.sub.2O.sub.3, or SiO.sub.2 may be in excess of the stoichiometric composition of cordierite. It will be understood that the cordierite may contain impurities derived from raw materials (inevitable impurities).

[0057] The second ceramic layer preferably contains 10 to 30% by mass of Al in terms of Al.sub.2O.sub.3, 50 to 65% by mass of Si in terms of SiO.sub.2, and 20 to 30% by mass of Sr in terms of SrCO.sub.3. The second ceramic layer may have an Al content lower than that of the first ceramic layer and thus have a higher content of the Sr anorthite phase as the common phase, which can make the contraction behavior of the second ceramic layer close to that of the first ceramic layer during firing and thus make it possible to prevent delamination and cracking.

[0058] Similarly to the first ceramic layer, the second ceramic layer in the invention preferably contains 0.5% by mass or less of B in terms of B.sub.2O.sub.3 and more preferably contains 0.1% by mass or less of B in terms of B.sub.2O.sub.3. When the amount of use of B is kept low, problems with the manufacturing process can be prevented, such as damage to firing furnace materials and dissolution of B in water or an alcohol and segregation of B during drying in the process of forming the inorganic composition into ceramic sheets.

[0059] In order to prevent delamination and cracking, the second ceramic layer preferably has a thermal expansion coefficient similar to that of the first ceramic layer, and specifically, the second ceramic layer preferably has a thermal expansion coefficient of 4×10.sup.−6 to 8×10.sup.−6/° C.

[0060] In view of dielectric constant and prevention of delamination and cracking, the second ceramic layer preferably has a Sr anorthite phase as a main phase.

[0061] The resulting first and second insulating materials are each formed into a layer. Specifically, a layer of the first insulating material and a layer of the second insulating material are formed, respectively, in which the first insulating material includes a powder of a mixture of at least glass capable of forming Sr anorthite; and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3, and the second insulating material includes a powder of a mixture of at least glass capable of forming Sr anorthite; and cordierite. The layers may be formed by a known method such as a printing method, an inkjet method, a coating method, a transfer method, a calender roll method, or a doctor blade method. For example, a solvent, an organic binder, and a plasticizer are added to the ground powder, and then they are dispersed to form a slurry, which is formed into a sheet by a doctor blade method. The organic binder may be of any known conventional type. The organic binder may be, for example, polyvinyl butyral (PVB) in view of the strength, the ability to be via-formed, the ability to be pressure-bonded, and the dimensional stability with respect to a ceramic green sheet obtained by forming the material into a sheet. The plasticizer may be of any known conventional type, such as butyl phthalyl butyl glycolate (BPBG), dibutyl phthalate (DBP), or dioctyl phthalate (DOP). The solvent used is preferably an organic solvent such as ethanol, butanol, toluene, or isopropyl alcohol.

[0062] The slurry may be subjected to degassing under vacuum, and volatile components such as the organic solvent and the air entrained during the degassing may be evaporated, so that the slurry can be adjusted to a predetermined concentration or viscosity. The adjusted viscosity is preferably from 8,000 to 10,000 cP. Subsequently, the mixture powder in the form of the slurry may be formed into a ceramic green sheet with a thickness of 20 to 250 μm on a carrier film by a known sheet-forming technique such as a doctor blade method. In view of mechanical strength, surface smoothness, and other properties, the carrier film is preferably a resin film such as a polyethylene terephthalate (PET) film. Subsequently, the sheet may be directly cut into pieces of a predetermined size without being separated from the carrier film, so that a plurality of ceramic green sheets can be obtained.

[0063] The organic solvent-containing slurries obtained by the wet grinding may be subjected to a sheet-forming process, respectively, to form a ceramic green sheet of the first insulating material and a ceramic green sheet of the second insulating material. The ceramic green sheet as formed by a doctor blade method is supported on a resin film such as a PET film. Via holes may be formed in the ceramic green sheet in such a state. Any known method may be used to form via holes. For example, the ceramic green sheet may be punched with a punching die having a plurality of punching pins, or via holes may be formed by perforating the ceramic green sheet by laser machining. The size of the via holes is preferably, for example, 30 to 80 μm in diameter.

[0064] Subsequently, the ceramic green sheet and a screen mask may be placed in a printing machine, where the via holes formed in the ceramic green sheet may be filled with a conductor paste by printing, and a conductor pattern such as wiring (wiring pattern) may be formed on the ceramic green sheet by printing. The conductor paste may be a known conductor paste. In view of resistivity, for example, a Ag paste or a Cu paste may be used as the conductor paste.

[0065] The ceramic green sheets may be stacked to forma laminate including the first and second insulating materials arranged in layers. In other words, a layer of the first insulating material and a layer of the second insulating material may be stacked to form a laminate. In addition, a composite ceramic green sheet may be formed by hollowing part of the ceramic green sheet of one insulating material and then filling the hollow with the other insulating material, or a composite ceramic green sheet may be formed by printing one insulating material on part of the ceramic green sheet of the other insulating material. The ceramic green sheet may also have a partial region with a dielectric constant different from that of the other region.

[0066] The resin film may be removed from each ceramic green sheet, and a plurality of the ceramic green sheets may be stacked. The stack of the ceramic green sheets may be 0.2 to 1.5 mm in thickness, which may include 5 to 20 stacked green sheet layers each with a thickness of 10 to 200 μm. The number of layers to be stacked (the number of stacks) and other conditions may be freely selected depending on the desired thickness of the ceramic substrate. The ceramic green sheets may be arranged in such a manner that via wiring parts overlap one another, and then a pressure may be applied in the thickness direction to the sheets using a press machine. In this process, a laminate is preferably formed by pressure-bonding the stacked ceramic green sheets at a binder-softening temperature such as a temperature of 60 to 90° C. with a pressure of 1 to 30 MPa applied for 100 seconds to 30 minutes. More preferably, a laminate is formed by placing the stack in a die composed of a metal frame and a pair of metal plates, then sealing the stack with a resin film, and then pressing the stack by CIP (with a hydrostatic isotropic press).

[0067] Subsequently, the laminate may be subjected to debinding and firing, in which Sr anorthite is produced by firing. In the firingprocess, the temperature is first preferably increased at a rate of 10 to 20° C. per hour from about 200° C., at which the binder starts to undergo thermal decomposition, to about 600° C., at which the thermal decomposition is completed, in order to prevent delamination of the ceramic green sheets, which would otherwise be caused by the pressure of generated gas. The debinding may be performed under a nitrogen atmosphere. Preferably, the debinding is performed while a sufficient amount of air is supplied and discharged in order to facilitate the decomposition and oxidation of the organic binder and to facilitate the removal of CO.sub.2 gas and gas generated by the decomposition. At 600° C. or higher, the content of organic materials reaches at most about 0.05% by mass. Therefore, from 600° C., the firing (sintering) may be performed by, for example, increasing the temperature at a rate of 150 to 250° C. per hour to 1,000° C. or lower (e.g., 900° C.) in the air or an N.sub.2 atmosphere and then maintaining the reached temperature for 1 to 3 hours, so that a ceramic substrate including a composite of first and second ceramic layers with different dielectric constants can be obtained by converting the first and second insulating materials into dielectric ceramics with different dielectric constants. In this process, Sr anorthite should be strongly bonded while being formed. For this purpose, the firing (sintering) should preferably be performed at 800 to 1,000° C.

[0068] The ceramic substrate of the invention includes a first ceramic layer including Sr anorthite and Al.sub.2O.sub.3 or an oxide dielectric with a dielectric constant higher than that of Al.sub.2O.sub.3; and a second ceramic layer including Sr anorthite and cordierite and having a dielectric constant lower than that of the first ceramic layer. Therefore, when semiconductor devices, inductances, and reactance elements such as capacitors are mounted on the ceramic substrate of the invention, low melting point metals such as Ag and Cu can be used to form wiring for connecting the semiconductor devices and other components and to form electrodes, while different dielectric constants are maintained in the ceramic substrate. SrAl.sub.2Si.sub.2O.sub.8 is formed as a common crystal phase in the first and second ceramic layers by the firing, so that the first and second ceramic layers can be strongly bonded together with less delamination and cracking at the bonded interface between the first and second ceramic layers.

[0069] In the ceramic substrate of the invention, the absolute value of the difference between the thermal expansion coefficients of the first and second ceramic layers is preferably 1×10.sup.−6/° C. or less, more preferably 0.5×10.sup.−6/° C. or less. In addition, the first and second ceramic layers preferably have close contraction behaviors during firing (close contraction starting temperatures and close contraction ending temperatures). Specifically, the difference between their contraction starting temperatures and the difference between their contraction ending temperatures are preferably within ±25° C. This makes it possible to suppress delamination and cracking even when thermal expansion difference-induced stress occurs at the bonded interface between the first and second ceramic layers in the process of mounting semiconductors and chip parts on the ceramic substrate by reflow soldering or the like, which induces rapid thermal changes. For the retention of dielectric characteristics, the ceramic substrate of the invention preferably has an fQ product of 10 THz or more, more preferably more than 10 THz, at a frequency of 15 GHz.

[0070] The ceramic substrate of the invention preferably has a porosity of 1.0% or less, more preferably 0.8% or less, even more preferably 0.7% or less. This feature makes it easy to obtain the desired dielectric characteristics.

EXAMPLES

[0071] Hereinafter, the invention will be described in detail with reference to examples. It will be understood that the examples below are not intended to limit the gist of the invention. First, the measurement conditions and methods, and other conditions will be described together for various items evaluated in the examples.

[0072] <Evaluations>

[0073] (1) Dielectric Constant and fQ Product

[0074] The dielectric characteristics were evaluated by dielectric resonator method (according to JIS R 1627) using a network analyzer (872D manufactured by Hewlett-Packard Company). The resonance frequency f and no-load Q value of a sample with a predetermined shape (11 mm in diameter, 5.5 mm in thickness) were measured, from which the fQ product was calculated, and the dielectric constant of the sample was calculated from the relationship between f and the dimensions of the sample. The dimensions were so selected as to achieve a resonance frequency of 15 GHz.

[0075] (2) Temperature Characteristic τf of Resonance Frequency

[0076] The sample for item (1) was used in the measurement of the resonance frequency in the temperature range of −20 to 60° C., from which the temperature characteristic τf was calculated based on the resonance frequency at 20° C.

[0077] (3) X-Ray Diffraction Intensity

[0078] X-ray diffractometry (XRD) was performed using a multifunctional X-ray diffractometer MRD (manufactured by Spectris Co., Ltd.) with Cu-Kα as a ray source.

[0079] (4) Density

[0080] The density was calculated from the outer diameter, thickness, and mass of the sample.

[0081] (5) Thermal Expansion Coefficient

[0082] After the upper and lower surfaces of a sintered product with a diameter of 5 mm and a height of 10 mm was figured, the sintered product was subjected to thermal mechanical analysis (TMA) measurement ata rate of temperature increase of 600° C./hour, from which the thermal expansion coefficient was calculated in the range of 40 to 400° C.

[0083] (6) Transverse Strength

[0084] Ten layers each having 110-μm-thickness of green sheet produced with each of the first and second insulating materials were stacked and then subjected to CIP (with a hydrostatic isotropic press) at 85° C. with a pressure of 30 MPa applied for 30 minutes to form a green sheet laminate. Subsequently, each green sheet laminate was cut so as to form 36-mm-long, 12-mm-wide, 1-mm-thick pieces after firing. Subsequently, the cut pieces were fired at 900° C. for 2 hours and then subjected to C chamfering. The resulting chamfered samples were subjected to the measurement of transverse strength (according to JIS R1601). The top five and bottom five values are excluded from the measurements of the samples (n=20), and the average of the ten measurements (n=10) is indicated.

[0085] (7) Vickers Hardness

[0086] The surface of the fired sample to be measured was subjected to mirror polishing and then subjected to the measurement of Vickers hardness based on JIS Z 2244 (test force 1.961 N (HV 0.2)).

[0087] (8) Contraction Starting and Ending Temperatures During Firing

[0088] A sample formed with a 5.5-mm-diameter, 12-mm-height shape was subjected to TMA at a rate of temperature increase of 10° C./minute, in which the contraction starting and ending temperatures were determined from intercepts at points of variation of the resulting contraction curve.

[0089] (9) Optical Microscope (Porosity) and Scanning Electron Microscope (Delamination and Cracking)

[0090] The resulting ceramic substrate was cut in the thickness direction. The resulting cross-section was subjected to mirror polishing and then observed with a microscope at a magnification of 100. In addition, the image was subjected to binarization, in which the pore portions of the image were black whereas the non-pore portions were white, and the area ratio of the black portions was calculated using image analysis software (ImageJ). Specifically, the porosity (%) in the area of the field of view was calculated by dividing the measured area of the pore portions by the total area of the field of view. After a process similar to the above, delamination and cracking at the bonded interface between the first and second ceramic layers were observed with a scanning electron microscope at a magnification of 2,000.

Example 1

[0091] <Preparation of Ceramic Substrate>

[0092] A first insulating material was prepared, which was to be fired to form a first ceramic layer. Raw materials, 50 kg in total mass, were weighed and mixed to form a composition of 45.5% by mass of Al.sub.2O.sub.3, 32.5% by mass of SiO.sub.2, 13.0% by mass of SrCO.sub.3, 3.5% by mass of TiO.sub.2, 2.3% by mass of Bi.sub.2O.sub.3, 2.4% by mass of Na.sub.2CO.sub.3, 0.3% by mass of CuO, and 0.5% by mass of Mn.sub.3O.sub.4 (100% by mass in total). The resulting mixed powder was placed in a firing setter and calcined in the air in the firing furnace at a temperature of 800° C. for 2 hours to form a calcined product. The resulting calcined product was ground to give a first insulating material. Crystal phases were identified by X-ray diffraction analysis of the first insulating material. Peaks indicating the presence of Al.sub.2O.sub.3 and SiO.sub.2 were observed in the X-ray diffraction pattern, and it was determined from the peak intensities that Al.sub.2O.sub.3 was the main phase. In addition, SrAl.sub.2Si.sub.2O.sub.8 was not identified.

[0093] A second insulating material was prepared, which was to be fired to form a second ceramic layer. Raw materials, 50 kg in total mass, were weighed and mixed to form a composition of 15.0% by mass of Al.sub.2O.sub.3, 53.8% by mass of SiO.sub.2, 21.2% by mass of SrCO.sub.3, 3.4% by mass of Bi.sub.2O.sub.3, 4.6% by mass of Na.sub.2CO.sub.3, 1% by mass of K.sub.2CO.sub.3, 0.4% by mass of CuO, and 0.6% by mass of Mn.sub.3O.sub.4 (100% by mass in total). The resulting mixed powder was placed in a firing setter and calcined in the air in the firing furnace at a temperature of 775° C. for 2 hours to form a calcined product. Like the first insulating material, peaks indicating the presence of Al.sub.2O.sub.3 and SiO.sub.2 were observed in the X-ray diffraction pattern of the calcined product, and it was determined from the peak intensities that Al.sub.2O.sub.3 was the main phase. In addition, SrAl.sub.2Si.sub.2O.sub.8 was not identified. A second insulting material was prepared by mixing 70% by mass of the resulting calcined product and 30% by mass of a commercially available 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 material (purity: 97.5%, median diameter D50: 1.65 μm, BET: 6.3 m.sup.2/g), grinding them under wet conditions in a ball mill, and then drying the ground mixture. Peaks indicating the presence of Al.sub.2O.sub.3, SiO.sub.2, and 2MgO.2Al.sub.2O.sub.3.5SiO.sub.2 were observed in the X-ray diffraction pattern of the second insulating material, and it was determined from the peak intensities that Al.sub.2O.sub.3 was the main phase.

[0094] A binder (PVA) was added to each of the resulting first and second insulating materials and mixed therewith. Each mixture was sieved with a mesh to give a granulated powder, which was packed into a die to form a molded product. The shape and dimensions of each molded product were according to those shown for the respective measurement items in the evaluation section above. Each molded product was fired at a temperature of 900° C. for 2 hours to form each dielectric ceramic. Each resulting dielectric ceramic was evaluated for density, dielectric constant, fQ product, temperature characteristic τf of resonance frequency, thermal expansion coefficient, and other characteristics. Table 1 shows the results.

TABLE-US-00001 TABLE 1 Dielectric ceramic Dielectric ceramic (first ceramic layer) (second ceramic layer) made from first made from second insulating material insulating material Dielectric constant εr 8.1 6.0 fQ product 13 THz 11 THz Temperature coefficient −17.0 × 10.sup.−6/° C. −18.1 × 10.sup.−6/° C. τf of resonance frequency Sintered density 3.20 × 10.sup.3 kg/m.sup.3 2.75 × 10.sup.3 kg/m.sup.3 Thermal expansion 5.3 × 10.sup.−6/° C. 5.6 × 10.sup.−6/° C. coefficient Contraction starting and Starting 732° C., Starting 757° C., ending temperatures ending 852° C. ending 847° C. during firing Vickers hardness 771 666 Porosity 0.03% 0.67%

[0095] The respective dielectric ceramics had a dielectric constant of 8.1 (first ceramic layer) and a dielectric constant of 6.0 (second ceramic layer) at 15 GHz. Both of the respective dielectric ceramics had an fQ product of at least 10 THz. The difference in thermal expansion coefficient between the respective dielectric ceramics was at most 1×10.sup.−6/° C., and the difference between the contraction starting and ending temperatures during the firing was also small and within ±25° C. As a result of the X-ray diffractometry of the respective dielectric ceramics, the dielectric ceramic made from the first insulating material was found to contain Al.sub.2O.sub.3, SiO.sub.2, SrAl.sub.2Si.sub.2O.sub.8, TiO.sub.2, and other components. An Al.sub.2O.sub.3 diffraction peak appeared higher than other crystal phase peaks, which showed that Al.sub.2O.sub.3 was the main phase of the dielectric ceramic. The dielectric ceramic made from the second insulating material was found to contain Al.sub.2O.sub.3, SiO.sub.2, SrAl.sub.2Si.sub.2O.sub.8, 2MgO.2Al.sub.2O.sub.8.5SiO.sub.2, and other components. An SrAl.sub.2Si.sub.2O.sub.8 diffraction peak appeared higher than other crystal phase peaks, which showed that SrAl.sub.2Si.sub.2O.sub.8 was the main phase.

[0096] A solvent (ethanol), a plasticizer (DOP), and a binder (PVB) were added to each of the first and second insulating materials. Each mixture was stirred to forma dispersion. Each dispersion was subjected to degassing under vacuum, and volatile components such as the organic solvent and the air entrained during the degassing were evaporated, so that a slurry with an adjusted viscosity was obtained. Each degassed slurry was formed into a 50-μm-thick ceramic green sheet by a doctor blade method.

[0097] Laser machining was performed to form via holes in each ceramic green sheet, which was supported on a PET resin film.

[0098] Subsequently, each ceramic green sheet and a screen mask were placed in a printing machine, where the via holes formed in the ceramic green sheet was filled with a conductor paste by printing using a squeegee, and a conductor pattern such as wiring was formed on the ceramic green sheet by printing. The conductor paste used was a Ag paste.

[0099] Subsequently, the resin film was removed from each ceramic green sheet, and then a plurality of the ceramic green sheets were stacked. The ceramic green sheets were fixed with a pressure-sensitive adhesive sheet to a press machine, and so arranged that via wiring portions overlapped one another. A stack of the ceramic green sheets was obtained by applying a pressure in the vertical direction to the arranged ceramic green sheets. The resulting stack was subjected to cold isostatic pressing (CIP) at a binder-softening temperature, 85° C., with a pressure of 15 MPa applied for 30 minutes so that the ceramic green sheets were pressure-bonded to form a laminate (1.5 mm in thickness).

[0100] Subsequently, the laminate was fired to form a ceramic substrate. The firing was performed by degreasing at 600° C. and then holding in the air at 900° C. for about 2 hours. The resulting ceramic substrate was cut in the thickness direction. The resulting cross-section was subjected to mirror polishing and then observed with an optical microscope at a magnification of 100. FIG. 2 shows a photograph of the observed cross-section. The ceramic substrate shown in FIG. 2 includes, in order from the lower side, two stacked 40-μm-thick first ceramic layers of the dielectric ceramic made from the first insulating material, following three stacked 40-μm-thick second ceramic layers of the dielectric ceramic made from the second insulating material, an intermediate Ag electrode, a first ceramic layer stacked thereon, another intermediate Ag electrode, a first ceramic layer stacked thereon, a further intermediate Ag electrode, following three stacked second ceramic layers, and following two stacked first ceramic layers. Ag electrodes are formed on the upper and lower surfaces of the ceramic substrate, which correspond to the upper and lower sides of the cross-sectional view.

[0101] As a result of observation with a scanning electron microscope at a magnification of 2,000, no delamination or cracking was observed at the bonded interface between the first and second ceramic layers, and they were found to be strongly bonded together. No delamination or cracking was also observed at the bonded interface between the first ceramic layer and the Ag electrode or at the bonded interface between the second ceramic layer and the Ag electrode.

[0102] Only ten 110-μm-thick ceramic green sheets made from the first insulating material were stacked and subjected to CIP at 85° C. with a pressure of 30 MPa applied for 30 minutes to form a laminate, which was cut so as to form 36-mm-long, 12-mm-wide, 1-mm-thick pieces after firing. Subsequently, the cut pieces were fired at 900° C. for 2 hours and then subjected to C chamfering, resulting in samples for evaluation of transverse strength. Similarly, only ten ceramic green sheets made from the second insulating material were stacked and used to form samples for evaluation of transverse strength, which were made of the second ceramic layers. In addition, only five ceramic green sheets made from the first insulating material were stacked, on which only five ceramic green sheets made from the second insulating material were then stacked. The resulting stack was used to form samples for evaluation of transverse strength, which were made of a composite of the first and second ceramic layers. Each sample for evaluation of transverse strength was subjected to the measurement of transverse strength using the evaluation method described above. As a result, the samples made of only the first ceramic layers had a transverse strength of 300 MPa, and the samples made of only the second ceramic layers had a transverse strength of 199 MPa. On the other hand, the samples made of a composite of the first and second ceramic layers had a transverse strength of 260 MPa.

Comparative Example 1

[0103] A second insulating material was prepared, which was to be fired to form a second ceramic layer. Raw materials, 50 kg in total mass, were weighed and mixed to form a composition of 15.0% by mass of Al.sub.2O.sub.3, 53.8% by mass of SiO.sub.2, 21.2% by mass of SrCO.sub.3, 3.4% by mass of Bi.sub.2O.sub.3, 4.6% by mass of Na.sub.2CO.sub.3, 1% by mass of K.sub.2CO.sub.3, 0.4% by mass of CuO, and 0.6% by mass of Mn.sub.3O.sub.4 (100% by mass in total). The resulting mixed powder was placed in a firing setter and calcined in the air in the firing furnace at a temperature of 775° C. for 2 hours to form a calcined product. Like the first insulating material, peaks indicating the presence of Al.sub.2O.sub.3 and SiO.sub.2 were observed in the X-ray diffraction pattern of the calcined product, and it was determined from the peak intensities that Al.sub.2O.sub.3 was the main phase. In addition, SrAl.sub.2Si.sub.2O.sub.8 was not identified. A second insulting material was prepared by mixing 86% by mass of the resulting calcined product and 14% by mass of commercially available quartz SiO.sub.2 (purity: 99.8%) , grinding them under wet conditions in a ball mill, and then drying the ground mixture. The X-ray diffraction pattern of the second insulating material showed that SiO.sub.2 was the main phase.

[0104] A binder (PVA) was added to the resulting second insulating material and mixed therewith. The mixture was sieved with a mesh to give a granulated powder, which was packed into a die to form a molded product. The shape and dimensions of the molded product were according to those shown for the respective measurement items in the evaluation section above. The molded product was fired at a temperature of 900° C. for 2 hours to form a dielectric ceramic. The resulting dielectric ceramic was evaluated for density, dielectric constant, fQ product, temperature characteristic τf of resonance frequency, thermal expansion coefficient, and other characteristics. Table 2 shows the results.

TABLE-US-00002 TABLE 2 Dielectric ceramic (second ceramic layer) made from second insulating material Dielectric constant εr 5.7 fQ product 10 THz Temperature coefficient −4.8 × 10.sup.−6/° C. τf of resonance frequency Sintered density 2.74 × 10.sup.3 kg/m.sup.3 Thermal expansion 10.7 × 10.sup.−6/° C. coefficient Contraction starting Starting 733° C., and ending temperatures ending 848° C. during firing Vickers hardness 639 Porosity 1.27%

[0105] The dielectric ceramic made from the second insulating material was found to contain Al.sub.2O.sub.3, SiO.sub.2, SrAl.sub.2Si.sub.2O.sub.8, and other components. An SrAl.sub.2Si.sub.2O.sub.8 diffraction peak appeared higher than other crystal phase peaks, which showed that SrAl.sub.2Si.sub.2O.sub.8 was the main phase.

[0106] Samples for evaluation of transverse strength were also prepared as in Example 1. The transverse strength of the samples was measured by the above evaluation method. Aa a result, the samples made of only the second ceramic layers of Comparative Example 1 had a transverse strength of 210 MPa.

[0107] The first insulating material obtained in Example 1 and the second insulating material obtained in Comparative Example 1 were used to form a ceramic substrate in a similar manner to Example 1. As a result of observation with a scanning electron microscope at a magnification of 2,000, cracking was observed in two of five samples. In two of five samples, delamination was also observed at the bonded interface between the first ceramic layer and the Ag electrode or at the bonded interface between the second ceramic layer and the Ag electrode. The first insulating material obtained in Example 1 and the second insulating material obtained in Comparative Example 1 seem to be similar in contraction behavior (contraction starting and ending temperatures). However, the second insulating material obtained in Comparative Example 1 seems to be more likely to cause cracking or delamination because it significantly differs in thermal expansion coefficient from the first insulating material and contracts at a higher percentage during firing.