Low-temperature fired ceramic and electronic component

Abstract

A low-temperature fired ceramic according to the present invention contains a fired glass component (A1) and an oxide (C1) of a ceramic crystal component. The fired glass component (A1) is RO-ZnO-Al2O3-B2O3-SiO2. RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. The proportion of RO, the proportion of ZnO, and the proportion of Al2O3 contained in the fired glass component (A1) are each 0.1-10 mol%. The sum of the proportion of RO, the proportion of ZnO, and the proportion of Al2O3 contained in the fired glass component (A1) is 15 mol% or less. The ratio (SiO2 / B2O3) of SiO2 and B2O3 contained in the fired glass component (A1) is less than 3.4. The oxide (C1) of a ceramic crystal component contains at least one selected from the group consisting of SiO2, BaAl3Si2O8, ZnAl2O4, and Zn2SiO4.

Description

Low-temperature fired ceramics and electronic components

[0001] The present invention relates to low-temperature co-fired ceramics and electronic components.

[0002] As a ceramic material for a ceramic multilayer wiring board, a glass ceramic material (LTCC material) that can be fired at a low temperature is known.

[0003] For example, the dielectric loss (dielectric loss tangent) of glass ceramics for LTCC substrates in the GHz frequency range is 20×10 －４ As a glass composition for further reducing the temperature, Patent Document 1 discloses RO-Al ２ O ３ -B ２ O ３ -SiO ２ (wherein RO is one or more of the group consisting of MgO, CaO, SrO, BaO, and ZnO), and ２ O ３ are all in the range of 1 to 25 mol%, and SiO ２ / B ２ O ３ The glass composition for low-temperature fired substrates has a mol % ratio of 1.3 or less, and a glass ceramic in which the glass composition for low-temperature fired substrates contains an aggregate.

[0004] Japanese Patent Application Laid-Open No. 2004-26529

[0005] In order to reduce the dielectric loss of glass ceramics, it is necessary to add modifier oxides such as RO and Al in the glass of the fired body. ２ O ３ However, in Patent Document 1, the content of RO and Al is low in the glass composition before firing. ２ O ３ However, the dielectric loss is limited to 16 × 10 －４ No means of lowering it are disclosed.

[0006] In view of the above, an object of the present invention is to provide a low-temperature co-fired ceramic having a low dielectric loss.

[0007] The first low-temperature fired ceramic of the present invention is a low-temperature fired ceramic containing a fired glass component (A1) and an oxide of a ceramic crystal component (C1), and the fired glass component (A1) is RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportion of RO, the proportion of ZnO, and the proportion of Al contained in the glass component (A1) after firing are ２ O ３ the proportions of RO, ZnO and Al contained in the fired glass component (A1) are 0.1 mol % or more and 10 mol % or less, respectively, ２ O ３ The sum of the proportions of SiO contained in the glass component (A1) after firing is 15 mol % or less. ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, and the oxide (C1) of the ceramic crystal component is SiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ The composition contains at least one selected from the group consisting of:

[0008] The second low-temperature fired ceramic of the present invention is a low-temperature fired ceramic containing a fired glass component (A2) and an oxide of a ceramic crystal component (C2), and the fired glass component (A2) is RO—ZnO—Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportion of RO, the proportion of ZnO, and the proportion of Al contained in the glass component (A2) after firing are ２ O ３the proportions of RO, ZnO and Al contained in the fired glass component (A2) are 0.1 mol % or more and 10 mol % or less, respectively, ２ O ３ The sum of the proportions of the oxides (C2) of the ceramic crystal components is 15 mol % or less, and the oxides (C2) of the ceramic crystal components are Ba, ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ The compound contains at least one selected from the group consisting of:

[0009] The first electronic component of the present invention includes the first low-temperature co-fired ceramic or the second low-temperature co-fired ceramic of the present invention.

[0010] A second electronic component of the present invention is an electronic component including a low-dielectric-constant ceramic layer and a high-dielectric-constant ceramic layer, wherein the low-dielectric-constant ceramic layer is formed of a first low-temperature-fired ceramic, and the high-dielectric-constant ceramic layer is formed of a second low-temperature-fired ceramic, the first low-temperature-fired ceramic containing a fired glass component (A1) and an oxide of a ceramic crystalline component (C1), the second low-temperature-fired ceramic containing the fired glass component (A2) and an oxide of a ceramic crystalline component (C2), and the fired glass component (A1) and the fired glass component (A2) are each selected from the group consisting of RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportions of RO, ZnO, and Al contained in the fired glass component (A1) and the fired glass component (A2) are ２ O３ are 0.1 mol % or more and 10 mol % or less, respectively, and the ratio of RO, the ratio of ZnO and the ratio of Al contained in the fired glass component (A1) and the fired glass component (A2) are ２ O ３ The sum of the proportions of SiO contained in the glass component (A1) after firing is 15 mol % or less. ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, and the first low-temperature fired ceramic further contains Al in addition to the glass component after firing. ２ O ３ and the Al contained in the low-temperature fired ceramic ２ O ３ The proportion of the ceramic crystal component (C1) is more than 0 wt % and 5 wt % or less, and the oxide (C1) of the ceramic crystal component is BaAl ２ Si ２ O ８ and SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The first low-temperature co-fired ceramic contains at least two selected from the group consisting of BaAl ２ Si ２ O ８ The proportion of the ceramic crystal component (C2) is more than 0% by weight and not more than 5% by weight, and the oxide of the ceramic crystal component (C2) is Ba. ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７The compound contains at least one selected from the group consisting of:

[0011] According to the present invention, it is possible to provide a low-temperature co-fired ceramic having a small dielectric loss.

[0012] Fig. 1 is a cross-sectional view schematically showing an example of a multilayer ceramic electronic component as a first electronic component of the present invention. Fig. 2 is a cross-sectional view schematically showing a multilayer green sheet (unfired state) produced in the process of manufacturing the multilayer ceramic electronic component shown in Fig. 1. Fig. 3 is a cross-sectional view schematically showing an example of a multilayer ceramic electronic component as a second electronic component of the present invention. Fig. 4 is a cross-sectional view schematically showing a multilayer green sheet (unfired state) produced in the process of manufacturing the multilayer ceramic electronic component shown in Fig. 3.

[0013] The low-temperature co-fired ceramic and electronic component of the present invention will be described below. Note that the present invention is not limited to the following configurations and may be modified as appropriate without departing from the gist of the present invention. In addition, a combination of multiple individual preferred configurations described below also constitutes the present invention.

[0014] The low-temperature co-fired ceramic of the present invention is a fired body obtained by firing a low-temperature co-fired ceramic (LTCC) material, which is a glass ceramic material that can be sintered at a firing temperature of 1000° C. or less.

[0015] In this specification, the low-temperature-fired ceramic of the present invention includes a first low-temperature-fired ceramic and a second low-temperature-fired ceramic. As described below, the first low-temperature-fired ceramic is a low-dielectric-constant low-temperature-fired ceramic (low-dielectric-constant ceramic), and the second low-temperature-fired ceramic is a high-dielectric-constant low-temperature-fired ceramic (high-dielectric-constant ceramic). Hereinafter, the first low-temperature-fired ceramic may be referred to as a low-dielectric-constant low-temperature-fired ceramic or a low-dielectric-constant ceramic. Furthermore, the second low-temperature-fired ceramic may be referred to as a high-dielectric-constant low-temperature-fired ceramic or a high-dielectric-constant ceramic. In this specification, a low-dielectric-constant ceramic has a dielectric constant of 7 or less, and a high-dielectric-constant ceramic has a dielectric constant greater than 7.

[0016] (First Low-Temperature-Coated Ceramic) The first low-temperature-coated ceramic of the present invention contains a fired glass component (A1) and an oxide of a ceramic crystal component (C1). The fired glass component (A1) is RO—ZnO—Al ２ O ３ -B ２ O ３ -SiO ２ and RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. RO is an alkaline earth metal oxide. The proportion of RO, the proportion of ZnO, and Al contained in the glass component (A1) after firing are ２ O ３ The proportions of RO, ZnO and Al contained in the glass component (A1) after firing are 0.1 mol % or more and 10 mol % or less, respectively. ２ O ３ In the first low-temperature fired ceramic of the present invention, the sum of the proportions of RO, ZnO, and Al contained in the glass component (A1) after firing is 15 mol % or less. ２ O ３ Since the ratio of is specified to be small, it is possible to obtain a low-temperature co-fired ceramic having small dielectric loss.

[0017] Among the components contained in the first low-temperature fired ceramic, the fired glass component (A1) has a large dielectric loss, while the oxide (C1) of the ceramic crystal component has a small dielectric loss. Since the dielectric loss of the fired glass component (A1) is dominant with respect to the dielectric loss of the first low-temperature fired ceramic, it is important to reduce the dielectric loss of the fired glass component (A1). Therefore, the ratio of RO, the ratio of ZnO and Al contained in the fired glass component (A1) are ２ O ３ By specifying the ratio of RO, ZnO, and Al to a small ratio, the dielectric loss of the first low-temperature co-fired ceramic is reduced. ２ O ３ is precipitated outside the glass by firing, and the proportion of RO, the proportion of ZnO and Al contained in the glass components after firing are ２ O ３The proportion of RO, ZnO and Al decreases by firing. ２ O ３ By precipitating the above out of the glass, it is possible to obtain a low-temperature fired ceramic having a small dielectric loss.

[0018] The proportion of RO contained in the fired glass component (A1) is preferably 0.3 mol % or more and 6.0 mol % or less, and more preferably 0.4 mol % or more and 5.5 mol % or less.

[0019] The proportion of ZnO contained in the glass component (A1) after firing is preferably 0.5 mol % or more and 6.0 mol % or less, and more preferably 2.0 mol % or more and 5.5 mol % or less.

[0020] Al contained in the glass component (A1) after firing ２ O ３ The ratio is preferably 0.5 mol % or more and 9.5 mol % or less, and more preferably 1.0 mol % or more and 9.5 mol % or less.

[0021] The proportion of RO, the proportion of ZnO and the proportion of Al contained in the glass component (A1) after firing ２ O ３ The sum of the proportions of is, for example, 1.0 mol % or more, and preferably 5.0 mol % or more.

[0022] The proportion of RO (alkaline earth metal oxide), the proportion of ZnO, and Al contained in the glass component (A1) after firing ２ O ３ The ratio of is obtained by measuring powder XRD (X-ray diffraction measurement) of the first low-temperature fired ceramic (fired body) at a scan speed as low as 0.2 deg / min, and determining the composition of the glass component by Rietveld analysis.

[0023] When measuring samples of a commercialized fired body, the composition of the glass component can be determined by measuring the glass region identified by STEM and electron beam diffraction of the exfoliated sample using WDS (wavelength dispersive X-ray analysis). Electron beam diffraction can also identify the crystalline phases present.

[0024] Furthermore, the fired glass component (A1) preferably does not contain any alkali metal oxide. The absence of alkali metal oxide in the fired glass component (A1) allows for a low-temperature fired ceramic with low dielectric loss. When the fired glass component (A1) contains alkali metal oxide, the proportion of alkali metal oxide contained in the fired glass component (A1) is preferably 0.1 mol % or less.

[0025] Preferably, RO is BaO. When the glass component (A1) after firing contains BaO, the dielectric loss can be reduced. ２ O ３ , B ２ O ３ and SiO ２ The preferred ratios of RO and ZnO are as follows: RO: 0.1 mol % or more and 10 mol % or less ZnO: 0.1 mol % or more and 10 mol % or less Al ２ O ３ : 0.1 mol% or more, 10 mol% or less B ２ O ３ :20 mol% or more, 45 mol% or less SiO ２ :45 mol% or more, 70 mol% or less

[0026] SiO contained in the glass component (A1) after firing ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4. ２ and B ２ O ３ If the ratio of the proportions is 3.4 or more, poor sintering occurs, and the Q value of the first low-temperature co-fired ceramic becomes low. ２ and B ２ O ３ The ratio of the proportions is preferably less than 3.3, more preferably less than 3.1. ２ and B ２ O ３ The ratio of the proportions is preferably 1.4 or more.

[0027] The first low-temperature fired ceramic contains SiO as the oxide (C1) of the ceramic crystal component. ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ Since none of these oxides has a high dielectric constant, the dielectric constant of the first low-temperature co-fired ceramic can be adjusted to 7 or less. ２ represents the SiO contained in the glass component (A1) after firing. ２ can be distinguished from.

[0028] The low dielectric constant ceramic further contains TiO as the oxide (C1) of the ceramic crystal component. ２ It is preferable that the glass component contains SiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ exhibits the property that the dielectric constant increases as the temperature increases, so TiO exhibits the property that the dielectric constant decreases as the temperature increases. ２ By including the above, it is possible to adjust the characteristics of the first low-temperature co-fired ceramic so that the dielectric constant does not change with temperature.

[0029] SiO as an oxide (C1) of a ceramic crystalline component contained in a low dielectric constant ceramic ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The preferred ratios are as follows: SiO ２ : 0% by weight or more and 50% by weight or less BaAl ２ Si ２ O ８ : 0% by weight or more and 30% by weight or less ZnAl２ O ４ :0 weight% or more, 30 weight% or less Zn ２ SiO ４ : 0% by weight or more and 25% by weight or less TiO ２ : 0.1% by weight or more, 10% by weight or less

[0030] The low dielectric constant ceramic is a ceramic crystal component oxide (C1) of BaAl ２ Si ２ O ８ and SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ As will be described later, in the case of producing a co-sintered body by laminating and pressure-bonding a sheet of low-dielectric-constant low-temperature-co-fired ceramic with a sheet of high-dielectric-constant low-temperature-co-fired ceramic together, if the oxides of the ceramic crystal components have the above composition, there is little difference in reaction between the materials and in shrinkage behavior during firing, and defects such as delamination are less likely to occur.

[0031] BaAl contained in low dielectric constant ceramic ２ Si ２ O ８ The proportion of BaAl is preferably more than 0% by weight and not more than 5% by weight. ２ Si ２ O ８ When the ratio of BaAl is within the above range, the temperature coefficient of capacitance change (TCC) can be further reduced. More preferably, it is more than 0.1 wt % and not more than 3 wt %. ２ Si ２ O ８ has the positive effect of increasing the TCC of low-temperature co-fired ceramics, while TiO ２ has the negative effect of increasing the TCC of low-temperature co-fired ceramics. ２ Si ２ O ８ and TiO ２ However, the amount of TiO ２When preparing a low dielectric constant ceramic, BaAl ２ Si ２ O ８ It is preferable to adjust the TCC by reducing the amount of BaAl contained in the low dielectric constant ceramic. ２ Si ２ O ８ The ratio of TiO ２ When no hydroxybenzoates are contained, the content is preferably more than 0% by weight and 5% by weight or less.

[0032] After firing, the low dielectric constant ceramic further contains Al in addition to the glass component (A1). ２ O ３ and Al other than the glass component (A1) after firing contained in the low-temperature fired ceramic. ２ O ３ The proportion of Al other than the glass component (A1) after firing contained in the low-temperature fired ceramic is preferably more than 0 wt % and not more than 5 wt %. ２ O ３ If the proportion of Al in the glass component (A1) exceeds 5% by weight, defects such as pores and cracks may occur in the co-sintered body obtained by laminating and pressing a sheet of low-dielectric-constant low-temperature-co-fired ceramic and a sheet of high-dielectric-constant low-temperature-co-fired ceramic together. ２ O ３ and other Al ２ O ３ can be distinguished from.

[0033] (Second Low-Temperature Co-fired Ceramic) The second low-temperature co-fired ceramic of the present invention comprises a fired glass component (A2) and an oxide of a ceramic crystal component (C2). The fired glass component (A2) contains SiO ２ and B ２ O ３ The glass component (A1) is the same as the glass component (A1) after firing, except that there is no limitation on the ratio of the components.

[0034] The second low-temperature fired ceramic (high dielectric constant ceramic) contains Ba as the oxide (C2) of the ceramic crystal component. ２ Ti ９ O ２０ , BaTi(BO ３ )２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ These oxides all have high dielectric constants, and can make the dielectric constant of the fired body greater than 7. The high dielectric constant ceramic contains Ba as one embodiment of the oxide (C2) of the ceramic crystal component. ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The sum of the proportions of Ba is preferably 5% by weight or more, more preferably 30% by weight or more, and even more preferably 40% by weight or more. ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The sum of the proportions of Ba and BaO is preferably 90% by weight or less. ２ Ti ９ O ２０ and BaTi(BO ３ ) ２ It may not include.

[0035] Ba ２ Ti ９ O ２０ and BaTi(BO ３ ) ２ The dielectric constant changes little even when the temperature rises.

[0036] The high dielectric constant ceramic contains Ba as one aspect of the oxide (C2) of the ceramic crystal component. ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The ratio of BaTi ４ O ９ The ratio of BaTi５ O １１ The proportion of Ba ４ Ti １３ O ３０ The ratio of BaZn ２ Ti ４ O １１ The ratio of Ba ４ ZnTi １１ O ２７ The sum of the proportions of Ba is preferably 5% by weight or more, more preferably 30% by weight or more, and even more preferably 40% by weight or more. ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ Proportion of BaTi ４ O ９ Proportion of BaTi ５ O １１ The proportion of Ba ４ Ti １３ O ３０ The ratio of BaZn ２ Ti ４ O １１ The ratio of Ba ４ ZnTi １１ O ２７ The sum of the proportions of Ba contained in the high dielectric constant ceramic is preferably 90% by weight or less. ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ Proportion of BaTi ４ O ９ Proportion of BaTi ５ O １１ The proportion of Ba ４ Ti １３ O ３０ The ratio of BaZn ２ Ti ４ O １１ The ratio of Ba ４ ZnTi １１ O ２７ The ratio of the above can be obtained by powder XRD (X-ray diffraction measurement) of the high dielectric constant ceramic (fired body), similarly to the ratio of alkaline earth metal oxides (RO) contained in the glass component after firing.

[0037] The oxide (C2) of the ceramic crystal component in the high dielectric constant ceramic further includes TiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ It is preferable that the composition contains at least two kinds of oxides selected from the group consisting of: When the composition contains at least two kinds of oxides, the TCC can be further reduced.

[0038] The oxide (C2) of the ceramic crystal component is TiO ２ and BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ and at least one selected from the group consisting of BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ exhibits the property that the dielectric constant increases as the temperature rises, and TiO ２ This is because the dielectric constant of a material decreases as the temperature increases.

[0039] Ba as an oxide of ceramic crystal component contained in high dielectric constant ceramics ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ , Ba ４ ZnTi １１ O ２７ , BaAl ２ Si ２ O８ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The preferred ratios are as follows: ２ Ti ９ O ２０ : 0% by weight or more and 55% by weight or less BaTi(BO ３ ) ２ : 0% by weight or more and 40% by weight or less BaTi ４ O ９ : 0% by weight or more and 35% by weight or less BaTi ５ O １１ : 0% by weight or more and 30% by weight or less Ba ４ Ti １３ O ３０ : 0% by weight or more and 30% by weight or less BaZn ２ Ti ４ O １１ : 0% by weight or more and 30% by weight or less Ba ４ ZnTi １１ O ２７ : 0% by weight or more and 25% by weight or less BaAl ２ Si ２ O ８ : 0% by weight or more and 40% by weight or less ZnAl ２ O ４ :0 weight% or more, 30 weight% or less Zn ２ SiO ４ : 0% by weight or more and 15% by weight or less TiO ２ : 0.1% by weight or more, 10% by weight or less

[0040] The following points are common to the first and second low-temperature co-fired ceramics. The low-temperature co-fired ceramic of the present invention may further contain CuO and / or Cu. When the low-temperature co-fired ceramic (LTCC) material contains CuO and / or Cu, the RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ From the glass material BaAl ２ Si ２ O ４ , ZnAl ２O ４ , Zn ２ SiO ４ This promotes the precipitation of crystals of RO, ZnO and Al in the glass material. ２ O ３ The amount of CuO can be reduced. The sum of the proportions of CuO and Cu contained in the low-temperature co-fired ceramic is preferably 1 wt % or less. The proportions of CuO and Cu contained in the low-temperature co-fired ceramic are obtained by X-ray fluorescence analysis. When the low-temperature co-fired ceramic of the present invention is fired in an air atmosphere, Cu is present in the low-temperature co-fired ceramic as CuO, and when the firing is performed in a reducing atmosphere, Cu is present.

[0041] The proportions of the post-fired glass component and the oxides of the ceramic crystalline component contained in the low-temperature fired ceramic are not particularly limited. For example, the post-fired glass component proportion can be 10 wt% to 55 wt% and the oxides of the ceramic crystalline component can be 45 wt% to 90 wt%. In particular, for low-dielectric ceramics, the post-fired glass component proportion is preferably 10 wt% to 30 wt% and the oxides of the ceramic crystalline component are preferably 70 wt% to 90 wt%. For high-dielectric ceramics, the post-fired glass component proportion is preferably 15 wt% to 55 wt% and the oxides of the ceramic crystalline component are preferably 45 wt% to 85 wt%.

[0042] The dielectric loss of the low-temperature co-fired ceramic is preferably 0.001 or less. In other words, the Q value, which is the reciprocal of the dielectric loss, is preferably 1000 or more. The relative permittivity and dielectric loss of the low-temperature co-fired ceramic in this specification are values ​​measured as the relative permittivity and dielectric loss at 3 GHz by a perturbation method.

[0043] (First Electronic Component) The first electronic component of the present invention comprises the low-temperature co-fired ceramic of the present invention. The low-temperature co-fired ceramic may be either a low-dielectric-constant ceramic or a high-dielectric-constant ceramic. Examples of the first electronic component of the present invention include a laminate comprising a plurality of low-temperature co-fired ceramic layers made of the low-temperature co-fired ceramic of the present invention, and a multilayer ceramic electronic component comprising a multilayer ceramic substrate using the laminate and a chip component mounted on the ceramic substrate. The first electronic component of the present invention has low dielectric loss because it comprises a low-temperature co-fired ceramic layer made of the low-temperature co-fired ceramic of the present invention.

[0044] The laminate having a plurality of low-temperature co-fired ceramic layers made of the low-temperature co-fired ceramic of the present invention can be used, for example, in a ceramic multilayer substrate for communication or a laminated dielectric filter. The first electronic component of the present invention has small dielectric loss and a high Q value, and is therefore particularly suitable as an electronic component for use in the millimeter wave band.

[0045] Fig. 1 is a cross-sectional view schematically showing an example of a multilayer ceramic electronic component as a first electronic component of the present invention. As shown in Fig. 1, the electronic component 2 includes a laminate 1 formed by laminating a plurality of low-temperature co-fired ceramic layers 3 (five layers in Fig. 1), and chip components 13 and 14 mounted on the laminate 1. The laminate 1 also serves as a multilayer ceramic substrate.

[0046] The low-temperature co-fired ceramic layer 3 is a fired body made of the low-temperature co-fired ceramic of the present invention. Therefore, the laminate 1 formed by stacking a plurality of low-temperature co-fired ceramic layers 3, the multilayer ceramic substrate using the laminate 1, and the electronic component 2 including chip components 13, 14 mounted on the multilayer ceramic substrate (laminate 1) are all electronic components of the present invention. The compositions of the plurality of low-temperature co-fired ceramic layers 3 may be the same or different, but are preferably the same.

[0047] The laminate 1 may further include a conductor layer. The conductor layer may constitute, for example, a passive element such as a capacitor or an inductor, or may constitute a connecting wiring that electrically connects elements. Such conductor layers include conductor layers 9, 10, and 11, and a via-hole conductor layer 12, as shown in FIG. 1 .

[0048] The conductor layers 9, 10, and 11 and the via-hole conductor layer 12 preferably contain Ag or Cu as a main component. The use of such low-resistance metals prevents signal propagation delays that occur with higher frequencies of electrical signals. Furthermore, the low-temperature co-fired ceramic layer 3 is a sintered body made of a low-temperature co-fired ceramic (LTCC) material, and can be formed by co-firing with Ag and Cu.

[0049] The first electronic component of the present invention preferably contains Cu wiring, and more preferably contains Cu wiring formed by co-firing a low temperature co-fired ceramic (LTCC) material and Cu.

[0050] The conductor layer 9 is disposed inside the laminate 1. Specifically, the conductor layer 9 is disposed at the interface between the low-temperature co-fired ceramic layers 3.

[0051] The conductor layer 10 is disposed on one of the main surfaces of the laminate 1 .

[0052] The conductor layer 11 is disposed on the other main surface of the laminate 1 .

[0053] The via hole conductor layer 12 is arranged to penetrate the low-temperature co-fired ceramic layer 3, and serves to electrically connect the conductor layers 9 of different layers, electrically connect the conductor layers 9 and 10, and electrically connect the conductor layers 9 and 11.

[0054] The laminate 1 is manufactured, for example, as follows.

[0055] (A) Preparation of glass composition B ２ O ３ , SiO ２ , ZnO, Al ２ O ３ and an alkaline earth metal oxide (RO) in a predetermined ratio to prepare a glass composition. BaO is preferably used as the alkaline earth metal oxide.

[0056] (B) Preparation of Glass Powder The glass composition is melted and the resulting melt is rapidly cooled to prepare cullets. The cullets are coarsely crushed and further crushed in a ball mill or the like to prepare glass powder having a predetermined particle size.

[0057] (C) Preparation of Low Temperature Co-fired Ceramic (LTCC) Material Low temperature co-fired ceramic (LTCC) material is prepared by mixing glass powder and oxides of ceramic crystal components. When producing low dielectric constant ceramic, SiO is used as the oxide of ceramic crystal component. ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ At least one selected from the group consisting of: ２ When producing a high dielectric constant ceramic, Ba is preferably used as the oxide of the ceramic crystal component. ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ At least one selected from the group consisting of BaAl ２ Si ２ O ８ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２It is preferable to use at least two kinds selected from the group consisting of: The proportion of glass powder in the low temperature co-fired ceramic (LTCC) material is preferably 10% by weight or more and 55% by weight or less.

[0058] (D) Preparation of Green Sheets A low-temperature co-fired ceramic (LTCC) material is mixed with a binder, a plasticizer, etc. to prepare a ceramic slurry. The ceramic slurry is then cast onto a substrate film (e.g., a polyethylene terephthalate (PET) film) and dried to prepare a green sheet.

[0059] (E) Preparation of Laminated Green Sheets A laminated green sheet (unfired state) is prepared by stacking green sheets. FIG. 2 is a cross-sectional schematic diagram showing a laminated green sheet (unfired state) prepared during the manufacturing process of the laminated ceramic electronic component shown in FIG. 1. As shown in FIG. 2, a laminated green sheet 21 is formed by stacking multiple green sheets 22 (five in FIG. 2). The green sheets 22 become the low-temperature fired ceramic layers 3 after firing. Conductive layers including conductor layers 9, 10, and 11 and via-hole conductor layers 12 may be formed on the laminated green sheet 21. The conductor layers can be formed by screen printing, photolithography, or the like using a conductive paste containing Ag or Cu.

[0060] (F) Firing of Laminated Green Sheet The laminated green sheet 21 is fired, resulting in a laminate 1 as shown in FIG.

[0061] The firing temperature of the laminated green sheet 21 is not particularly limited as long as it is a temperature at which the low-temperature co-fired ceramic (LTCC) material constituting the green sheet 22 can be sintered, and may be, for example, 1000° C. or lower.

[0062] The firing atmosphere for the laminated green sheet 21 is not particularly limited, but an air atmosphere is preferred when a material that is resistant to oxidation, such as Ag, is used for the conductor layers 9, 10, 11 and the via-hole conductor layer 12, and a low-oxygen atmosphere such as a nitrogen atmosphere is preferred when a material that is resistant to oxidation, such as Cu, is used. The firing atmosphere for the laminated green sheet 21 may also be a reducing atmosphere.

[0063] The laminated green sheet 21 may be fired while sandwiched between constraining green sheets. The constraining green sheets are made of an inorganic material (e.g., Al) that does not substantially sinter at the sintering temperature of the low-temperature co-fired ceramic (LTCC) material that constitutes the green sheet 22. ２ O ３ ) as a main component. Therefore, the constraining green sheets do not shrink when the laminated green sheets 21 are fired, and act to suppress shrinkage of the laminated green sheets 21 in the main surface direction. As a result, the dimensional accuracy of the obtained laminate 1 (particularly the conductor layers 9, 10, 11 and the via-hole conductor layer 12) is improved.

[0064] Chip components 13 and 14 may be mounted on the laminate 1 in a state where they are electrically connected to the conductor layer 10. In this way, an electronic component 2 having the laminate 1 is constructed.

[0065] Examples of the chip components 13 and 14 include an LC filter, a capacitor, an inductor, and the like.

[0066] The electronic component 2 may be mounted on a mounting substrate (for example, a motherboard) so as to be electrically connected via the conductor layer 11 .

[0067] (Second Electronic Component) If a co-sintered body could be produced by laminating and pressing a sheet of low-dielectric-constant low-temperature-co-fired ceramic with a sheet of high-dielectric-constant low-temperature-co-fired ceramic together, the co-sintered body could be used in an LTCC substrate to form wiring and coils using the low-dielectric-constant layer and a capacitor using the high-dielectric-constant layer, thereby enabling miniaturization of electronic components. However, the prior art does not disclose such a sintered body. Furthermore, when materials with different dielectric constants are co-sintered, defects such as delamination, pores, and cracks can occur due to reactions between the materials and differences in shrinkage behavior during sintering, but the prior art does not disclose any means for resolving such defects.

[0068] A second electronic component of the present invention is an electronic component comprising a low-dielectric-constant ceramic layer and a high-dielectric-constant ceramic layer. The low-dielectric-constant ceramic layer is formed of a first low-temperature-fired ceramic, and the high-dielectric-constant ceramic layer is formed of a second low-temperature-fired ceramic. The first low-temperature-fired ceramic contains a fired glass component (A1) and an oxide of a ceramic crystalline component (C1), and the second low-temperature-fired ceramic contains a fired glass component (A2) and an oxide of a ceramic crystalline component (C2). The fired glass component (A1) is RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportion of RO, the proportion of ZnO, and the proportion of Al contained in the glass component (A1) after firing are ２ O ３ are 0.1 mol % or more and 10 mol % or less, respectively, and the proportion of RO, the proportion of ZnO and the proportion of Al contained in the fired glass component (A1) are ２ O ３ The sum of the proportions of SiO contained in the glass component (A1) after firing is 15 mol % or less. ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4. The oxide (C1) of the ceramic crystal component is BaAl ２ Si ２ O ８ and SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The second electronic component of the present invention includes a co-sintered body obtained by laminating and pressing a sheet of low-dielectric-constant low-temperature-fired ceramic and a sheet of high-dielectric-constant low-temperature-fired ceramic together, and the oxide (C1) of the ceramic crystal component is selected from the group consisting of BaAl ２ Si２ O ８ The fired glass component (A2) needs to contain SiO ２ and B ２ O ３ The ceramic crystal oxide (C2) is the same as the glass component (A1) after firing, except that there is no limitation on the ratio of the components. ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ The second low-temperature fired ceramic contains at least one barium titanate compound selected from the group consisting of: ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The ratio of BaTi ４ O ９ The ratio of BaTi ５ O １１ The proportion of Ba ４ Ti １３ O ３０ The ratio of BaZn ２ Ti ４ O １１ The ratio of Ba ４ ZnTi １１ O ２７ The sum of the proportions of Al is preferably 40% by weight or more. ２ O ３ The proportion of BaAl is 5% by weight or less, ２ Si ２ O ８ The first low-temperature fired ceramic contains BaAl as the ceramic crystal oxide (C1). ２Si ２ O ８ is essential, and after firing, in addition to the glass component (A1), Al ２ O ３ and the Al contained in the first low-temperature co-fired ceramic ２ O ３ The second low-temperature co-fired ceramic may be the same as the high-dielectric-constant ceramic, except that the ratio of the first low-temperature co-fired ceramic is greater than 0 wt % and is not more than 5 wt %.

[0069] The second electronic component of the present invention will be described below with reference to Figures 3 and 4. Only the differences from the first electronic component will be described.

[0070] Fig. 3 is a cross-sectional view schematically showing an example of a multilayer ceramic electronic component as a second electronic component of the present invention. As shown in Fig. 3, the electronic component 200 includes a laminate 100 formed by laminating two low-dielectric-constant ceramic layers 4, two high-dielectric-constant ceramic layers 5, and two low-dielectric-constant ceramic layers 4, and chip components 13 and 14 mounted on the laminate 100. The laminate 100 also serves as a multilayer ceramic substrate.

[0071] The low dielectric constant ceramic layer 4 is a fired body made of the above-mentioned low dielectric constant ceramic, and the high dielectric constant ceramic layer 5 is a fired body made of the above-mentioned high dielectric constant ceramic. The compositions of the multiple low dielectric constant ceramic layers 4 may be the same as each other or different from each other, but are preferably the same as each other. The compositions of the multiple high dielectric constant ceramic layers 5 may be the same as each other or different from each other, but are preferably the same as each other. The laminate 100 may further include a conductor layer.

[0072] The second electronic component of the present invention preferably contains Cu wiring, and more preferably contains Cu wiring formed by co-firing a low temperature co-fired ceramic (LTCC) material and Cu.

[0073] The laminate 100 is manufactured, for example, as follows.

[0074] Except for the preparation of two types of materials, one for a low dielectric constant ceramic and the other for a high dielectric constant ceramic, (A) the preparation of the glass composition, (B) the preparation of the glass powder, (C) the preparation of the low temperature co-fired ceramic (LTCC) material, and (D) the production of the green sheet can be performed in the same manner as in the production of the laminate 1 of the first electronic component.

[0075] (E) Preparation of Laminated Green Sheets Figure 4 is a cross-sectional schematic diagram showing a laminated green sheet (unfired state) prepared during the manufacturing process of the laminated ceramic electronic component shown in Figure 3. As shown in Figure 4, the laminated green sheet 110 is formed by laminating two low-dielectric-constant ceramic layer green sheets 23, two high-dielectric-constant ceramic layer green sheets 24, and two low-dielectric-constant ceramic layer green sheets 23. The low-dielectric-constant ceramic layer green sheets 23 become the low-dielectric-constant ceramic layer 4 after firing. The high-dielectric-constant ceramic layer green sheets 24 become the high-dielectric-constant ceramic layer 5 after firing. Conductor layers including conductor layers 9, 10, and 11 and via-hole conductor layers 12 may be formed on the low-dielectric-constant ceramic layer green sheets 23 and the high-dielectric-constant ceramic layer green sheets 24.

[0076] (F) Firing of Laminated Green Sheet The laminated green sheet 110 is fired, resulting in a laminate 100 as shown in FIG.

[0077] The second electronic component of the present invention is formed from the low-dielectric-constant ceramic and high-dielectric-constant ceramic, which are low-temperature co-fired ceramics of the present invention. Therefore, there is little difference in reaction between the materials and in shrinkage behavior during firing, and defects such as delamination, pores, and cracks are less likely to occur.

[0078] The present specification discloses the following:

[0079] <1> A low-temperature fired ceramic containing a fired glass component (A1) and an oxide of a ceramic crystal component (C1), wherein the fired glass component (A1) is RO—ZnO—Al ２ O ３ -B ２ O ３ -SiO ２wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportion of RO, the proportion of ZnO, and the proportion of Al contained in the glass component (A1) after firing are ２ O ３ the proportions of RO, ZnO and Al contained in the fired glass component (A1) are 0.1 mol % or more and 10 mol % or less, respectively; ２ O ３ The sum of the proportions of SiO contained in the glass component (A1) after firing is 15 mol % or less. ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, and the oxide (C1) of the ceramic crystal component is SiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ A low-temperature co-fired ceramic comprising at least one selected from the group consisting of:

[0080] <2> The oxide (C1) of the ceramic crystal component further contains TiO ２ The low-temperature co-fired ceramic according to <1>, comprising:

[0081] <3> The oxide (C1) of the ceramic crystal component is BaAl ２ Si ２ O ８ and SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The low-temperature co-fired ceramic according to <1> or <2>, comprising at least two selected from the group consisting of:

[0082] <4> BaAl contained in the low-temperature co-fired ceramic ２ Si ２ O ８The low-temperature co-fired ceramic according to any one of <1> to <3>, wherein the proportion of is more than 0 wt % and 5 wt % or less.

[0083] <5> In addition to the above-mentioned fired glass component (A1), further Al ２ O ３ and the low-temperature fired ceramic contains Al other than the glass component (A1) after firing. ２ O ３ <4> The low-temperature co-fired ceramic according to any one of <1> to <4>, wherein the proportion of is more than 0 wt % and 5 wt % or less.

[0084] <6> A low-temperature fired ceramic containing a fired glass component (A2) and an oxide of a ceramic crystal component (C2), wherein the fired glass component (A2) is RO—ZnO—Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportion of RO, the proportion of ZnO, and the proportion of Al contained in the glass component (A2) after firing are ２ O ３ the proportions of RO, ZnO and Al contained in the fired glass component (A2) are 0.1 mol % or more and 10 mol % or less, respectively, ２ O ３ The sum of the proportions of the oxides (C2) of the ceramic crystal components is 15 mol % or less, and the oxides (C2) of the ceramic crystal components are Ba, ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ A low-temperature co-fired ceramic comprising at least one selected from the group consisting of:

[0085] <7> Ba contained in the low-temperature fired ceramic ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The low-temperature co-fired ceramic according to <6>, wherein the sum of the proportions of is 40% by weight or more.

[0086] <8> Ba contained in the low-temperature co-fired ceramic ２ Ti ９ O ２０ The ratio of BaTi(BO ３ ) ２ The ratio of BaTi ４ O ９ The ratio of BaTi ５ O １１ The proportion of Ba ４ Ti １３ O ３０ The ratio of BaZn ２ Ti ４ O １１ The ratio of Ba ４ ZnTi １１ O ２７ The low-temperature co-fired ceramic according to <6>, wherein the sum of the proportions of is 40% by weight or more.

[0087] <9> The oxide (C2) of the ceramic crystal component further contains TiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ <6> to <8>, comprising at least two selected from the group consisting of:

[0088] <10> The oxide (C2) of the ceramic crystal component is TiO ２ and BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ and at least one selected from the group consisting of:

[0089] <11> The low-temperature co-fired ceramic according to any one of <1> to <10>, wherein the RO is BaO.

[0090] <12> The low-temperature co-fired ceramic according to any one of <1> to <11>, further comprising CuO and / or Cu, wherein the sum of the proportion of CuO and the proportion of Cu contained in the low-temperature co-fired ceramic is 1 wt % or less.

[0091] <13> An electronic component comprising the low-temperature co-fired ceramic according to any one of <1> to <12>.

[0092] <14> The electronic component according to <13>, which has a built-in Cu wiring.

[0093] <15> An electronic component including a low-dielectric-constant ceramic layer and a high-dielectric-constant ceramic layer, wherein the low-dielectric-constant ceramic layer is formed of a first low-temperature-fired ceramic, and the high-dielectric-constant ceramic layer is formed of a second low-temperature-fired ceramic, the first low-temperature-fired ceramic containing a fired glass component (A1) and an oxide of a ceramic crystalline component (C1), the second low-temperature-fired ceramic containing the fired glass component (A2) and an oxide of a ceramic crystalline component (C2), and the fired glass component (A1) and the fired glass component (A2) are each selected from the group consisting of RO—ZnO—Al ２ O ３ -B ２ O ３ -SiO ２ wherein the RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO, and the proportions of RO, ZnO, and Al contained in the fired glass component (A1) and the fired glass component (A2) are ２ O ３ are 0.1 mol % or more and 10 mol % or less, respectively, and the ratio of RO, the ratio of ZnO and the ratio of Al contained in the fired glass component (A1) and the fired glass component (A2) are ２ O ３ The sum of the proportions of SiO contained in the glass component (A1) after firing is 15 mol % or less. ２ and B ２ O ３ The ratio of the proportions (SiO２ / B ２ O ３ ) is less than 3.4, and the first low-temperature fired ceramic further contains Al in addition to the glass component (A1) after firing. ２ O ３ and Al other than the glass component (A1) after firing contained in the first low-temperature fired ceramic. ２ O ３ The proportion of the ceramic crystal component (C1) is more than 0 wt % and 5 wt % or less, and the oxide (C1) of the ceramic crystal component is BaAl ２ Si ２ O ８ and SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ and at least two selected from the group consisting of BaAl contained in the first low-temperature co-fired ceramic. ２ Si ２ O ８ The proportion of the ceramic crystal component (C2) is more than 0% by weight and not more than 5% by weight, and the oxide of the ceramic crystal component (C2) is Ba. ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ An electronic component comprising at least one selected from the group consisting of:

[0094] <16> The electronic component according to <15>, which has a built-in Cu wiring.

[0095] The following examples will be given to more specifically disclose the low-temperature co-fired ceramic and electronic device of the present invention, but the present invention is not limited to these examples.

[0096] (Preparation of low dielectric constant ceramic 1) (A) Preparation of glass Glass powders G1 to G7 (all in powder form) were prepared by the following method. First, glass raw material powders were mixed to obtain a glass composition. The glass composition was placed in a Pt crucible and melted at 1600°C for 30 minutes or more in an air atmosphere. Then, the obtained melt was quenched to prepare cullets. Note that carbonate (BaCO ３ ) was used. ３ ) becomes alkaline earth metal oxide (BaO) upon firing, and Table 1 shows the compounding amounts converted to BaO. The cullet was then coarsely crushed and placed in a container together with ethanol and PSZ balls (diameter: 5 mm) and mixed in a ball mill. By adjusting the crushing time during mixing in the ball mill, a glass powder with a median particle size of 1.0 μm was obtained. Here, "median particle size" refers to the median particle size D50 measured by laser diffraction / scattering.

[0097] (B) Preparation of Green Sheet Next, glass powders G1 to G7 and ceramic crystal component oxides C1 to C7 (median particle size 1.0 μm) in the combinations shown in Table 1 were placed in ethanol and mixed in a ball mill, and then a binder liquid prepared by dissolving polyvinyl butyral in ethanol and a dioctyl phthalate (DOP) plasticizer liquid were mixed to form a slurry. The slurry was cast onto a PET film with a doctor blade and dried at 40°C to obtain a green sheet 50 microns thick.

[0098] (C) Preparation and Evaluation of Evaluation Samples 1. Dielectric Constant and Q Value To measure the dielectric constant and Q value, 20 green sheets were cut into 50 mm x 50 mm pieces and stacked together, placed in a mold, and pressed using a press. This pressed assembly was fired in air at 900°C to 950°C for 60 minutes to obtain a low-temperature co-fired ceramic. The dielectric constant and Q value (the reciprocal of the dielectric loss) of the resulting low-temperature co-fired ceramic were measured at 25°C and 3 GHz using a perturbation method. The measurement conditions were as follows: [Measurement Equipment and Conditions] Network Analyzer: Keysight 8757D Signal Generator: Keysight Synthesized Sweeper 83751 Resonator: Homemade jig (resonant frequency: 3 GHz) Prior to the measurement, the network analyzer and signal generator were connected to measure cable loss. The resonator was calibrated using a standard substrate (made of quartz, relative dielectric constant: 3.73, Q value: 9091 @ 3 GHz, thickness: 0.636 mm).

[0099] 2. Temperature Coefficient of Capacitance Change (TCC) To evaluate the TCC, 20 green sheets were cut into 10 mm x 10 mm pieces and stacked together. These were then placed in a mold and pressed together using a press. Pure Cu paste was printed on the top and bottom principal surfaces of the pressed assembly as counter electrodes for the capacitor. After drying, the assembly was fired in a reducing atmosphere at 900°C to 950°C for 60 minutes. After firing, the sample was placed in a temperature chamber and the dielectric constant was measured using an LCR meter (Agilent, model number E4980A) in the range of -40°C to 125°C. The temperature coefficient of capacitance change (TCC) was calculated, and the temperature dependence of the dielectric constant was evaluated.

[0100] 3. Composition of Low-Temperature Sintered Ceramic To further analyze the composition of the sintered body, powder XRD of the sintered body was measured at a scan rate as low as 0.2 deg / min, and the proportion of the sintered glass component contained in the sintered body and the composition of the sintered glass component were determined by Rietveld analysis. To determine the composition, it was assumed that the total amount of oxide of each element remained unchanged before and after sintering. The composition of the oxides of the ceramic crystalline components contained in the sintered body was also determined. The proportions of CuO and Cu contained in the sintered body were determined by X-ray fluorescence analysis. These results are shown in Table 1.

[0101]

[0102] The low-temperature fired ceramics of Samples No. L1 and L5 to L7 have the following characteristics: the proportion of BaO (the proportion of RO), the proportion of ZnO, and the proportion of Al contained in the glass components after firing. ２ O ３ are 0.1 mol% or more and 10 mol% or less, respectively, and the proportion of BaO (proportion of RO), the proportion of ZnO and Al contained in the glass components after firing are ２ O ３ The sum of the proportions of SiO is 15 mol% or less, ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, and the oxide (C1) of the ceramic crystal component is SiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ Since the samples contain at least one selected from the group consisting of: －１ Above 60 ppm ° C －１ The temperature dependence of the dielectric constant was found to be small. ２ Because of the high concentration, the TCC is -60 ppm℃ －１ It is thought to have become smaller.

[0103] (Preparation of high dielectric constant ceramic 1) (A) Preparation of glass Glass powders G1 to G10 (all in powder form) were prepared in the same manner as in "(A) Preparation of glass" in Preparation of low dielectric constant ceramic 1. Of the glass powders G1 to G10, glass powders G1 to G7 are the same as the glass powders G1 to G7 prepared in the preparation of low dielectric constant ceramic.

[0104] (B) Preparation of Green Sheets Next, green sheets were obtained in the same manner as in “(B) Preparation of Green Sheets” in Preparation of Low Dielectric Ceramic 1, except that glass powders G1 to G10 and ceramic crystal component oxides C8 to C17 (median particle size 1.0 μm) were used in the combinations shown in Table 2.

[0105] (C) Preparation and Evaluation of Evaluation Samples Low-temperature co-fired ceramics were obtained in the same manner as in "(C) Preparation and Evaluation of Evaluation Samples" in Preparation of Low-Dielectric-Constant Ceramic 1, and the dielectric constant, Q value, TCC, and composition of the obtained low-temperature co-fired ceramics were determined. These results are shown in Table 2.

[0106]

[0107] The low-temperature fired ceramics of Samples H1 and H5 to H10 have the following characteristics: the proportion of BaO (the proportion of RO), the proportion of ZnO, and the proportion of Al contained in the glass components after firing. ２ O ３ are 0.1 mol% or more and 10 mol% or less, respectively, and the proportion of BaO (proportion of RO), the proportion of ZnO and Al contained in the glass components after firing are ２ O ３ The sum of the proportions of the oxides (C2) of the ceramic crystal components is 15 mol % or less, and the oxides (C2) of the ceramic crystal components are Ba ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ These samples contain at least one material selected from the group consisting of: －１Above 60 ppm ° C －１ The relative dielectric constant was found to be within the range below, indicating that the temperature dependence of the relative dielectric constant was small. In addition, the relative dielectric constant was high for all samples.

[0108] (Preparation of Electronic Component Having Low-Dielectric-Constant Ceramic Layer and High-Dielectric-Constant Ceramic Layer 1) (A) Preparation of Glass Glass powders G1, G11 to G12 (all in powder form) were prepared in the same manner as in "(A) Preparation of Glass" in Preparation of Low-Dielectric-Constant Ceramic 1. Glass powder G1 is the same as the glass powder G1 prepared in Preparation of Low-Dielectric-Constant Ceramic 1.

[0109] (B) Preparation of Green Sheets Next, low-dielectric-constant green sheets were obtained in the same manner as in "(B) Preparation of Green Sheets" in Preparation of Low-Dielectric-Constant Ceramic 1, except that glass powders G1, G11-G12 and ceramic crystalline component oxides C1, C3, and C18 (median particle size 1.0 μm) were used in the combinations shown in Table 3. The ceramic crystalline component oxides C1 and C3 were the same as C1 and C3 used in Preparation of Low-Dielectric-Constant Ceramic 1. Furthermore, high-dielectric-constant green sheets were obtained in the same manner as in "(B) Preparation of Green Sheets" in Preparation of Low-Dielectric-Constant Ceramic 1, except that glass powders G1, G11-G12 and ceramic crystalline component oxides C8, C19-C20 (median particle size 1.0 μm) were used in the combinations shown in Table 4. The ceramic crystalline component oxide C8 was the same as C8 used in Preparation of High-Dielectric-Constant Ceramic 1.

[0110] (C) Preparation and Evaluation of Evaluation Samples Samples for evaluating sinterability were prepared according to the following procedure. The low-dielectric-constant green sheets and high-dielectric-constant green sheets prepared above were cut into 50 mm x 50 mm pieces, and the resulting sheets were stacked in the order of 8 low-dielectric-constant green sheets, 4 high-dielectric-constant green sheets, and 8 low-dielectric-constant green sheets in the combinations shown in Table 5. The stacks were placed in a mold and pressed using a press. The pressed body was fired in a reducing atmosphere at 900°C to 950°C for 60 minutes to obtain a fired body.

[0111] The obtained fired body was embedded in resin and cured, and the cross section was polished and the boundary between the ceramic layers with different relative dielectric constants was observed with a scanning electron microscope (SEM) to check for defects such as delamination, pores, and cracks.

[0112] The glass composition in the fired body was determined by wavelength dispersive X-ray analysis (WDS) of the glass region identified by scanning transmission electron microscopy (STEM) and electron diffraction of the exfoliated fired body sample. The crystal species and crystal amount in the fired body were determined by XRD of the surface of the fired body sample for the ceramic layer portion with a low dielectric constant. For the ceramic layer portion with a high dielectric constant, the low dielectric constant portion was removed from the surface of the fired body sample by polishing to expose the layer with a high dielectric constant, and the glass composition was determined by XRD of the surface.

[0113] Table 3 shows the composition of the ceramic layer with a high relative dielectric constant, Table 4 shows the composition of the ceramic layer with a low relative dielectric constant, and Table 5 shows the presence or absence of defects in the boundary portion of the ceramic layers with different relative dielectric constants.

[0114]

[0115]

[0116]

[0117] In the electronic component of Sample No. E1, both the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer were formed from the low-temperature co-fired ceramic of the present invention, and thus corresponds to the electronic component of the present invention. In the electronic component of Sample No. E1, no defects were found at the boundary between the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer. On the other hand, in the electronic components of Samples E2 to E5, in which at least one of the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer was formed from a low-temperature co-fired ceramic other than the present invention, delamination, pores, and cracks were observed at the boundary between the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer.

[0118] (Preparation of low dielectric constant ceramic 2) (A) Preparation of glass Glass powder was prepared in the same manner as in "(A) Preparation of glass" in Preparation of low dielectric constant ceramic 1 so that the glass components after firing would have the values ​​shown in Table 6.

[0119] (B) Preparation of Green Sheets Next, green sheets were obtained in the same manner as in "(B) Preparation of Green Sheets" in Preparation of Low Dielectric Ceramic 1, except that the glass powder and oxides of ceramic crystal components (median particle size 1.0 μm) prepared above were used so that the low-temperature fired ceramic composition after firing would be the values ​​shown in Table 6.

[0120] (C) Preparation and Evaluation of Evaluation Samples Low-temperature co-fired ceramics were obtained in the same manner as in "(C) Preparation and Evaluation of Evaluation Samples" in Preparation of Low-Dielectric-Constant Ceramic 1, and the dielectric constant, Q value, TCC, and composition of the obtained low-temperature co-fired ceramics were determined. These results are shown in Table 6.

[0121]

[0122] The low-temperature fired ceramics of Samples No. L10 to L12 and L14 to L18 have the following characteristics: the proportion of BaO (the proportion of RO), the proportion of ZnO, and the proportion of Al contained in the glass components after firing. ２ O ３ are 0.1 mol% or more and 10 mol% or less, respectively, and the proportion of BaO (proportion of RO), the proportion of ZnO and Al contained in the glass components after firing are ２ O ３ The sum of the proportions of SiO is 15 mol% or less, ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, and the oxide of the ceramic crystal component (C1) is SiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ Since the sample No. L10 contains at least one selected from the group consisting of BaAl ２ Si ２ O ８ The sample No. L11 contains 5.1 wt % of BaAl ２ Si ２O ８ was 9.8 wt %, and both were TiO ２ Since the sample No. L10 and the sample No. L11 did not contain SiO, the TCC of the sample No. L10 and the TCC of the sample No. L11 were higher than those of the sample Nos. L12 to L18. ２ / B ２ O ３ The Q value was 3.4, and was low due to poor sintering.

[0123] (Preparation of High Dielectric Ceramic 2) (A) Preparation of Glass Glass powder was prepared in the same manner as in "(A) Preparation of Glass" in Preparation of Low Dielectric Ceramic 1 so that the glass components after firing would have the values ​​shown in Table 7.

[0124] (B) Preparation of Green Sheets Next, green sheets were obtained in the same manner as in "(B) Preparation of Green Sheets" in Preparation of Low Dielectric Ceramic 1, except that the glass powder and oxides of ceramic crystal components (median particle size 1.0 μm) prepared above were used so that the low-temperature fired ceramic composition after firing would be the values ​​shown in Table 7.

[0125] (C) Preparation and Evaluation of Evaluation Samples Low-temperature co-fired ceramics were obtained in the same manner as in "(C) Preparation and Evaluation of Evaluation Samples" in Preparation of Low-Dielectric-Constant Ceramic 1, and the dielectric constant, Q value, TCC, and composition of the obtained low-temperature co-fired ceramics were determined. These results are shown in Table 7.

[0126]

[0127] The low-temperature fired ceramics of Samples H13 to H34 have the following characteristics: the proportion of BaO (the proportion of RO), the proportion of ZnO, and the proportion of Al contained in the glass component after firing. ２ O ３ are 0.1 mol% or more and 10 mol% or less, respectively, and the proportion of BaO (proportion of RO), the proportion of ZnO and Al contained in the glass components after firing are ２ O ３ The sum of the proportions of the oxides (C2) of the ceramic crystal components is 15 mol % or less, and the oxides (C2) of the ceramic crystal components are Ba ２ Ti ９ O ２０ , BaTi(BO ３ )２ ,BaTi ４ O ９ ,BaTi ５ O １１ , Ba ４ Ti １３ O ３０ , BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ These samples contain at least one selected from the group consisting of: －１ Above, 35 ppm℃ －１ The dielectric constant was found to be within the range below, and the temperature dependency of the dielectric constant was found to be very small. Furthermore, the dielectric constant was high in all samples. Sample No. H33 had a slightly low dielectric constant and a relatively high TCC value because the proportion of the barium titanate compound, which is an oxide of the ceramic crystal component, was less than 40% by weight. Sample No. H34 had a ceramic crystal component other than the barium titanate compound, which was BaAl ２ Si ２ O ８ Since there is only one type, the TCC is 73 ppm ° C. －１ The sample No. H35 had a relatively high value of RO, ZnO and Al contained in the glass components after firing. ２ O ３ The sum of the proportions of exceeded 15 mol %, resulting in a low Q value.

[0128] (Preparation 2 of an Electronic Component Including a Low-Dielectric-Constant Ceramic Layer and a High-Dielectric-Constant Ceramic Layer) Samples for evaluating sinterability were prepared according to the following procedure. The low-dielectric-constant green sheets and high-dielectric-constant green sheets prepared above were cut into 50 mm x 50 mm pieces, and the resulting sheets were stacked in the order of 8 low-dielectric-constant green sheets, 4 high-dielectric-constant green sheets, and 8 low-dielectric-constant green sheets in the combinations shown in Table 8. The stacks were placed in a mold and pressed using a press. The pressed body was fired in a reducing atmosphere at 900°C to 950°C for 60 minutes to obtain a fired body.

[0129] The obtained fired body was embedded in resin and cured, and the cross section was polished and the boundary between the ceramic layers with different relative dielectric constants was observed with a scanning electron microscope (SEM) to check for defects such as delamination, pores, and cracks.

[0130] The glass composition in the fired body was determined by wavelength dispersive X-ray analysis (WDS) of the glass region identified by scanning transmission electron microscopy (STEM) and electron diffraction of the exfoliated fired body sample. The crystal species and crystal amount in the fired body were determined by XRD of the surface of the fired body sample for the ceramic layer portion with a low dielectric constant. For the ceramic layer portion with a high dielectric constant, the low dielectric constant portion was removed from the surface of the fired body sample by polishing to expose the layer with a high dielectric constant, and the glass composition was determined by XRD of the surface.

[0131] Table 8 shows the presence or absence of defects in the boundary portion of the ceramic layers with different dielectric constants.

[0132]

[0133] In the electronic components of Samples E6, E9, and E11, both the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer are formed of the low-temperature co-fired ceramic of the present invention, and thus correspond to the electronic components of the present invention. In the electronic components of Samples E6, E9, and E11, no defects were found at the boundary between the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer. In Sample E7, the low-dielectric-constant ceramic of Sample L16 was BaAl ２ Si ２ O ８ Since the low dielectric constant ceramic layer does not contain Al, when the low dielectric constant ceramic layer is co-sintered with the high dielectric constant ceramic, delamination is observed at the boundary between the low dielectric constant ceramic layer and the high dielectric constant ceramic layer. ２ O ３Since the low-dielectric-constant ceramic contains more than 5 wt % of the low-dielectric-constant ceramic, when the low-dielectric-constant ceramic and the high-dielectric-constant ceramic are co-sintered, pores and cracks are observed at the boundary between the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer. It has been found that even if the low-dielectric-constant ceramic of the present invention has a composition that does not cause any particular problems when used in electronic components without co-sintering the low-dielectric-constant ceramic and the high-dielectric-constant ceramic, when the low-dielectric-constant ceramic and the high-dielectric-constant ceramic are co-sintered, delamination, pores, and cracks may occur at the boundary between the low-dielectric-constant ceramic layer and the high-dielectric-constant ceramic layer.

[0134] REFERENCE SIGNS LIST 1, 100 Laminate 2, 200 Electronic component 3 Low-temperature co-fired ceramic layer 4 Low-dielectric ceramic layer 5 High-dielectric ceramic layer 9, 10, 11 Conductor layer 12 Via-hole conductor layer 13, 14 Chip component 21, 110 Laminated green sheet 22 Green sheet 23 Green sheet for low-dielectric ceramic layer 24 Green sheet for high-dielectric ceramic layer

Claims

1. This is a low-temperature fired ceramic containing a glass component (A1) and an oxide of the ceramic crystal component (C1) after firing. The aforementioned post-fired glass component (A1) is RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ And, The RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. The proportion of RO, the proportion of ZnO, and Al ２ O ３ in the fired glass component (A1) are each 0.1 mol% or more and 10 mol% or less, and the sum of the proportion of RO, the proportion of ZnO, and the proportion of Al ２ O ３ in the fired glass component (A1) is 15 mol% or less, and the ratio (SiO ２ to B ２ O ３ of the proportion in the fired glass component (A1) (SiO ２ / B ２ O ３ ) is less than 3.4, The oxide (C1) of the aforementioned ceramic crystal component is SiO ２ BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ A low-temperature fired ceramic comprising at least one selected from the group consisting of the following.

2. The oxide (C1) of the aforementioned ceramic crystal component is further TiO ２ The low-temperature fired ceramic according to claim 1, comprising:

3. The oxide (C1) of the aforementioned ceramic crystal component is BaAl ２ Si ２ O ８ It includes, and furthermore, SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ The low-temperature fired ceramic according to claim 1, comprising at least two selected from the group consisting of the following.

4. BaAl contained in the low-temperature fired ceramic ２ Si ２ O ８ The low-temperature fired ceramic according to claim 1, wherein the proportion is greater than 0% by weight and 5% by weight or less.

5. In addition to the aforementioned post-fired glass component (A1), further Al ２ O ３ It includes Al other than the post-fired glass component (A1) contained in the low-temperature fired ceramic. ２ O ３ The low-temperature fired ceramic according to claim 1, wherein the proportion of is greater than 0% by weight and less than or equal to 5% by weight.

6. This is a low-temperature fired ceramic containing a glass component (A2) and an oxide of the ceramic crystal component (C2) after firing. The aforementioned post-fired glass component (A2) is RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ And, The RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. The proportion of RO, the proportion of ZnO, and Al contained in the glass component (A2) after firing. ２ O ３ The proportions of each are 0.1 mol% or more and 10 mol% or less, and the proportion of RO, the proportion of ZnO and the Al contained in the post-fired glass component (A2) are... ２ O ３ The sum of the proportions is 15 mol% or less. The oxide (C2) of the aforementioned ceramic crystal component is Ba ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ , BaTi ４ O ９ , BaTi ５ O １１ Ba ４ Ti １３ O ３０ BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ Low-temperature fired ceramics comprising at least one selected from the group consisting of the following.

7. Ba contained in the low-temperature fired ceramic ２ Ti ９ O ２０ The ratio and BaTi(BO ３ ) ２ The low-temperature fired ceramic according to claim 6, wherein the sum of the proportions is 40% by weight or more.

8. Ba contained in the low-temperature fired ceramic ２ Ti ９ O ２０ ratio, BaTi(BO ３ ) ２ ratio, BaTi ４ O ９ ratio, BaTi ５ O [[ID=A]] １１ ratio, Ba ４ Ti １３ O ３０ ratio, BaZn ２ Ti ４ O １１ ratio and Ba ４ ZnTi １１ O ２７ The low-temperature fired ceramic according to claim 6, wherein the sum of the ratios is 40% by weight or more. It should be noted that there seems to be an error in the original text where the tag １１ is mislabeled as <000008A> in the translation above. It should be １１ throughout. The corrected translation would be: Ba contained in the low-temperature fired ceramic ２ Ti ９ O ２０ ratio, BaTi(BO ３ ) ２ ratio, BaTi ４ O ９ ratio, BaTi ５ O １１ ratio, Ba k ４ Ti １３ O ３０ ratio, BaZn ２ Ti ４ O １１ ratio and Ba <000,0088> [[ID=3,2]]ZnTi １１ O ２７ The low-temperature fired ceramic according to claim 6, wherein the sum of the ratios is 40% by weight or more.

9. The oxide (C2) of the ceramic crystal component further contains TiO ２ , BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ The low-temperature fired ceramic according to claim 6, comprising at least two selected from the group consisting of

10. The oxide (C2) of the aforementioned ceramic crystal component is TiO ２ And, BaAl ２ Si ２ O ８ , ZnAl ２ O ４ and Zn ２ SiO ４ The low-temperature fired ceramic according to claim 9, comprising at least one selected from the group consisting of the following:

11. The low-temperature fired ceramic according to any one of claims 1 to 10, wherein the RO is BaO.

12. The low-temperature fired ceramic according to any one of claims 1 to 10, further comprising CuO and / or Cu, wherein the sum of the proportion of CuO and Cu contained in the low-temperature fired ceramic is 1% by weight or less.

13. An electronic component comprising a low-temperature fired ceramic according to any one of claims 1 to 10.

14. The electronic component according to claim 13, which has built-in copper wiring.

15. An electronic component comprising a low-dielectric-constant ceramic layer and a high-dielectric-constant ceramic layer, The low dielectric constant ceramic layer is formed from a first low-temperature fired ceramic, The aforementioned high dielectric constant ceramic layer is formed from a second low-temperature fired ceramic, The first low-temperature fired ceramic comprises a glass component (A1) and an oxide of the ceramic crystal component (C1) after firing. The second low-temperature fired ceramic comprises a glass component (A2) and an oxide of the ceramic crystal component (C2) after firing. The aforementioned post-fired glass component (A1) and post-fired glass component (A2) are RO-ZnO-Al ２ O ３ -B ２ O ３ -SiO ２ And, The RO is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. The proportion of RO, the proportion of ZnO, and Al contained in the aforementioned post-fired glass component (A1) and the aforementioned post-fired glass component (A2) ２ O ３ The proportions of each are 0.1 mol% or more and 10 mol% or less, and the proportion of RO, the proportion of ZnO, and the Al contained in the post-fired glass component (A1) and the post-fired glass component (A2) are also specified. ２ O ３ The sum of the proportions is 15 mol% or less. The SiO contained in the glass component (A1) after firing ２ and B ２ O ３ The ratio of the proportions (SiO ２ / B ２ O ３ ) is less than 3.4, The first low-temperature fired ceramic further contains Al in addition to the glass component (A1) after firing. ２ O ３ Includes Al other than the post-fired glass component (A1) contained in the first low-temperature fired ceramic. ２ O ３ The proportion is greater than 0% by weight and less than or equal to 5% by weight. The oxide (C1) of the aforementioned ceramic crystal component is BaAl ２ Si ２ O ８ And, SiO ２ , ZnAl ２ O ４ , Zn ２ SiO ４ and TiO ２ It includes at least two types selected from the group consisting of, The BaAl contained in the first low-temperature fired ceramic ２ Si ２ O ８ The proportion is greater than 0% by weight and less than or equal to 5% by weight. The oxide (C2) of the aforementioned ceramic crystal component is Ba ２ Ti ９ O ２０ , BaTi(BO ３ ) ２ , BaTi ４ O ９ , BaTi ５ O １１ Ba ４ Ti １３ O ３０ BaZn ２ Ti ４ O １１ and Ba ４ ZnTi １１ O ２７ An electronic component comprising at least one selected from the group consisting of the following.

16. The electronic component according to claim 15, which has built-in copper wiring.