JP4577956B2 - Glass ceramic sintered body and wiring board using the same - Google Patents

Description

【００５３】
【表２】

【００５４】
【表３】

【００５５】
表１〜表３から明らかなように、ガラス量が５０体積％より少ない試料Ｎｏ．１１、２６、４５では、１０００℃での焼成により焼結体を緻密化することができなかった。またガラス量が７０体積％より多い試料Ｎｏ．１９、２９については、８００℃での焼成により焼結体の焼結が進行しすぎて誘電損失が増大し、Ｃｕメタライズとの同時焼成ができなかった。
【００５６】
また、Ｃｒ_２Ｏ_３を添加しない試料Ｎｏ．１では、着色することができず、さらに、Ｃｒ₂Ｏ₃を添加せず、他の特定遷移金属を添加した試料Ｎｏ．４２、５２、およびＷＯ₃またはＭｏＯ_３を添加した試料Ｎｏ．６２、６３でも、誘電損失が増大した。また、Ｃｒ_２Ｏ_３量が０．０５重量％より少ない試料Ｎｏ．２、２０では誘電損失が高いものであった。また、Ｃｒ_２Ｏ_３量またはＣｒ_２Ｏ_３および特定金属の含有量が総量で１０重量％を越える試料Ｎｏ．１０、２５、４５、４８、５１、５５、５８、６１では、内部に気孔が多く見られ良好な緻密体が得られず、誘電損失が増加した。
【００５７】
これに対して、本発明にもとづく試料Ｎｏ．３〜９、１２〜１８、２１〜２４、２７、２８、４３、４４、４６、４７、４９、５０、５３、５４、５６、５７、５９、６０では、いずれも着色でき、かつ誘電損失は１０×１０^-4以下となり、Ｃｕメタライズとの同時焼成も可能であった。
【００５８】
【発明の効果】
以上詳述したように、本発明のガラスセラミックス焼結体は、ＢａＯを３７〜５５重量％、ＳｉＯ_２を２９〜４１重量％、Ｂ_２Ｏ_３を７〜１０重量％、Ａｌ_２Ｏ_３を２〜７重量％含有するバリウム珪酸ガラスを５０〜７０体積％とフィラーを総量で３０〜５０体積％の割合で含有するガラスセラミック焼結体であって、前記フィラーが、ａ）チタン酸ランタンと、ｂ）チタン酸カルシウム、チタン酸ストロンチウム、チタン酸バリウム、チタニア、チタン酸マグネシウムの群から選ばれる少なくとも１種と、ｃ）ジルコニウム含有酸化物とを含み、前記ガラスセラミック焼結体が前記ガラスおよび前記フィラーの総量１００重量部に対して、Ｃｒ酸化物をＣｒ_２Ｏ_３換算で０．０５〜１０重量部の割合で含有することによって、白色以外の色に着色できるので、良好な外観で生産性の高いガラスセラミック焼結体を作製できるとともに、高周波帯での誘電損失を低減することができる。また、フィラーとして、上述した組み合わせによって低誘電率、高誘電率の種々の特性のガラスセラミック焼結体を作製することができ、例えば、高誘電率焼結体を絶縁層としてその両面に電極体を形成することにより、該絶縁層をコンデンサとして機能させることができ、これを絶縁基板内に積層することによってコンデンサを内蔵した配線基板を形成することもでき、外部回路基板の小型化および実装コストの削減が図れる。
【図面の簡単な説明】
【図１】本発明のガラスセラミック焼結体を絶縁層として用いた多層配線基板の一例を示す概略断面図である。
【符号の説明】
Ａ 多層配線基板
１ 絶縁基板
１ａ〜１ｃ 絶縁層
２ メタライズ配線層
３ 電極体
４ スルーホール導体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colored glass-ceramic sintered body that is fired at a low temperature and can be co-fired with Cu or Ag and is suitable as an insulating substrate in a wiring board or a package for housing a semiconductor element.
[0002]
[Prior art]
Conventionally, a ceramic multilayer wiring board is most widely used in which a wiring layer made of a refractory metal such as tungsten or molybdenum is formed on or inside an insulating substrate made of an alumina sintered body.
[0003]
In recent years, with the advent of advanced information technology, the frequency band used is increasingly shifting to higher frequencies. In such a high-frequency wiring board that requires transmission of a high-frequency signal, the resistance of the conductor forming the wiring layer is small in order to transmit the high-frequency signal without loss, and the dielectric in the high-frequency region of the insulating substrate. Small loss is required.
[0004]
However, conventional refractory metals such as tungsten (W) and molybdenum (Mo) have high conductor resistance, slow signal propagation speed, and signal propagation in a high frequency region of 1 GHz or more is difficult. It is necessary to use low resistance metals such as copper, silver, and gold instead of metals such as Mo.
Since the wiring layer made of such a low-resistance metal has a low melting point and cannot be co-fired with alumina, recently, so-called glass ceramics made of glass or a composite material of glass and ceramics is insulated. A wiring substrate used as a substrate is being developed.
[0005]
In recent years, as a glass ceramics with high thermal expansion in order to reduce the difference in thermal expansion between the printed circuit board for mounting the wiring board, even glass-ceramics was added and mixed a filler component such as such as click O over Tsu barium silicate glass proposed Has been.
[0006]
On the other hand, for ceramics used as an insulating substrate, contrast is provided when optically detecting the bonding position when wire bonding is performed, and appearance defects due to preference or color unevenness of the white insulating substrate are prevented. In order to improve the yield, this is colored.
Conventionally, as a coloring method, for example, alumina ceramics and the like are colored by adding metal elements such as W and Mo, and W and Mo are also applied to glass ceramics. It has been studied to color by adding.
[0007]
[Problems to be solved by the invention]
However, when glass ceramics mainly composed of barium silicate glass is used as the insulating substrate, there is a problem that dielectric loss at a high frequency is larger than that of an alumina sintered body. Specifically, the alumina sintered body is about 5 × 10 ⁻⁴ at a measurement frequency of 1 MHz, whereas the glass ceramic sintered body is as large as about 15 × 10 ⁻⁴ . Moreover, when the above-described W or Mo is added as a colorant for the glass ceramic sintered body, the dielectric loss of the sintered body tends to increase.
[0008]
Accordingly, an object of the present invention is to provide a glass-ceramic sintered body that can be co-fired with a wiring layer such as Cu or Ag, can be colored to a desired color, and can reduce dielectric loss. And
[0009]
[Means for Solving the Problems]
As a result of repeated investigations on the composition of the glass ceramic sintered body with respect to the above-mentioned problems, the inventors of the present invention have compared Cr oxide, or its oxide, to a glass ceramic sintered body mainly containing barium silicate glass and containing a filler. By adding a part of which is replaced with at least one selected from the group consisting of Cu, V, Fe, Ni, Mn and Co or a compound thereof, the desired color can be obtained without impairing the properties of the glass ceramic sintered body. It was found that the dielectric loss of the sintered body can be reduced while being able to be colored.
[0010]
That is, a glass ceramic sintered body of the present invention, the BaO 37-55 wt%, a SiO ₂ 29 to 41 _wt%, the B 2 _{O 3} 7 to 10 wt%, the _Al 2 _{O 3} 2 to 7 wt% It contains 50 to 70% by volume of barium silicate glass and 30 to 50% by volume of filler in a total amount, and the glass ceramic sintered body has a total amount of 100 parts by weight of the glass and the filler. in contrast, the Cr oxide containing 0.05 to 10 wt% in terms _{of Cr} 2 _{O 3,} and with exhibits a color other than white state, and are dielectric loss 10 × ^{10 -4} or less at a frequency 1 MHz, the filler A) lanthanum titanate, b) at least one selected from the group consisting of calcium titanate, strontium titanate, barium titanate, titania, magnesium titanate, and c And) a zirconium-containing oxide . Here, it is desirable to replace a part of the Cr compound with at least one compound selected from the group consisting of Cu, V, Fe, Ni, Mn and Co.
[0011]
Further, the glass ceramic sintered body in a high dielectric constant, as a pre-Symbol filler, Rukoto the Yusuke containing is not good the titanium salt.
[0012]
In concrete terms, a) containing a lanthanum titanate, b) and calcium titanate, c) it is desirable to include a zirconium-containing oxide, of the filler, the content of a) x, b) When the weight ratio between the two components is expressed as (1-x), x is in the range of 0.2 ≦ x ≦ 0.8, the content of c) is y, the above a) and b) When the weight ratio of the two components is expressed as (1-y), the y is preferably in the range of 0.05 ≦ y ≦ 0.3. It is desirable that the coefficient of thermal expansion at ˜400 ° C. is 8 × 10 ⁻⁶ / ° C. or more and the dielectric constant at 1 MHz is 14 or more.
[0013]
The wiring board according to the present invention has a metallized wiring layer disposed on and / or inside an insulating substrate comprising at least one ceramic insulating layer, wherein at least one layer of the ceramic insulating layer comprises , and it is characterized in glass ceramic sintered compact Tona Rukoto the above-described one.
[0014]
Here, the insulating substrate is Rutotomoni such a plurality of the ceramic insulating layer, the dielectric constant of one layer of ceramic insulating layer may be different from the dielectric constant of the other of the ceramic insulating layer is desirable.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The glass-ceramic sintered body of the present invention comprises 50 to 70% by volume of barium silicate glass containing 30 to 60% by weight of BaO having an average particle size of 0.5 to 20 μm and a filler having an average particle size of 0.5 to 20 μm. The total amount is 30 to 50% by volume.
[0016]
Barium silicate system of the present invention as is (BaO-SiO ₂₎ glass, be one which contains a proportion of 3 7 to 55 wt% of BaO, in particular, suitable composition, the SiO _{2 2} 9 ~ 41 weight %, _B 2 _{O 3} and 7-1 0% by weight, the _Al 2 _{O 3} contained each in an amount of 2-7% by weight, still _{more, ZnO, ZrO 2, MgO,} SrO, TiO 2, P 2 O 5 It is desirable to contain at least one selected from the group of 10% by weight or less.
[0017]
Furthermore, it is desirable that the yield point of the glass is 400 to 800 ° C, particularly 400 to 700 ° C. This is because when molding a mixture consisting of glass and filler, a molding binder such as an organic resin is added, but this binder is removed efficiently, and the metallization that is fired at the same time as the insulating substrate is matched with the firing conditions. Necessary for the purpose, and when the yield point is lower than 400 ° C., the glass starts sintering at a low temperature. For example, co-firing with a metallization of Ag, Cu or the like with a sintering temperature of 600 to 800 ° C. This is because the binder cannot be decomposed and volatilized since the densification of the molded body starts at a low temperature, and the binder component remains, resulting in an influence on the characteristics. On the other hand, if the yield point is higher than 800 ° C., it is difficult to sinter unless the amount of glass is increased, and the amount of relatively expensive glass used increases, which hinders cost reduction.
[0018]
In addition, the barium silicate glass may form an amorphous phase in the sintered body, in terms of reducing dielectric loss, increasing strength, increasing thermal conductivity, and controlling the dielectric constant of the sintered body. after firing, for example, it may be obtained by precipitation of the crystal phase, such as _{BaO · 2SiO 2, BaAl 2 Si} 2 O 8, BaB 2 Si 2 O 8 from the glass.
[0021]
Further, according to the present invention, in achieving a high dielectric constant greater than high thermal expansion and dielectric constant 8, it is not good for containing titanate as the filler.
[0022]
Specifically ,
a) Lanthanum titanate (α = 15 × 10 ⁻⁶ / ° C., ε = 45)
b) Calcium titanate (α = 13 × 10 ⁻⁶ / ° C., ε = 180), strontium titanate (α = 9 × 10 ⁻⁶ / ° C., ε = 300), barium titanate (α = 14 × 10 ^{− 6} / ° C., ε = 13000), titania (α = 9 × 10 ⁻⁶ / ° C., ε = 80), at least selected from the group ^{consisting of} magnesium titanate (α = 10 × 10 ⁻⁶ / ° C., ε = 20). you as essential components at least one of the three ceramic of one c) a zirconium-containing oxide.
[0023]
According to these components, component a) contributes to higher dielectric constant, higher thermal expansion and improved sinterability of the material. Further, component b) supplements the fact that only component a) has a limitation on the increase in dielectric constant, and plays a role in further increasing the dielectric constant of the sintered body. Component c) serves to improve the sinterability of the material and to increase the dielectric constant.
[0024]
Lanthanum titanate is represented by the general formula La ₂ O ₃ .nTiO ₂ (n = 2 to 5), specifically,
La ₂ O ₃ .2TiO ₂ (α = 15 × 10 ⁻⁶ ) / ° C., ε = 45)
La ₂ O ₃ .3TiO ₂ (α = 14 × 10 ⁻⁶ ) / ° C., ε = 47)
La ₂ O ₃ · 4TiO ₂ (α = 14 × 10 ⁻⁶ ) / ° C., ε = 51)
La ₂ O ₃ .5TiO ₂ (α = 13 × 10 ⁻⁶ ) / ° C., ε = 55)
Is mentioned.
[0025]
In addition, as c) zirconium containing oxide,
ZrO ₂ (α = 10 × 10 ⁻⁶ / ° C., ε = 30)
MgZrO ₃ (α = 9.2 × 10 ⁻⁶ / ° C., ε = 32)
CaZrO ₃ (α = 9.2 × 10 ⁻⁶ / ° C., ε = 32)
SrZrO ₃ (α = 9.5 × 10 ⁻⁶ / ° C., ε = 30)
BaZrO ₃ (α = 9.3 × 10 ⁻⁶ / ° C., ε = 40)
ZrO ₂ is most desirable from the viewpoint of at least one selected from the group consisting of the above, especially the improvement of sinterability and thermal expansion.
[0026]
Furthermore, according to the present invention, in the system containing a) b) c), when the weight ratio of the two components is represented by x as the content of a) and b) as (1-x), It is desirable that x is in a range of 0.2 ≦ x ≦ 0.8 in that a dense body having high thermal expansion characteristics and a desired high dielectric constant can be obtained at an appropriate firing temperature.
[0027]
In addition, when the content of component c) is y, and the total amount of a) and b) is (1-y) and the weight ratio of both components is expressed, high thermal expansion characteristics and desired high dielectric constant at an appropriate firing temperature It is desirable that y is in the range of 0.05 ≦ y ≦ 0.3 in that a dense body showing a rate can be obtained.
[0029]
Furthermore, according to the present invention, with respect to 100 parts by weight of the main component composition composed of the glass component and the filler component, the Cr oxide is 0.05 to 10 parts by weight, particularly 0.2 to 0.2 parts in terms of Cr ₂ O _3. The main feature is that it is contained in a ratio of 6 parts by weight. This makes it possible to color the sintered body in a color other than white, and to reduce dielectric loss in the high frequency band of the sintered body. it can. In the sintered body, the Cr oxide is desirably present as Cr ₂ O ₃ , and may be a non-stoichiometric oxide in which the valence of Cr is changed depending on the firing atmosphere.
[0030]
As the Cr compound, Cr ₂ O ₃ is most desirable, but carbonates, nitrates, acetates, Cr-containing organic compounds, etc. that form oxides during the sintering process may be used, and Cr carbides and nitrides may be used. Etc. also have a coloring effect and a dielectric loss reducing effect.
[0031]
Cr can also be added to the glass raw material, but it is desirable to add it as a metal or ceramic powder from the standpoint of adjusting the softening point of the glass and ease of production.
[0032]
The Cr oxide content is in the above range because if the oxide equivalent amount is less than 0.05% by weight, coloring is insufficient and the dielectric loss of the sintered body can be reduced. On the contrary, if the content exceeds 10% by weight, the sinterability is hindered, and the densification and strength of the sintered body are adversely affected. A sintered body exhibiting a green color can be obtained by including a Cr oxide in the sintered body.
[0033]
Further, according to the present invention, a part of the Cr oxide can be substituted with at least one selected from the group consisting of Cu, V, Fe, Ni, Mn, and Co, or a compound thereof. Even in this case, it is desirable to contain 0.05 parts by weight or more of Cr oxide in terms of Cr ₂ O _{3 in} terms of reduction of dielectric loss and coloring, and Cr oxide and the above-mentioned specific metal or It contains so that the sum total of the oxide conversion amount of the compound may be 10 weight part or less.
[0034]
By adding these specific metals or their compounds, the color of the sintered body can be changed from green to desired colors such as red, blue, yellow, and black without inhibiting the effect of adding the Cr compound. Can be made.
[0035]
Next, the glass ceramic sintered body of the present invention has 50 to 70% by volume of barium silicate glass powder containing 30 to 60% by weight of BaO having an average particle size of 0.5 to 20 μm, and an average particle size of 0.5 to the various fillers with weighed in a ratio of 30 to 50 vol% in total of the previous SL C r oxide 0.05 to 10 parts by weight terms _{of Cr} 2 _{O 3} of 20 [mu] m, in particular 0.2 to 6 Add and mix at a ratio of parts by weight. After adding an appropriate organic resin binder to the mixture containing the raw materials described above, the desired molding means, for example, die press, cold isostatic press, injection molding, extrusion molding, doctor blade method, calendar roll It is formed into an arbitrary shape by a method, a rolling method or the like.
[0036]
Next, in firing the above-mentioned molded body, first, the binder component blended for molding is removed. The removal of the binder is performed in an air atmosphere at around 700 ° C., but when using, for example, Cu as the wiring conductor, in a non-oxidizing atmosphere containing water vapor at 100 to 750 ° C. to prevent oxidation of Cu. It is desirable to be performed at. At this time, the shrinkage start temperature of the molded body is preferably about 700 to 850 ° C., and if the shrinkage start temperature is lower than this, it becomes difficult to remove the binder. It is desirable to control the yield point as described above.
[0037]
Firing is performed in an oxidizing atmosphere or a non-oxidizing atmosphere at 850 to 1050 ° C., particularly 850 to 950 ° C., which allows simultaneous firing with a metallized wiring layer containing a low resistance conductor such as Cu or Ag. It is densified to a density of 90% or higher.
[0038]
In the thus produced glass ceramic sintered body of the present invention, the crystal phase generated from the glass component, the crystal phase generated by the reaction between the glass component and the filler component, the filler component, or the filler component is decomposed and generated. In some cases, a glass phase exists in the grain boundary of these crystal phases. In addition, the coloring component is present as a reaction product that reacts with the glass raw material at the time of addition or in the form of vitrification, at the grain boundary of the crystal phase.
[0039]
The glass ceramic sintered body can be used publicly as an insulating substrate of a wiring board. Therefore, FIG. 1 shows a schematic cross-sectional view of a multilayer wiring board which is an example of a wiring board having an insulating layer made of the sintered glass ceramic of the present invention.
[0040]
According to FIG. 1, a multilayer wiring board 1 is provided with a metallized wiring layer 2 on the surface and / or inside of an insulating substrate 1 in which insulating layers 1a, 1b and 1c made of a glass ceramic sintered body are laminated in multiple layers. ing. Further, according to FIG. 1, at least one layer 1b of the insulating layers 1a, 1b, and 1c is the same as described above, for example, high thermal expansion and dielectric having an average coefficient of thermal expansion of 8 × 10 ⁻⁶ / ° C. or more at 40 to 400 ° C. The average thermal expansion coefficient of the other insulating layers 1a and 1c at 40 to 400 ° C. is 8 × 10 ⁻⁶ / ° C. above high thermal expansion, dielectric constant of 8 or less, is formed by the especially 7 or less of the glass ceramic sintered body, to form an electrode layer 3-3 made of a conductor such as Cu and below the insulating layer 1b, thru-hole conductor 4 By connecting to the metallized wiring layer 2 on the substrate surface via -4 or the like, a predetermined capacitance can be taken out between the wiring layers 2-2.
[0041]
Here, the insulating layer 1b is comprised by the glass ceramic sintered compact containing a titanate as a filler mentioned above. Further, thermal expansion laminated on upper and lower surfaces of the insulating layer 1b, a low dielectric constant insulating layer 1a and 1c, by the Turkey to contain SiO ₂ filler as filler as described above, the thermal expansion coefficient and dielectric loss without impairing the other properties equal, easily dielectric constant make lower that can be used.
[0042]
Further, at least one of the insulating layers 1a, 1b, and 1c needs to be a glass ceramic sintered body obtained by adding and mixing a filler to barium silicate glass. As for, it does not necessarily need to be barium silicate glass, The combination of at least 1 sort (s) chosen from the group of borosilicate glass, aluminosilicate glass, and alkali silicate glass, and a filler may be sufficient. Even in this case, it is desirable that the insulating layer 1b and the insulating layers 1a and 1c have similar colors, dielectric losses, thermal expansion coefficients, firing temperatures, and the like.
[0043]
In order to produce the multilayer wiring board, a slurry is prepared by adding and mixing an appropriate organic binder, a solvent, and a plasticizer to the glass ceramic composition having a low dielectric constant consisting of the glass powder and filler powder described above. The slurry is formed into a green sheet by a green sheet forming method by a known coating method such as a doctor blade.
[0044]
Then, as a metallized wiring layer, a metal paste obtained by adding and mixing an organic binder, a solvent, and a plasticizer to an appropriate metal powder is printed and applied to the green sheet in a predetermined pattern by a well-known screen printing method. In some cases, the green sheet is appropriately punched to form a through hole, and this hole is filled with a metallized paste.
[0045]
On the other hand, a glass ceramic green sheet having a high thermal expansion and a high dielectric constant, which is formed, stamped, and printed with an electrode layer by the same method as described above, is produced.
[0046]
Then, laminating the glass-ceramic green sheets having a low dielectric constant glass-ceramic green sheets and a high dielectric constant described above, by performing co-firing of the green sheet laminate and the metallization, internal insulating layer serving as a capacitor A multilayer wiring board can be obtained.
[0047]
Since the wiring board of the present invention can be colored in a desired color, the production yield is improved and the appearance is good. Further, since the dielectric loss in the high frequency band can be reduced, the transmission loss of the high frequency signal can be reduced and the signal can be transmitted satisfactorily. In addition, since the thermal expansion coefficient of the insulating board can be approximated to an external circuit board such as a printed board containing an organic resin, the wiring board is mounted on the external circuit board via ball-shaped solder terminals or solder. In addition, long-term reliability for temperature cycling is possible.
[0048]
In addition, by controlling the composition of the glass ceramic sintered body, high dielectric constant and low dielectric constant glass ceramic sintered bodies can also be produced. For example, a multilayer wiring board with a built-in capacitor is produced. can also, conventionally, since the capacitor that has been mounted on an external circuit board is not required, it is possible to reduce the size and implementation cost of an external circuit board.
[0049]
【Example】
The following two types of glass were prepared as glass powders.
A: _SiO 2: 41 wt% -BaO: 37 _wt% -B ₂ O 3: 10 _wt% -Al _{2 O} 3: 7 wt% -CaO: 5 wt%
(Deformation point 700 ° C., thermal expansion coefficient 6.5 × 10 ⁻⁶ / ° C., Pb content 50 ppm or less)
B: _SiO 2: 29 wt% -BaO: 55 _wt% -B _{2 O} 3: 7 _wt% -Al _{2 O} 3: ₂ wt% -ZnO: 7 wt%
(Bend point 657 ° C., coefficient of thermal expansion 10.8 × 10 ⁻⁶ / ° C., Pb content 50 ppm or less)
(1) For these glasses A and B, La ₂ Ti ₂ O ₇ , CaTiO ₃ , ZrO ₂ and Cr ₂ O ₃ were prepared as fillers, and these were mixed at a ratio shown in Table 1.
The ratios in Table 1 are weight ratios where the content of La ₂ Ti ₂ O ₇ is x, the content of CaTiO ₃ is (1-x), the content of ZrO ₂ is y, La ₂ Ti ₂ O ₇ and CaTiO 3 The total amount of ₃ is (1-y).
(2) the glass A, click O over Tsu _(SiO 2), alumina _{(Al 2 O} 3), titania _(TiO 2), calcium titanate (CaTiO _3), forsterite were mixed in a ratio of Table 2 Then, Cr ₂ O ₃ was mixed at a ratio shown in Table 2 with respect to 100 parts by weight of the mixture.
(3) For glass A, La ₂ Ti ₂ O ₇ , CaTiO ₃ , and ZrO ₂ are used as fillers. The content of La ₂ Ti ₂ O ₇ is x, and the content of CaTiO ₃ is (1-x ) X = 0.4, ZrO ₂ content was y, and the total amount of La ₂ Ti ₂ O ₇ and CaTiO ₃ was (1-y) and weighed and mixed so that y = 0.1.
To this mixture, Cr ₂ O ₃ and various transition metal oxides shown in Table 3 were added and mixed at a ratio shown in Table 3.
[0050]
A solvent is added to each of the above mixed powders (1), (2) and (3) and pulverized and mixed using a ball mill. Then, an organic binder and a plasticizer are added and mixed well to prepare a slurry. A 500 μm green sheet was prepared. With the obtained green sheet , a sample of 60 mm × 60 mm was prepared, debindered at 750 ° C. in a nitrogen atmosphere containing water vapor, and then fired at the temperature shown in the table.
[0051]
Next, the dielectric constant, dielectric loss, and average thermal expansion coefficient at 40 to 400 ° C. were measured with an impedance analyzer on the sintered body obtained as described above. Moreover, the color tone of the sintered compact was confirmed.
[0052]
[Table 1]

[0053]
[Table 2]

[0054]
[Table 3]

[0055]
As is apparent from Tables 1 to 3, the sample No. In 11, 26 and 45, the sintered body could not be densified by firing at 1000 ° C. Sample No. with a glass content greater than 70% by volume. Regarding Nos. 19 and 29, sintering of the sintered body proceeded excessively by firing at 800 ° C., resulting in an increase in dielectric loss, and simultaneous firing with Cu metallization could not be performed.
[0056]
In addition, Sample No. to which Cr ₂ O ₃ was not added was added. No. 1 could not be colored, and Cr ₂ O ₃ was not added, and sample No. 1 was added with another specific transition metal. Sample No. 42, 52, and WO ₃ or MoO ₃ added. In 62 and 63, the dielectric loss increased. In addition, Sample No. in which the amount of Cr ₂ O ₃ is less than 0.05% by weight. The 2,2 0 were those dielectric loss is high. Sample No. ₂ in which the Cr ₂ O ₃ content or the Cr ₂ O ₃ content and the specific metal content exceeds 10% by weight in total. In 10, 25, 45, 48, 51, 55, 58 and 61, many pores were observed inside, a good dense body could not be obtained, and the dielectric loss increased.
[0057]
On the other hand, sample no. 3-9 , 12-18 , 21-24, 27 , 28, 43 , 44, 46 , 47, 49 , 50, 53 , 54, 56 , 57, 59 , 60, all can be colored and dielectric loss Was 10 × 10 ⁻⁴ or less, and simultaneous firing with Cu metallization was possible.
[0058]
【The invention's effect】
As described above in detail, the glass ceramics sintered body of the present invention, the BaO 37 to 55 wt%, a SiO ₂ twenty-nine to forty-one _wt%, the B 2 _{O 3} 7 to 10 wt%, the _Al 2 _{O 3} A sintered glass-ceramic containing 50 to 70% by volume of barium silicate glass containing 2 to 7% by weight and a total amount of filler of 30 to 50% by volume, wherein the filler is a) lanthanum titanate and B) at least one selected from the group consisting of calcium titanate, strontium titanate, barium titanate, titania and magnesium titanate, and c) a zirconium-containing oxide, wherein the glass ceramic sintered body comprises the glass and By containing Cr oxide in a proportion of 0.05 to 10 parts by weight in terms of Cr ₂ O ₃ with respect to 100 parts by weight of the total amount of the filler, Since it can be colored in an outer color, a glass ceramic sintered body having a good appearance and high productivity can be produced, and dielectric loss in a high frequency band can be reduced. Further, as a filler, a glass ceramic sintered body having various characteristics having a low dielectric constant and a high dielectric constant can be produced by the combination described above . For example, a high dielectric constant sintered body is used as an insulating layer and electrode bodies on both surfaces thereof. By forming the insulating layer, the insulating layer can function as a capacitor, and by laminating the insulating layer in the insulating substrate, a wiring board with a built-in capacitor can be formed. Can be reduced.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a multilayer wiring board using a glass ceramic sintered body of the present invention as an insulating layer.
[Explanation of symbols]
A Multilayer wiring board 1 Insulating boards 1a to 1c Insulating layer 2 Metallized wiring layer 3 Electrode body 4 Through-hole conductor

Claims (8)

The BaO thirty-seven to fifty-five wt%, a SiO ₂ 29 to 41 _wt%, the B 2 _{O 3} 7 to 10 wt%, and 50-70% by volume of barium silicate glass containing _Al 2 _{O 3} 2 to 7 wt% The glass ceramic sintered body contains a filler in a proportion of 30 to 50% by volume in total, and the glass ceramic sintered body contains Cr oxide and Cr oxide with respect to 100 parts by weight of the total amount of the glass and the filler. in a proportion of 0.05 to 10 parts by weight ₂ O ₃ in terms, with exhibits a color other than white state, and are dielectric loss 10 × ^{10 -4} or less at a frequency 1 MHz, the filler, a) titanate Lanthanum, b) at least one selected from the group consisting of calcium titanate, strontium titanate, barium titanate, titania, magnesium titanate, and c) zirconium-containing oxidation A glass ceramic sintered body characterized by comprising:   The glass ceramic sintered body according to claim 1, wherein a part of the Cr compound is substituted with at least one compound selected from the group consisting of Cu, V, Fe, Ni, Mn and Co. The glass ceramic sintered body according to claim 1 or 2, wherein the filler includes a ) lanthanum titanate, b) calcium titanate, and c) a zirconium-containing oxide. Among the fillers, when the weight ratio of the two components is expressed with the content of a) being x and the content of b) being (1-x), x is in the range of 0.2 ≦ x ≦ 0.8. The glass ceramic sintered body according to claim 3 . When the content of c) is y, and the total amount of a) and b) is (1-y) and the weight ratio of both components is expressed, y is in the range of 0.05 ≦ y ≦ 0.3. The glass-ceramic sintered body according to claim 3 or 4, wherein the glass-ceramic sintered body is provided. Thermal expansion coefficient at 40 to 400 ° C. is not less 8 × ^{10 -6} / ℃ or higher, and a glass ceramic sintered according to any one of claims 3 to 5 dielectric constant at 1MHz is characterized in that 14 or more body. 7. The wiring board in which a metallized wiring layer is disposed on and / or inside an insulating substrate made of at least one ceramic insulating layer, wherein at least one of the ceramic insulating layers is any one of claims 1 to 6 . A wiring board comprising the glass ceramic sintered body according to claim 1. The wiring according to claim 7, wherein the insulating substrate includes a plurality of ceramic insulating layers, and a dielectric constant of one of the ceramic insulating layers is different from a dielectric constant of another ceramic insulating layer. substrate.

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