JP4044752B2 - Low temperature fired porcelain composition and method for producing low temperature fired porcelain - Google Patents

Description

【００５１】
表１の結果より明らかなように、サンプルＮｏ．５〜１９、２４〜４１は何れも４０℃〜４００℃における線熱膨張係数が８．０〜１０．７×１０^−６／℃、１ＭＨｚにおける比誘電率が１６以上、かつ−４０〜８５℃における比誘電率の温度係数が−１９３〜１９４×１０^−６／℃であった。
【００５２】
また、熱サイクル試験の結果によれば、上記本発明のサンプルＮｏ．５〜１９、２４〜４１を用いた配線基板は、１０００サイクルまでの試験に十分に耐えるものであった。
【００５３】
また、無機フィラー全量中にＣａＴｉＯ₃を４０〜６０質量％、ＣａＴｉＳｉＯ₅を４０〜６０質量％含有させたサンプルＮｏ．６〜１０、１３〜１９、２５〜２９、３６〜４１では、比誘電率の温度係数が−７０〜７０×１０^-6／℃なり大きく改善された。
【００５４】
さらに、ＣａＴｉＯ₃を４５〜５５質量％、ＣａＴｉＳｉＯ₅を４５〜５５質量％含有させたサンプルＮｏ．７〜９、１４〜１９、２６〜２８、および３６〜４１では、比誘電率の温度係数が−３５〜３５×１０^-6／℃の改善された。
【００５５】
特に、上記の組成に対し、クオーツ、酸化クロムのうち少なくとも１種を添加したサンプルＮｏ．１４〜１９および３６〜４１では、比誘電率の温度係数が８以下となりさらに小さくできた。
【００５６】
一方、無機フィラーとしてＣａＴｉＯ₃かＣａＴｉＳｉＯ₅のうちいずれか一方のみを含有した試料Ｎｏ．１〜４、２０〜２３では、−４０〜８５℃における比誘電率の温度係数が−３１８×１０^-6／℃以下あるいは２５６×１０^-6／℃以上であった。
【００５７】
【発明の効果】
以上詳述したように、本発明によれば、アルカリ土類金属酸化物とＳｉＯ_２を含有するガラスに、無機フィラーとしてＣａＴｉＯ_３（線熱膨張係数：１３×１０^−６／℃、比誘電率：１８０、比誘電率の温度係数：−１６３０×１０^−６／℃）とＣａＴｉＳｉＯ５（線熱膨張係数：６．５×１０^−６／℃、比誘電率：３５、比誘電率の温度係数：１２００×１０^−６／℃）と酸化クロムとを所定比率で組み合わせることによって、磁器の高熱膨張化、高誘電率化とともに、誘電率の温度安定性を得ることができる。
【図面の簡単な説明】
【図１】 本発明の低温焼成磁器組成物を用いて焼成して得られた低温焼成磁器を配線基板に適用した例を説明するための概略断面図である。
【符号の説明】
１ 絶縁基板
１ａ 低誘電率層
１ｂ 高誘電率層
２ 蓋体
３ メタライズ配線層
４ 接続端子
４ａ 電極パッド
４ｂ ボール状端子
５ 半導体素子
６ キャビティ
７ 絶縁体
８ 配線導体
９ 電極層
１０ ビアホール導体
Ａ 半導体素子収納用パッケージ
Ｂ 外部回路基板[0001]
BACKGROUND OF THE INVENTION
  The present invention,Low-temperature fired porcelain composition and low-temperature fired porcelain having high thermal expansibility, high dielectric constant, and excellent temperature stability of relative dielectric constantManufacturing methodAbout.
[0002]
[Prior art]
Conventionally, ceramic multilayer wiring boards capable of high-density wiring are frequently used as multilayer wiring boards, for example, semiconductor element housing packages for housing semiconductor elements such as LSIs. A ceramic multilayer wiring board is composed of an insulating substrate made of ceramics such as alumina and a wiring conductor layer made of a refractory metal such as W or Mo formed on the surface thereof. A cavity is formed, a semiconductor element is accommodated in the cavity, and the cavity is hermetically sealed by a lid.
[0003]
In recent years, higher integration has been achieved in wiring substrates applied to the above-described semiconductor element storage packages mounting semiconductor elements such as ICs and LSIs, which have been increasingly integrated, and hybrid integrated circuit devices mounted with various electronic components. Lower resistance, smaller size and lighter weight are required, and multilayer wiring boards using glass ceramics that can achieve lower dielectric constants and lower resistance of wiring conductor layers than alumina-based ceramic materials are attracting more attention Has been.
[0004]
In such a glass-ceramic multilayer wiring board, in order to cope with high-speed integration of semiconductor elements, an increase in the degree of integration with higher frequencies, and high-density mounting for further downsizing of electronic devices, Ball grid array (BGA) with ball-shaped connection terminals fixed is formed, and in order to improve the connection reliability with the external circuit board, the thermal expansion coefficient of the insulating board is close to that of the external circuit board. It has been proposed to use a natural porcelain.
[0005]
On the other hand, in portable information terminals such as mobile phones and laptop computers, for example, a switching circuit and a power amplifier circuit of a mobile phone are composed of a plurality of resistors and capacitors. Conventionally, these elements are individually provided on a circuit board. Although it is installed, there is a strong demand for miniaturization of electronic components to be mounted along with miniaturization of portable information terminals, so that a multilayer formed using an insulating material such as glass ceramic as described above. A multilayer wiring board in which a high dielectric constant layer is interposed inside a wiring board and a functional element such as a capacitor is built in has been proposed.
[0006]
[Problems to be solved by the invention]
However, in the multilayer wiring board as described above, as a high dielectric constant layer, BaO-TiO has been conventionally used.₂System, PbO-TiO₂Composite perovskite-based dielectric materials, mainly composed of bismuth, etc., are used, but with such dielectric materials, it is difficult to co-fire with ceramics made of glass ceramics as an insulating material, and the thermal expansion of the insulating layer There has been a problem that it becomes difficult to control.
[0007]
In addition, in terms of electrical characteristics of the high dielectric constant layer, the use of the dielectric material as described above can increase the dielectric constant, but the performance as a resonator due to the large temperature coefficient of the relative dielectric constant. There was a problem of low.
[0008]
  Therefore, the present invention is a low-temperature fired ceramic composition that can be fired at the same time as a low-temperature fired ceramic with high thermal expansion and low dielectric constant, has high thermal expansion and high dielectric constant, and is excellent in temperature stability of dielectric constant. And low-temperature fired porcelainManufacturing methodIs intended to provide.
[0009]
[Means for Solving the Problems]
As a result of repeated studies on the above problems, the present inventors have found that alkaline earth metal oxides and SiO₂As a inorganic filler, CaTiO_ThreeAnd CaTiSiO_FiveIt was found that the temperature stability of the dielectric constant can be obtained as well as the high thermal expansion and high dielectric constant of the porcelain by combining the above with a predetermined ratio.
[0010]
  That is, the low-temperature fired porcelain composition of the present invention contains 15 to 70% by mass of alkaline earth metal oxide.andSiO₂Containing 30 to 60% by massThe20-80% by volume,CaTiO in the total amount ₃ 45-49 mass%, CaTiSiO ₅ 45 to 49 mass% and chromium oxide in a ratio of 2 to 10 mass%From 20 to 80% by volume of inorganic fillerBecomeIt is characterized by that.
  The glass is made of Al. ₂ O ₃ And B ₂ O ₃ Containing Al or Al ₂ O ₃ , B ₂ O ₃ And ZrO ₂ It is desirable that it is either of the thing containing.
[0011]
  MaThe low-temperature fired porcelain of the present inventionManufacturing methodThe aboveLow temperature fired porcelainAfter molding the composition, firing at 800 to 1100 ° CCharacterized by.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
  (Composition / Porcelain)
  The low-temperature fired ceramic composition of the present invention comprises 15 to 70% by mass of an alkaline earth metal oxide and SiO 2₂20 to 80% by volume of glass containing 30 to 60% by mass and 20 to 80% by volume of inorganic filler, and the inorganic filler is CaTiO.₃And CaTiSiO₅WhenWith chromium oxideIn which the temperature coefficient of relative permittivity is −200 × 10^-6/ ° C. to 200 × 10^-6The linear thermal expansion coefficient is 13 x 10^-6/ ° C., relative permittivity is 180, and relative permittivity temperature coefficient is −1630 × 10^-6CaTiO that is / ℃₃20 to 80% by mass and the coefficient of linear thermal expansion is 6.5 × 10^-6/ ° C., relative permittivity is 35, and relative permittivity temperature coefficient is 1200 × 10^-6CaTiSiO // ° C₅20 to 80% by mass. ThisAs shown, the temperature characteristic of the negative side relative permittivity is CaTiO.₃And CaTiSiO showing the temperature characteristics of the relative dielectric constant on the + side₅In combination, the temperature coefficient of the dielectric constant can be reduced and stabilized, and can be controlled to an arbitrary temperature coefficient.
[0017]
CaTiO contained in inorganic filler_ThreeAnd CaTiSiO_FiveIs limited to the above range._ThreeIs less than 20% by mass or CaTiSiO_FiveIs more than 80% by mass, the linear thermal expansion coefficient of the porcelain obtained after firing is 8 × 10^-6It becomes difficult to raise the temperature above / ° C, or it becomes difficult to raise the relative dielectric constant to 16 or more, or the temperature coefficient of the relative dielectric constant is 200 × 10^-6It becomes difficult to keep the temperature below / ° C, and CaTiO_ThreeIs more than 80% by mass or CaTiSiO_FiveIs less than 20% by mass, the temperature coefficient of the relative permittivity of the porcelain obtained is -200 × 10^-6This is because it becomes difficult to increase the temperature to more than / ° C.
[0018]
  In particular, the amount of CaTiO3 is 45% by mass to49% By mass, and the amount of CaTiSiO5 is 45% by mass to49% By massis important. The above CaTiO3 and CaTiSiO5 are 80% by mass or more, particularly 90% by mass or more, more preferably 95% by mass or more in total in the inorganic filler, in order to increase the relative dielectric constant at 1 MHz of the obtained porcelain to 16 or more. It is included in the ratio.
[0019]
Further, according to the present invention, the content of the alkaline earth metal oxide in the glass is 15 to 70% by mass, SiO 2₂It is important that the content of is 30 to 60% by mass. This is because the alkaline earth metal oxide content is less than 15% by mass or SiO 2₂When the content of S is more than 60% by mass, it is difficult to soften the glass, and the coefficient of linear thermal expansion becomes low. The resulting ceramic has a coefficient of linear thermal expansion at 40 to 400 ° C. of 8 × 10.^-6It is difficult to increase to more than / ° C., and the content of alkaline earth metal oxide is more than 70% by mass or SiO 2₂When the content of is less than 30% by mass, vitrification is difficult, and the characteristics tend to become unstable.
[0020]
According to the present invention, the glass and the inorganic filler are mixed at an appropriate ratio according to the purpose such as the firing temperature and the final thermal expansion coefficient of the porcelain. The glass used in the present invention has a shrinkage start temperature of 700 ° C. or lower when no inorganic filler is added, and melts at 850 ° C. or higher, so that a metallized wiring layer or the like cannot be provided. However, by mixing the inorganic filler, crystal precipitation occurs in the firing process, and a liquid phase for liquid phase sintering of the inorganic filler can be formed at an appropriate temperature. In addition, the shrinkage start temperature of the entire molded body can be increased. In addition, since the shrinkage start temperature of the entire molded body can be increased, matching of the simultaneous firing conditions with the metallized wiring layer can be achieved by adjusting the content of the inorganic filler depending on the type of metallized used.
[0021]
Moreover, the low-temperature-fired porcelain composition of this invention mixes the said glass amount in 20-80 volume% and the said inorganic filler amount in the ratio of 20-80 volume%. The amount of the glass and the inorganic filler is limited to the above range because the glass amount is less than 20% by volume, in other words, if the amount of the inorganic filler is more than 80% by volume, liquid phase sintering is difficult and the firing temperature is low. The metallized wiring layer may be melted at the time of simultaneous firing with the metallized wiring layer. Also, if the amount of glass is more than 80% by volume, in other words, if the amount of inorganic filler is less than 20% by volume, the properties of the porcelain greatly depend on the properties of the glass, making it difficult to control the material properties and starting sintering. Since the temperature is lowered, there arises a problem that simultaneous firing with the metallized wiring layer becomes difficult. Moreover, since the amount of glass is large, the cost of raw materials tends to increase.
[0022]
In addition, it is desirable that the amount of the inorganic filler is appropriately adjusted according to the yield point of the glass. That is, when the yield point of glass is as low as 400 ° C. to 700 ° C., the sinterability at low temperatures is enhanced, so that the amount of inorganic filler can be relatively large such as 40 to 80% by volume. On the other hand, when the yield point of the glass is as high as 700 ° C. to 800 ° C., the sinterability is lowered, so that the filler amount is desirably 20-50% by volume, which is relatively small.
[0023]
Further, in the above composition, as one of the inorganic filler components, the coloring component includes chromium oxide, cobalt oxide, manganese oxide, nickel oxide, iron oxide, copper oxide, barium chromate, silicon, and quartz. You may mix | blend the at least 1 sort (s) chosen in the ratio of 10 mass% or less. In this case, the temperature coefficient of the relative dielectric constant can be made closer to 0 and stabilized.
[0024]
  According to the present invention, the mixture of the low-temperature fired porcelain composition is molded and then fired.LowThe warm-fired porcelain is composed of a crystal phase and a glass phase, and the crystal phase contains CaTiO3 and CaTiSiO5. The linear thermal expansion coefficient is 8-15 × 10^-6The relative permittivity is 16 or more at 1 ° C / ° C, and the temperature coefficient of the relative permittivity at -40 to 85 ° C is3-8x10 ^-6 / ℃It is made of porcelain with high thermal expansion, high dielectric constant, and excellent dielectric constant temperature stability..
[0025]
In the low-temperature fired ceramic composition and the low-temperature fired ceramic, the linear thermal expansion coefficient at 40 to 400 ° C. is 6 × 10 6 as one of the inorganic filler components or one of the crystal phases.^-6/ Quartz (SiO₂), Cristobalite (SiO₂), Tridymite (SiO₂), Forsterite (2MgO · SiO₂), Spinel (MgO · Al₂O_Three), Wollastonite (CaO.SiO)₂), Monticeranite (CaO / MgO / SiO)₂), Nepheline (Na₂O ・ Al₂O_Three・ SiO₂), Diopside (CaO · MgO · 2SiO₂ ), Melvinite (3CaO · MgO · 2SiO₂), Achelite (2CaO · MgO · 2SiO₂), Magnesia (MgO), alumina (Al₂O_Three), Carne Gite (Na₂O ・ Al₂O_Three・ 2SiO₂), Enstatite (MgO · SiO₂), Magnesium borate (2MgO · B₂O_Three), Celsian (BaO · Al₂O_Three・ 2SiO₂), B₂O_Three・ 2MgO ・ 2SiO₂, Garnite (ZnO · Al₂O_Three) At least one selected from the group of Among these, at least one selected from the group of quartz, cristobalite, tridymite, forsterite, and enstatite is desirable for achieving high thermal expansion.
[0026]
(Production method)
In the present invention, a specific manufacturing method for obtaining the above-mentioned low-temperature fired ceramic is first to appropriately form a mixture of glass and inorganic filler as described in the above-mentioned low-temperature fired ceramic composition. After adding the organic resin binder for the desired shape, it can be formed into any shape by any desired molding means such as die press, cold isostatic pressing, injection molding, extrusion molding, doctor blade method, calendar roll method, rolling method, etc. The obtained molded body is fired. In baking, the binder component mix | blended for shaping | molding is removed first. The removal of the binder is performed in an air or nitrogen atmosphere at 700 ° C to 800 ° C. At this time, the shrinkage start temperature of the molded body is preferably about 500 to 850 ° C. If the shrinkage start temperature is lower than this, it is difficult to remove the binder.
[0027]
When preparing a wiring board, a slurry is prepared by adding and mixing an appropriate organic binder, solvent, and plasticizer to the mixture of glass and inorganic filler as described above. A green sheet is produced by a green sheet forming method using a coating method such as a blade. Furthermore, a metal paste obtained by adding and mixing an organic binder, a plasticizer, and a solvent to a metal powder composed of one or more of copper, silver, nickel, palladium, and gold is predetermined on the green sheet by a well-known screen printing method. Print and apply to the pattern. In some cases, the green sheet is appropriately punched to form a via hole, and this hole is filled with a metallized paste. A plurality of these green sheets are laminated and pressure-bonded and then fired. In firing, the binder component blended for molding is removed, but the binder is removed by nitrogen containing water vapor at 100 to 800 ° C. when copper is used as the wiring conductor for forming the metallized wiring layer, for example. Performed in an atmosphere.
[0028]
  Firing is performed at an optimum firing temperature of 800 ° C. to 1100 ° C.is important. If the optimum firing temperature is lower than 800 ° C., it cannot be densified, and if it is higher than 1100 ° C., simultaneous firing with the metallized wiring layer becomes difficult. However, when copper is used as the component of the wiring conductor, it is desirable to fire in a non-oxidizing atmosphere at 800 to 1100 ° C.
[0029]
  (Construction)
  FIG.Obtained by firing using the low-temperature fired ceramic composition of the present inventionAs an application example of a low-temperature fired ceramic, it is a schematic cross-sectional view showing an example of a multilayer wiring board, in particular, a BGA type semiconductor element housing package and its mounting structure. This package has a basic structure of a so-called wiring board in which a metallized wiring layer is disposed on the surface or inside of an insulating board, A is a package for housing a semiconductor element, and B is an external circuit board.
[0030]
The semiconductor element storage package A includes an insulating substrate 1, a lid 2, a metallized wiring layer 3, and connection terminals 4, and the insulating substrate 1 and the lid 2 have a cavity 6 for accommodating the semiconductor element 5 in an airtight manner. Form. In the cavity 6, the semiconductor element 5 is bonded and fixed to the insulating substrate 1 through an adhesive such as glass or resin.
[0031]
A metallized wiring layer 3 is disposed on the surface and inside of the insulating substrate 1 so as to be electrically connected to the semiconductor element 5 and the connection terminal 4 formed on the lower surface of the insulating substrate 1. ing. According to the semiconductor element housing package A of FIG. 1, the connection terminal 4 has a ball-shaped terminal 4b made of high-melting-point solder (tin-lead alloy) attached through a connection pad 4a with a brazing material.
[0032]
On the other hand, the external circuit board B is composed of an insulator 7 and a wiring conductor 8, and the insulator 7 is made of an insulating material containing at least an organic resin, specifically, a glass-epoxy composite material or the like. The linear thermal expansion coefficient at 40 to 400 ° C. is 12 to 16 × 10^-6In general, a printed circuit board or the like is used. Also, the wiring conductor 8 formed on the surface of the substrate B is usually copper, gold, silver, aluminum, nickel, lead in terms of consistency of thermal expansion coefficient with the insulator 7 and good electrical conductivity. -It consists of metal conductors, such as tin.
[0033]
In order to mount the semiconductor element housing package A on the external circuit board B, the ball-like terminals 4b on the lower surface of the insulating substrate 1 of the package A are placed on and contacted with the wiring conductors 8 of the external circuit board B, Mounting is performed by melting the solder at a temperature of about 250 to 400 ° C. with a soldering material such as solder having a melting point and joining the wiring conductor 8 and the ball-shaped terminal 4 b. At this time, it is desirable that a brazing material is previously formed on the surface of the wiring conductor 8 in order to easily connect the ball terminal 4b with the brazing material.
[0034]
As shown in FIG. 1, the insulating substrate 1 in the semiconductor element housing package A is composed of a low dielectric constant layer 1a and a high dielectric constant layer 1b. The high dielectric constant layer 1b is made of the low-temperature fired ceramic of the present invention. Further, electrode layers 9 made of a metal conductor such as copper are formed on the upper and lower sides of the high dielectric constant layer 1b, and connected to the metallized wiring layer 3 on the substrate surface via the via-hole conductor 10 or the like. The predetermined electrostatic capacity can be taken out.
[0035]
Such a low dielectric constant layer 1a has a linear thermal expansion coefficient of 8 to 15 × 10 4 at 40 to 400 ° C.^-6It is desirable to comprise a low-temperature-fired porcelain having a high thermal expansion and a low dielectric constant of 1 / MHz and a relative dielectric constant of 1 or less at 1 MHz.
[0036]
Such a high thermal expansion, low dielectric constant porcelain is composed of 15 to 70% by mass of an alkaline earth metal oxide and SiO 2 in the same manner as the low temperature fired porcelain composition forming the high dielectric constant layer of the present invention.₂Of 30 to 60% by mass, and the coefficient of linear thermal expansion at 40 to 400 ° C. is 6 × 10.^-6It is desirable that it be formed from an inorganic filler containing a metal oxide at / C or higher.
[0037]
This is because the metal oxide is included as a crystal phase of the high thermal expansion, low dielectric constant porcelain after firing, and the linear thermal expansion coefficient of the high thermal expansion, low dielectric constant porcelain at 40 to 400 ° C. 8-15x10^-6This is because it is easy to make the relative dielectric constant at / ° C. and 1 MHz 8 or less.
[0038]
This high thermal expansion, low dielectric constant porcelain is made of the same glass as that forming the high dielectric constant layer 1b, and has a linear thermal expansion coefficient of 6 × 10 4 at 40 to 400 ° C.^-6Can be prepared by mixing and firing a metal oxide filler at / ° C. or higher, and in particular for producing a multilayer wiring board, the low dielectric constant can be obtained by the same method as that for forming the high dielectric constant layer 1b. After forming and punching the composition for the dielectric constant layer 1a, printing the electrode layer 9, etc., producing a high thermal expansion, low dielectric constant green sheet and laminating it with the green sheet for the high dielectric constant layer 1b of the present invention By simultaneously firing the green sheet laminate and metallization, a multilayer wiring board with a built-in capacitor can be obtained.
[0039]
The difference in linear thermal expansion coefficient at 40 to 400 ° C. between the low dielectric constant layer 1a and the high dielectric constant layer 1b is 0.5 × 10.^-6/ ° C. or less is desirable. This linear thermal expansion coefficient difference is 0.5 × 10^-6When it is higher than / ° C., in the firing stage, breakdown is likely to occur in or between the low dielectric constant layer 1a and the high dielectric constant layer 1b, and the difference in coefficient of linear thermal expansion is 0.5 × 10.^-6Greater than 1 ° C^-6Even in the case of / ° C. or lower, simultaneous firing is possible, but cracks may occur in the multilayer wiring board within the layers or between the layers. Therefore, for the reason that the low dielectric constant layer 1a and the high dielectric constant layer 1b are simultaneously fired and the occurrence of cracks or the like in the multilayer substrate is prevented, the difference in coefficient of linear thermal expansion between these is 0.5 × 10.^-6/ ° C. or less is desirable.
[0040]
The adjustment of the thermal expansion is carried out by adjusting the linear thermal expansion coefficient of the low temperature fired ceramic forming the high dielectric constant layer 1b with the linear thermal expansion coefficient of the low temperature fired ceramic forming the low dielectric constant layer 1a. CaTiO which is a filler component in the layer 1b_ThreeAnd CaTiSiO_FiveIt can be easily controlled by appropriately adjusting the content of.
[0041]
  HighIt is composed of a thermal expansion low dielectric constant layer 1a and a high thermal expansion high dielectric layer 1b.RucoHigh thermal expansion glass-ceramic multilayer wiring board with built-in capacitor has linear thermal expansion with external circuit board B even when mounted on a printed circuit board containing an organic resin via ball-like terminals 4b made of solder or solder. Due to the approximation of the coefficients, it is possible to implement long-term reliability against temperature cycling. In addition, by incorporating the capacitor, it is possible to reduce the size of the external circuit board B such as a printed board on which the board is mounted.
[0042]
【Example】
Example 1
Alkaline earth metal oxides and SiO₂As contained glass, SiO₂: 44% by mass-Al₂O_Three: 7% by mass-B₂O_Three: Glass A consisting of 14% by mass-CaO: 12% by mass-BaO: 23% by mass (deflection point: 690 ° C), SiO₂: 37% by mass-Al₂O_Three: 5% by mass-B₂O_Three: 13 mass%-CaO: 17 mass%-BaO: 25 mass%-ZrO₂: Glass B composed of 3% by mass (deflection point: 710 ° C), CaTiO as filler_Three, CaTiSiO_Five, Quartz and chromium oxide were prepared and weighed and mixed at the ratios shown in Table 1. After pulverizing this mixture, an organic binder and an organic solvent were added and mixed well to prepare a slurry, and a green sheet having a thickness of 300 μm was prepared by a doctor blade method. After stacking and pressing 8 sheets of the obtained green sheets, a sample of 50 mm × 50 mm was prepared, and after removing the binder in a nitrogen atmosphere containing 700 ° C. water vapor, in a nitrogen atmosphere of 900 ° C. × 1 hour. Firing was performed.
[0043]
Next, for the porcelain obtained as described above, the linear thermal expansion coefficient at 40 to 400 ° C., the relative dielectric constant at 1 MHz, and the temperature coefficient τ of the relative dielectric constant at −40 to 85 ° C._εWas measured. As for the temperature coefficient of the relative permittivity, the relative permittivity ε at 25 ° C._{twenty five}As a reference value, relative permittivity ε at −40 ° C._-40And dielectric constant ε at 85 ° C.₈₅From the following formula.
[0044]
τ_ε= (Ε₈₅−ε_-40) / Ε_{twenty five}/ (85-(-40))
The results are shown in Table 1.
[0045]
Further, when X-ray diffraction measurement was performed on the sintered body, CaTiO was used._ThreeFor all the samples with added CaTiO_ThreeAnd CaTiSiO_FiveThe crystal phase of CaTiSiO_FiveFor all the samples to which CaTiSiO was added_FiveIt was confirmed that a crystalline phase of
Example 2
In addition, a green sheet to be a high dielectric constant layer having a thickness of 500 μm was prepared by the doctor blade method using the composition in Example 1, and low dielectric constant was obtained by using quartz and diopside as fillers in the glass A and glass B. The green sheet used as a layer was produced. In this case, the amount of addition of quartz and diopside is such that the difference in thermal expansion coefficient from the high dielectric constant layer is 0.5 × 10^-6In order to adjust within / ° C., the quartz amount was appropriately adjusted within the range of 15 to 25% by mass and the diopside within the range of 75 to 85% by mass.
[0046]
Next, a copper metallized paste was applied to the green sheet surface based on a screen printing method. In addition, via holes were formed at predetermined locations on the green sheet, and copper metallized paste was filled therein. Then, six green sheets coated with the metallized paste were stacked and pressure-bonded while being aligned between the through holes. One of them was a green sheet to be a high dielectric constant layer.
[0047]
Next, the laminate is subjected to binder removal treatment in a nitrogen atmosphere containing water vapor at 700 ° C., and then the metallized wiring layer and the insulating substrate are simultaneously formed in a nitrogen atmosphere at 860 ° C. × 1 hour + 910 ° C. × 1 hour. Firing was performed to produce a multilayer wiring board.
[0048]
Next, as shown in FIG. 1, a ball-shaped solder composed of 90% by mass of lead-10% by mass of tin is low-melting solder (37% by mass of lead-63% by mass of tin) on the electrode pad provided on the lower surface of the multilayer wiring board. Attached by. The connection terminal is 1cm²It was formed on the entire lower surface of the wiring board with a density of 30 terminals per hit.
[0049]
And this multilayer wiring board consists of a glass-epoxy board | substrate, and the linear thermal expansion coefficient in 40-800 degreeC is 13 * 10.^-6It was mounted on the surface of an external circuit board in which a wiring conductor made of copper foil was formed on the surface of an insulator at / ° C. For mounting, the wiring conductor on the external circuit board and the ball-shaped terminal of the wiring board were aligned and connected by low melting point solder. The results are shown in Table 1.
[0050]
[Table 1]

[0051]
  As is clear from the results in Table 1., SaSample No. 5 to 19 and 24 to 41 all have a linear thermal expansion coefficient of 8.0 to 10.7 × 10 at 40 ° C. to 400 ° C.^-6/ ° C., relative permittivity at 1 MHz is 16 or more, and temperature coefficient of relative permittivity at −40 to 85 ° C. is −193 to 194 × 10^-6/ ° C.
[0052]
Further, according to the result of the thermal cycle test, the sample No. of the present invention described above. Wiring boards using 5 to 19 and 24 to 41 were sufficiently resistant to tests up to 1000 cycles.
[0053]
In addition, CaTiO in the total amount of inorganic filler_Three40-60 mass%, CaTiSiO_FiveSample No. containing 40 to 60% by mass. In 6 to 10, 13 to 19, 25 to 29, and 36 to 41, the temperature coefficient of relative permittivity is −70 to 70 × 10.^-6/ ° C, greatly improved.
[0054]
In addition, CaTiO_Three45-55 mass%, CaTiSiO_FiveSample No. containing 45 to 55% by mass. In 7-9, 14-19, 26-28, and 36-41, the temperature coefficient of relative permittivity is −35 to 35 × 10^-6/ ° C improved.
[0055]
In particular, sample No. 1 in which at least one of quartz and chromium oxide was added to the above composition. In 14-19 and 36-41, the temperature coefficient of the relative permittivity was 8 or less, which could be further reduced.
[0056]
On the other hand, CaTiO as an inorganic filler_ThreeOr CaTiSiO_FiveSample No. containing only one of them. 1 to 4, 20 to 23, the temperature coefficient of the relative dielectric constant at −40 to 85 ° C. is −318 × 10^-6/ ° C or less or 256 × 10^-6/ ° C or higher.
[0057]
【The invention's effect】
  As detailed above, according to the present invention, alkaline earth metal oxides and SiO₂CaTiO as an inorganic filler in glass containing₃(Linear thermal expansion coefficient: 13 × 10^-6/ ° C., relative dielectric constant: 180, temperature coefficient of relative dielectric constant: −1630 × 10^-6/ ° C.) and CaTiSiO5 (linear thermal expansion coefficient: 6.5 × 10^-6/ ° C., relative dielectric constant: 35, temperature coefficient of relative dielectric constant: 1200 × 10^-6/ ℃)And chromium oxideBy combining these at a predetermined ratio, it is possible to obtain the temperature stability of the dielectric constant as well as the high thermal expansion and high dielectric constant of the porcelain.
[Brief description of the drawings]
FIG. 1 of the present inventionLow-temperature fired porcelain obtained by firing using a low-temperature fired porcelain compositionWiring boardApplied toIt is a schematic sectional drawing for demonstrating an example.
[Explanation of symbols]
1 Insulating substrate
1a Low dielectric constant layer
1b High dielectric constant layer
2 lid
3 Metallized wiring layer
4 connection terminals
4a electrode pad
4b Ball terminal
5 Semiconductor elements
6 cavity
7 Insulator
8 Wiring conductor
9 Electrode layer
10 Via-hole conductor
A Package for storing semiconductor elements
B External circuit board

Claims (3)

15-70 wt% of an alkaline earth metal oxide and 20 to 80% by volume glass containing SiO ₂ 30 to 60 wt%, a CaTiO ₃ in the total amount of 45 to 49 wt%, the CaTiSiO ₅ 45-49 A low-temperature fired porcelain composition comprising 20 to 80% by volume of an inorganic filler containing 2% by mass and 2% by mass of chromium oxide . The glass is Al ₂ O ₃ And B ₂ O ₃ Containing Al or Al ₂ O ₃ , B ₂ O ₃ And ZrO ₂ The low-temperature-fired porcelain composition according to claim 1, wherein the composition is any one of the above-described ones. A method for producing a low-temperature fired ceramic , comprising molding the low-temperature fired ceramic composition according to claim 1 or 2 and firing at 800 to 1100 ° C.

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