JP2010285346A - Glass ceramic dielectric material and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anorthite-based glass ceramic dielectric material in which the position of a surface silver conductor is easily recognized by an optical reading device. <P>SOLUTION: In a glass ceramic dielectric material composed of a SiO<SB>2</SB>-Al<SB>2</SB>O<SB>3</SB>-CaO-B<SB>2</SB>O<SB>3</SB>based glass powder and an Al<SB>2</SB>O<SB>3</SB>-containing ceramic powder and fired simultaneously with a silver conductor, the glass powder contains by mass% 35.0-65.0% SiO<SB>2</SB>, 8.0-25.0% Al<SB>2</SB>O<SB>3</SB>, 15.0-35.0% CaO, 4.0-12.0% B<SB>2</SB>O<SB>3</SB>and 0.1-1.0% Fe<SB>2</SB>O<SB>3</SB>and has a property of precipitating an anorthite by firing. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a glass-ceramic dielectric material used for manufacturing a ceramic multilayer substrate, and more particularly to a glass-ceramic dielectric material suitable for firing at a low temperature of 1000 ° C. or lower.

As a glass ceramic dielectric material for depositing anorthite, a dielectric material made of SiO ₂ —CaO—Al ₂ O ₃ —B ₂ O ₃ glass powder and alumina powder is known (for example, Patent Document 1). This type of material is characterized by high mechanical strength. Further, it can be fired at 1000 ° C. or lower, and can be fired simultaneously with silver or copper having a low melting point. Silver conductors, in particular, have the advantage that, unlike copper conductors that require firing in nitrogen, they are not oxidized even when fired in air, and are inexpensive to manufacture.

Japanese Patent Publication No. 3-53269 JP 2001-207776 A JP 2003-152337 A

  On the fired circuit board, a semiconductor package and a passive chip component are connected and mounted on the surface conductor. The position of the surface conductor is recognized by an optical reader such as a CCD camera, and the component is automatically mounted. However, when a silver conductor is used, there is no difference in the signal level between the reflected light from the glass ceramic substrate and the reflected light from the silver conductor, which makes it difficult to read the conductor position.

  An object of the present invention is to provide an anorthite glass ceramic dielectric material in which the position of a surface silver conductor can be easily recognized by an optical reader.

Glass ceramic dielectric material of the present _invention, a glass ceramic dielectric is Do Ri, baked silver conductive simultaneously from a ceramic powder comprising _{SiO 2 -Al 2 O 3 -CaO-} B 2 O 3 based glass powder and _Al 2 _{O 3} in the body material, glass powder, _SiO 2 from 35.0 to _65.0% by _{mass%, Al 2 O 3 8.0~25.0%} , CaO 15.0~35.0%, B 2 O 3 4 0.0 to 12.0%, Fe ₂ O ₃ It is contained in an amount of 0.1 to 1.0% by mass and has a property of precipitating anorthite .

_{SiO 2 -Al 2 O 3 -CaO-} B 2 O 3 based glass _powder, B 2 _{O 3} containing 5 to 9% by weight and _B 2 _{O 3} in SiO when the total amount was replaced by SiO _{2 2} - The liquidus temperature of the Al ₂ O ₃ —CaO ternary glass is preferably 1300 ° C. or lower.

Glass powder _also, B a 2 _{O 3} containing 5-9 wt%, and _B 2 _{O SiO} 2 the total amount of time that is substituted with SiO ₂ of _{3, Al} 2 _{O 3} and the composition ratio of CaO are, SiO ₂ - Point A (SiO ₂ 64.4 parts by mass, Al ₂ O ₃ 16.9 parts by mass, CaO 18.7 parts by mass), point B (SiO ₂ 62.1 parts by mass) in the Al ₂ O ₃ —CaO ternary composition diagram Part, Al ₂ O ₃ 9.9 parts by mass, CaO 28.0 parts by mass), and C point (SiO ₂ 47.3 parts by mass, Al ₂ O ₃ 19.0 parts by mass, CaO 33.7 parts by mass). It is preferable that it exists in the area | region of the triangle used as a vertex.

The mixing ratio of the ceramic powder containing glass powder and _Al 2 _{O 3} glass powder 40-65 wt%, preferably ceramic powder 35-60% by weight comprises _Al 2 _{O 3.}

The method for producing a glass ceramic sintered body according to the present invention includes SiO 2 ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ Glass powder and Al ₂ O ₃ In a method for producing a glass ceramic sintered body in which a ceramic powder containing sinter is co-fired with a silver conductor and anorthite is deposited, ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ SiO2 as a glass powder in mass% ₂   35.0-65.0%, Al ₂ O ₃   8.0-25.0%, CaO 15.0-35.0%, B ₂ O ₃   4.0-12.0%, Fe ₂ O ₃   Using glass powder containing 0.1-1.0% by mass, L ^* a ^* b ^* In the color system, L ^* = 85-94, a ^* = -2 to -0.5, b ^* = Sintered body in the range of 0.5 to 2 is produced.

  SiO ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ Glass powder is B ₂ O ₃ 5-9 mass%, and B ₂ O ₃ The total amount of SiO ₂ SiO when substituted with ₂ -Al ₂ O ₃ The liquid phase temperature of the —CaO ternary glass is preferably 1300 ° C. or lower.

  The glass powder is B ₂ O ₃ 5-9 mass%, and B ₂ O ₃ The total amount of SiO ₂ SiO when substituted with ₂ , Al ₂ O ₃ And the composition ratio of CaO is SiO ₂ -Al ₂ O ₃ -Point A in the CaO ternary composition diagram (SiO ₂   64.4 parts by mass, Al ₂ O ₃   16.9 parts by mass, CaO 18.7 parts by mass), point B (SiO ₂   62.1 parts by mass, Al ₂ O ₃   9.9 parts by mass, CaO 28.0 parts by mass), and C point (SiO 2 ₂   47.3 parts by mass, Al ₂ O ₃   19.0 parts by mass and CaO 33.7 parts by mass) are preferably in a triangular region having a vertex.

  The mixing ratio of the glass powder and the ceramic powder is preferably 40 to 65% by mass of the glass powder and 35 to 60% by mass of the ceramic powder.

The glass-ceramic sintered body of the present invention is produced by the method described above.

  The glass ceramic dielectric material of the present invention can be fired at a temperature of 1000 ° C. or less, and can be fired simultaneously with a silver or copper conductor material. And since anorthite precipitates, a sintered compact with high mechanical strength can be obtained.

  Furthermore, the substrate of the present invention exhibits a green color when fired. When a silver conductor is used for the surface layer, since the contrast with the silver conductor is high, recognition by an optical reader becomes easy. Therefore, it is suitable as a dielectric material for circuit boards for automatically mounting electronic components.

A SiO ₂ -Al ₂ O ₃ -CaO ternary composition diagram.

Glass powder used in the present _{invention, SiO 2 -Al 2 O 3 -CaO} -B 2 O 3 based glass Powder or Ranaru.

Glass _powder, as a main component _{SiO 2, Al 2 O 3,} CaO and _B 2 _{O 3.} Composition range of _{SiO 2, Al 2 O 3,} CaO and _B 2 _{O 3} is, _SiO 2 from 35.0 to _65.0%, respectively by _{weight%, Al 2 O 3 8.0~25.0%} , CaO 15. _{0~35.0%, B 2 O 3 4.0~12.0} %, in particular _{SiO 2 38.3~59.4%, Al 2 O} 3 9.9~19.0%, CaO 18.7~ 33.7 _percent, it is preferred that _B 2 O 3 _5.0~9.0%. Glass powder, eg if _MgO, Na 2 _O, no problem even in the glass containing less than 3% in total of optional components such as TiO 2, SrO. When this type of glass is fired together with a ceramic powder containing Al ₂ O ₃ , it is possible to precipitate anorthite.

Furthermore the glass powder in the present invention, the _Fe 2 _{O 3} containing 0.1 to 1.0 mass%. When the amount of Fe ₂ O ₃ is less than 0.1% by mass, the sintered body is hardly colored and there is almost no difference from the signal level of the reflected light from the silver conductor. Moreover, when it exceeds 1.0 mass%, a dielectric loss will raise and it is unpreferable. A preferable range of the amount of Fe ₂ O ₃ is 0.15 to 0.5%.

Further, regarding the composition ratio of SiO ₂ , Al ₂ O ₃ , CaO and B ₂ O ₃ which are the main components of glass, from the viewpoint of glass production, specifically from the viewpoint of producing a stable quality material at low cost. There is a more preferred range.

  That is, when the liquidus temperature is high, crystals are likely to precipitate during glass cooling. When glass powder with crystals deposited is used as a glass-ceramic dielectric material, the crystals serve as nuclei, and crystallization starts at a lower temperature than when normal (when no crystals are present in the glass) when firing the dielectric material. To do. Crystallization at a low temperature inhibits the flowability of the glass and prevents the glass ceramic from being sintered densely, so that only a low-reliability dielectric having many pores can be obtained. Moreover, in order to melt glass having a high liquidus temperature, it is necessary to melt at a high temperature. To melt at high temperatures, a large amount of energy must be used. In addition, the high temperature operation shortens the life of the melting furnace, which increases the manufacturing cost. For this reason, the one where the liquidus viscosity of glass is low is preferable, and specifically, it is desirable that it is 1200 degrees C or less.

  In addition, when the chemical durability of the glass powder is low, problems such as deterioration of the glass due to aging and inability to maintain insulation, plating on the substrate in an acidic plating bath, and the like occur. For this reason, the higher the chemical durability of the glass, the better.

As a result of various considerations, the present inventors have found that the liquid phase temperature of the SiO ₂ —Al ₂ O ₃ —CaO—B ₂ O ₃ glass decreases as the SiO ₂ substitution amount of B ₂ O ₃ increases. Tend. Conversely, if it decreases, chemical durability tends to improve. In order to reduce the liquidus temperature of the glass to 1200 ° C. or less while substituting B ₂ O ₃ with SiO ₂ within the allowable range of chemical durability, SiO ₂ —Al ₂ O before B ₂ O ₃ substitution is used. The liquid phase temperature of the _3- CaO ternary composition is desirably 1300 ° C. or lower. In the same ternary composition, the range in which the liquidus temperature is 1300 ° C. or lower substantially matches the triangle connecting the three points A, B, and C in FIG. Specifically, point A (SiO ₂ 64.4% by mass, Al ₂ O ₃ 16.9% by mass, CaO 18.7% by mass), point B (SiO ₂ 62.1% by mass, Al ₂ O ₃ 9. 9 mass%, CaO 28.0 mass%), and within the triangular region with the C point (SiO ₂ 47.3 mass%, Al ₂ O ₃ 19.0 mass%, CaO 33.7 mass%) as vertices is there. In the glass composition in this range, if 5 to 9% by mass of SiO ₂ is replaced with B ₂ O ₃ , the liquidus temperature can be made 1200 ° C. or less without deteriorating chemical durability. Incidentally amount of B ₂ O ₃ chemical durability is considerably deteriorated when more than 9 mass%. Moreover, if it is less than 5 mass%, liquidus temperature cannot be 1200 degrees C or less. In addition, when the basic composition of the SiO ₂ —Al ₂ O ₃ —CaO ternary system is outside the above range, it is difficult to obtain a glass having a liquidus temperature of 1200 ° C. or lower.

In the present invention, the mixing ratio of the glass powder and the ceramic powder containing Al ₂ O ₃ is desirably 40 to 65% by mass of the glass powder and 35 to 60% by mass of the ceramic powder. If the ceramic powder is more than 60%, it becomes difficult to densify. On the other hand, if the ceramic powder is less than 35%, the bending strength becomes too low. As the ceramic powder containing Al ₂ O ₃ , alumina, mullite, cordierite, aluminate spinel, etc. can be used, but alumina is desirable from the viewpoint of substrate strength.

When the glass ceramic dielectric material of the present invention having the above composition is fired, a sintered body in which anorthite is deposited is obtained. This sintered body exhibits a greenish color tone due to the contained Fe ₂ O ₃ . In particular, in the L ^* a ^* b ^* color system defined by JIS Z8729, the color tone is in the range of L ^* = 85 to 94, a ^* = − 2 to −0.5, b ^* = 0.5 to 2. It is preferable to present. When the color coordinates are within this range, a green color tone that can be clearly distinguished from the silver conductor is exhibited. The sintered body preferably has a relative dielectric constant of 6 to 8 and a dielectric loss of 0.005 or less in a high frequency region of 1 to 20 GHz or more. If the relative permittivity and the dielectric loss are within the above ranges, they can be suitably used as a dielectric for performing signal processing in a high frequency band.

  Next, a method of using the glass ceramic dielectric material of the present invention will be described.

  First, a predetermined amount of a binder, a plasticizer, and a solvent are added to the glass ceramic dielectric material to prepare a slurry. Examples of the binder include polyvinyl butyral resin and methacrylic acid resin, examples of the plasticizer include dibutyl phthalate, and examples of the solvent include toluene and methyl ethyl ketone.

Next, the slurry is formed into a green sheet by a doctor blade method. Thereafter, the green sheet is dried and cut to a predetermined size, and then mechanical processing is performed to form a via hole, and a silver conductor serving as a conductor or an electrode is printed on the surface of the through hole and the green sheet. Subsequently, a plurality of green sheets are laminated and integrated by thermocompression bonding.

Furthermore, a multilayer substrate having a glass ceramic sintered body as an insulating layer can be obtained by firing the laminated green sheet. The firing temperature of the material is desirably 800 to 1000 ° C., particularly 800 to 950 ° C. It is also desirable to burn formed in air from the use of silver conductors.

  Hereinafter, the present invention will be described based on examples.

  Table 1 shows Examples (Sample Nos. 1 to 5) and Comparative Examples (Sample Nos. 6 and 7) of the present invention.

  First, glass raw materials were prepared so as to have the composition shown in Table 1, and then put in a platinum crucible and melted at 1400 ° C. to 1550 ° C. for 3 hours, and then formed into a thin plate shape by a water-cooled roller. Next, this compact was roughly crushed by a ball mill, and then pure water was added and wet pulverized to obtain a glass powder having an average particle size of 3 μm. Further, alumina powder or mullite powder (average particle size 2 μm) was added and mixed to prepare a sample.

  Various characteristics were evaluated for the obtained samples. The results are shown in Table 1.

  As is apparent from the table, Example No. In each of the samples 1 to 5, good dense bodies were obtained by firing. Moreover, the sintered body was green, and the silver conductor could be automatically recognized by the optical reader.

  On the other hand, Comparative Example No. The sample 6 had a white sintered body, and automatic recognition of the silver conductor by an optical reader was impossible. No. Sample 7 was capable of automatic recognition, but the dielectric loss was considerably higher than each sample of the example.

  The firing temperature and denseness of the sintered body are obtained by firing a press-molded sample at various temperatures, wiping after applying the ink to the obtained sintered body, and leaving no ink (= sintered densely). Of these, the firing temperature of the one fired at the lowest temperature is described. Also, the denseness was good (= ◯). However, the upper limit of the firing temperature was 1000 ° C., and when the ink remained even at the firing temperature of 1000 ° C., the denseness was evaluated as x.

  The color coordinates were evaluated as follows. First, a binder, a plasticizer, and a solvent were added to each sample to prepare a slurry. Next, the obtained slurry was formed into a green sheet by a doctor blade method, dried, and then cut into predetermined dimensions. Subsequently, a plurality of green sheets were laminated and integrated by thermocompression bonding, and then fired at the firing temperature shown in the table to obtain a sintered body. The sintered body thus obtained was used for measurement using a chromaticity meter.

  The automatic recognition of the silver conductor was performed by printing a silver paste on a fired substrate and firing it again at 900 ° C. and applying it to an optical reader to determine whether or not the silver pattern was recognized.

  Dielectric loss was measured by printing a silver conductor on a fired substrate and measuring tan δ at a frequency of 1 MHz using an LCR meter.

The liquid phase temperature of the ternary composition was measured by the following method. Was determined _SiO 2 _-Al 2 _O 3 -CaO ternary composition first, the _B 2 _{O 3} of each sample was whole amount replaced SiO _2. Sample No. The 5 were converted to more 100% in three components _SiO 2, _Al 2 _{O 3} and CaO. Next, the glass raw material was prepared so that it might become the calculated | required ternary system composition, it put into the platinum crucible, and it fuse | melted at 1450-1600 degreeC for 2 hours. Subsequently, it was poured into a platinum boat, held in a temperature gradient furnace for 24 hours, and then taken out. The maximum temperature at which crystals were observed in the glass was observed as the liquid phase temperature by microscopic observation. The liquid phase temperature of the glass sample was determined in the same manner as described above after preparing the glass raw material so as to have the composition shown in Table 1.

Water resistance is evaluated using a sintered body produced by evaluating the firing temperature (the sintered body with the lowest firing temperature among the densely sintered bodies), and the sintered body is boiled in pure water for 1 hour. The weight loss after
Those with less than 01% were marked as ◯.

  The bending strength was evaluated as follows. First, a binder, a plasticizer, and a solvent were added to each sample to prepare a slurry. Next, the obtained slurry was formed into a green sheet by a doctor blade method, dried, and then cut into predetermined dimensions. Subsequently, a plurality of green sheets were laminated and integrated by thermocompression bonding, and then fired at the firing temperature shown in the table to obtain a sintered body. Using the sintered body thus obtained, a three-point bending test was used.

In this specification, the method of using the material of the present invention as a multilayer substrate has been described. However, the present invention is not limited to this, and can be used as an electronic component material such as a semiconductor package or a multilayer chip component. It is. Moreover, although the example which uses a green sheet was given as a manufacturing method of a sintered compact, this invention is not limited to this, The various methods generally used for manufacture of a ceramic are applicable.

Claims (9)

Ri Do ceramic powder containing _{SiO 2 -Al 2 O 3 -CaO-} B 2 O 3 based glass powder and _Al 2 _{O 3,} in the silver conductor and the glass ceramic dielectric material are co-fired, glass powder, mass% SiO ₂ 35.0-65.0%, Al ₂ O ₃ 8.0-25.0%, CaO 15.0-35.0%, B ₂ O ₃ 4.0-12.0%, Fe ₂ O ₃ A glass-ceramic dielectric material containing 0.1 to 1.0% by mass and having a property of precipitating anorthite . _{SiO 2 -Al 2 O 3 -CaO-} B 2 O 3 based glass _powder, B 2 _{O 3} containing 5 to 9% by weight and _B 2 _{O 3} in SiO when the total amount was replaced by SiO _{2 2} - _2. The glass ceramic dielectric material according to claim 1, wherein the liquid phase temperature of the Al ₂ O ₃ —CaO ternary glass is 1300 ° C. or lower. _{SiO 2 -Al 2 O 3 -CaO-} B 2 O 3 based glass _powder, B 2 _{O 3} containing 5 to 9% by weight and _B 2 _{O 3} of _SiO 2 when the total amount was replaced by SiO _2, The composition ratio of Al ₂ O ₃ and CaO is point A in the SiO ₂ —Al ₂ O ₃ —CaO ternary composition diagram (SiO ₂ 64.4 parts by mass, Al ₂ O ₃ 16.9 parts by mass, CaO 18. 7 parts by mass), B point (SiO ₂ 62.1 parts by mass, Al ₂ O ₃ 9.9 parts by mass, CaO 28.0 parts by mass), and C point (SiO ₂ 47.3 parts by mass, Al ₂ O ₃ 19.0 parts by weight, the glass ceramic dielectric material of claim 1, wherein it is in the area of the triangle whose vertices CaO 33.7 parts by mass). The glass ceramic dielectric material according to any one of claims 1 to 3 , wherein a mixing ratio of the glass powder and the ceramic powder is 40 to 65 mass% of the glass powder and 35 to 60 mass% of the ceramic powder. SiO ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ Glass powder and Al ₂ O ₃ In a method for producing a glass ceramic sintered body in which a ceramic powder containing sinter is co-fired with a silver conductor and anorthite is deposited, ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ SiO2 as a glass powder in mass% ₂   35.0-65.0%, Al ₂ O ₃   8.0-25.0%, CaO 15.0-35.0%, B ₂ O ₃   4.0-12.0%, Fe ₂ O ₃   Using glass powder containing 0.1-1.0% by mass, L ^* a ^* b ^* In the color system, L ^* = 85-94, a ^* = -2 to -0.5, b ^* = A method for producing a sintered glass ceramic body, comprising producing a sintered body in a range of 0.5 to 2. SiO ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ Glass powder is B ₂ O ₃ 5-9 mass%, and B ₂ O ₃ The total amount of SiO ₂ SiO when substituted with ₂ -Al ₂ O ₃ 6. The method for producing a glass ceramic sintered body according to claim 5, wherein the liquid phase temperature of the -CaO ternary glass is 1300 [deg.] C. or lower. SiO ₂ -Al ₂ O ₃ -CaO-B ₂ O ₃ Glass powder is B ₂ O ₃ 5-9 mass%, and B ₂ O ₃ The total amount of SiO ₂ SiO when substituted with ₂ , Al ₂ O ₃ And the composition ratio of CaO is SiO ₂ -Al ₂ O ₃ -Point A in the CaO ternary composition diagram (SiO ₂   64.4 parts by mass, Al ₂ O ₃   16.9 parts by mass, CaO 18.7 parts by mass), point B (SiO ₂   62.1 parts by mass, Al ₂ O ₃   9.9 parts by mass, CaO 28.0 parts by mass), and C point (SiO 2 ₂   47.3 parts by mass, Al ₂ O ₃   The method for producing a glass-ceramic sintered body according to claim 5 or 6, wherein the glass-ceramic sintered body is in a triangular region having a vertex of 19.0 parts by mass and 33.7 parts by mass of CaO. The mixing ratio of the glass powder and the ceramic powder is 40 to 65 mass% of the glass powder and 35 to 60 mass% of the ceramic powder, The production of the sintered glass ceramic body according to any one of claims 5 to 7 Method. A glass ceramic sintered body produced by the method according to claim 5.