JP3520407B2 - Crystallized glass sintered body for circuit board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Circuit board used as electrical insulating material in circuit board
Related to crystallized glass sintered bodies for
Glass forPowderLow-temperature sintering
The crystallized glass sintered body obtained by firing
It is related to the improvement to make. [0002] 2. Description of the Related Art In recent years, semiconductors such as ICs and LSIs have been developed.
As a result of the development of integrated circuit devices,
Molding and densification are progressing rapidly, and
For circuit boards for mounting conductor integrated circuit elements
Are also required to be smaller and denser, and
Electrical wiring is becoming finer and more multilayered. In general, the speed of a signal propagating in a conductor is
Degree is delayed as the dielectric constant of the material forming the surroundings increases
Electrical insulation for high speed propagation
The material is required to have a low dielectric constant. However, the thermal expansion coefficient of a low dielectric constant insulating material
Is generally smaller than the coefficient of thermal expansion of conductive materials such as electrodes.
Small when used in multi-layers of various materials
Deformation and cracks due to the difference in thermal expansion coefficient
Come. In connection with this, for example, Japanese Patent Laid-Open No. 3-45
No. 94 discloses that a dielectric layer having a large coefficient of thermal expansion is
Capacitor built-in composite with built-in structure sandwiched between layers
In order to realize a circuit board, Mg contained in a specific ratio
O, SiO_TwoAnd an insulator layer composed mainly of CaO
Increases the coefficient of thermal expansion of the insulator layer
It has been proposed. Insulator layer described in this publication
Is calcined at a temperature of 1000 ° C. to 1300 ° C.
By firing at a temperature of 240 ° C to 1340 ° C,
Forsterite (Mg_TwoSiO_FourPrecipitate the main crystalline phase
And thereby increase its coefficient of thermal expansion
Is being done. [0006] However, the above public
The electric insulating material constituting the insulator layer described in the report is 100
Sintering at temperatures below 0 ° C. is not possible. Therefore,
For example, a circuit board with a conductor containing silver formed on the surface or inside
It cannot be used as an electrical insulating material for boards
No. [0007] Forsterite (Mg)_TwoSi
O_Four) As a crystalline phase having a larger coefficient of thermal expansion than
Melwinite (Ca_ThreeMgSi_TwoO₈), Montice
Light (CaMgSiO_Four) And calcium silicate
(CaSiO_Three, Ca_ThreeSi_TwoO ₇, Ca_TwoSiO_FourMa
Or Ca_ThreeSiO_Five) Is known,
The electrically insulating material for the insulating layer
Is a composition region where precipitation of is relatively small. [0008] Therefore, the object of the present invention is to reduce the temperature to 1000 ° C or lower.
Sinterable at lower temperatures and forsterite
(Mg_TwoSiO_Four) Having a larger coefficient of thermal expansion than
Melwinite (Ca_ThreeMgSi_TwoO₈), Montice
Light (CaMgSiO_Four) And calcium silicate
(CaSiO_Three, Ca_ThreeSi_TwoO₇, Ca_TwoSiO_FourYou
And Ca_ThreeSiO_FiveAt least one ofResultCrystal phase
Is efficiently deposited at a low temperature of 1000 ° C. or less as described above.
So that the relative permittivity is 10 or less,
Low dielectric constant such as thermal expansion coefficient of 10ppm / ℃ or more
Provides electrical insulation material for circuit board with high thermal expansion coefficient
Can be a circuit boardConcludingProvide crystallized glass sintered body
Is to try. [0009] A circuit board according to the present invention
The crystallized glass sintered body for use solves the technical problems described above.
Therefore, the main component is SiO_Two, MgO and CaO
And (1) Al_TwoO_Three,
(2) At least one of BaO and SrO
Alkaline earth metal oxide and / or ZnO, (3) L
i_TwoO, Na_TwoO and K_TwoAt least one of O
Alkali metal oxides, and (4) B_TwoO_ThreeOut of
And at least one of the above-mentioned main components of SiO_TwoAnd M
Composition ratio by weight% of gO and CaO (SiO_Two, Mg
O, CaO) in the ternary composition diagram shown in FIG.
And point I (30, 19, 51), point J (30, 5, 6)
5), point K (44, 5, 51), and point L (44, 1)
9, 37), and the sub-component is the main component
0.5 to 50 parts by weight in total with respect to 100 parts by weight
Together with (1) Al_TwoO_ThreeIf you include
0.5 to 25 parts by weight, (2) of BaO and SrO
At least one alkaline earth metal oxide thereof; and
And / or when containing ZnO, 0.5 to 10 times
(3) Li_TwoO, Na_TwoO and K_TwoO no
When containing at least one alkali metal oxide
Contains 0.5 to 5 parts by weight of (B)_TwoO_ThreeIncluding
If this is the case, include 0.5 to 25 parts by weight of
WhatGlass powderWith a crystallized glass sintered body obtained by firing
Oh, Melwinite (Ca_ThreeMgSi_TwoO₈), Mo
Anticellite (CaMgSiO_Four) And calciu
Silicate (CaSiO_Three, Ca_ThreeSi_TwoO₇, Ca_TwoS
iO_FourAnd Ca_ThreeSiO_FiveAt least one of
Characterized by containing a crystal phase of [0010] [0011] [0012] The above-mentioned specific crystal phase is subjected to a heat treatment.
Usually, it precipitates after processing, but some
In some cases, they have precipitated. In addition, these specific crystal phases
Other crystal phases may be included,
The phase also precipitates after heat treatment, or already
Some may be precipitated. Also, thisGlass powderFrom the above
Heat treatment to precipitate a certain crystal phase is usually
It is carried out at a temperature above the crystallization temperature. This crystallization temperature is
1000 ° C. or less, and thus at relatively low temperatures
Can be generated. [0015] [0016] [0017] [0018] [0019] EXAMPLE As a starting material for a glass component, SiO 2 was used._Two, M
gCO_Three, CaCO_Three, Al_TwoO _Three, ZnO, SrCO
_Three, BaCO_Three, Li_TwoCO_Three, Na_TwoCO_Three, K_TwoC
O _Three, And B_TwoO_ThreePrepare each of these, and
Glass compositions (parts by weight) as shown in Tables 1 to 5
After mixing, the resulting mixture is
It was melted at a temperature of 50 ° C. to produce a molten glass. So
After that, after putting this molten glass into pure water and quenching,
This was crushed to obtain a glass powder. [0020] [Table 1] [0021] [Table 2][0022] [Table 3][0023] [Table 4][0024] [Table 5]Glass composition of each sample shown in Tables 1 to 5
The main component, SiO_TwoOf MgO, MgO and CaO
The results are also described as weight percent between these three parties.
Are plotted in the ternary composition diagram of FIG.
You. That is, in Tables 1 to 5, "correspondence in the ternary composition diagram"
In the column of "reference code", each code of A to S is described.
However, these symbols A to S are in the glass composition of each sample.
Represents the composition of the main component of
To S, respectively. Next, an organic bath is added to each of these glass powders.
Add and mix toluene and solvent
And then kneading well with a ball mill,
A slurry in which glass powder was uniformly dispersed was prepared. Next
Then, this slurry was degassed under reduced pressure. Next, the slurry thus obtained is
The casting method using a doctor blade
Green sheet with a thickness of 0.2 mm on the film.
Each green sheet is molded and dried
For drying, peeling off the film and punching
Therefore, a green sheet having a predetermined size was obtained. Next, a plurality of these green sheets are stacked.
A molded article was obtained by layering and pressing. Next
Each of these compacts was subjected to a speed of 200 ° C./hour.
While heating at 1000 ° C. for 2 hours,
A lath sintered body was obtained. Next, these crystallized glass sintered bodies will be described.
, Relative dielectric constant, insulation resistance, coefficient of thermal expansion, 1000 ° C or less
Sintering and the crystal phase were evaluated. More specifically, the relative permittivity is 1
Using a sample having dimensions of 0 mm × 10 mm × 0.5 mm, L
Using a CR meter, frequency 1 MHz, voltage 1 Vrms and
The capacitance was measured under the conditions of
The relative permittivity was calculated from the capacitance. Regarding the insulation resistance value, the case of the relative dielectric constant
Using a sample of the same size, applying a DC voltage of 50 V,
This was measured after seconds. Regarding the coefficient of thermal expansion, 2 mm × 2 mm ×
Using a sample with a size of 10 mm, a temperature of 30 ° C. to 400 ° C.
The average coefficient of thermal expansion in the range was measured. The crystal phase was analyzed by X-ray diffraction.
The sample was identified by the X-ray diffraction pattern on the evaluation sample surface. The above evaluation results are shown in Tables 6 to 10.
Have been. In Tables 1 to 10, sample numbers
Those marked with * in the right column of the items are outside the scope of the present invention.
It is. [0034] [Table 6] [0035] [Table 7][0036] [Table 8][0037] [Table 9][0038] [Table 10]See Tables 1 to 5, 6 to 10 and FIG.
While using the circuit board according to the present inventionCrystallized glass sintering
Glass powder to get bodyOf composition range for
The reason will be described. First, for a circuit board within the scope of the present invention
Glass powder for obtaining crystallized glass sintered bodyIs the main component
As SiO_Two, Containing MgO and CaO
In addition, (1) Al_TwoO_Three, (2) BaO
At least one alkaline earth metal of SrO and SrO
Oxide and / or ZnO, (3) Li_TwoO, Na_Two
O and K_TwoAt least one alkali metal of O
Oxides and (4) B_TwoO_ThreeAt least one of
Contains seeds. In view of the above, Table 1 containing no sub-components
Samples 1 to 18 shown in the above are out of the scope of the present invention.
For these samples 1 to 18, as shown in Table 6, 10
Below 00 ° C., sufficient sintering is not possible. [0041] In the glass compositions shown in Tables 1 to 5,
XSiO which is the main component_Two-YMgO-zCaO (only
And x, y, and z are% by weight).
In the original composition diagram,Point I (30, 19, 51), Point J
(30, 5, 65), point K (44, 5, 51), and
Point L (44, 19, 37)In the area enclosed by
Are within the scope of the present invention. That is, in FIG.
hand, "G ", ""I", "J", "K", "L"and
Each composition of "M" is included within the scope of the present invention. With respect to the composition of such a main component,
Regions X in FIG. 1 that are outside the range of
There are “P” compositions, each of which is listed in Table 1
Samples 25 and 26 of Table 2, Samples 65 and 66 of Table 2, Table
Samples 105 and 106 of Table 3 and Sample 16 of Table 5
3 and 164. For these samples
Samples 25 and 26 shown in Table 6 and Sample 6 shown in Table 7
5 and 66, Samples 105 and 106 shown in Table 8,
And that of samples 163 and 164 shown in Table 10.
As can be seen from the respective sintering properties, firing at 1000 ° C or lower
It is not enough. With respect to the composition of the main component,
In the region Y of FIG. 1 outside the range, there is a composition of “S”,
This composition is included in Sample 187 in Table 5. This sample
Of the thermal expansion coefficient and the thermal expansion coefficient of the sample 187 shown in Table 10.
And the precipitated crystals, as can be seen from the melwinite (Ca
_ThreeMgSi_TwoO₈), Monticerite (CaMgSi)
O_Four) And calcium silicate (CaSiO_Three, Ca
_ThreeSi_TwoO₇, Ca_TwoSiO_FourAnd Ca_ThreeSiO_Fiveof
None of them precipitate and thermal expansion
The coefficient is less than 10 ppm / ° C. Further, regarding the composition of the main component,
Regions Z of FIG. 1 outside the scope of the invention include "Q" and
There are compositions of “R”, each of which is shown in Table 1
Samples 27 and 28 of Table 2, Samples 67 and 68 of Table 2, Table
Samples 107 and 108 of Table 3 and Sample 16 of Table 5
5 and 166. About these samples
Are the samples 27 and 28 shown in Table 6 and the samples shown in Table 7.
Samples 67 and 68, Samples 107 and 10 shown in Table 8
8, and samples 165 and 166 shown in Table 10.
As can be seen from each coefficient of thermal expansion, the coefficient of thermal expansion is 10
ppm / ° C. This is such a pair
Forsterite, Melwinite, Mont
Thermal expansion more than Ticerite or calcium silicate
Diopsite with small coefficient (CaMgSi_TwoO_Four) And
Enstatite (MgSiO_Three) Becomes the main crystal
That's why. Further, the circuit board according to the present inventionCrystallization
Glass powder for obtaining lath sintered bodyIs as described above
In addition, (1) Al_TwoO_Three, (2) BaO
At least one alkaline earth metal of SrO and SrO
Oxide and / or ZnO, (3) Li_TwoO, Na_Two
O and K_TwoAt least one alkali metal of O
Oxides and (4) B_TwoO_ThreeAt least one of
Including the seeds, these subcomponents are based on 100 parts by weight of the main component.
To contain 0.5 to 50% by weight in total, and (1)
Al_TwoO_ThreeWhen containing 0.5 to 25 parts by weight
(2) at least one of BaO and SrO
Containing some alkaline earth metal oxides and / or ZnO.
(3) L
i_TwoO, Na_TwoO and K_TwoAt least one of O
When containing an alkali metal oxide of
5% by weight, (4) B_TwoO_ThreeIf you include
It must contain 0.5 to 25 parts by weight. Regarding the lower limit of the content of the subcomponents described above,
For example, this subcomponentGlass powderBelow 1000 ° C
It improves sinterability, but this effect is substantially reduced.
In order to demonstrate, as described above, the main component 100 weight
Not more than 0.5 parts by weight in total
No. On the other hand, regarding the upper limit of the content of the subcomponent,
Consider below. [0049]ViceRegarding the composition of the components,
Focusing on samples that exceed the upper limit of the volume range,
In samples 35 to 40, as shown in Table 1,
For 00 parts by weight,(1)Al_TwoO_ThreeContent of 25
As shown in Table 6, the amount exceeds 1000 parts by weight.
It is difficult to sinter below ℃. Samples 53-58, 75-80 and
93 to 98, as shown in Tables 2 and 3,
For 100 parts by weight, of BaO and SrO
Since the content of one kind exceeds 10 parts by weight, Table 7 and
As shown in Table 8, sintering at 1000 ° C or less is difficult.
ing. Similarly, in sample 186, as shown in Table 5,
Contains both ZnO and SrO, which are subcomponents of
The total content of these components is 100 parts by weight of the main component.
As shown in Table 10,
Thus, sintering at 1000 ° C. or less is difficult. Samples 115 to 120, 133 to 13
8 and 151 to 156, as shown in Tables 3 and 4.
As described above, with respect to 100 parts by weight of the main component, Li_TwoO, Na
_TwoO and K_TwoAlkali metal oxidation of any of O
Since the content of the substance exceeds 5 parts by weight, Table 8 and Table
As shown in FIG. 9, the relative dielectric constant exceeds 10. As well
In addition, in sample 185, as shown in Table 5,
And Li_TwoO, Na _TwoO and K_TwoIncluding all of O
However, the total content of these is 100 parts by weight of the main component
The relative dielectric constant exceeds 10
I get it. For samples 173 to 178, Table 5
As described above, 100 parts by weight of the main component_TwoO_Threeof
As shown in Table 10, the content exceeds 25 parts by weight.
Thus, the thermal expansion coefficient falls below 10 ppm / ° C. For sample 184, as shown in Table 5,
Al, which is a subcomponent of (1),_TwoO_Three, The subcomponent of (2)
ZnO and B as a subcomponent of (4)_TwoO_ThreeAnd
And each sub-component based on 100 parts by weight of the main component
The individual contents of are within the scope of the present invention.
However, the total content exceeds 50 parts by weight. That
,tableAs shown in FIG.
The following sintering is difficult. For these, tableTests shown in Table 1 and Table 6
Charges 19 to 24 and 29 to 34, shown in Tables 2 and 7
Samples 41-52, 59-64 and 69-74, Table 3
And samples 81 to 92, 99 to 104 and 1 shown in Table 8
09-114, Samples 121-13 shown in Tables 4 and 9
2 and 139-150, and Tables 5 and 10
Samples 157 to 162, 167 to 172, 179 to
183 and 188-195,
(Mg_TwoSiO_FourHas a larger coefficient of thermal expansion than
Melwinite (Ca_ThreeMgSi_TwoO₈), Monte
Iserite (CaMgSiO_Four) And calcium silicon
Acid salt (CaSiO_Three, Ca_ThreeSi_TwoO₇, Ca_TwoSiO
_FourAnd Ca_ThreeSiO_FiveAt least one of the following)
At least one crystal phase is precipitated,
Good sintering is possible at temperatures below ℃ C.
Rate is 10 or less, coefficient of thermal expansion is 10 ppm / ° C or more, insulation
The circuit board has a resistance (logIR) of more than 9
Characteristics are given as an electrical insulating material. In particular, regarding the main component,A, B, C and D
Area within the area surrounded by the points
In the ternary composition diagram shown in FIG. 1, the point E (25, 4
5, 30), point B (25, 0, 75), point C (44,
0, 56), point F (44, 22, 34), point G (40,
19, 41) and point H (29, 40, 31)
Samples 20 and 2 shown in Tables 1 and 6 in the
1, 23, 30, 31, and 33, and shown in Tables 2 and 7.
Samples 42, 43, 45, 48, 49, 51, 60, 6
1, 63, 70, 71 and 73, and shown in Tables 3 and 8.
Samples 82, 83, 85, 88, 89, 91, 100,
101, 103, 110, 111 and 113, Table 4 and
And samples 122, 123, 125, 128 shown in Table 9
129, 131, 140, 141, 143, 146, 1
47 and 149, and Tables 5 and 10
Samples 158, 159, 161, 168, 169, 17
1, 179-183 and 188-195,
Larger thermal expansion coefficient, ie, heat of 12 ppm / ° C or more
The expansion coefficient has been obtained. Further, E, B, C, F, G, and
And the more limited area within the area enclosed by points H
Area, that is,Within the scope of the present invention,
In the ternary composition diagram shown in FIG. 1, point I (30, 19, 5)
1), point J (30, 5, 65), point K (44, 5, 5)
1) and an area surrounded by a point L (44, 19, 37)
, Samples 23 and 33 shown in Tables 1 and 6,
Samples 45, 51, 63 and 7 shown in Tables 2 and 7
3, samples 85, 91, 103 and
And 113, and samples 125 and 131 shown in Tables 4 and 9;
143 and 149 and Tables 5 and 10
Samples 161, 171, 179-183 and 192-
According to 195, the aforementioned Melwinite, Montise
Both light and calcium silicate precipitate
And more than 12 ppm / ° C (most
not less than pm / ° C.)
And the insulation resistance (logIR) exceeds 11,
Edge properties can be obtained. For example, according to the sample 24 in Table 1.set
Molten molten glassIs cooled on a metal plate.
Light precipitates in the quenched solid and is heat treated.
If you do, forsterite or diopsite or Aker
Manite became the main crystal, and the desired crystal phase did not precipitate.
As a result, the thermal expansion coefficient may be less than 12 ppm / ° C.
Has been confirmed. Thus, in the case of the same glass composition,
Even if there is a crystallized glass sintered body having a desired crystal phase,
Whether it can be obtained depends on the manufacturing method. [0058] As will be apparent from the above description of the embodiment.
The crystallized glass sintered body for a circuit board according to the present invention
Then, the main component, SiO_TwoOf MgO and MgO and CaO
In the three-dimensional composition diagram shown in FIG.
19, 51), point J (30, 5, 65), point K (44,
5, 51) and point L (44, 19, 37)
(1) Al_TwoO_Three,
(2) At least one of BaO and SrO
Alkaline earth metal oxide and / or ZnO, (3) L
i_TwoO, Na_TwoO and K_TwoAt least one of O
Alkali metal oxides, and (4) B_TwoO_ThreeOut of
And at least one of the main components 100
0.5 to 50 parts by weight with respect to parts by weight
In the case where the above (1) is included, it is added to
In the case where the above (2) is contained,
10 parts by weight, when (3) is included,
0.5 to 5% by weight.
Such as 0.5 to 25 parts by weight.Glass powderTo
A crystallized glass sintered body obtained by firing,
Innight (Ca_ThreeMgSi_TwoO₈), Monticerite
(CaMgSiO_Four) And calcium silicate (Ca
SiO_Three, Ca_ThreeSi_TwoO₇, Ca_TwoSiO_FourAnd C
a_ThreeSiO_FiveAt least one of the crystalline phases
It can be sintered at a temperature of 1000 ° C or less.
Has a relative dielectric constant of 10 or less and a thermal expansion coefficient of 10 p
low dielectric constant and high thermal expansion coefficient
Electrical insulation for circuit boards with high insulation resistance
Can be used as a fee. [0059] [0060] Therefore, the circuit board connection according to the present invention
Crystallized glassSukiyakiThe unity is reduced in size and density, and the signal
Power supply for circuit boards such as multilayer boards that require high-speed propagation
It can be advantageously used as a gas insulating material.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing SiO contained as a main component in glass powder for obtaining a crystallized glass sintered body for a circuit board according to the present invention.
FIG. 3 is a ternary composition diagram showing a composition range of ₂ , MgO, and CaO.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shizuharu Watanabe 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto Inside Murata Manufacturing Co., Ltd. (72) Inventor Hiroshi Takagi 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto In Murata Manufacturing Co., Ltd. (56) References JP-A-61-205637 (JP, A) JP-A-2000-86288 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 10 / 04 C04B 35/16

Claims (1)

(57) [Claim 1] At least one of (1) Al ₂ O ₃ , (2) BaO and SrO as a main component, while containing SiO ₂ , MgO and CaO as main components. One kind of alkaline earth metal oxide and / or ZnO, (3) at least one kind of alkali metal oxide of Li ₂ O, Na ₂ O and K ₂ O, and (4) one of B ₂ O ₃ The composition ratio (SiO ₂ , MgO, CaO) by weight% of the main component SiO ₂ , MgO and CaO is shown in FIG.
In the ternary composition diagram shown in FIG.
1), point J (30, 5, 65), point K (44, 5, 5)
1) and in a region surrounded by a point L (44, 19, 37), wherein the subcomponent contains 0.5 to 50 parts by weight in total with respect to 100 parts by weight of the main component, and (1) Al ₂
When O ₃ is contained, it is contained in an amount of 0.5 to 25 parts by weight,
(2) When it contains at least one kind of alkaline earth metal oxide and / or ZnO of BaO and SrO, it contains 0.5 to 10 parts by weight,
At least one of Li ₂ O, Na ₂ O and K ₂ O
When containing a kind of alkali metal oxide,
Comprising 5 parts by weight, in the case containing the (4) B ₂ O ₃ is
A crystallized glass sintered body obtained by sintering such a glass powder containing 0.5 to 25 parts by weight of the glass powder , wherein melwinite (Ca ₃ MgSi ₂ O ₈ ), monticelite (CaMgSiO ₄ ) and A crystallized glass sintered body for a circuit board, comprising a crystal phase of calcium silicate (at least one of CaSiO ₃ , Ca ₃ Si ₂ O ₇ , Ca ₂ SiO ₄ and Ca ₃ SiO ₅ ).