JP2000327363A - Structural body for sealing low-melting glass and glass ceramic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject structural body where a metallic cap is sealed via low-melting glass on a glass ceramic base in a surface-mounted type quartz oscillator or the like, causing no debonding at the seal interface between the low-melting glass and glass ceramic. SOLUTION: This structural body has such a scheme that Ag/Pd electrodes 3, 4 and Ag/Pd terminals 5, 6 are provided on an insulation base having both glass ceramic bottom plate 1 and frame 2, a quartz oscillator piece 8 is jointedly stuck on the Ag/Pd electrodes 3, 4, and a metallic cap 10 is stuck and sealed, via a low-melting glass 9 prepared by incorporating a phosphate-based low- melting glass with at least one substance selected from the group consisting of Al, Ni, Ag, BaTiO3, NiCr, TiB and TiO2, on the upper surface of the frame 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-melting glass and a glass-ceramic sealing structure using the low-melting glass. The present invention relates to a glass-ceramic sealing structure sealed with glass-ceramic containing alkali glass using low-melting glass.

[0002]

2. Description of the Related Art Recently, miniaturization and surface mounting of electronic components have been promoted. For example, a surface mount type crystal unit B
Has a structure as shown in FIG. FIG. 4A is a plan view in which a part is cut out so that the internal structure can be seen.
FIG. 4B is a sectional view taken along a longitudinal center line, and FIG. 4C is a bottom view. The surface mount type crystal unit B shown in FIG.
It has a bottom plate portion 21 and a frame portion 22 made of glass ceramic, and the surface of one end portion of the bottom plate portion 21 in the longitudinal direction is formed of Ag / Pd.
The electrodes 23 and 24 are formed, and the Ag / Pd electrodes 23 and 2 are formed.
4 are led out to the outside of both ends in the longitudinal direction through the space between the bottom plate portion 31 and the frame 22, respectively, and further connected to the Ag / Pd terminals 25 and 26 formed on the back surface through the end surface of the bottom plate portion 21. . Numeral 27 denotes a support part called a "pillow" for supporting a crystal vibrating piece (28) described later in a horizontal state, and is formed simultaneously with the Ag / Pd electrodes 23 and 24 using the same material. . And the Ag / Pd electrode 2
The crystal vibrating piece 28 is connected and fixed to the third and third conductive materials with a conductive adhesive, and the low melting glass 2
9, a ceramic cap 30 is fixedly sealed. Although not shown in the drawings, the Ag / Pd electrodes 23 and 24 and the Ag / Pd terminals 25 and 26 are each provided with a Ni plating layer or an Au plating layer in order to prevent rust and / or solderability. Is formed.

[0003]

The surface mount type crystal resonator B has a bottom plate 21, a frame 22 and a cap 30 formed of ceramic, and has a difference in thermal expansion coefficient from the crystal resonator element 28. Due to the quartz vibrating piece 28
, There is a serious problem that the vibration characteristics fluctuate. Also, when the cap 30 made of ceramic is used, there is a problem that there is a limit to the reduction in thickness in terms of mechanical strength, and therefore, there is a limit to a reduction in the height of the entire crystal unit B. Therefore, the applicant of the present application has previously proposed that the bottom plate portion 21 and the frame portion 22 be made of glass ceramic and that a metal cap made of stainless steel or the like be used instead of the ceramic cap.
The glass ceramic has, for example, a thermal expansion coefficient of 10 to 15 ppm / ° C. in which fine powder of forsterite is dispersed in alkali glass at 30 to 70 wt%, and a difference in thermal expansion coefficient between the quartz vibrating piece 28 and the metal cap. This is an excellent feature that the variation in characteristics of the crystal vibrating piece 28 due to the stress caused by the difference in thermal expansion coefficient and the detachment of the metal cap can be prevented.

However, a crystal resonator B having a metal cap fixedly sealed on the glass-ceramic frame 22 via a low-melting glass 29 having a thermal expansion coefficient equal or close to that of the glass ceramic is sealed. When stored at a high temperature and a high humidity, a phenomenon was observed in which the film was peeled off between the frame 22 and the low-melting glass 29.

The present inventors have thoroughly pursued the cause, and as a result, the alkali glass constituting the glass ceramic elutes the phosphoric acid constituting the low-melting glass to form a composition of the low-melting glass. Was found to be peeled off due to a change in the sealability. Further, as a result of thoroughly pursuing a method for preventing such a phenomenon, it was found that the phenomenon can be prevented by adding a certain additive to the low-melting glass.

Accordingly, an object of the present invention is to provide a low melting point glass which can be sealed with the above glass ceramic based on the above findings. Another object of the present invention is to provide a glass-ceramic sealing structure in which a glass ceramic is sealed using the above-mentioned low-melting glass.

[0007]

The low-melting glass of the present invention comprises Al, Ni, Ag, and BaTi added to the low-melting glass.
A low-melting glass characterized by adding one or more selected from the group consisting of O ₃ , NiCr, TiB, and TiO ₂ . The glass-ceramic sealing structure using the low-melting glass of the present invention has a low-melting glass with Al, N
i, Ag, BaTiO ₃ , NiCr, TiB, TiO ₂
A low-melting glass to which any one or two or more selected from the group is added is sealed with a glass ceramic.

[0008]

According to the above-mentioned low melting point glass, the additive suppresses or prevents the dissolution of phosphoric acid in the low melting point glass due to the alkali glass component in the glass ceramic. It has the effect of being able to Further, according to the above glass-ceramic sealing structure, the additive in the low-melting glass suppresses or prevents the dissolution of phosphoric acid in the low-melting glass due to the alkali glass component in the glass ceramic. An effect is provided that a sealing structure can be provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION
Al, Ni, Ag, BaTiO ₃ , N
A low-melting glass to which one or more selected from the group consisting of iCr, TiB and TiO ₂ is added. According to the above low-melting glass, the additive can suppress or prevent the dissolution of phosphoric acid in the low-melting glass due to the alkali glass component in the glass ceramic, and can be a low-melting glass that can be sealed with the glass ceramic. .

The invention according to claim 2 of the present invention relates to a method of preparing a silver-phosphate-based low-melting glass with Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, low melting glass doped with any one or more selected from the group of TiO _2.
According to the above low-melting glass, the additive can suppress or prevent the dissolution of phosphoric acid in the low-melting glass due to the alkali glass component in the glass ceramic, and can be a low-melting glass that can be sealed with the glass ceramic. .

[0011] The invention according to claim 3 of the present invention is to provide a silver-phosphoric acid-based low melting glass with Al, Ni, Ag, BaTi.
Low melting glass characterized by adding 0.1 to 10 vol% of one or more selected from the group consisting of O ₃ , NiCr, TiB and TiO ₂ . According to the above low-melting glass, the additive can suppress or prevent the dissolution of phosphoric acid in the low-melting glass due to the alkali glass component in the glass ceramic, and can be a low-melting glass that can be sealed with the glass ceramic. .

The invention according to a fourth aspect of the present invention is to provide a low melting point glass having Al, Ni, Ag, BaTiO ₃ , NiCr, T
A glass-ceramic sealing structure, wherein a low-melting glass to which one or more selected from the group consisting of iB and TiO ₂ is added is sealed with a glass ceramic. According to the above glass-ceramic sealing structure, the additive in the low-melting glass suppresses or prevents the dissolution of phosphoric acid in the low-melting glass due to the alkali glass component in the glass ceramic. Structure can be provided.

The invention according to claim 5 of the present invention relates to a method of preparing a silver-phosphate-based low-melting glass with Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, a low melting glass doped with any one or more selected from the group of TiO _2, a glass ceramic seal assembly being characterized in that sealed glass ceramics and sealing. According to the above glass-ceramic sealing structure, the additive in the low-melting glass suppresses or prevents the dissolution of phosphoric acid in the phosphoric acid-based low-melting glass due to the alkali glass component in the glass ceramic, and the glass ceramic is airtight. High sealing structure can be provided.

According to a sixth aspect of the present invention, a silver-phosphate-based low-melting glass is made of Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, glass-ceramic seal assembly, characterized in that the low-melting glass doped 0.1～10Vol% any one or two or more selected from the group of TiO _2, was sealed glass ceramic and sealing It is. According to the above sealing structure with the glass ceramic, the additive in the low-melting glass suppresses or prevents the dissolution of phosphoric acid in the phosphate-based low-melting glass due to the alkali glass component in the glass ceramic, and has an airtight property. A high glass-ceramic sealing structure can be provided.

[0015] The invention according to claim 7 of the present invention is to provide a silver-phosphoric acid based low melting point glass containing Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, that the low-melting glass doped with any one or more selected from the group of TiO _2, was sealed glass ceramic and sealing dispersed fine powder of forsterite glass having the following composition It is a glass-ceramic sealing structure which is a feature. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more _{of) B 2 O 3: 1~ 8wt} % ZnO: 2~15wt% R 2 O: 5~30wt% (R is Na, K, one or more of Li) above the glass ceramic seal assembly According to this, the additive in the low-melting glass suppresses or prevents the dissolution of phosphoric acid in the phosphate-based low-melting glass due to the alkali glass component in the glass ceramic, and a highly airtight glass-ceramic sealing structure can be provided. .

According to the invention of claim 8 of the present invention, the silver-phosphoric acid-based low melting glass is made of Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, that the low-melting glass doped with any one or more selected from the group of TiO _2, was sealed glass ceramic and sealing dispersed fine powder of forsterite glass having the following composition It is a sealing structure with a glass ceramic as a feature. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more of) _B 2 _O 3: is a 5-30 wt% (R is Na, K, one or more of Li): 1~ 8wt% ZnO: 2~15wt% R 2 O. According to the above glass-ceramic sealing structure, the additive of the phosphate-based low-melting glass suppresses or prevents the dissolution of phosphoric acid in the phosphate-based low-melting glass due to the alkali glass component in the glass ceramic, and has high airtightness. A glass ceramic high sealing structure can be provided.

According to the invention of claim 8 of the present invention, the silver-phosphate low melting point glass is made of Al, Ni, Ag, BaTiO ₃ ,
NiCr, TiB, a low melting glass doped with any one or more selected from the group of TiO _2, a fine powder of forsterite glass having the following composition 30
It is a sealing structure of a glass ceramic characterized by being sealed with a glass ceramic dispersed by about 70 wt%. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more of) _B 2 _O 3: is a 5-30 wt% (R is Na, K, one or more of Li): 1~ 8wt% ZnO: 2~15wt% R 2 O. According to the above glass-ceramic sealing structure, the additive of the phosphate-based low-melting glass suppresses or prevents the dissolution of phosphoric acid in the phosphate-based low-melting glass due to the alkali glass component constituting the glass ceramic, and has an airtight property. And a glass-ceramic sealing structure having a high hardness can be provided.

[0018]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a surface mount type crystal unit A as an example of a glass-ceramic sealing structure using the low-melting glass of the present invention, and FIG. 1A is a plan view partially cut away so that the internal structure can be seen. FIG. 1B is a cross-sectional view along a longitudinal center line, and FIG. 1C is a bottom view. In FIG. 1, reference numerals 1 and 2 denote a glass ceramic bottom plate portion and a frame portion, both of which are integrally formed to form a glass ceramic base. The bottom plate portion 1 and the frame portion 2 are, for example, 30 to 70 wt% of a fine powder of forsterite having a particle size of about 0.3 to 3 μm dispersed in a fine alkali glass powder having a particle size of about 0.3 to 3 μm. The green expansion coefficient obtained by molding and firing the green sheet is 1
It has a rectangular shape and a frame shape of 0 to 15 ppm / ° C., and the bottom plate 1 has a longitudinal dimension of 3.0 to 12.0 mm, a lateral dimension of 2.0 to 10.0 mm, and a thickness dimension. Is 0.2
About 1.0 mm, and the frame 2 is, for example,
The inner dimension in the longitudinal direction is 2.0 to 11.0 mm, the inner dimension in the lateral direction is 1.0 to 9.0 mm, and the thickness is 0.2.
It is about 1.0 mm.

The alkali glass of the first embodiment constituting the glass ceramic has, for example, the following composition:
Contains alkaline components such as ₂ O, K ₂ O, and LiO ₂ . _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, one or more of _{Ba) B 2 O 3: 1~8wt} % ZnO: 2~15wt _{% R 2 O: 5~30wt% (} R is Na, K, one or more of Li)

An Ag / Pd paste is applied and baked on the upper surface near one end in the longitudinal direction of the bottom plate portion 1 to have a thickness of 40 to 40 mm.
Ag / Pd electrodes 3 and 4 of about 50 μm are formed. One Ag / Pd electrode 3 passes between the bottom plate 1 and the frame 2 and is led out of one end of the bottom plate 1 in the longitudinal direction, and the other Ag / Pd electrode 4 is Ag / Pd formed on the lower surface at both ends in the longitudinal direction of the bottom plate 1 through the end surface of the bottom plate 1, respectively, being led out of the other end of the bottom plate 1, bypassing under the frame 2. They are connected to terminals 5 and 6. These Ag / Pd electrodes 3, 4 and A
The g / Pd terminals 5 and 6 may be formed separately or simultaneously. Further, the Ag /
A so-called “pillow” is provided at a position opposite to the Pd electrodes 3 and 4 to support a crystal vibrating piece (10) described later in a horizontal state.
Is formed. This support part 7
Are formed simultaneously with the same material and in the same thickness as the Ag / Pd electrodes 3 and 4.

The Ag / Pd electrodes 3 and 4 and Ag / Pd
Although not shown, an electroless Ni plating layer and / or an electroless Au plating layer are formed on the d terminals 5 and 6. On the Ag / Pd electrodes 3 and 4, a crystal vibrating piece 8 having electrodes (not shown) on both surfaces is connected and fixed by a conductive adhesive or the like. In addition, the support part 7 is for supporting the quartz-crystal vibrating piece 8 in a horizontal state as described above, and does not require bonding or the like. Then, a metal cap 10 made of stainless steel or the like and having a thickness of about 0.05 to 0.2 mm is adhesively sealed on the frame 2 via the low melting point glass 9 of the present invention. I have.

Next, an embodiment of the low melting point glass 9 of the present invention will be described. First, the low-melting glass used as the base material of the low-melting glass of the present invention is Ag-PIO (Ag ₂ O, AgI, P ₂ O ₅₎ which is the following silver-phosphate low melting glass. The mixture is mixed in the form of an oxide, melted, and then pulverized.
Atomic weight%, I: 5-15 atomic weight%)
30-70 wt% silver-phosphate glass at 00-230 ° C
A phosphoric acid compound or niobium pentoxide as a filler was added in an amount of 70 to 30 wt% to match or approximate the thermal expansion coefficient of the glass ceramic.
Low melting point glass of about 290 ° C. The low-melting glass of the present invention is a silver-phosphate-based low-melting glass serving as the base material,
Al, Ni, Ag, BaTiO ₃ , NiCr, TiB,
One selected from the group of TiO ₂ one or two or more is obtained by adding 0.1~10vol%. Here, Al, Ni, Ag, BaTiO ₃ , NiCr, Ti
If the addition amount of any one or more selected from the group of B and TiO ₂ is less than 0.1 vol%, no improvement effect of the sealing strength is observed in the high pressure and high humidity test, and 10 vol.
If it exceeds 1%, the working temperature of the low-melting glass 9 rises, the glass becomes difficult to flow, and low-temperature sealing becomes difficult. Therefore, Al, Ni, Ag, BaTiO ₃ , NiCr,
TiB, any one or more of the amount selected from the group of TiO ₂ is limited to 0.1~10vol%.

Next, the results of the sealing strength test on the glass-ceramic sealing structure using the low-melting glass of the present invention will be described with reference to the results of the sealing strength test on the conventional glass-ceramic sealing structure using the low-melting glass. This will be described in contrast. Actually, a glass ceramic piece 12 (5.0 mm long × 3.2 mm wide × 0.6 m thick) as shown in FIG.
m), through a low-melting glass 13 having a thickness of 0.1 mm, the same dimensions as the glass ceramic piece 12 and a thickness
The test piece 11 to which the stainless steel piece 14 mm was adhered was performed. The sealing strength test is performed by measuring the peeling strength after a severe test called a pressure cooker test (PCT) in which the test piece 11 is left in a closed container kept at high pressure and high humidity. Was.
The results are as shown in Tables 1 and 2, and FIG. Table 1 shows the case where the additive was added alone, and Table 2 shows the case where two or more additives were added in combination. In Fig. 3, the horizontal axis indicates the pressure cooker test (PC
T) Indicates time (Hr), and the vertical axis indicates peel strength (kg)
/ Mm ² ).

[0025]

[Table 1]

[0026]

[Table 2]

From the above test results, it is clear that the low melting point glass according to the present invention has better sealing properties for glass ceramics than the conventional low melting point glass. Regarding the sealing portion between the low-melting glass and the stainless steel piece 14, there is no particular difference in the sealing characteristics between the low-melting glass 13 according to the present invention and the conventional low-melting glass without additives. Was.

Actually, even in a glass ceramic package in which a stainless steel cap 10 is sealed with an insulating base having a glass ceramic bottom plate 1 and a frame 2 via a low melting point glass 9 of the present invention. Similar tests were performed with similar results.

As the glass-alkali alkali glass constituting the bottom plate 1 and the frame 2, in addition to those shown in the above-mentioned embodiment, those having the compositions of the following second and third embodiments are also the same. The result was obtained.

[0030]

[Alkali glass composition of the second embodiment] SiO ₂ : 40
_{~55wt% A1 2 O 3: 20~30wt} % P 2 O 5: 1~20wt% BaO: 0.2~5wt% R 2 O: 5~10wt% (R is Na, K)

[0031]

[Alkali glass composition of the third embodiment] SiO ₂ : 70-
_{85wt% P 2 O 5: 1~5wt} % MgO: 1~5wt% R 2 O: 8~25wt% (R is Li, K)

Further, ZrO, SnO ₂ , P ₂ O ₅ , and ZrO are added to the alkali glass having the composition of the first embodiment.
Similar results were obtained for a glass ceramic to which 1.2 to 5 wt% of one or more fine powders (0.1 to 1 μm) of MoO ₃ was added.

The above embodiment of the present invention relates to a glass ceramic sealing structure using the low melting point glass of the present invention.
Although the crystal resonator A having a specific configuration has been described, the present invention is not limited to the above embodiment, and it goes without saying that various modifications can be made without departing from the spirit of the present invention. .

For example, in the crystal unit A of the above embodiment, the support 7 supporting the crystal resonator element 8
The description has been given of the case where the Pd electrodes 3 and 4 are formed of the same material. However, the present invention can be similarly applied to the case where the bottom plate 1 and the frame 2 are formed of the same material.

The present invention can be similarly applied to a quartz resonator having a structure in which the metal cap 10 is grounded. In this case, the metal cap 10 may be provided with a leg for grounding, and may be directly grounded.
Ag is applied to the low melting point glass 9 and the end faces of the frame 2 and the bottom plate 1.
/ Pd or other conductive layer may be formed to be grounded, or a low-melting glass 9 made of conductive low-melting glass in which conductive particles are dispersed, and the end surfaces of the frame 2 and the bottom plate 1 may be used. Alternatively, a conductive layer such as Ag / Pd may be formed and grounded.

Further, the present invention can be similarly applied to a surface acoustic wave device other than a crystal oscillator, a glass ceramic package such as a semiconductor device or an electronic component.

[0037]

According to the present invention, Al, N
i, Ag, BaTiO ₃ , NiCr, TiB, TiO ₂
A low-melting glass characterized by adding one or more selected from the group consisting of: a low-melting glass suitable for a glass ceramic, especially a sealing structure with a glass ceramic containing alkali glass. Can be provided. The present invention also provides Al, Ni, Ag, BaTiO ₃ , NiCr, T
A glass-ceramic sealing structure characterized by being sealed with a glass ceramic using a low-melting glass to which one or more selected from the group of iB and TiO ₂ is added. Has the effect of providing a glass-ceramic sealing structure which does not peel off at the sealing interface even if it contains alkali glass.

[Brief description of the drawings]

FIGS. 1A and 1B show a surface mount type crystal unit A which is an example of a glass-ceramic sealing structure using a low-melting glass of the present invention, in which FIG. Sectional view along line, (c) bottom view

FIG. 2 is a perspective view of a test piece subjected to a sealing test of a glass ceramic sealing structure using the low melting point glass of the present invention.

FIG. 3 is a characteristic diagram showing a sealing strength test result of a glass ceramic sealing structure using the low melting point glass of the present invention;
(A) is without additives, (b) is with Ni added, (c) is with A
l

FIGS. 4A and 4B show a surface-mount type crystal unit B as an example of a conventional glass-ceramic sealing structure using a low-melting glass, in which FIG. 4A is a plan view in which a part is cut away, and FIG. Sectional view along line, (c) bottom view

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Bottom plate part 2 Frame part 3, 4 Ag / Pd electrode 5, 6 Ag / Pd terminal 7 Support part 8 Quartz vibrating piece 9 Low melting point glass 10 Metal cap 11 Test piece 12 Glass ceramic piece 13 Low melting point glass 14 Stainless steel Piece

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G061 AA09 BA05 CA02 CB04 CB12 CB13 CC03 CD24 DA32 4G062 AA08 AA09 AA15 BB01 DA06 DB03 DB04 DC03 DD01 DE03 DE04 DF01 EA01 EA02 EA03 EA04 EA10 EB01 EC03 EC03 EB02 EC03 EE02 EE03 EE04 EF01 EF02 EF03 EF04 EG01 EG02 EG03 EG04 FA01 FA10 FB01 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 KK01 GE01 HH01 HH03 HH05 HHH HHH HH HH HH HH HH HH NN26 NN32 PP04 PP05 PP09 PP10 PP12

Claims (9)

[Claims] 1. Low-melting glass is made of Al, Ni, Ag, Ba.
A low-melting glass to which one or more selected from the group consisting of TiO ₃ , NiCr, TiB and TiO ₂ is added. 2. A silver-phosphoric acid-based low melting point glass containing Al, N
i, Ag, BaTiO ₃ , NiCr, TiB, TiO ₂
A low-melting glass characterized by adding one or more selected from the group consisting of: 3. A silver-phosphoric acid-based low melting point glass containing Al, N
i, Ag, BaTiO ₃ , NiCr, TiB, TiO ₂
Any one or two or more selected from the group of 0.
Low melting glass characterized by adding 1 to 10 vol%. 4. A low melting glass made of Al, Ni, Ag, BaT.
iO _{3, NiCr, TiB,} glass-ceramic seal assembly, characterized in that the low-melting glass doped with any one or more selected from the group of TiO _2, was sealed glass ceramic and sealing. 5. A silver-phosphate-based low-melting glass having Al, Ni,
_{Ag, BaTiO 3, NiCr, TiB} , glass-ceramic seal assembly, characterized in that the low-melting glass doped with any one or more selected from the group of TiO _2, was sealed glass ceramic and sealing. 6. A silver-phosphoric acid-based low melting point glass comprising Al, Ni,
_{0.1~ Ag, BaTiO 3, NiCr,} TiB, any one or more selected from the group of TiO ₂
A glass-ceramic sealing structure, wherein a low-melting glass to which 10 vol% is added is sealed with a glass ceramic. 7. A silver-low-melting glass comprising Al, Ni, Ag, B
a low-melting glass to which one or more selected from the group consisting of aTiO ₃ , NiCr, TiB, and TiO ₂ is added and sealed with a glass ceramic in which fine powder of forsterite is dispersed in glass having the following composition: A glass-ceramic sealing structure characterized by the following. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more _{of) B 2 O 3: 1~ 8wt} % ZnO: 2~15wt% R 2 O: 5~30wt% (R is Na, K, one or more of Li) 8. A silver-phosphoric acid-based low melting point glass comprising Al, Ni,
Ag, BaTiO ₃ , NiCr, TiB, TiO ₂ and a low-melting glass to which at least one selected from the group is added, and fine powder of forsterite dispersed in glass having the following composition in an amount of 30 to 70 wt%. A glass-ceramic sealing structure characterized by being sealed with a molded glass-ceramic. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more _{of) B 2 O 3: 1~ 8wt} % ZnO: 2~15wt% R 2 O: 5~30wt% (R is Na, K, one or more of Li) 9. A silver-phosphate low melting point glass comprising Al, Ni,
_{0.1~ Ag, BaTiO 3, NiCr,} TiB, any one or more selected from the group of TiO ₂
Low melting glass to which 10 vol% is added, fine powder of forsterite is added to glass having the following composition in an amount of 30 to 70 wt.
What is claimed is: 1. A glass-ceramic sealing structure, which is sealed with a glass ceramic dispersed in%. _{SiO 2: 50~70wt% Al 2 O} 3: 2~15wt% RO: 5~30wt% (R is Ca, Sr, Ba
One or more _{of) B 2 O 3: 1~ 8wt} % ZnO: 2~15wt% R 2 O: 5~30wt% (R is Na, K, one or more of Li)