JP2003238202A - Crystallized glass for joining anode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide crystallized glass for joining an anode in which the difference in thermal expansion coefficient with silicon is suppressed to the minimum, and which has an anode joining temperature of ≤250°C. <P>SOLUTION: The crystallized glass for joining the anode consists of β-quartz or a β-quartz solid solution as the main crystals. The crystallized glass substantially does not contain Na<SB>2</SB>O, and contains, by mol, 60 to 69% SiO<SB>2</SB>, 12 to 18% Al<SB>2</SB>O<SB>3</SB>, 6 to 10% Li<SB>2</SB>O, 1 to 6% MgO, 0 to 4% ZnO, 1 to 6% TiO<SB>2</SB>, 0 to 3% ZrO<SB>2</SB>and 0 to 3% P<SB>2</SB>O<SB>5</SB>, and the content of a crystal phase is controlled to 10 to 50 vol.%. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallized glass which is used as a member of a semiconductor sensor or the like and can be preferably anodically bonded to silicon. In addition, the simple "%" display used in this specification shall show "mol%."

[0002]

2. Description of the Related Art Conventionally, a semiconductor sensor for measuring the pressure of gas or liquid or the acceleration of a moving body has been widely put into practical use in the fields of automobiles and measuring instruments. These mainly detect strains applied to silicon and changes in electrostatic capacity, and miniaturization, cost reduction and high sensitivity are being advanced by micromachining technology.

On the other hand, glass having a coefficient of thermal expansion close to that of silicon is used as a pedestal for supporting silicon in a member of a semiconductor sensor. This glass also has a characteristic that it can be bonded to silicon by an anodic bonding method that does not use an adhesive or the like, and since residual strain at the bonding interface is suppressed as much as possible, it has contributed to the improvement of sensor characteristics.

[0004] Anodic bonding is a method in which glass is heated to a temperature at which mobile cations are easily moved, and the silicon side serves as an anode, the glass side serves as a cathode, and a DC voltage is applied to heat-bond them. Is. As a result of the cations in the glass migrating to the cathode, the non-bridging oxygen ions at the interface with silicon are covalently bonded to silicon, which is said to result in a strong bond.

Conventionally, as a glass suitable for such an application, a low-expansion aluminosilicate glass has been invented and is disclosed in JP-A-4-83733. The thermal expansion curves of these glasses are similar to the thermal expansion curves of silicon, and each is characterized by containing sodium as a mobile cation for anodic bonding.

[0006] However, since sodium is a component that sharply increases the thermal expansion of glass, its content is limited, and as a result, the amount of sodium ions that can move during anodic bonding is also limited. In order to carry out anodic bonding efficiently, it is indispensable to move more sodium ions, and therefore high temperature and high voltage are required. Specifically, the actual condition is that the operation is performed at 400 ° C. and about 800 V.

On the other hand, in recent years, due to the development of micromachining technology, the sensor has been highly integrated and has a complicated structure, and silicon, glass lamination, and sandwich structure elements have been developed. Anodic bonding has come into use. In addition, the process of forming a circuit, a pattern, and the like on a substrate and then performing anodic bonding has also increased.

Under these circumstances, along with the demand for higher efficiency in anodic bonding, there has been a demand for lowering the temperature during anodic bonding in order to prevent thermal damage during bonding of the sensor element. In JP-A-5-9039, the temperature is lowered by using crystallized glass that precipitates crystals in the glass.

[0009]

However, since at least two kinds of alkalis, lithium and sodium, coexist in the above-mentioned crystallized glass of JP-A-5-9039, so-called mixed alkali effect causes both of them to exist. There is a problem that movement in the crystallized glass is suppressed and dielectric breakdown occurs when a high voltage is applied for anodic bonding.

Therefore, in order to solve the above-mentioned problems, the present invention further promotes the movement of alkali by using crystallized glass containing only a single alkali, and the anodic bonding temperature is 250 ° C. or less. The purpose is to provide a crystallized glass.

[0011]

SUMMARY OF THE INVENTION The inventors of the present invention have found that the coefficient of thermal expansion of silicon is maintained while maintaining the heating temperature at the time of anodic bonding of crystallized glass having β-quartz or a β-quartz solid solution as a main crystal at a low temperature. SiO ₂ , Al
₂ O ₃ , R ₂ O (R is Li, Na, K), MgO, Zn
Β of O, B ₂ O ₃ , BaO, TiO ₂ , P ₂ O ₅ , ZrO _2, etc.
-As a result of studying the content in the crystallized glass of components that affect the formation of quartz or β-quartz solid solution and the coefficient of thermal expansion, only Li ₂ O is contained as an alkaline component and the proportion of the crystal phase is limited. Therefore, it was found that the thermal expansion coefficient of the crystallized glass can be adjusted while maintaining the heating temperature at a low temperature.

That is, the invention corresponding to claim 1 of the present invention is a crystallized glass for anodic bonding which contains β-quartz or a β-quartz solid solution as a main crystal and does not substantially contain Na ₂ O, and The content of Li ₂ O was 6 to 10% in terms of mol% and the proportion of the crystal phase was 10 to 50% by volume.

In this crystallized glass for anodic bonding, L
i ₂ O acts as a crystal component of the β-quartz solid solution, and this crystal precipitation contributes to a reduction in expansion to approximate the thermal expansion of silicon. Further, by remaining in the glass phase, it acts as a mobile cation during anodic bonding and enables anodic bonding at a low temperature of 250 ° C. or lower. Further, it is a component that lowers the viscosity of the mother glass before crystallization and improves the meltability.

When the content is less than 6%, it becomes difficult to melt the mother glass, and the low temperature of anodic bonding is hindered. On the other hand, if it exceeds 10%,
Since the coefficient of thermal expansion of the mother glass is considerably higher than that of silicon, it is difficult to control the thermal expansion and the chemical durability tends to be deteriorated.

Further, in the above range of the Li ₂ O content, when the proportion of the crystal phase is less than 10% by volume, the effect of reducing the coefficient of thermal expansion of the crystal phase precipitated in the glass becomes small, and as a result, the crystal The difference in the coefficient of thermal expansion between the fog glass and silicon widens, and thermal strain occurs after anodic bonding. On the other hand, when the proportion of the crystal phase is more than 50%, the effect of reducing the thermal expansion coefficient of the crystal phase precipitated in the glass becomes large, and as a result, the difference in the thermal expansion coefficient between the crystallized glass and the silicon widens. As a result, thermal distortion occurs after anodic bonding, and the sensitivity and accuracy of the sensor cannot be improved.

As described above, Na ₂ O may increase the volume resistivity of the crystallized glass due to the mixed alkali effect with Li ₂ O and hinder the lowering of the anodic bonding temperature. do not do. However, when it is mixed as an impurity from a raw material or the like, it is allowed as long as the object of the present invention is not impaired, but it is preferably less than 0.5%, more preferably less than 0.2%, further preferably 0%. It is less than 1%.

The invention corresponding to claim 2 of the present invention is the crystallized glass for anodic bonding according to claim 1, which has an average coefficient of thermal expansion from room temperature to 300 ° C. of 25 × 10 ^-7 to 40.
× 10 ⁻⁷ / ° C., and the anodic bonding temperature was 250 ° C. or lower.

The invention corresponding to claim 3 of the present invention is the crystallized glass for anodic bonding according to claim 1 or 2,
By _{mol%, SiO 2: 60~69%, Al} 2 O 3: 1
_{2~18%, Li 2 O: 6~10} %, MgO: 1~6
%, ZnO: 0~4%, TiO 2: 1~6%, ZrO 2:
0~3%, P ₂ O _5: was to contain 0-3%.

The reasons for limiting the composition of each component of the crystallized glass of the present invention are shown below. SiO ₂ is an essential component constituting β-quartz or a β-quartz solid solution generated when the mother glass is heat-treated, and also serves as a glass skeleton. If the content is less than 60%, it becomes difficult to adjust the amount of crystals deposited, and the chemical durability tends to deteriorate, and if it exceeds 69%, the viscosity of the mother glass increases and the meltability is increased. Noticeably worse. Preferably 62-6
It is in the range of 7%.

Al ₂ O ₃ is a component that constitutes the β-quartz solid solution and also a component that improves the stability and chemical durability of the mother glass. When the content is less than 12%, it becomes difficult to adjust the amount of crystals precipitated and the tendency of phase separation increases, and when it exceeds 18%, it becomes difficult to uniformly melt the mother glass. Preferably 13-1
It is in the range of 6%.

MgO is a component capable of forming a solid solution in β-quartz, is a component that stabilizes the mother glass and improves the meltability, and is also a component that is effective for fine adjustment of the coefficient of thermal expansion.
When the content is less than 1%, there is no effect that the meltability can be improved and the thermal expansion coefficient can be finely adjusted, and when it exceeds 6%, different crystals are likely to precipitate and the volume resistivity increases. It is preferably in the range of 2 to 5%.

ZnO is an optional component, but it is a component that, when contained in glass, can obtain the same effect as MgO. However, if the content exceeds 4%, heterogeneous crystals tend to precipitate. It is preferably up to 3%.

TiO ₂ is an effective component for forming crystal nuclei, and plays a role of precipitating fine and uniform crystals. When the content is less than 1%, the crystal nuclei are reduced and the main crystals are coarsened. If it exceeds 6%, no further effect as crystal nuclei can be obtained, and the devitrification tendency of the mother glass becomes stronger. It is preferably in the range of 1 to 4%.

ZrO ₂ is an optional component, but when it is contained in glass, it is a component that can obtain the same effect as TiO ₂ . However, if the content exceeds 3%, there is a high possibility that it will remain in the mother glass as an unmelted material. It is preferably up to 2%.

P ₂ O ₅ is also an optional component, but may be contained up to 3% for the purpose of improving the meltability of the mother glass. However, if its content exceeds 3%, the grain size of the main crystal tends to increase and the volume resistivity tends to increase.

Not listed as a component of the above crystallized glass
However, as other optional ingredients, B ₂O₃, CaO, Sr
O, BaO, Sb₂O₃, SO₃, Chloride, fluoride, etc.
You may contain suitably.

B ₂ O ₃ is a component effective for improving the melting property of the mother glass, but since it tends to increase the grain size of the main crystal and the volume resistivity, B ₂ O ₃ is contained even if 3 is included. % Or less is desirable.

Further, CaO, SrO and BaO can also be contained in order to improve the meltability of the mother glass. However, if the content of each component exceeds 2%, the volume resistivity of the crystallized glass increases and the anodic bonding temperature increases. Inhibits low temperature.

Sb ₂ O ₃ , SO ₃ , chloride and fluoride may contain up to 1% of at least one component as a fining agent in the melting of the mother glass.

The invention corresponding to claim 4 of the present invention uses the crystallized glass according to any one of claims 1 to 3 in a pedestal for bonding silicon. An invention corresponding to claim 5 of the present invention is a semiconductor sensor including a pressure detection part made of a silicon base and a pedestal joined to the pressure detection part, wherein the pedestal according to claim 4 is attached to the pedestal. used. As described above, by using the above-mentioned crystallized glass for the semiconductor sensor, it is possible to obtain good bonding property and bonding strength with the silicon used as the pressure detecting portion.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The crystallized glass for anodic bonding of this embodiment has an oxide composition of SiO ₂ : 60 to 69%, A
_{l 2 O 3: 12~18%,} Li 2 O: 6~10%, Mg
O: 1~6%, ZnO: 0~4 %, TiO 2: 1~6
%, ZrO ₂ : 0 to 3%, and P ₂ O ₅ : 0 to 3% are used as the mother glass. Or, in addition to this composition, B
_A glass to which at least one of ₂ O ₃ : 0 to 3%, CaO: 0 to 2 and BaO: 0 to 2% is added is used as a mother glass. Then, this mother glass is heated and melted at 1550 to 1650 ° C., cast into a mold material, etc., and gradually cooled to produce a glass block. After that, place the glass block at 650-850.
The mixture is heated to ℃ and held for 1 to 24 hours to deposit and grow a predetermined amount of main crystal (β-quartz or β-quartz solid solution), and after cooling, it is processed into a predetermined size. In order to efficiently precipitate crystal nuclei, a heat treatment step may be added as the primary heat treatment at 600 to 750 ° C. for 1 to 5 hours before the above heating. Further, as the fining agent, at least one of Sb ₂ O ₃ , SO ₃ , chloride and fluoride may be added.

Since the crystallized glass for anodic bonding of the present invention thus obtained contains a large amount of lithium as a mobile cation and the ratio of the crystal phase is in the range of 10 to 50% by volume, the room temperature to Average thermal expansion coefficient at 300 ℃ is 25 × 10
^-7 to 40 x 10 ^-7 / ° C, which is very close to the thermal expansion curve of silicon. Therefore, by using the crystallized glass of the present invention, the thermal damage to the bonded body after the anodic bonding was suppressed to an extremely small level, and the sensor characteristics could be improved.

[0033]

EXAMPLES Examples of the present invention are shown in Table 1.

[Table 1]

(Example 1) Crystallized glass for anodic bonding was S
_{iO 2: 64%, Al 2} O 3: 16%, Li 2 O: 8%, M
gO: 6%, ZnO: 2%, TiO ₂ : 2%, ZrO ₂ :
A glass containing 1% and B ₂ O ₃ : 1% is used as a mother glass.
This mother glass is obtained by mixing raw materials such as oxides, hydroxides, carbonates and nitrates. Then, the prepared raw material is 16
Put in a resistance heating type electric furnace at 30 ℃, melt for 10 hours,
After defoaming and homogenizing, it was poured into a mold material and gradually cooled at a predetermined temperature to prepare a glass block. Next, this glass block was held in an electric furnace at 760 ° C. for 3 hours to precipitate crystals, and after slow cooling, a crystallized glass block was formed. This crystallized glass was transparent.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as a main crystal from the diffraction pattern. Also, β
The proportion of the crystal phase of the quartz and the β-quartz solid solution was observed by a scanning electron microscope to be 30% by volume, and the maximum grain size of the precipitated crystal did not exceed 100 nm.

Then, a test piece for measuring the thermal expansion of the crystallized glass block and a plate material (φ100 mm) whose surface was mirror-polished for anodic bonding were processed. Using this test piece, the coefficient of thermal expansion was measured with a differential thermal expansion meter to measure the room temperature to 300 ° C.
The average coefficient of thermal expansion of was calculated to be 34 × 10 ^-7 / ℃
Met.

Further, as shown in FIG. 1, the anodic bonding is carried out in an apparatus provided with a pair of heaters 3 and 4 made of carbon, a plus electrode 5 and a minus electrode which also serves as the heater 3. Specifically, a crystallized glass plate material 2 in which at least an anodic bonding portion is mirror-polished is placed on the minus electrode / heater 3, a silicon wafer 1 is superposed on the crystallized glass plate material 2, and the silicon wafer 1 is positively added. The electrode 5 is attached, the inside of the apparatus is evacuated, the temperature is raised to a predetermined temperature by the heaters 3 and 4, and a DC voltage of 800 V is applied to the silicon wafer 1 and the crystallized glass plate material 2 for 10 minutes to perform anodic bonding. The heating temperatures were set to 190 ° C., 220 ° C., and 250 ° C., and as a result of observing the appearance of the bonded sample, 93%, 92%, 98 at the respective temperatures were observed.
% Bonding area was formed, and good bonding was obtained without peeling. In this appearance observation, the joint portion from the crystallized glass side after anodic bonding was visually confirmed, and the joint region was determined by image processing. This joint area is 90
If it is less than%, there is a possibility that sufficient strength as a semiconductor sensor may not be obtained.

(Example 2) Crystallized glass for anodic bonding is S
_{iO 2: 67%, Al 2} O 3: 13%, Li 2 O: 7%, M
gO: 4%, ZnO: 2%, TiO ₂ : 1%, ZrO ₂ :
_{2%, P 2 O 5:} 2%, B 2 O 3: 1%, BaO: to be 1% formulated oxides, hydroxides, carbonates, the starting material of the nitrates. Then, the prepared raw material was placed in a resistance heating type electric furnace at 1640 ° C. and melted for 12 hours to prepare a glass block in the same manner as in Example 1. Next, this glass block was heat-treated at 680 ° C. for 3 hours in an electric furnace to generate crystal nuclei in the glass, and then heat-treated at 720 ° C. for 5 hours to precipitate crystals in the glass and crystallize. A glass block was formed. This crystallized glass block was also transparent.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as a main crystal from the diffraction pattern. Also,
When the proportion of the crystal phase of β-quartz and the solid solution of β-quartz was observed by a scanning electron microscope, it was 10% by volume,
The maximum grain size of the precipitated crystals did not exceed 100 nm.

The temperature of the crystallized glass is from room temperature to 300.
The average coefficient of thermal expansion up to ° C was measured by a differential thermal expansion meter and found to be 36 × 10 ^-7 / ° C. A bonding test between silicon and a crystallized glass plate was carried out in the same manner as in Example 1. At 190 ° C., 78% of unbonded parts remained relatively, but at 220 ° C., 94%, and at 250 ° C. 96
% And the bonding area was 90% or more, and good bonding was obtained.

(Example 3) Mother of crystallized glass for anodic bonding
Glass is SiO₂: 66%, Al₂O ₃: 15%, Li
₂O: 8%, MgO: 4%, ZnO: 3%, TiO₂: 2
%, ZrO₂: 1%, P₂O_FiveOxidize to 1%
Raw materials such as substances, hydroxides, carbonates and nitrates are prepared. So
The prepared raw material was thrown into a resistance heating type electric furnace at 1620 ° C.
Put in, melt for 11 hours, and in the same manner as in Example 1, glass block
Ku was made. Next, this glass block is placed in an electric furnace for 7
Heat treatment at 40 ° C for 10 hours to crystallize in glass
Allowed to form a crystallized glass block.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as a main crystal from the diffraction pattern. Also,
The proportion of the crystal phase of β-quartz and the solid solution of β-quartz was observed by a scanning electron microscope to be 30% by volume,
The maximum grain size of the precipitated crystals did not exceed 130 nm.

Then, the crystallized glass of 30 to 400
The average coefficient of thermal expansion up to ° C was 33 x 10 ^-7 / ° C when measured with a differential thermal expansion meter. Further, a bonding test between silicon and the crystallized glass plate material was carried out in the same manner as in Example 1, and it was 91% at 190 ° C. and 97 at 220 ° C.
%, 96% at 250 ° C., 90% or more of the bonding region was formed at any heating temperature, and good bonding was obtained.

Example 4 A mother of crystallized glass for anodic bonding
Glass is SiO₂: 61%, Al₂O ₃: 17%, Li
₂O: 7%, MgO: 4%, ZnO: 4%, TiO₂: 5
%, CaO: 1%, BaO: 1% to oxidize
Raw materials such as substances, hydroxides, carbonates and nitrates are prepared. So
The prepared raw material was thrown into a resistance heating type electric furnace at 1650 ° C.
Put in, melt for 12 hours, and in the same manner as in Example 1, glass block
Ku was made. Next, this glass block is placed in an electric furnace for 7
After heat treatment at 10 ℃ for 1 hour, crystal nuclei are formed in the glass.
Then, heat treatment is performed at 770 ° C for 1 hour.
Crystallized glass block by precipitating crystals in glass
Was formed.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as a main crystal from the diffraction pattern. Also,
The proportion of the crystal phases of β-quartz and the β-quartz solid solution was 20% by volume when observed by a scanning electron microscope.
The maximum grain size of the precipitated crystals did not exceed 160 nm.

The temperature of this crystallized glass is from room temperature to 300.
The average coefficient of thermal expansion up to ℃ was 37 × 10 ^-7 / ℃ when measured by a differential thermal expansion meter. Further, a bonding test between silicon and the crystallized glass plate material was carried out in the same manner as in Example 1. As a result, at 190 ° C., a relatively large unbonded portion remained at 83%, but at 220 ° C., 90%, at 250 ° C. 92
% And the bonding area was 90% or more, and good bonding was obtained.

Example 5 A mother of crystallized glass for anodic bonding
Glass is SiO₂: 62%, Al₂O ₃: 18%, Li
₂O: 9%, MgO: 5%, ZnO: 2%, TiO₂: 3
%, ZrO₂1% oxide, hydroxide,
Prepare raw materials such as carbonates and nitrates. And the blended raw
Material into a resistance heating type electric furnace at 1600 ° C for 10 hours
It melted and the glass block was produced like Example 1.
Next, heat treatment is performed at 780 ° C. for 6 hours to bond the glass.
Crystals were precipitated to form a crystallized glass block.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as the main crystal from the diffraction pattern. Also,
When the proportion of the crystal phase of β-quartz and the solid solution of β-quartz was observed by a scanning electron microscope, it was 50% by volume,
The maximum grain size of the precipitated crystals did not exceed 120 nm.

The temperature of the crystallized glass is from room temperature to 300.
The average coefficient of thermal expansion up to ℃ was 29 × 10 ^-7 / ℃ when measured by a differential thermal expansion meter. A bonding test between silicon and a crystallized glass plate was conducted in the same manner as in Example 1, and it was 95% at 190 ° C and 93% at 220 ° C.
%, 95% at 250 ° C., 90% or more of the bonding region was formed at any heating temperature, and good bonding was obtained.

Example 6 A mother of crystallized glass for anodic bonding
Glass is SiO₂: 63%, Al₂O ₃: 16%, Li
₂O: 10%, MgO: 2%, ZnO: 3%, TiO₂:
2%, ZrO₂: 2%, P₂O_Five: Acid to be 2%
Prepare raw materials such as oxides, hydroxides, carbonates, and nitrates.
Then, the prepared raw material is put into a resistance heating type electric furnace at 1580 ° C.
Charge, melt for 12 hours, and in the same manner as in Example 1, use a glass blower.
Was made. Next, in an electric furnace, this glass block
After heat treatment at 660 ° C for 3 hours, crystal nuclei in the glass
Then, heat treatment is performed at 720 ° C. for 8 hours.
Crystallized glass block by precipitating crystals in glass
Was formed.

When this crystallized glass block was analyzed by an X-ray diffractometer, β-quartz or β-quartz solid solution was precipitated as a main crystal from the diffraction pattern. Also,
The proportion of the crystal phases of β-quartz and the β-quartz solid solution was 40% by volume when observed with a scanning electron microscope.
The maximum grain size of the precipitated crystals did not exceed 150 nm.

The temperature of the crystallized glass is from room temperature to 300.
The average coefficient of thermal expansion up to ° C was measured by a differential thermal dilatometer and found to be 30 × 10 ^-7 / ° C. Further, a bonding test between silicon and the crystallized glass plate material was conducted in the same manner as in Example 1, and it was 97% at 190 ° C. and 95% at 220 ° C.
%, 95% at 250 ° C., 90% or more of the bonding region was formed at any heating temperature, and good bonding was obtained.

In the above embodiment, the applied voltage is 800V.
And the application time was 10 minutes, but the applied voltage was 500V.
However, if the application time is set to 30 minutes, good bonding area and bonding strength can be obtained.

Comparative Example Comparative Example 1 is an example in which borosilicate glass was used as the glass for anodic bonding. This glass has an average coefficient of thermal expansion of 32 × 10 ⁻⁷ / ° C. and is close to silicon to be bonded, so there is no risk of problems due to strain after bonding,
It was not possible to join unless the heating temperature at the time of joining with silicon was raised to 350 ° C.

Comparative Example 2 is an example using crystallized glass obtained by heat treating a mother glass containing Li ₂ O to precipitate crystals, as in the present application. This crystallized glass has an average coefficient of thermal expansion of 28 × 10 ⁻⁷ / ° C. and can be approximated to the coefficient of thermal expansion of silicon, but since it contains little Li ₂ O, the heating temperature at the time of bonding with silicon is 300. Joining was not possible unless the temperature was raised to ℃.

In Comparative Example 3, Li₂O and Na₂Contains O
Crystallized glass obtained by heat treating mother glass to precipitate crystals
This is an example using a space. This crystallized glass also has an average thermal expansion
Coefficient is 34 × 10^-7/ ° C and thermal expansion coefficient of silicon
I could do it, but Li ₂Part of O and Na₂O is
Since it coexists in the glass phase, the heating temperature during bonding with silicon
If you don't raise the temperature to 320 ℃
Without a fine crack on a part of the surface of the crystallized glass after bonding.
Ku also existed.

[0057]

Since the crystallized glass of the present invention contains a large amount of only lithium ions as mobile cations, it can be anodically bonded at a temperature of 250 ° C. or lower and has a coefficient of thermal expansion of 25 × 10 ^{−. 7} to 40 × 10 ⁻⁷ / ° C., which is a value close to that of silicon. The crystallized glass of the present invention has not only a thermal expansion coefficient close to that of silicon but also anodic bonding with silicon at a low temperature, so that the thermal distortion of the silicon-crystallized glass bonded body after cooling is extremely small, and excellent sensor characteristics can be obtained. A silicon-crystallized glass joint having is obtained. Further, it also has the effects of improving the yield of anodic bonding and shortening the tact time. In addition to protecting the sensor circuit, it has the effect of widening the range of use of members that are relatively heat-sensitive. Therefore, the crystallized glass of the present invention is suitable as crystallized glass that is anodically bonded to silicon.

[Brief description of drawings]

FIG. 1 is an explanatory diagram illustrating an outline of anodic bonding.

[Explanation of Codes] 1 ... Silicon, 2 ... Crystallized glass for anodic bonding, 3 ... Minus electrode / cathode side heater, 4 ... Anode side heater, 5 ... Plus electrode

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Claims (5)

[Claims] 1. A crystallized glass having β-quartz or a β-quartz solid solution as a main crystal, which does not substantially contain Na ₂ O but contains Li ₂ O: 6 to 10% in terms of mol%, The crystallized glass for anodic bonding is characterized in that the proportion of the crystal phase is 10 to 50% by volume. 2. The average thermal expansion coefficient from room temperature to 300 ° C. is 25 × 10 ⁻⁷ to 40 × 10 ⁻⁷ / ° C., and the anodic bonding temperature is 250 ° C. or lower. Crystallized glass for anodic bonding. 3. SiO ₂ : 60-69 in terms of mol%.
%, Al ₂ O ₃ : 12 to 18%, Li ₂ O: 6 to 10%,
MgO: 1-6%, ZnO: 0-4%, TiO ₂ : 1-
The crystallized glass for anodic bonding according to claim 1 or 2, which contains 6%, ZrO ₂ : 0 to 3%, and P ₂ O ₃ : 0 to 3%. 4. A pedestal for silicon bonding, which is made of the crystallized glass according to any one of claims 1 to 3. 5. A semiconductor sensor comprising a pressure detecting section made of a silicon base and a pedestal joined to the pressure detecting section, wherein the pedestal is the pedestal according to claim 4.