JP2013095644A - Polycrystalline ceramic joined body, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycrystalline ceramic joined body having high strength, causing little deformation of a polycrystalline ceramic substrate, and hardly generating contamination even when being used as a member for a production apparatus of a semiconductor or a liquid crystal, and to provide a method for manufacturing the same.SOLUTION: This polycrystalline ceramic joined body is formed by joining a first polycrystalline ceramic substrate containing YOas a major phase with a second polycrystalline ceramic substrate containing AlOor YOas a major phase through a joining layer, wherein the joining layer comprises a composite oxide containing at least three kinds of oxides selected from YO, AlO, SiOand ZrO.

Description

  The present invention relates to a polycrystalline ceramic joined body and a method for producing the same, and more particularly to a polycrystalline ceramic joined body used in manufacturing a semiconductor or a liquid crystal and a method for producing the same.

  In the manufacturing process of semiconductors and liquid crystals, plasma processing using plasma of halogen-based corrosive gas such as fluorine or chlorine is generally performed. The plasma treatment is used, for example, in a process such as a dry etching process or plasma coating in semiconductor manufacturing.

  Plasma typically has a high electron temperature and ion bombardment energy. For this reason, high plasma resistance is required for a member in contact with plasma, such as an inner wall in the plasma processing apparatus, in order to prevent corrosion due to plasma.

  Conventionally, yttria, high-purity alumina or the like has been used as such a material having high plasma resistance. However, since yttria and high-purity alumina are expensive, the cost of the member increases if the entire member that contacts the plasma is made of yttria or high-purity alumina.

  Therefore, among the members that come into contact with the plasma, only the necessary parts exposed to the plasma are made of a material having high plasma resistance such as yttria and high-purity alumina, and the parts that are not exposed to the plasma are inexpensive such as general-purpose alumina. It has been proposed that a polycrystalline ceramic joined body is obtained by producing the materials and joining them together.

  In a polycrystalline ceramic joined body, a member having high plasma resistance such as yttria or high-purity alumina and a member having low plasma resistance such as general-purpose alumina include, for example, organic adhesives and inorganic nano-powder. Or the like by using a metal braze or the like.

  Moreover, a polycrystalline ceramic joined body can also be obtained by bringing molded bodies before firing of different ceramic materials into contact with each other, firing and joining them.

  For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2002-192655) discloses a ceramic base material and a corrosion-resistant sintered body mainly composed of Group 2 and Group 3 elements of the periodic table, and ceramic base material and corrosion resistance. A polycrystalline ceramic joined body joined via an interdiffusion layer with a sintered body is described.

  This polycrystalline ceramic joined body is formed by forming a composite formed body using a ceramic base body formed as a raw material for a ceramic base and a corrosion-resistant sintered body formed as a raw material for a corrosion-resistant sintered body, followed by firing. A ceramic base material and a corrosion-resistant sintered body are joined by forming an interdiffusion layer.

JP 2002-192655 A

  However, when used in semiconductor and liquid crystal manufacturing equipment, polycrystalline ceramics bonded with an organic adhesive or metal brazing will generate dust, contamination, and degassing due to the adhesive. Thus, there has been a problem of contaminating wafers and the like in the manufacturing apparatus.

  On the other hand, even if the polycrystalline ceramic joined body joined using nanopowder is used in a semiconductor or liquid crystal manufacturing apparatus, impurities and the like can be suppressed to a low level. However, the polycrystalline ceramic joined body joined using the nano powder has a problem that it is easily damaged because of its low joining strength.

  In addition, there has been a problem that a polycrystalline ceramic joined body obtained by directly joining different materials is likely to be peeled off due to a difference in thermal expansion between the materials.

  In order to increase the bonding strength of the polycrystalline ceramic bonded body, a method of bonding by baking at a higher temperature is also conceivable. However, when firing at higher temperatures, there is a problem that deformation (creep) is likely to occur in the polycrystalline ceramic substrate.

  The present invention has been made in view of the above circumstances, and has high strength, little deformation of a polycrystalline ceramic base material, and low occurrence of contamination even when used as a member for a semiconductor or liquid crystal manufacturing apparatus. An object of the present invention is to provide a ceramic joined body and a method for producing the same.

The polycrystalline ceramic joined body and the method for producing the same according to the present invention include a first polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase, and a _second crystal containing Al ₂ O ₃ or Y ₂ O ₃ as a main phase. When the bonding layer for bonding the polycrystalline ceramic base material is a complex oxide containing three or more kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ , high strength, It has been completed by finding that a polycrystalline ceramic joined body can be obtained in which the deformation of the crystalline ceramic base material is small and the occurrence of contamination is small even when used as a member for a semiconductor or liquid crystal manufacturing apparatus.

The polycrystalline ceramic joined body of the present invention solves the above-mentioned problems, and mainly comprises a first polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase, and Al ₂ O ₃ or Y ₂ O ₃ . The second polycrystalline ceramic base material included as a phase is a polycrystalline ceramic joined body joined via a joining layer, wherein the joining layer comprises Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO. _It consists of a complex oxide containing at least three kinds of oxides selected from ₂ .

In addition, the method for producing a polycrystalline ceramic joined body of the present invention solves the above-described problems, and includes a first polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase, and Al ₂ O ₃ or Y _A method of manufacturing a polycrystalline ceramic joined body in which a second polycrystalline ceramic base material containing ₂ O ₃ as a main phase is bonded via an adhesive and heat-treated to join, wherein the adhesive is Y It is an adhesive containing at least three kinds of oxides selected from ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ .

  According to the polycrystalline ceramic joined body and the method for producing the same of the present invention, the high strength, the deformation of the polycrystalline ceramic base material is small, and the occurrence of contamination is small even when used as a member for a semiconductor or liquid crystal production apparatus. A crystal ceramic joined body and a method for producing the same are obtained.

[Polycrystalline ceramic bonded body]
The polycrystalline ceramic joined body of the present invention is a joined body in which a first polycrystalline ceramic base material and a second polycrystalline ceramic base material are joined via a joining layer.

(First polycrystalline ceramic substrate)
The 1st polycrystalline ceramic base material used by this invention is a polycrystalline ceramic base material joined with a 2nd polycrystalline ceramic base material through a joining layer.

The first polycrystalline ceramic base material is a polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase.

Here, the first polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase means that the mass ratio of the Y ₂ O ₃ crystalline phase in the first polycrystalline ceramic base material is the largest. .

The first polycrystalline ceramic base material further includes, as a subordinate phase, a crystal phase such as Al ₂ O ₃ , ZrO ₂ and SiO ₂ , or an oxide containing two or more elements selected from Y, Al, Zr and Si. It may contain a crystalline phase or an amorphous phase comprising a product.

In the first polycrystalline ceramic substrate, the mass ratio of the Y ₂ O ₃ crystal phase is usually 70 to 100% by mass, preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.

In the first polycrystalline ceramic substrate, it is preferable that the mass ratio of the Y ₂ O ₃ crystal phase is in the above range because the plasma resistance is high.

(Second polycrystalline ceramic substrate)
The second polycrystalline ceramic substrate used in the present invention is a polycrystalline ceramic substrate that is bonded to the first polycrystalline ceramic substrate through a bonding layer.

The second polycrystalline ceramic base material is a polycrystalline ceramic base material containing Al ₂ O ₃ or Y ₂ O ₃ as a main phase.

Here, the second polycrystalline ceramic base material contains Al ₂ O ₃ or Y ₂ O ₃ as a main phase means that the Al ₂ O ₃ crystalline phase or Y ₂ O _{3 in the second} polycrystalline ceramic base material. It means that the mass ratio of the crystal phase is the largest.

Hereinafter, for the second polycrystalline ceramic base material, a _second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and a second polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase Separately described.

< _Second polycrystalline ceramic substrate containing Al ₂ O ₃ as a main phase>
The second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase is a polycrystalline ceramic base material having the largest mass ratio of the Al ₂ O ₃ crystalline phase in the _second polycrystalline ceramic base material.

The second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase further includes, for example, a crystal phase such as Y ₂ O ₃ , ZrO ₂ and SiO ₂ , or Y, Al, Zr and Si as a subordinate phase. A crystalline phase or an amorphous phase made of an oxide containing two or more selected elements may be included.

For example, the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase includes those containing a ZrO ₂ crystal phase as a dependent phase and those containing no ZrO ₂ crystal phase.

Hereinafter, for the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase, a second polycrystalline ceramic base material containing a ZrO ₂ crystalline phase as a subordinate phase and a second polycrystalline ceramic base material containing no ZrO ₂ crystalline phase The explanation will be divided into the polycrystalline ceramic substrate.

[ _Second polycrystalline ceramic substrate containing Al ₂ O ₃ as a main phase and ZrO ₂ as a subordinate phase]
The second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and containing ZrO ₂ as a subordinate phase has the largest mass ratio of the Al ₂ O ₃ crystalline phase in the _second polycrystalline ceramic base material, And a polycrystalline ceramic substrate containing a ZrO ₂ crystal phase.

In the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and containing ZrO ₂ as a dependent phase, the mass ratio of the Al ₂ O ₃ crystal phase is usually 50 to 99% by mass, preferably 70 to 99% by mass. %, More preferably 85 to 99% by mass.

In addition, the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and containing ZrO ₂ as a subordinate phase has a mass ratio of the ZrO ₂ crystal phase of usually 1 to 50% by mass, preferably 1 to 30% by mass. %, More preferably 1 to 15% by mass.

In the second polycrystalline ceramic substrate including Al ₂ O ₃ as a main phase and a ZrO ₂ crystal phase as a subordinate phase, when the mass ratio of the Al ₂ O ₃ crystal phase and the ZrO ₂ crystal phase is within the above range, This is preferable because the difference in coefficient of thermal expansion with the first polycrystalline ceramic substrate is small.

[ _Second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and not containing ZrO ₂ ]
The second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and not containing ZrO ₂ has the largest mass ratio of the Al ₂ O ₃ crystalline phase in the _second polycrystalline ceramic base material, and ZrO 2. ₂ is a polycrystalline ceramic substrate substantially free of ₂ .

In the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and not containing ZrO ₂ , the mass ratio of the Al ₂ O ₃ crystal phase is usually 90% by mass or more, preferably 95 to 100% by mass, Preferably it is 99-100 mass%.

In the second polycrystalline ceramic base material containing Al ₂ O ₃ as a main phase and not containing ZrO ₂ , if the mass ratio of the Al ₂ O ₃ crystal phase is within the above range, adhesion to the bonding material (affinity) ) Is high and the strength of the substrate is also high, which is preferable.

< _Second polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase>
The second polycrystalline ceramic substrate containing Y ₂ O ₃ as a main phase is a polycrystalline ceramic substrate having the largest mass ratio of the Y ₂ O ₃ crystalline phase in the _second polycrystalline ceramic substrate.

The second polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase further includes, for example, a crystal phase such as Al ₂ O ₃ , ZrO ₂ and SiO ₂ , or Y, Al, Zr and Si as a dependent phase. A crystalline phase or an amorphous phase made of an oxide containing two or more selected elements may be included.

In the second polycrystalline ceramic substrate containing Y ₂ O ₃ as a main phase, the mass ratio of the Y ₂ O ₃ crystal phase is usually 90 to 100% by mass, preferably 95 to 100% by mass, more preferably 99 to 99%. 100% by mass.

In the second polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase, it is preferable that the mass ratio of the Y ₂ O ₃ crystal phase is in the above range because adhesion (affinity) with the bonding material is high. .

In addition, when the second polycrystalline ceramic substrate is a polycrystalline ceramic substrate containing Y ₂ O ₃ as a main phase, the second polycrystalline ceramic substrate and the first polycrystalline ceramic substrate are: This coincides with a polycrystalline ceramic base material containing Y ₂ O ₃ as a main phase.

For this reason, in the polycrystalline ceramic joined body in which the polycrystalline ceramic base materials containing Y ₂ O ₃ as a main phase are joined via the joining layer, any of the polycrystalline ceramic base materials is used as the first polycrystalline ceramic base. The problem is whether to determine the material or the second polycrystalline ceramic substrate.

In this case, one of the polycrystalline ceramic substrates containing Y ₂ O ₃ as a main phase is appropriately determined as the first polycrystalline ceramic substrate, and the other polycrystalline ceramic substrate is used as the second polycrystalline ceramic substrate. What is necessary is just to determine with a base material.

(Difference in average thermal expansion coefficient between the first polycrystalline ceramic substrate and the second polycrystalline ceramic substrate)
The first polycrystalline ceramic substrate and the second polycrystalline ceramic substrate are an average coefficient of thermal expansion of 20 to 900 ° C. of the first polycrystalline ceramic substrate and 20 of the second polycrystalline ceramic substrate. When the difference from the average coefficient of thermal expansion of ˜900 ° C. is small, it is preferable because the polycrystalline ceramic joined body hardly breaks at the joining layer.

  Specifically, the absolute value of the difference between the average thermal expansion coefficient of 20 to 900 ° C. of the first polycrystalline ceramic substrate and the average thermal expansion coefficient of 20 to 900 ° C. of the second polycrystalline ceramic substrate is: It is usually 10% or less, preferably 5% or less, more preferably 2% or less with respect to the larger value of the average thermal expansion coefficient of 20 to 900 ° C. of the first or second polycrystalline ceramic substrate.

  When the absolute value of the difference between the average thermal expansion coefficient of 20 to 900 ° C. of the first polycrystalline ceramic substrate and the average thermal expansion coefficient of 20 to 900 ° C. of the second polycrystalline ceramic substrate is within the above range. Since the internal stress due to the difference in thermal expansion between the polycrystalline ceramic substrates is small, it becomes difficult to break at the bonding layer during bonding.

  On the other hand, the absolute value of the difference between the average coefficient of thermal expansion of 20 to 900 ° C. of the first polycrystalline ceramic substrate and the average coefficient of thermal expansion of 20 to 900 ° C. of the second polycrystalline ceramic substrate exceeds 10%. Since the internal stress due to the difference in thermal expansion between the polycrystalline ceramic base materials is large, the joining layer easily breaks during joining.

(Bonding layer)
The bonding layer is made of a complex oxide containing at least three kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ , and the first polycrystalline ceramic substrate is formed from the complex oxide. And the second polycrystalline ceramic substrate are joined together.

The composite oxide constituting the bonding layer is Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ based composite oxide composed of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ , or Y ₂ O ₃ , Al ₂ O. ₃ , Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide composed of SiO ₂ and ZrO ₂ is preferable because of its high plasma resistance.

  In the present invention, there is a possibility that contamination composed of simple elements such as Y, Al, Si and Zr may occur from the composite oxide constituting the bonding layer during the plasma treatment. However, contamination such as Y, Al, Si and Zr is not particularly problematic because it does not interfere much with plasma processing such as dry etching process and plasma coating in semiconductor manufacturing.

_{<Y 2 O 3 -Al 2 O} 3 -SiO 2 composite oxide>
When the composite oxide constituting the bonding layer is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ composite oxide composed of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ , Y ₂ O ₃ —Al ₂ The O ₃ —SiO ₂ composite oxide is typically 5 to 400 parts by weight, preferably 50 to 350 parts by weight, and more preferably 50 to 200 parts by weight of Al ₂ O ₃ with respect to 100 parts by weight of Y ₂ O _3. Including parts.

_{Further, Y 2 O 3 -Al 2 O} 3 -SiO 2 based composite _oxide, with respect to Y ₂ O 3 100 parts by weight, the SiO _2, usually 40 to 1,000 parts by weight, preferably 100 to 800 parts by weight, More preferably, it contains 100 to 500 parts by mass.

When the content of Al ₂ O ₃ and SiO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ composite oxide constituting the bonding layer is within the above range, the plasma resistance of the polycrystalline ceramic bonded body And 4-point bending strength becomes high. Here, the 4-point bending strength means a 4-point bending strength based on JIS R 1601.

On the other hand, when the content of Al ₂ O ₃ and SiO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ composite oxide constituting the bonding layer is outside the above range, the composite oxide has a high melting point. Therefore, problems such as difficulty in joining, deformation of the polycrystalline ceramic base material during joining, and reduction in joining strength are likely to occur.

The Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ based composite oxide constituting the bonding layer has plasma resistance of the polycrystalline ceramic bonded body when the contents of Al ₂ O ₃ and SiO ₂ are within the above ranges, respectively. This is preferable because the properties and the four-point bending strength are higher.

_{<Y 2 O 3 -Al 2 O} 3 -SiO 2 -ZrO 2 composite oxide>
When the composite oxide constituting the bonding layer is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ composite oxide composed of Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ , Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide is usually 5 to 400 parts by mass, preferably 50 to 350 parts by mass of Al ₂ O ₃ with respect to 100 parts by mass of Y ₂ O _3. Part, more preferably 50 to 200 parts by mass.

In addition, the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide has a SiO ₂ content of usually 40 to 1000 parts by mass, preferably 100 to 800 parts per 100 parts by mass of Y ₂ O _3. Part by mass, more preferably 100 to 500 parts by mass are included.

Further, the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide has a ZrO ₂ content of usually 0.001 to 1000 parts by mass, preferably 100 to 100 parts by mass of Y ₂ O _3. -800 mass parts is contained, More preferably, 200-600 mass parts is contained.

When the content of Al ₂ O ₃ , SiO ₂ and ZrO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ composite oxide constituting the bonding layer is within the above range, polycrystalline ceramics The plasma resistance of the joined body is increased.

On the other hand, if the content of Al ₂ O ₃ , SiO ₂ and ZrO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide constituting the bonding layer is outside the above range, the composite Since the melting point of the oxide becomes too high, it becomes difficult to join, problems such as deformation of the polycrystalline ceramic base material during joining, and a reduction in joining strength tend to occur.

The Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide constituting the bonding layer is polycrystalline when the contents of Al ₂ O ₃ , SiO ₂ and ZrO ₂ are within the above ranges, respectively. This is preferable because the plasma resistance of the ceramic joined body becomes higher.

<Junction layer thickness>
The bonding layer has a thickness of usually 5 to 500 μm, preferably 25 to 400 μm, and more preferably 30 to 250 μm.

  When the thickness of the bonding layer is within the above range, it is possible to obtain a bonding layer that has high bonding strength and is less likely to crack or break in the bonding layer.

  On the other hand, if the thickness of the bonding layer exceeds 500 μm, the bonding layer is likely to be cracked or broken. Moreover, there exists a possibility that joining strength may become it low that the thickness of a joining layer is less than 5 micrometers.

  The polycrystalline ceramic joined body of the present invention can be used as, for example, a polycrystalline ceramic joined body for a semiconductor manufacturing apparatus or a liquid crystal manufacturing apparatus.

[Production method of polycrystalline ceramic joined body]
The method for producing a polycrystalline ceramic joined body according to the present invention is a method in which a first polycrystalline ceramic base material and a second polycrystalline ceramic base material are bonded via an adhesive and heat-treated to join them. .

  The first polycrystalline ceramic base material and the second polycrystalline ceramic base material used in the method for producing a polycrystalline ceramic joined body of the present invention are the same as those explained in the polycrystalline ceramic joined body of the present invention. The description is omitted.

(adhesive)
The adhesive used in the present invention is an adhesive containing at least three kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ .

The adhesive is obtained, for example, by mixing at least three kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ with water to form a paste.

_{Adhesives, Y 2 O 3, Al 2} O 3, including SiO ₂ and water _{Y 2 O 3 -Al 2 O 3} -SiO 2 based adhesive, or _{Y 2 O 3, Al 2 O} 3, SiO 2, A Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based adhesive containing ZrO ₂ and water is preferable because a bonding layer having high plasma resistance can be obtained.

Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ used as raw materials for the adhesive are obtained by applying the adhesive to the bonding surface of the first polycrystalline ceramic substrate or the second polycrystalline ceramic substrate. It is preferable that it is powdery so that it may be easy.

_{<Y 2 O 3 -Al 2 O} 3 -SiO 2 based adhesive>
When the adhesive is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ -based adhesive, the adhesive includes Y ₂ O ₃ , Al ₂ O _3, and SiO ₂ , and Y ₂ O ₃ − constituting the bonding layer. The Al ₂ O ₃ —SiO ₂ composite oxide is included at the same mass ratio.

That is, the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ -based adhesive is usually 5 to 400 parts by mass, preferably 50 to 350 parts by mass of Al ₂ O ₃ with respect to 100 parts by mass of Y ₂ O _3. More preferably, it contains 50 to 200 parts by mass.

_{Further, Y 2 O 3 -Al 2 O} 3 -SiO 2 based _adhesive, to the Y ₂ O 3 100 parts by weight, the SiO _2, usually 40 to 1,000 parts by weight, preferably 100 to 800 parts by weight, more Preferably it contains 100-500 mass parts.

When the content of Al ₂ O ₃ and SiO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ adhesive is within the above range, the plasma resistance and the four-point bending strength of the polycrystalline ceramic joined body are reduced. Get higher.

On the other hand, when the content of Al ₂ O ₃ and SiO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ adhesive is outside the above range, the melting point of the composite oxide obtained by firing the adhesive Therefore, the bonding becomes difficult, the polycrystalline ceramic base material is deformed during the bonding, and the bonding strength is lowered.

The Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ -based adhesive has 4 points of plasma resistance and 4 points of the resulting polycrystalline ceramic joined body when the contents of Al ₂ O ₃ and SiO ₂ are within the above ranges, respectively. Since bending strength becomes higher, it is preferable.

_{<Y 2 O 3 -Al 2 O} 3 -SiO 2 -ZrO 2 based adhesive>
When the adhesive is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ adhesive, the adhesive comprises Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ to form a bonding layer. Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based composite oxide is included at the same mass ratio.

That is, the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based adhesive is usually 5 to 400 parts by mass, preferably 50 to 100 parts by mass of Al ₂ O ₃ with respect to 100 parts by mass of Y ₂ O _3. 350 mass parts, More preferably, it contains 50-200 mass parts.

The Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based adhesive is usually 40 to 1000 parts by mass, preferably 100 to 800 parts by mass of SiO ₂ with respect to 100 parts by mass of Y ₂ O _3. Parts, more preferably 100 to 500 parts by mass.

Further, the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based adhesive is usually 0.001 to 1000 parts by mass, preferably 100 to 100 parts by mass of ZrO ₂ with respect to 100 parts by mass of Y ₂ O _3. It contains 800 parts by mass, more preferably 200-600 parts by mass.

When the content of Al ₂ O ₃ , SiO ₂ and ZrO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ adhesive is within the above range, the plasma resistance of the polycrystalline ceramic joined body Becomes higher.

On the other hand, when the content of Al ₂ O ₃ , SiO ₂ and ZrO _{2 in} the Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ adhesive is outside the above range, the adhesive is fired. Since the melting point of the composite oxide is too high, it becomes difficult to join, the polycrystalline ceramic base material is deformed during the joining, and the joining strength is liable to be lowered.

Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ -based adhesive has the following contents when the contents of Al ₂ O ₃ , SiO ₂ and ZrO ₂ are within the above ranges. This is preferable because the plasma resistance becomes higher.

<Thickness of adhesive layer>
The adhesive is applied to the bonding surface of the first polycrystalline ceramic substrate or the second polycrystalline ceramic substrate.

  The adhesive layer to which the adhesive is applied has a thickness of usually 5 to 500 μm, preferably 25 to 400 μm, and more preferably 30 to 250 μm.

The adhesive layer is selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ by being heat-treated in an oxidation furnace or the like together with the first polycrystalline ceramic substrate and the second polycrystalline ceramic substrate. The bonding layer is made of a composite oxide containing at least three kinds of oxides.

  The temperature of heat processing is 1400-1700 degreeC normally, Preferably it is 1400-1600 degreeC, More preferably, it is 1450-1550 degreeC. It is preferable that the temperature of the heat treatment be in the above range because the bonding strength of the bonding layer is high. Moreover, the time of heat processing is 1 to 10 hours normally, Preferably it is 3 to 6 hours.

  Examples are shown below, but the present invention is not construed as being limited thereto.

[Example 1-1]
(Production of polycrystalline ceramic joined body)
<First polycrystalline ceramic substrate>
As the first polycrystalline ceramic base material, a plate-like yttria polycrystalline ceramic base material made only of yttria (Y ₂ O ₃ ) was prepared (base material A-1).
About the base material A-1, the average thermal expansion coefficient in 20-900 degreeC was measured.
The average coefficient of thermal expansion (1 / K) at 20 to 900 ° C. is measured in accordance with JIS R 1618.

Table 1 shows the composition of the substrate A-1.

<Second polycrystalline ceramic substrate>
As the second polycrystalline ceramic base material, a plate-like alumina polycrystalline ceramic base material made only of alumina (Al ₂ O ₃ ) was prepared (base material B-1).
Moreover, about the base material B-1, it carried out similarly to base material A-1, and measured the average thermal expansion coefficient in 20-900 degreeC.

Table 2 shows the composition of the substrate B-1.

<Ratio of difference in average thermal expansion coefficient>
The difference was calculated | required from the average thermal expansion coefficient in 20-900 degreeC of the base material A-1 and the average thermal expansion coefficient in 20-900 degreeC of the base material B-1, and this difference was represented as an absolute value.
The absolute value of the difference in average coefficient of thermal expansion is the larger of the average coefficient of thermal expansion of the base material A-1 at 20 to 900 ° C. and the average coefficient of thermal expansion of the base material B-1 at 20 to 900 ° C. The ratio (%) of the difference in average thermal expansion coefficient was calculated by dividing by.
<Adhesive>
As an adhesive, 100 parts by mass of yttria (Y ₂ O ₃ ) powder, 200 parts by mass of alumina (Al ₂ O ₃ ) powder, and 400 parts by mass of silica (SiO ₂ ) powder are mixed with water, and yttria, A paste containing alumina and silica was prepared.
<Joining of the first and second polycrystalline ceramic substrates>
A paste as an adhesive is applied on the surface of the base material A-1 so that the thickness of the bonding layer after firing becomes 200 μm, and the base material B-1 is placed on the surface to which the paste is applied. Then, a temporary bonded body in which the base A-1 and the base B-1 were temporarily bonded with an adhesive was produced.
When this temporary adhesion body was heat-processed in air | atmosphere at 1500 degreeC for 5 hours, the polycrystalline-ceramics joined body by which the base material A-1 and the base material B-1 were joined by the joining layer was obtained.
(Evaluation of bonded polycrystalline ceramics)
The obtained polycrystalline ceramic joined body was measured for four-point bending strength according to JIS R 1601. The sample for measuring the 4-point bending strength was prepared so that the bonding layer of the polycrystalline ceramic bonded body had a fracture surface.
Table 3 shows the ratio of the difference between the type of base material and the average thermal expansion coefficient. Table 4 shows the measurement results of the oxide composition in the paste, the thickness of the bonding layer, and the 4-point bending strength.
In addition, also about the Example and comparative example which are shown below, Table 3 shows the ratio of the difference of the kind of base material and an average thermal expansion coefficient, Table 4 shows the composition of the oxide in paste, the thickness of a joining layer, and The measurement results of 4-point bending strength are shown.

[Examples 1-2 to 1-7]
A polycrystalline ceramic joined body was produced in the same manner as in Example 1-1 except that the composition of the oxide in the paste as the adhesive or the thickness of the joining layer was changed as shown in Table 4.
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 1-1.

[Example 1-8]
<First polycrystalline ceramic substrate>
As the first polycrystalline ceramic base material, a plate-shaped yttria polycrystalline ceramic base material made only of yttria (Y ₂ O ₃ ) was prepared (base material A-2).
About base material A-2, it carried out similarly to base material A-1, and measured the average coefficient of thermal expansion in 20-900 degreeC.
Table 1 shows the composition of the substrate A-2.
<Second polycrystalline ceramic substrate>
As the second polycrystalline ceramic base material, a plate-like alumina polycrystalline ceramic base material made only of alumina (Al ₂ O ₃ ) was prepared (base material B-2).
About base material B-2, it carried out similarly to base material A-1, and measured the average coefficient of thermal expansion in 20-900 degreeC.
Table 2 shows the composition of the substrate B-2.
<Ratio of difference in average thermal expansion coefficient>
About base material A-2 and base material B-2, it carried out similarly to Example 1-1, and computed the ratio of the difference of an average thermal expansion coefficient.
<Joining of the first and second polycrystalline ceramic substrates>
In the same manner as in Example 1-1 except that the base material A-2 was used instead of the base material A-1 and the base material B-2 was used instead of the base material B-1, a polycrystalline ceramic joined body was obtained. Produced.
(Evaluation of bonded polycrystalline ceramics)
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 1-1.

[Examples 1-11 to 1-16]
A polycrystalline ceramic joined body was produced in the same manner as in Example 1-1 except that the composition of the oxide in the paste as the adhesive or the thickness of the joining layer was changed as shown in Table 4.
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 1-1.

[Example 1-17]
<First polycrystalline ceramic substrate>
As the first polycrystalline ceramic base material, a plate-like yttria polycrystalline ceramic base material made only of yttria (Y ₂ O ₃ ) was prepared (base material A-3).
About base material A-3, it carried out similarly to base material A-1, and measured the average coefficient of thermal expansion in 20-900 degreeC.
Table 1 shows the composition of the substrate A-3.
<Second polycrystalline ceramic substrate>
As the second polycrystalline ceramic base material, a plate-like alumina polycrystalline ceramic base material made only of alumina (Al ₂ O ₃ ) was prepared (base material B-3).
About base material B-3, it carried out similarly to base material A-1, and measured the average coefficient of thermal expansion in 20-900 degreeC.
Table 2 shows the composition of the substrate B-2.
<Ratio of difference in average thermal expansion coefficient>
About base material A-3 and base material B-3, it carried out similarly to Example 1-1, and computed the ratio of the difference of an average thermal expansion coefficient.
<Joining of the first and second polycrystalline ceramic substrates>
In the same manner as in Example 1-1 except that the base material A-3 was used instead of the base material A-1 and the base material B-3 was used instead of the base material B-1, a polycrystalline ceramic joined body was obtained. Produced.
(Evaluation of bonded polycrystalline ceramics)
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 1-1.

[Example 2-1]
(Production of polycrystalline ceramic joined body)
<First polycrystalline ceramic substrate>
Substrate A-1 was used as the first polycrystalline ceramic substrate.
<Second polycrystalline ceramic substrate>
Substrate B-1 was used as the second polycrystalline ceramic substrate.
<Adhesive>
As an adhesive, 100 parts by mass of yttria (Y ₂ O ₃ ) powder, 200 parts by mass of alumina (Al ₂ O ₃ ) powder, 400 parts by mass of silica (SiO ₂ ) powder, and 300 parts by mass of zirconia (ZrO ₂ ) powder Were mixed with water to prepare a paste containing yttria, alumina, silica and zirconia.
<Joining of the first and second polycrystalline ceramic substrates>
A polycrystalline ceramic joined body was produced in the same manner as in Example 1-1 except that the above adhesive was used.
(Evaluation of bonded polycrystalline ceramics)
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 1-1.

[Examples 2-2 to 2-9]
A polycrystalline ceramic joined body was produced in the same manner as in Example 2-1, except that the composition of the oxide in the paste as the adhesive or the thickness of the joining layer was changed as shown in Table 4.
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 2-1.

[Example 2-10]
<First polycrystalline ceramic substrate>
Substrate A-2 was used as the first polycrystalline ceramic substrate.
<Second polycrystalline ceramic substrate>
Substrate B-2 was used as the second polycrystalline ceramic substrate.
<Joining of the first and second polycrystalline ceramic substrates>
A polycrystalline ceramic joined body was obtained in the same manner as in Example 2-1, except that the base material A-2 was used instead of the base material A-1, and the base material B-2 was used instead of the base material B-1. Produced.
(Evaluation of bonded polycrystalline ceramics)
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 2-1.

[Examples 2-11 to 2-17]
A polycrystalline ceramic joined body was produced in the same manner as in Example 2-1, except that the composition of the oxide in the paste as the adhesive or the thickness of the joining layer was changed as shown in Table 4.
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 2-1.

[Example 2-18]
<First polycrystalline ceramic substrate>
Substrate A-3 was used as the first polycrystalline ceramic substrate.
<Second polycrystalline ceramic substrate>
Substrate B-3 was used as the second polycrystalline ceramic substrate.
<Joining of the first and second polycrystalline ceramic substrates>
In the same manner as in Example 2-1, except that the base material A-3 was used instead of the base material A-1 and the base material B-3 was used instead of the base material B-1, a polycrystalline ceramic joined body was obtained. Produced.
(Evaluation of bonded polycrystalline ceramics)
About the obtained polycrystalline ceramic joined body, the 4-point bending strength was measured in the same manner as in Example 2-1.

[Comparative Examples 1 and 2]
A polycrystalline ceramic joined body was tried in the same manner as in Example 1-1 except that the composition of the oxide in the adhesive paste or the thickness of the joining layer was changed as shown in Table 4.
However, the base material A-1 and the base material B-1 could not be joined.

  The polycrystalline ceramic joined body and the method for producing the same according to the present invention can be used, for example, for a polycrystalline ceramic joined body used in plasma processing for manufacturing semiconductors and liquid crystals.

Claims (8)

A first polycrystalline ceramic substrate containing Y ₂ O ₃ as a main phase;
A _second polycrystalline ceramic substrate containing Al ₂ O ₃ or Y ₂ O ₃ as a main phase,
A polycrystalline ceramic joined body joined via a joining layer,
The polycrystalline ceramic joined body, wherein the joining layer is made of a composite oxide containing at least three kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ . The composite oxide constituting the bonding layer is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ based composite oxide composed of Y ₂ O ₃ , Al ₂ O ₃ and SiO ₂ .
_{2. The} polycrystal according to claim 1, wherein the composite oxide includes ₅ to 400 parts by mass of Al ₂ O ₃ and 40 to 1000 parts by mass of SiO ₂ with respect to 100 parts by mass of Y ₂ O _3. Ceramic bonded body. The composite oxide constituting the bonding layer is a Y ₂ O ₃ —Al ₂ O ₃ —SiO ₂ —ZrO ₂ based composite oxide composed of Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ and ZrO ₂ .
The composite oxide contains ₅ to 400 parts by mass of Al ₂ O ₃ , 40 to 1000 parts by mass of SiO ₂ , and 0.001 to 1000 parts by mass of ZrO ₂ with respect to 100 parts by mass of Y ₂ O _3. The polycrystalline ceramic joined body according to claim 1, wherein Said second polycrystalline ceramic substrate, a polycrystalline ceramic assembly according to claim 1, characterized in that a polycrystalline ceramic substrate containing Al ₂ O ₃ as a main phase . The polycrystalline ceramic joined body according to any one of claims 1 to 4, wherein the second polycrystalline ceramic base material contains ZrO ₂ as a dependent phase. The polycrystalline ceramic joined body according to any one of claims 1 to 5, wherein the joining layer has a thickness of 5 to 500 µm. The absolute value of the difference between the average thermal expansion coefficient of 20 to 900 ° C. of the first polycrystalline ceramic substrate and the average thermal expansion coefficient of 20 to 900 ° C. of the second polycrystalline ceramic substrate is the first value. It is 10% or less with respect to the value with the larger average thermal expansion coefficient of 20-900 degreeC of the 1st or 2nd polycrystalline ceramic base material, The any one of Claims 1-6 characterized by the above-mentioned. Polycrystalline ceramic joined body. A first polycrystalline ceramic substrate containing Y ₂ O ₃ as a main phase;
A _second polycrystalline ceramic base material containing Al ₂ O ₃ or Y ₂ O ₃ as a main phase;
It is a method for producing a polycrystalline ceramic joined body that is bonded via an adhesive and heat-bonded for bonding,
The method for producing a polycrystalline ceramic joined body, wherein the adhesive is an adhesive containing at least three kinds of oxides selected from Y ₂ O ₃ , Al ₂ O ₃ , SiO _2, and ZrO ₂ .