JP5270306B2 - Ceramic bonded body and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low thermal expansion ceramic joint having the bending strength and stiffness almost same to a sintered body and having a small dimensional change with time. <P>SOLUTION: In the low thermal expansion ceramic joint formed by joining sintered compact themselves consisting of the low thermal expansion ceramic without blending an inclusion, a material constituting the sintered body is composed of lithium aluminosilicate, silicon carbide and/or silicon nitride and an average thermal expansion coefficient at 20-30&deg;C is -1&times;10<SP>-6</SP>to 1&times;10<SP>-6</SP>/&deg;C. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a ceramic bonded body used as a member of a semiconductor manufacturing apparatus, an inspection device, and the like, and a manufacturing method thereof.

Ceramics are often used as members of semiconductor manufacturing equipment and the like. This is because ceramics are excellent in corrosion resistance and rigidity. In recent years, ceramics have been used in devices that handle large-diameter semiconductor substrates, large FPD glass substrates, and the like, and it has become necessary to increase the size of ceramic members.

However, if an attempt is made to increase the size of ceramics, cracking and deformation are likely to occur when the ceramics are sintered, and manufacturing is very difficult. Therefore, it has been studied to manufacture a large member by bonding ceramics.

For example, Patent Document 1 discloses a ceramic joined body as a structural member of an XY stage of a positioning device, and examples of the material include alumina and silicon nitride. Further, as a joining method, re-sintering or joining using an adhesive is cited.

Further, the present applicant has developed a technique for joining ceramics by re-sintering, and is a joining method of a calcium silicate-based sintered body containing a calcium silicate crystal and a lithium aluminosilicate crystal as essential components. Disclosed is a method for joining calcium silicate-based sintered bodies, characterized in that the calcium silicate-based sintered bodies are joined to each other at a predetermined temperature and a predetermined pressure without providing inclusions between the bonded bodies. (Patent Document 2).

Further, the present applicant configures the bonding material with a low thermal expansion ceramic having a lower melting temperature than the low thermal expansion ceramic of the base material, and heats the bonding material at a temperature higher than the melting temperature of the bonding material and lower than the melting temperature of the base material. Accordingly, a bonded body having a rigidity comparable to that of ordinary ceramics and a high bonding strength while maintaining a low thermal expansion coefficient is disclosed (Patent Document 3).

JP-A-11-142555 Japanese Patent Laid-Open No. 10-259072 JP 2004-59402 A

According to the joined body of Patent Document 1, since the structural member constituting the positioning device is a hollow ceramic joined body, it is possible to achieve light weight, high strength, and high rigidity. However, semiconductor circuits tend to become finer, and even a slight deformation of the manufacturing apparatus causes a decrease in yield. Therefore, a low thermal expansion material has been used as a member for semiconductor manufacturing apparatuses, etc. Alumina and silicon nitride described in 1 are not preferable because of large thermal expansion.

In the case of a joined body of calcium silicate-based sintered bodies described in Patent Document 2, it is possible to obtain a material having a low thermal expansion, but if low thermal expansion is required, the rigidity will decrease and the rigidity will increase. As a result, the thermal expansion increases, so that a material satisfying both of them cannot be obtained.

A joined body using the joining material of Patent Document 3 is excellent in thermal expansion and rigidity, and can be sufficiently put into practical use as a structural member. However, when a very fine flat surface is used for a member such as a bar mirror of a positioning device, there is a problem that a dimensional change may occur as the usage time elapses. In addition, when a bonded structure having a hollow structure is produced, there is a case where the bonding material oozes out or voids are generated in the bonding material, and the shape accuracy of the hollow portion cannot be obtained or complete airtightness cannot be ensured. There was a problem.

Further, in joining via the joining layer, even if the thermal expansion coefficient and Young's modulus are approximated between the joining layer and the base material, there may be a problem because other physical properties are different. For example, in Patent Document 3, since the volume resistivity of the base material is low and the volume resistivity of the bonding layer is high, conduction is interrupted by the bonding layer, so there is a restriction on the design of the member.

The present invention has been made in view of these problems, and provides a low thermal expansion ceramic joined body having bending strength and rigidity comparable to those of a sintered body alone and having a small dimensional change over time. .

In order to solve these problems, the present invention is a low thermal expansion ceramic joined body formed by joining sintered bodies made of low thermal expansion ceramics without providing inclusions, and constitutes the sintered body. material, lithium aluminosilicate, consists of a silicon carbide and / or silicon nitride, Ri average thermal expansion coefficient of ^{-1 × 10 -6 ~1 × 10 -6} / ℃ der at 20 to 30 ° C., 4 points Provided is a low thermal expansion ceramic joined body characterized in that a bending strength is 115 MPa or more, a Young's modulus is 120 GPa or more, and iron contained in the sintered body is 70 to 210 ppm .

The joined body of the present invention is joined without any inclusions. Thereby, it can be used for a member for which extremely fine dimensional accuracy is required, and the change with time can be extremely small. Further, since there is no inclusion such as a bonding layer having different characteristics such as volume resistivity, the bonded body can be handled in the same manner as the sintered body, and the design restrictions of the members can be eliminated.

In the present invention, the material constituting the sintered body is composed of lithium aluminosilicate and silicon carbide and / or silicon nitride. By using such a material, the average thermal expansion coefficient at 20 to 30 ° C. can be set to −1 × 10 ⁻⁶ to 1 × 10 ⁻⁶ / ° C., the bending strength is 115 MPa or more, and the Young's modulus is 120 GPa or more. A bonded body having low strength and high thermal expansion can be realized.

Furthermore, examples of lithium aluminosilicate include β-eucryptite, β-spodumene, petalite and the like. These are ceramics having a low coefficient of thermal expansion. Of these, β-eucryptite is desirable. β-spodumene is about 1 × 10 ⁻⁶ / ° C., whereas β-eucryptite exhibits a negative thermal expansion coefficient, which is −2 × 10 ⁻⁶ / ° C. Compounding and compounding with silicon carbide and / or silicon nitride, which has a positive thermal expansion and is a high rigidity material, the average thermal expansion coefficient at 20 to 30 ° C. is −1 × 10 ⁻⁶ to 1 ×. 10 ⁻⁶ / ° C.

The iron contained in the sintered body is preferably 70 to 210 ppm (parts per million by mass). The low thermal expansion ceramic sintered body used in the present invention exhibits low thermal expansion by absorbing thermal expansion by generating microcracks in the particles and grain boundaries of the sintered body as the temperature changes. The present inventor has adjusted the occurrence of microcracks in the joined body by adjusting the iron content within the above range, and has come to the invention. That is, if the iron content is less than 70 ppm, the melting temperature of the sintered body becomes high, and it is necessary not only to increase the processing temperature of the bonding heat treatment itself, but also the progress of fusion of the bonding surface becomes slow. As a result, voids are generated at the joint. On the other hand, when the content is higher than 210 ppm, the melting temperature of the sintered body is lowered, so that during the heat treatment for bonding, grain growth is promoted and the microcracks inherent in the sintered body structure are destroyed as a starting point.

The four-point bending strength of the low thermal expansion ceramic joined body of the present invention is 95% or more of the four-point bending strength of the sintered body. The Young's modulus is 95% or more of the Young's modulus of the sintered body. Since the structure of the low thermal expansion ceramic joined body is the same as that of the sintered body in the joined portion, the bending strength and Young's modulus are hardly decreased.

The present invention also provides a low thermal expansion ceramic joined body having a four-point bending strength defined in JIS R1601 of 115 MPa or more and a Young's modulus defined in JIS R1602 of 120 GPa or more. By setting it as the above materials and compositions, low thermal expansion property and high intensity | strength can be made compatible.

The composition of the sintered body is preferably 50 to 95% by mass of β-eucryptite and 5 to 50% by mass of silicon carbide and / or silicon nitride. In this range, a relatively large amount of liquid phase is generated in the sintered body at a relatively low temperature, and a softening phenomenon occurs at the time of joining and joining can be performed. When β-eucryptite is less than 50%, silicon carbide and / or silicon nitride having positive thermal expansion becomes dominant, and a low thermal expansion ceramic is not obtained. When β-eucryptite is more than 95%, not only does the coefficient of thermal expansion become −1.0 × 10 ⁻⁶ / ° C. or less, but β-eucryptite has microcracks in the structure. Therefore, the strength and rigidity are remarkably reduced.

The joined body of the present invention can be obtained by a joining method of low thermal expansion ceramics obtained by joining sintered bodies made of low thermal expansion ceramics without providing inclusions. More specifically, a step of preparing a sintered body composed of β-eucryptite 50 to 95% by mass and silicon carbide and / or silicon nitride 5 to 50% by mass;
The step of processing the surface roughness of the joint surface of the sintered body to 0.1 to 0.8 μm and the joint surfaces of the sintered body are combined, and 1000 to 1400 while applying a load of ^{2 to} 50 g / cm ^2. And a heat treatment step of heating to ° C.

The reason why the surface roughness of the bonding surface is 0.1 to 0.8 μm is that, in such a range, an integrated structure can be obtained without a boundary at the bonding portion. When the surface roughness is smaller than 0.1 μm, the supply of nitrogen to the bonding surface is remarkably reduced, so that the expansion and contraction of the lattice constant due to the solid solution of nitrogen hardly occurs, and the fusion of the bonding surface may not proceed. . On the other hand, when it is larger than 0.8 μm, the contact state of the joint surface is poor, and it becomes difficult to progress the fusion to the entire joint surface due to generation of the liquid phase.

The load of ^{2 to} 50 g / cm ^{2 is} less than 2 g / cm ² , so that it is difficult for the bonding surface to progress, and voids are generated in the bonding layer. When it is larger than 50 g / cm ² , plastic deformation of the sintered body occurs, which leads to deformation of the joined body, which is not preferable.

The heat treatment temperature of 1000 to 1400 ° C. is not preferable at a temperature lower than 1000 ° C. because the fusion of the joint surface does not proceed. At a temperature higher than 1400 ° C., the crystal grains of the sintered body grow abnormally. This is not preferable because the bonded body is damaged due to the microcracks.

Provided is a low thermal expansion ceramic joined body having bending strength and rigidity comparable to those of a single sintered body and small dimensional change with time.

Hereinafter, the low thermal expansion ceramic joined body of the present invention will be described in more detail.

In the low thermal expansion ceramic joined body of the present invention, the sintered bodies are joined together without providing inclusions. Therefore, there is no boundary at the joint (the part that was the joint surface), and the particles of each sintered body cause a new necking and have an integrated structure.

Such a structure can be confirmed by the following method. When a boundary exists in the joint, when the cross section perpendicular to the joint surface is observed, the particle size of the joint is different from the particle size of the other portions, so that the presence or absence of the boundary can be identified visually. Specifically, it is grasped by comparing the average particle diameter d1 of the joint portion appearing in the cross section with the average particle diameter d2 of the other portion. In the joined body of the present invention, since d1 / d2 is in the range of 0.8 to 1.2, the presence of the boundary cannot be confirmed. If the fusion is insufficient or abnormal grain growth occurs, d1 / d2 becomes smaller than 0.8 or larger than 1.2. In such a case, the boundary of the joint can be confirmed visually, and a decrease in Young's modulus and bending strength of the joined body is also observed.

The average particle size is measured by the intercept method. Specifically, it can be performed by the following procedure. After a cross section perpendicular to the joint surface of the joined body is exposed by grinding, mirror polishing is performed, and further, thermal etching treatment or the like is performed as necessary. Thereafter, the cross section is observed with an electron microscope, and a line segment of a predetermined length is drawn for the joint portion that can be confirmed by marking in advance and other portions, and the number of particles crossed by the line segment is measured. A value obtained by dividing the length of the line segment by the number of particles is defined as an average particle size (μm).

The bending strength and Young's modulus of the joined body are the same as those of the sintered body alone. Specifically, the bending strength of the joined body is 95% or more of the bending strength of the sintered body, and the Young's modulus of the joined body is 95% or more of the Young's modulus of the sintered body. As described above, since the structure of the joined body is equivalent to the sintered body in the joined portion, the bending strength and Young's modulus are hardly reduced.

There is almost no dimensional change before and after joining. Specifically, the thickness is perpendicular to the joint surface, and the dimensional change is 0.5% or less. Since there is almost no dimensional deviation before and after joining, the dimensional defect of the product can be remarkably reduced.

Next, a method for manufacturing the joined body will be described.

As a raw material lithium aluminosilicate, β-eucryptite powder may be used, or alumina, silica, and lithium oxide may be adjusted to a predetermined composition to be β-eucryptite by sintering. In any case, it is necessary to adjust the iron content to 70 to 210 ppm. If the iron content exceeds 210 ppm, the bonding temperature and the sintering temperature are remarkably lowered, so that abnormal grain growth and plastic deformation during bonding occur. On the other hand, if the content is less than 70 ppm, the sinterability of lithium aluminosilicate is lowered, so that joining becomes difficult. Examples of other impurities include alkali metal oxides and the like, and it is desirable that they are 1000 ppm or less in total.

When silicon carbide powder is added, it may be α-type or β-type, and the purity is preferably 99.9% or more. Even when silicon nitride powder is added, the purity is preferably 99.9% or more.

In order to pulverize and mix these powders, a known mixing method such as ball mill pulverization and mixing may be used, and the particle size of the mixed powder is desirably 2.0 μm or less. When the particle size of the mixed powder is larger than 2.0 μm, the sinterability is lowered and joining becomes difficult.

The sintered body is formed by a known method such as dry molding such as CIP, and after appropriately degreasing the binder component in the air, it is sintered at 1200 to 1500 ° C. in nitrogen. If it is in this temperature range, it can sinter without the problem that it cannot densify or raise | generates abnormal grain growth.

Adjustment of the surface roughness of the sintered body joint surface can be performed by a known processing method. When a surface grinder is used, it is preferable to use a grindstone with a # 100 to # 600 count.

Next, the joined surfaces are put together, a load of ^{2 to} 50 g / cm ² is applied, and a heat treatment is performed at 1000 to 1400 ° C. to obtain a joined body. The atmosphere during the heat treatment is preferably an inert atmosphere, and more preferably in nitrogen. This is because when nitrogen dissolves in eucryptite, the lattice constant expands and contracts, and in particular, the fusion in the vicinity of the joint surface easily proceeds. The heat treatment temperature is preferably equal to or lower than the firing temperature of the sintered body, and the difference between the heat treatment temperature and the firing temperature is preferably within 100 ° C. Needless to say, if the joining temperature is higher than the firing temperature, abnormal grain growth and plastic deformation occur. If the joining temperature is lower than 100 ° C. than the firing temperature, the fusion of the joining surface tends to be insufficient. There is a possibility that it cannot be joined.

EXAMPLES Hereinafter, the Example of this invention is specifically given with a comparative example, and this invention is demonstrated in detail.

First, β-eucryptite powder and silicon carbide powder were mixed in a pot mill at a ratio shown in Table 1 and dried to prepare a ceramic raw material mixed powder. This mixed powder was uniaxially pressed to prepare a molded body of 70 mm × 70 mm × 50 mm, and CIP-treated at 150 MPa. In a nitrogen atmosphere, firing was performed in the range of 1300 to 1430 ° C. to obtain a low thermal expansion ceramic sintered body.

Cut out 3 mm x 4 mm x 40 mm test pieces from the sintered body, measure the Young's modulus of these sintered bodies by the resonance method according to JIS R1602, and perform a 4-point bending test according to JIS R1601. did. Further, a 4 mm × 4 mm × 12 mm test piece was cut out from the sintered body, and the displacement amount of the test piece was measured at 20 to 30 ° C. using a laser interference thermal expansion measurement device (LIX-1 manufactured by ULVAC-RIKO), The thermal expansion coefficient was determined. When the iron content of the sintered body was measured with an ICP mass spectrometer (ICPM-8500, manufactured by Shimadzu Corporation), all were 140 ppm.

Next, the obtained sintered body was processed into 50 mm × 50 mm × 40 mm by a surface grinder, and in particular, the bonding surface (50 mm × 50 mm) was processed using a # 60 to # 170 ground diamond grindstone. The roughness was adjusted to a predetermined value. The bonded surfaces were overlapped with each other, a load of 10 g / cm ² was applied, and heat treatment was performed in a nitrogen atmosphere in the range of 1000 to 1400 ° C. to obtain a low thermal expansion ceramic bonded body.

A test piece of 3 mm × 4 mm × 40 mm was cut out from each joined body so that the joined portion was in the center, and using these test pieces, the Young's modulus of these joined bodies was measured by a resonance method according to JIS R1602, and further JIS R1601 A 4-point bending test was performed according to the above.

For comparison, a joined body in which inclusions were arranged on the joining surface was produced (Test No. 14). As a bonding material, β-eucryptite and silicon nitride were mixed in a pot mill at 65:35 and dried to prepare a mixed powder for the bonding material. This mixed powder was mixed with a 15% α-terpineol solution of ethyl cellulose so that the inorganic content was 30 vol%, and made into a paste using a three roll. A sintered body having the same composition was produced for this bonding material, and the Young's modulus and thermal expansion coefficient were determined in the same manner as the sintered body of the base material. The Young's modulus was 160 GPa and the thermal expansion coefficient was 0.01 × 10. It was ⁻⁶ / ° C. A sintered body was prepared in the same procedure as in the example, and the paste was printed on the bonding surface of the base material to a thickness of 30 μm using a screen mask to obtain a bonding material. After degreasing at 500 ° C., the printed surfaces were bonded together and a load of 20 g / cm ² was applied. Subsequently, test No. 1 in which the heat treatment was performed at a temperature of 1340 ° C. in a nitrogen atmosphere to melt the bonding material and the bonding material was interposed between the base materials. 14 joined bodies were obtained.

Moreover, the test for measuring the time-dependent change of flatness was done about the joined body of each test. Sintered body (A) 500 mm x 32 mm x 27 mm with the same composition as in each test, sintered body (B) 500 mm x 32 mm x 8 mm was machined, and the same joining conditions were used with a surface of 500 mm x 32 mm as the joint surface. Thus, a low thermal expansion ceramic joined body was produced. The upper surface (surface of 500 mm × 32 mm) of the sintered body (B) was mirror finished until the flatness was λ / 20. And the time-dependent change of flatness when 1 year passed from a process was measured. The flatness is measured using a laser interferometer type shape measuring instrument (GPI-XP manufactured by Zygo Co., Ltd.). If the change rate from the flatness λ / 20 is less than 5%, the change rate is 5%. If it was more, it was evaluated as x. The average particle size was measured by an intercept method using an electron micrograph.

The results are shown in Table 1.

Test No. within the scope of the present invention. In 1 to 10, a bonded body equivalent to the sintered body alone was obtained in terms of 4-point bending and Young's modulus. Specifically, all the bonded bodies had a 4-point bending strength of 95% or more and a Young's modulus of 95% or more with respect to the sintered body. In addition, the change with time in flatness after one year was less than 5%.

On the other hand, Test No. which is outside the scope of the present invention. In 11-13, both bending strength and Young's modulus were lower than those of the sintered body alone. In addition, Test No. in which a bonding material was interposed was used. No. 14, a bending strength and Young's modulus equivalent to those of the sintered body were obtained, but a change in flatness with time was observed.

Next, the same test was conducted by adjusting the iron content. The composition of the raw material powder was determined by test no. As in 3, the iron content was changed.

Test No. within the scope of the present invention. In Nos. 21 to 23, a joined body equivalent to the sintered body alone was obtained in both the 4-point bending and Young's modulus. However, no. In No. 24, both the 4-point bending and Young's modulus were lower than those of the sintered body alone, and a boundary was observed at the joint. In addition, No. with a large iron content. In No. 25, cracks were observed in the bonded body after bonding heat treatment, and physical properties were not measured.

Claims (5)

A low thermal expansion ceramic joined body obtained by joining sintered bodies made of low thermal expansion ceramics without providing inclusions, wherein the material constituting the sintered body is lithium aluminosilicate, silicon carbide, and / or or consists of a silicon nitride, 20 to 30 Ri average thermal expansion coefficient of ^{-1 × 10 -6 ~1 × 10 -6} / ℃ der in ° C., and the bending strength 4 points 115MPa or more, a Young's modulus of 120GPa The low thermal expansion ceramic joined body as described above, wherein iron contained in the sintered body is 70 to 210 ppm . Low thermal expansion ceramic bonding article according to claim 1, wherein the lithium aluminosilicate is β- eucryptite. The low thermal expansion ceramic joined body according to claim 1 or 2 , wherein the joined body has a four-point bending strength of 95% or more of a sintered body's four-point bending strength. The low thermal expansion ceramic joined body according to any one of claims 1 to 3, wherein Young's modulus of the joined body is 95% or more of Young's modulus of the sintered body. The composition of a sintered compact is (beta) -eucryptite 50-95 mass%, and a silicon carbide and / or silicon nitride 5-50 mass%, The low thermal expansion ceramic joined body as described in any one of Claims 2-4 .