JP2020026116A - Composite member and adhesive composition - Google Patents

Abstract

To provide a composite member capable of suppressing peeling of an adhesive member from a ceramic member or a base member and warpage of the ceramic member when being used under a high temperature.SOLUTION: A composite member has a ceramic member, a base member and an adhesive member arranged between the ceramic member and the base member and jointing the ceramic member and the base member. The adhesive member contains an addition curable silicone resin and carbon powder. A BET specific surface area of the carbon powder is 40 m/g or less.SELECTED DRAWING: Figure 3

Description

  The technology disclosed in the present specification relates to a composite member and an adhesive composition.

  As one of composite members including a base member formed of metal, a ceramic member formed of ceramics, and an adhesive member for bonding the base member and the ceramic member, a static member for holding a wafer when manufacturing a semiconductor. There is an electric chuck. The electrostatic chuck has a chuck electrode, and uses an electrostatic attraction generated when a voltage is applied to the chuck electrode to attract and hold the wafer on the surface of the ceramic member.

  As a bonding member for bonding a base member of an electrostatic chuck and a ceramic member, a member including a silicone resin is known (for example, see Patent Document 1).

JP 2014-207374 A

  In recent years, some of the semiconductor manufacturing processes may be performed at a high temperature of about 200 ° C. In such a case, it is required that the electrostatic chuck maintain good physical properties even at a high temperature. For example, there is a large difference in thermal expansion between the ceramic constituting the ceramic member of the electrostatic chuck and the material (eg, metal) constituting the base member. For this reason, an adhesive member for adhering the ceramic member and the base member is required to maintain not only adhesiveness but also flexibility even at a high temperature in order to reduce the difference in thermal expansion.

  In addition, such a problem is not limited to the electrostatic chuck including the bonding member for bonding the base member and the ceramic member, but also includes another holding device such as a vacuum chuck including the bonding member and the bonding member. This is a problem common to other composite members such as parts for semiconductor manufacturing equipment such as a shower head.

  This specification discloses a technique capable of solving the above-described problem.

  The technology disclosed in this specification can be realized, for example, as the following modes.

(1) A composite member disclosed in the present specification includes a ceramic member, a base member having a coefficient of thermal expansion different from that of the ceramic member, and a member arranged between the ceramic member and the base member. In a composite member including an adhesive member for joining the ceramic member and the base member, the adhesive member includes an addition-curable silicone resin and a carbon powder, and a BET specific surface area of the carbon powder is 40 m. ² / g or less.

  The composite member contains an addition-curable silicone resin as an adhesive member. Addition-curable silicone resins have good flexibility. Therefore, good flexibility of the adhesive member can be maintained. Further, since the addition-curable silicone resin is a type of resin that is cured by addition polymerization, there is no generation of by-products that occur when the condensation-curable silicone resin is cured. Therefore, no bubbles are generated due to the by-products, and no bubbles remain in the cured adhesive member. Therefore, since the adhesion between the bonding member, the ceramic member, and the base member is not hindered by air bubbles, good adhesion between the bonding member, the ceramic member, and the base member can be maintained.

  In the present composite member, the adhesive member contains carbon powder. Since carbon powder has a radical scavenging ability, it can scavenge radicals generated when the composite member is used at a high temperature of about 200 ° C. For this reason, chain degradation of the addition-curable silicone resin due to radicals can be suppressed, and good flexibility of the adhesive member can be maintained.

Further, the BET specific surface area of the carbon powder contained in the adhesive member of the present composite member is 40 m ² / g or less. With such a configuration, the amount of the addition-curable silicone resin that coats the surface of the carbon powder is smaller than when the BET specific surface area of the carbon powder exceeds 40 m ² / g. The amount of the addition-curable silicone resin that can flow between the powder and the powder is large. Thereby, in the present composite member, the increase in the viscosity of the addition-curable silicone resin is suppressed, and the excellent flexibility of the adhesive member can be maintained.

  As described above, according to the present composite member, since the adhesive member has good flexibility, the difference in thermal expansion coefficient between the ceramic member and the base member when the composite member is used at a high temperature of about 200 ° C. The thermal stress caused by the above is alleviated. Therefore, in the present composite member, it is possible to suppress a decrease in flatness of the ceramic member due to warpage or the like of the ceramic member.

  For example, when the composite member is used as a holding device such as an electrostatic chuck for holding an object such as a wafer, an adhesive member and a ceramic member can be used even when the electrostatic chuck is used at a high temperature of about 200 ° C. In addition, it is possible to maintain good adhesion to the base member, and to suppress a decrease in flatness of the ceramic member. For this reason, also in the electrostatic chuck, it is possible to suppress the decrease in the flatness of the ceramic member while improving the controllability of the temperature distribution of the object.

(2) The composite member disclosed in the present specification includes a ceramic member, a base member having a coefficient of thermal expansion different from that of the ceramic member, and a member arranged between the ceramic member and the base member. In a composite member including an adhesive member that joins the ceramic member and the base member, the adhesive member includes an addition-curable silicone resin and a carbon powder, and is an average of primary particles constituting the carbon powder. The particle size is 80 nm or more.

  The composite member contains an addition-curable silicone resin as an adhesive member. Addition-curable silicone resins have good flexibility. Therefore, good flexibility of the adhesive member can be maintained. Further, since the addition-curable silicone resin is a type of resin that is cured by addition polymerization, there is no generation of by-products that occur when the condensation-curable silicone resin is cured. Therefore, no bubbles are generated due to the by-products, and no bubbles remain in the cured adhesive member. Therefore, since the adhesion between the bonding member, the ceramic member, and the base member is not hindered by air bubbles, good adhesion between the bonding member, the ceramic member, and the base member can be maintained.

  Further, in the present composite member, the adhesive member contains carbon powder. Since carbon powder has a radical scavenging ability, it can scavenge radicals generated when the composite member is used at a high temperature of about 200 ° C. For this reason, chain degradation of the addition-curable silicone resin due to radicals can be suppressed, and good flexibility of the adhesive member can be maintained.

  The average particle size of the primary particles constituting the carbon powder contained in the adhesive member of the present composite member is 80 nm or more. Because of such a configuration, an addition-curable type that coats the surface of the carbon powder as compared with a case where the average particle diameter of primary particles constituting the carbon powder (hereinafter, also referred to as “average primary particle diameter”) is less than 80 nm. The amount of silicone resin is small, and the amount of addition-curable silicone resin that can flow between carbon powders in the entire adhesive member is large. Thereby, in the present composite member, the increase in the viscosity of the addition-curable silicone resin is suppressed, and the excellent flexibility of the adhesive member can be maintained.

  As described above, according to the present composite member, since the adhesive member has good flexibility, the difference in thermal expansion coefficient between the ceramic member and the base member when the composite member is used at a high temperature of about 200 ° C. The thermal stress caused by the above is alleviated. Therefore, in the present composite member, it is possible to suppress a decrease in flatness of the ceramic member due to warpage or the like of the ceramic member.

  For example, when the composite member is used as a holding device such as an electrostatic chuck for holding an object such as a wafer, an adhesive member and a ceramic member can be used even when the electrostatic chuck is used at a high temperature of about 200 ° C. In addition, it is possible to maintain good adhesion to the base member, and to suppress a decrease in flatness of the ceramic member. For this reason, also in the electrostatic chuck, it is possible to suppress the decrease in the flatness of the ceramic member while improving the controllability of the temperature distribution of the object.

(3) In the composite member, the carbon powder may be one or more selected from the group consisting of carbon black, carbon fiber, carbon nanotube, and graphene. According to the present composite member, radicals generated when the present composite member is used at a high temperature of about 200 ° C. can be effectively captured. For this reason, chain degradation of the addition-curable silicone resin due to radicals can be suppressed, and good flexibility of the adhesive member can be maintained. Also, carbon black is easily available on the market.

(4) In the composite member, the carbon powder is carbon black, and the amount of the carbon black in the adhesive member is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin. May be adopted. When the addition amount of carbon black in the composite member is less than 2 parts by weight with respect to 100 parts by weight of the addition-curable silicone resin, the degree of increase in rubber hardness after use at a high temperature increases, and After use, the degree of reduction in shear bond strain increases. If the amount of carbon black in the composite member exceeds 20 parts by weight with respect to 100 parts by weight of the addition-curable silicone resin, the amount of the addition-curable silicone resin coating the surface of the carbon black is large, and Since the amount of the addition-curable silicone resin capable of flowing between carbon black and carbon black is small, the viscosity of the resin is increased, and the flexibility is lowered at the time of curing, that is, before use at a high temperature. In addition, the degree of increase in rubber hardness after use at high temperatures increases. In the present composite member, the addition amount of carbon black in the adhesive member is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin, so that the adhesive member exhibits a good paste viscosity, Good rubber hardness and good shear bond distortion can be exhibited even after use at high temperatures. In the present composite member, since the adhesive member having such characteristics is used, good flexibility can be effectively maintained even after use at high temperatures.

(5) In the composite member, the ratio of the rubber hardness of the heated adhesive member after the adhesive member is further heated at 240 ° C. for 2,000 hours to the rubber hardness of the adhesive member may be 1.2 or less. Good. That is, in the present composite member, the degree of curing deterioration of the adhesive member caused by using the present composite member at a high temperature for a long time is low. Therefore, the adhesive member of the present composite member can maintain good flexibility before long-time use at high temperature even after long-time use at high temperature.

(6) In the above composite member, a ratio of a shear bond distortion of the heated adhesive member after the adhesive member is further heated at 240 ° C. for 2,000 hours to a shear bond distortion of the adhesive member is 0.8 or more. It may be. That is, in the present composite member, the degree of curing deterioration of the adhesive member caused by using the present composite member at a high temperature for a long time is low. Therefore, the adhesive member of the present composite member can maintain good flexibility before long-time use at high temperature even after long-time use at high temperature.

(7) The adhesive composition disclosed in this specification is an adhesive composition containing an addition-curable silicone resin and carbon powder, wherein the carbon powder has a BET specific surface area of 40 m ² / g or less. is there. According to the present adhesive composition, as described above, good flexibility can be maintained even when used at a high temperature of about 200 ° C.

(8) The adhesive composition disclosed in this specification is an adhesive composition containing an addition-curable silicone resin and carbon powder, wherein the average particle diameter of primary particles constituting the carbon powder is 80 nm. That is all. According to the present adhesive composition, as described above, good flexibility can be maintained even when used at a high temperature of about 200 ° C.

(9) In the adhesive composition, the ratio of the paste viscosity at a shear rate of 1 s ^-1 of the adhesive composition to the paste viscosity at a shear rate of 10 s ^-1 of the adhesive composition is 2.4 or less. It may be configured. In other words, in the present adhesive composition, since the thixotropy is small and the flowability is good, similarly, in the composition to which carbon black is added, more flexible curing even after being sufficiently heated at 240 ° C. for 2,000 hours. Things are obtained. For example, when the present adhesive composition is used for a composite member as an adhesive member, since the adhesive member having such characteristics is used as the adhesive member, even after being used at a high temperature, Good flexibility can be effectively maintained.

  The technology disclosed in the present specification can be realized in various forms. For example, a holding device such as an electrostatic chuck, a component for a semiconductor manufacturing device such as a shower head, and a manufacturing method thereof. And the like.

FIG. 1 is a perspective view schematically showing an external configuration of an electrostatic chuck 100 according to the embodiment. FIG. 2 is an explanatory diagram schematically showing an XZ cross-sectional configuration of the electrostatic chuck 100 according to the embodiment. FIG. 9 is an explanatory diagram showing performance evaluation results. FIG. 9 is an explanatory diagram showing performance evaluation results. It is explanatory drawing which shows roughly the measuring method of the average particle diameter of the primary particle and secondary particle which comprise a carbon powder. It is explanatory drawing which shows typically the identification method of shear adhesion distortion.

A. Embodiment:
A-1. Configuration of electrostatic chuck 100:
FIG. 1 is a perspective view schematically illustrating an external configuration of the electrostatic chuck 100 according to the present embodiment, and FIG. 2 is an explanatory diagram schematically illustrating an XZ cross-sectional configuration of the electrostatic chuck 100 according to the present embodiment. . Each drawing shows XYZ axes orthogonal to each other for specifying the direction. In this specification, for the sake of convenience, the positive direction of the Z axis is referred to as an upward direction, and the negative direction of the Z axis is referred to as a downward direction. However, the electrostatic chuck 100 is actually installed in a direction different from such a direction. May be done.

  The electrostatic chuck 100 is a device that attracts and holds an object (for example, a wafer W) by electrostatic attraction, and is used, for example, for fixing the wafer W in a vacuum chamber of a semiconductor manufacturing apparatus. The electrostatic chuck 100 includes a ceramic member 10 and a base member 20 arranged side by side in a predetermined arrangement direction (in the present embodiment, a vertical direction (Z-axis direction)). The ceramic member 10 and the base member 20 are arranged such that the lower surface S2 of the ceramic member 10 (see FIG. 2) and the upper surface S3 of the base member 20 face each other in the arrangement direction. The electrostatic chuck 100 further includes an adhesive member 30 disposed between the lower surface S2 of the ceramic member 10 and the upper surface S3 of the base member 20. The electrostatic chuck 100 corresponds to a composite member in the claims.

  The ceramic member 10 is a plate-shaped member having a substantially circular upper surface S1 (hereinafter, also referred to as “adsorption surface S1”) substantially orthogonal to the above-described arrangement direction (Z-axis direction), and is formed of ceramics. The diameter of the ceramic member 10 is, for example, about 100 mm to 500 mm (generally, about 200 mm to 350 mm), and the thickness of the ceramic member 10 is, for example, about 1 mm to 10 mm.

Various ceramics can be used as a material for forming the ceramic member 10. For example, aluminum oxide (alumina, Al ₂ O ₃ ) or aluminum nitride (AlN) is used in view of strength, wear resistance, plasma resistance, and the like. It is preferable to use a ceramic mainly composed of Here, the main component means a component having the largest content ratio (weight ratio).

  Inside the ceramic member 10, a chuck electrode 40 formed of a conductive material (for example, tungsten, molybdenum, platinum, or the like) is provided. When a voltage is applied to the chuck electrode 40 from a power supply (not shown), an electrostatic attraction is generated, and the wafer W is fixed to the suction surface S1 of the ceramic member 10 by the electrostatic attraction.

  Further, inside the ceramic member 10, a heater electrode 50 formed of a resistance heating element containing a conductive material (for example, tungsten, molybdenum, platinum, or the like) is provided. The shape of the heater electrode 50 as viewed in the Z-axis direction is, for example, a substantially spiral shape. When a voltage is applied to the heater electrode 50 from a power supply (not shown), the heater electrode 50 generates heat, thereby heating the ceramic member 10 and the wafer W held on the suction surface S1 of the ceramic member 10. Thereby, the temperature control of the wafer W is realized.

  The base member 20 is, for example, a substantially circular flat plate-shaped member having the same diameter as the ceramic member 10 or having a larger diameter than the ceramic member 10. The diameter of the base member 20 is, for example, about 220 mm to 550 mm (usually, about 220 mm to 350 mm), and the thickness of the base member 20 is, for example, about 20 mm to 40 mm. The base member 20 has a coefficient of thermal expansion different from the coefficient of thermal expansion of the ceramic member 10, and is formed of, for example, a metal or various composite materials. As the metal, Al (aluminum), Ti (titanium), or an alloy thereof is preferably used. As the composite material, it is preferable to use a composite material in which a porous ceramic mainly composed of silicon carbide (SiC) is melted with an aluminum alloy mainly composed of aluminum and is infiltrated with pressure. The aluminum alloy contained in the composite material may contain Si (silicon) or Mg (magnesium), or may contain other elements within a range that does not affect properties and the like.

  A coolant channel 21 is formed inside the base member 20. When a coolant (for example, a fluorine-based inert liquid or water) flows through the coolant channel 21, the base member 20 is cooled. The ceramic member 10 is cooled by heat transfer (heat drawing) between the base member 20 and the ceramic member 10 via the bonding member 30, and the wafer W held on the suction surface S1 of the ceramic member 10 is cooled. Thereby, control of the temperature distribution of the wafer W is realized.

  The bonding member 30 is disposed between the lower surface S2 of the ceramic member 10 and the upper surface S3 of the base member 20, and joins the ceramic member 10 and the base member 20. The thickness of the bonding member 30 is, for example, about 0.1 mm to 1 mm. Note that the adhesive member 30 may be disposed on the entire lower surface S2 of the ceramic member 10, or may be disposed on only a part of the lower surface S2.

A-2. Detailed configuration of the bonding member 30:
Next, the configuration of the bonding member 30 will be described in detail.

A-2-1. Composition of adhesive member 30:
First, the composition of the bonding member 30 will be described.

  In the present embodiment, the adhesive member 30 is an adhesive composition containing an addition-curable silicone resin and carbon powder (hereinafter, also referred to as an “addition-curable silicone resin composition”).

  The addition-curable silicone resin comprises at least (A) an organosiloxane having at least two silicon-bonded alkenyl groups in one molecule (hereinafter referred to as “component A”), and (B) at least two organosiloxanes in one molecule. It includes an organosiloxane having a silicon-bonded hydrogen atom (specifically, a hydrosilyl group) (hereinafter, referred to as “component B”), and (C) a catalyst for hydrosilylation reaction (hereinafter, referred to as “component C”).

  As the alkenyl group in the component A, for example, a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexenyl group, or the like can be used. The alkenyl group in component A is more preferably a vinyl group or a hexenyl group. Two or more alkenyl groups in the component A can be used in combination. The alkenyl group is usually bonded to a silicon atom of the polyorganosiloxane forming the main chain or the skeleton (for example, a terminal silicon atom or a silicon atom inside the main chain).

  Examples of the polyorganosiloxane forming the main chain or the skeleton include, for example, polydimethylsiloxane, polydiethylsiloxane, polyalkylalkylsiloxane (polydialkylsiloxane) such as polymethylethylsiloxane, and polyalkylarylsiloxane. In addition, a copolymer (for example, poly (dimethylsiloxane-diethylsiloxane) or the like) using a plurality of silicon atom-containing monomer components can be used. The polyorganosiloxane forming the main chain or the skeleton is more preferably polydimethylsiloxane. The polyorganosiloxanes forming the main chain or skeleton can be used in combination of two or more.

  That is, as the polyorganosiloxane containing an alkenyl group as a functional group in the molecule, for example, polydimethylsiloxane having a vinyl group as a functional group, polydimethylsiloxane having a hexenyl group as a functional group, or a mixture thereof can be used. .

  Component B is a component that acts as a crosslinking agent. Specifically, the silicon-bonded hydrogen atom (hydrosilyl group (Si-H group)) in the component B undergoes an addition reaction with the silicon-bonded alkenyl group in the component A to be cross-linked to form a cured product. The silicon atom having a Si—H bond in the component B may be any of a silicon atom in a main chain and a silicon atom in a side chain. That is, the silicon atom having a Si—H bond in the component B may be contained as a constituent unit of the main chain, or may be contained as a constituent unit of the side chain. The number of silicon atoms in the Si—H bond is not particularly limited as long as it is three or more in one molecule.

As the component B, any conventionally known crosslinking agent can be used and is not particularly limited. Component B is preferably an organohydrogenpolysiloxane having at least three hydrosilyl groups in one molecule. As such a component B, for example, polymethylhydrogensiloxane, poly (dimethylsiloxane-methylhydrogensiloxane), or the like can be used. In addition, the said component B can be used individually by 1 type or in combination of 2 or more types. The addition amount of the component B, the mol ratio of _[CH 2 = CH-] groups [Si-H] group and in component A in component B and _{"[Si-H] / [CH} 2 = CH-] " When represented, the value is 0.5 or more and 1.5 or less. If the amount is less than 0.5, the crosslinking of the polyorganosiloxane tends to be insufficient, and sufficient strength tends not to be obtained. On the other hand, if the added amount exceeds 1.5, the crosslinking proceeds excessively, and the flexibility tends to be lost. The addition amount is more preferably 0.7 or more and 1.3 or less, and still more preferably 0.9 or more and 1.1 or less.

  Component C is a component that promotes the curing of the addition-curable silicone resin by promoting the hydrosilylation reaction between the alkenyl group and the silicon-bonded hydrogen atom. As the component C, any conventionally known curing catalyst can be used and is not particularly limited. As the component C, for example, organotin, inorganic tin, a titanium catalyst, a bismuth catalyst, a metal complex, a platinum catalyst, a basic substance, an organic phosphor and the like can be used. Component C is more preferably a platinum catalyst or a rhodium catalyst. The platinum catalyst is, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, or a platinum complex having a chelate structure. In addition, the above curing catalysts can be used alone or in combination of two or more. The amount of the curing catalyst to be added is 5 ppm or more and 100 ppm or less by weight of platinum based on the polyorganosiloxane. If the amount is less than 5 ppm, the curing of the polyorganosiloxane tends to be insufficient. On the other hand, if the added amount exceeds 100 ppm, the progress of the curing is accelerated, so that a uniform composition tends not to be obtained. The added amount is more preferably 10 ppm or more and 70 ppm or less, and further preferably 15 ppm or more and 40 ppm or less.

  The carbon powder contained in the adhesive composition that constitutes the adhesive member 30 of the present embodiment captures radicals that deteriorate the addition-curable silicone resin, and aims to suppress the curing deterioration of the addition-curable silicone resin. Is added. By suppressing the curing deterioration of the addition-curable silicone resin, the flexibility of the adhesive member 30 can be easily maintained. Further, by suppressing the curing deterioration of the addition-curable silicone resin, it becomes easy to suppress the density unevenness of the adhesive member 30. This is because it is considered that the density unevenness of the adhesive member 30 occurs as a result of a change in a component in the adhesive composition constituting the adhesive member 30. As described above, since the density unevenness can be suppressed, it is easy to make the thermal conductivity of the bonding member 30 uniform, and thus the variation in the surface temperature of the wafer W held by the electrostatic chuck 100 is reduced ( It is easy to improve the controllability of the temperature distribution of the wafer W). As the carbon powder, for example, carbon black, carbon fiber, carbon nanotube, graphene, or the like can be used. The carbon powder is more preferably carbon black. In addition, two or more kinds of the above carbon powders can be used in combination.

  When carbon black is employed as the carbon powder to be added to the adhesive member 30 of the present embodiment, the amount of carbon black added is 100 parts by weight of the addition-curable silicone resin in the adhesive composition (that is, the adhesive member 30). 2 parts by weight or more and 20 parts by weight or less. When the addition amount of the carbon black is less than 2 parts by weight, the degree of increase in rubber hardness after use at a high temperature increases, and the degree of reduction in shear bond strain after use at a high temperature tends to increase. There is. This is because it is not possible to sufficiently capture radicals that deteriorate the addition-curable silicone resin and to suppress curing deterioration of the addition-curable silicone resin. If the addition amount exceeds 20 parts by weight, the amount of the addition-curable silicone resin that coats the surface of the carbon black is large, and the addition-curable silicone resin that can flow between the carbon black and the carbon black in the entire adhesive member. Since the amount of the resin is small, the viscosity of the resin becomes high, and the flexibility tends to decrease from the time of curing, that is, before use at a high temperature. On the other hand, if the addition amount is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin, the degree of increase in rubber hardness after use at a high temperature becomes small, and There is a tendency for the degree of reduction in shear bond strain after use at high temperatures to be reduced. If the addition amount is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin, the addition-curable silicone capable of flowing between carbon black and carbon black in the entire adhesive member. Since the amount of the resin can be satisfactorily secured, the increase in the viscosity of the resin can be suppressed. This makes it easy to reduce the variation in sheet thickness (reducing the variation in sheet thickness) when producing an adhesive sheet from the adhesive composition, and to apply the adhesive paste produced from the adhesive composition to a ceramic member. When applying to the base member 20 and the base member 20, it is easy to apply the coating more uniformly (reduction in coating unevenness). By facilitating the reduction in the variation in the sheet thickness and the reduction in the uneven coating, the heat transfer becomes uniform throughout the adhesive member 30, and the temperature distribution of the ceramic member 10 becomes uniform. The addition amount is more preferably 3 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin, and still more preferably 5 parts by weight based on 100 parts by weight of the addition-curable silicone resin. Not less than 10 parts by weight.

The BET specific surface area of the carbon powder added to the bonding member 30 of the present embodiment is 40 m ² / g or less. When the BET specific surface area exceeds 40 m ² / g, the amount of the addition-curable silicone resin coating the surface of the carbon powder is large, and the addition-curable silicone resin capable of flowing between the carbon powder and the carbon powder in the entire adhesive member 30. Since the amount of the silicone resin is small, the viscosity of the resin becomes high, and the flexibility tends to decrease from the time of curing, that is, before use at a high temperature. On the other hand, when the BET specific surface area is 40 m ² / g or less, it is possible to satisfactorily secure the amount of the addition-curable silicone resin that can flow between the carbon powder and the carbon powder in the entire adhesive member 30. Therefore, an increase in the viscosity of the resin can be suppressed. This makes it easy to reduce the variation in sheet thickness (reducing the variation in sheet thickness) when producing an adhesive sheet from the adhesive composition, and to apply the adhesive paste produced from the adhesive composition to a ceramic member. When applying to the base member 20 and the base member 20, it is easy to apply the coating more uniformly (reduction in coating unevenness). By facilitating the reduction in the variation in the sheet thickness and the reduction in the uneven coating, the heat transfer becomes uniform throughout the adhesive member 30, and the temperature distribution of the ceramic member 10 becomes uniform. The BET specific surface area of the carbon powder is more preferably 35 m ² / g or less, further preferably 25 m ² / g or less. The BET specific surface area of the carbon powder can be measured as follows. First, a carbon powder sample is degassed at 100 ° C. for 60 minutes. Next, measurement is performed by the BET flow method (one-point method). The gas at the time of measurement is a mixed gas of He and N _2, and their volume ratio is He: N ₂ = 7: 3. The average value of the three measurements is defined as the BET specific surface area.

  The average primary particle size of the primary particles constituting the carbon powder added to the adhesive member 30 of the present embodiment (hereinafter, also simply referred to as “average primary particle size of the carbon powder”) is 80 nm or more. When the average primary particle diameter is less than 80 nm, the amount of the addition-curable silicone resin that coats the surface of the carbon powder is large, and the addition-curable silicone that can flow between the carbon powder and the carbon powder in the entire adhesive member 30. Since the amount of the resin is small, the viscosity of the resin becomes high, and the flexibility tends to decrease from the time of curing, that is, before use at a high temperature. On the other hand, when the average primary particle diameter is 80 nm or more, the amount of the addition-curable silicone resin that can flow between the carbon powder and the carbon powder in the entire adhesive member 30 can be sufficiently secured. An increase in the viscosity of the resin can be suppressed. This makes it easy to reduce the variation in sheet thickness (reducing the variation in sheet thickness) when producing an adhesive sheet from the adhesive composition, and to apply the adhesive paste produced from the adhesive composition to a ceramic member. When applying to the base member 20 and the base member 20, it is easy to apply the coating more uniformly (reduction in coating unevenness). By facilitating the reduction in the variation in the sheet thickness and the reduction in the uneven coating, the heat transfer becomes uniform throughout the adhesive member 30, and the temperature distribution of the ceramic member 10 becomes uniform. The average primary particle diameter of the carbon powder is more preferably 90 nm or more, and further preferably 100 nm or more.

  In addition, as shown in FIG. 5, the carbon powder usually exists as secondary particles Ps in a state where spherical primary particles Pp are aggregated. The average secondary particle diameter of the carbon powder (secondary particles) added to the adhesive member 30 of the present embodiment is preferably 0.1 μm or more and 300 μm or less. When the average secondary particle diameter is less than 0.1 μm, the amount of the addition-curable silicone resin coating the surface of the carbon powder is large, and the addition that can flow between the carbon powder and the carbon powder in the entire adhesive member 30 is performed. Since the amount of the curable silicone resin is small, the viscosity of the resin becomes high, and the flexibility tends to decrease at the time of curing, that is, before use at a high temperature. Further, when the average secondary particle size exceeds 300 μm, when applying the adhesive paste prepared from the adhesive composition to the ceramic member 10 or the base member 20, the surface of the coating film of the adhesive paste is coated with carbon powder. Irregularities due to secondary particles are formed, and it tends to be difficult to apply uniformly. On the other hand, when the average secondary particle diameter is 0.1 μm or more and 300 μm or less, the amount of the addition-curable silicone resin that can flow between the carbon powder and the carbon powder in the entire adhesive member 30 is sufficiently secured. Therefore, it is possible to suppress an increase in the viscosity of the resin. This makes it easy to reduce the variation in sheet thickness (reducing the variation in sheet thickness) when producing an adhesive sheet from the adhesive composition, and to apply the adhesive paste produced from the adhesive composition to a ceramic member. When applying to the base member 20 and the base member 20, it is easy to apply the coating more uniformly (reduction in coating unevenness). By facilitating the reduction in the variation in the sheet thickness and the reduction in the uneven coating, the heat transfer becomes uniform throughout the adhesive member 30, and the temperature distribution of the ceramic member 10 becomes uniform. The average secondary particle diameter of the carbon powder is more preferably 0.2 μm or more and 150 μm or less, and still more preferably 0.3 μm or more and 100 μm or less.

  FIG. 5 is an explanatory view schematically showing a method for measuring the average primary particle diameter and the average secondary particle diameter of the carbon powder. The average primary particle size of the carbon powder can be determined by observation using a scanning electron microscope (SEM). The average primary particle diameter of the carbon powder is obtained by observing the carbon powder (secondary particles) at a magnification of about 50,000 times by SEM, and measuring the particle diameter (diameter Dpp) of 100 observable primary particles Pp. The average value of the measured diameters Dpp of the 100 primary particles Pp is defined as the average primary particle diameter.

  The secondary particles Ps of the carbon powder are aggregates in which a plurality of primary particles Pp are fused, and their normal shape is irregular. The average secondary particle diameter Dps of the carbon powder is the diameter of a sphere Sp having the same volume as the volume occupied by the secondary particles Ps. The average secondary particle size Dps is determined by a mass average value D50 in a particle size distribution measurement using a known particle size distribution measuring device (for example, a laser diffraction / scattering type particle size distribution measuring device Microtrac MT3300EXII manufactured by Microtrac Bell Inc.). (Or median diameter). In the particle size distribution measurement, a solution in which carbon powder is dispersed in a dispersion medium (for example, ethanol) can be used as a sample. In addition, since the primary particles of the carbon powder are fused, they are not crushed by an impact or energy that is sufficient to disperse them in the dispersion medium. Therefore, the average secondary particle diameter of the carbon powder can be measured in the particle size distribution measurement by the laser light diffraction method.

  In addition, the BET specific surface area, the average primary particle diameter, and the addition amount of the carbon powder contained in the adhesive composition (the cured adhesive composition) that has been bonded to the adherend can be measured by the following methods. . First, the adhesive composition is scraped off from the adherend using a knife or the like, and the cured adhesive composition is dissolved. Next, the carbon powder and the filler are separated from the obtained solution of the adhesive composition. Thereafter, the separated carbon powder and the filler are dried to obtain the carbon powder and the filler in the state of the secondary particles. Using the obtained carbon powder, the BET specific surface area and the average primary particle diameter can be measured by the above-described method. In addition, the respective addition amounts (%) of the carbon powder and the filler are calculated by dividing the respective weights of the obtained carbon powder and the filler by the weight of the adhesive composition before melting. Can be. Based on the calculated addition amount (%), the respective addition amounts (parts by weight) of the carbon powder and the filler with the silicone resin being 100 parts by weight can be calculated.

  For example, carbon black can be separated from an adhesive composition containing a silicone resin, a filler, and carbon black as carbon powder by the following method. First, a silicone resin in the above-mentioned cured adhesive composition is mixed with a known dissolving agent, for example, KSR-1, KSR-2 (all manufactured by Kanto Chemical Co., Ltd.), Dynasolve 711 (Air Brown Co., Ltd.), silicon Dissolve using cleaners X-50, X-100, X-200, X-300 and resin cleaner EX-100 (all manufactured by Nissin Chemical Laboratory Co., Ltd.). Next, the carbon black and the filler are separated from the solution of the silicone resin by using a known separation membrane, for example, a mesh, filter paper, or a membrane filter. Here, the average secondary particle diameter of the carbon black is 0.1 μm or more and 300 μm or less as described above, and the average particle diameter of the filler is 5 nm or more and 50 μm or less as described later. For this reason, the carbon black and the filler can be separated from the solution of the silicone resin by variously changing the opening diameter of the separation membrane or by combining with the separation method described below. This is because if a separation membrane having a large opening diameter is used, a filler having a large particle diameter can be separated, and a filler having a small particle diameter remains in the liquid. Other methods of separation include gravity (difference in falling speed and drop position of particles during sedimentation) applied to carbon black and filler particles depending on the size and density of carbon black and filler, and inertial force (in fluids). The inertia force of the silicone resin) and the centrifugal force (swirl of the fluid, centrifugal separation) and the sedimentation speed of the carbon black and the filler in the solution of the silicone resin. It is also possible to separate the carbon black and the filler from each other.

  The adhesive composition may include other components in addition to the addition-curable silicone resin and the carbon powder. Other components include, for example, a filler, a silane coupling agent, a reaction inhibitor, and a viscosity modifier.

  The filler can be added for the purpose of controlling at least one of the thermal conductivity and strength of the adhesive composition constituting the adhesive member 30 and adjusting the viscosity. As the filler, any conventionally known filler can be used and is not particularly limited. As the filler, for example, silica (eg, wet silica, dry silica, fumed silica, fused silica, or fused spherical silica), alumina, aluminum nitride, boron nitride, zirconia, silicon nitride, silicon carbide, or silicon carbide is used. Can be used. The filler is more preferably silica, alumina, aluminum nitride, or boron nitride, and even more preferably, alumina or aluminum nitride. In addition, two or more kinds of the above fillers can be used in combination.

  The average particle size of the filler added to the adhesive composition constituting the adhesive member 30 of the present embodiment is not particularly limited, but is preferably 5 nm or more and 50 μm or less. When the average particle diameter is less than 5 nm, the specific surface area of the filler becomes large, so that more addition-curable silicone resins cover the surface of the filler than when the specific surface area of the filler is small. For this reason, there is little addition-curable silicone resin that can flow between fillers in the entire adhesive composition, the viscosity of the resin increases, and, consequently, the moldability during sheet molding or the like tends to decrease. There is. On the other hand, when the average particle diameter exceeds 50 μm, the particle diameter is large, and it becomes more difficult to control the sheet thickness at the time of sheet molding or the like as compared with the case where the particle diameter is small. The flatness on the surface tends to decrease. The average particle size of the filler is more preferably 50 nm or more and 40 μm or less, and still more preferably 100 nm or more and 30 μm or less. The average particle diameter of the filler can be determined as a mass average value D50 (or median diameter) in particle size distribution measurement by a laser light diffraction method. The shape of the filler component is not particularly limited.

  The surface of the filler added to the adhesive composition constituting the adhesive member 30 of the present embodiment may be subjected to a hydrophobic treatment (surface treatment) from the viewpoint of improving the dispersibility in the polyorganosiloxane. For example, silica as a filler may be surface-treated with a surface treating agent such as an organosilane, an organosilazane, or an organosilicon compound such as diorganopolysiloxane. The amount of the surface treatment agent added and the surface treatment method are not particularly limited.

  The filler added to the adhesive composition constituting the adhesive member 30 of the present embodiment may be added to the adhesive composition in the form of a powder, or a slurry in which the filler is dispersed in an organic solvent. It may be added to the adhesive composition in a state.

  The amount of the filler added to the adhesive composition constituting the adhesive member 30 of the present embodiment is 1 part by weight or more and 600 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin. If the amount is less than 1 part by weight, the effect of controlling the thermal conductivity and strength or adjusting the viscosity tends to be hardly obtained. On the other hand, if the amount exceeds 600 parts by weight, the flexibility of the adhesive composition tends to decrease. The addition amount of the filler is more preferably 100 parts by weight or more and 500 parts by weight or less, and further preferably 200 parts by weight or more and 400 parts by weight or less.

  The silane coupling agent added to the adhesive composition constituting the adhesive member 30 of the present embodiment can be added for the purpose of imparting adhesiveness. Any conventionally known silane coupling agent can be used as the silane coupling agent, and is not particularly limited. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrismethoxyethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Mercaptopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane can be used. The silane coupling agents can be used alone or in combination of two or more. The addition amount of the silane coupling agent is 0.1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the silicone resin. If the amount is less than 0.1 part by weight, sufficient adhesiveness tends not to be provided to the adhesive composition. On the other hand, if the amount exceeds 20 parts by weight, curing of the polyorganosiloxane tends to be inhibited. The addition amount is more preferably 0.5 part by weight or more and 15 parts by weight or less, and still more preferably 1 part by weight or more and 10 parts by weight or less. In addition, you may use a titanate coupling agent or an aluminate coupling agent instead of the said silane coupling agent.

  The reaction inhibitor can be added for the purpose of adjusting the curing speed of the adhesive composition. Any conventionally known reaction inhibitor can be used as the reaction inhibitor, and is not particularly limited. As a reaction inhibitor, for example, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxy Cyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7- Tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, Li allyl isocyanurate and the like. The reaction inhibitor is more preferably 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyl Disiloxane and triallyl isocyanurate. In addition, the said reaction inhibitor can be used individually by 1 type or in combination of 2 or more types. The addition amount of the reaction inhibitor is 10 parts by weight or less based on 100 parts by weight of the silicone resin. When the amount exceeds 10 parts by weight, normal curing is inhibited, and poor curing tends to occur. The addition amount of the reaction inhibitor is more preferably 0.1 part by weight or more and 6 parts by weight or less, and further preferably 0.2 parts by weight or more and 2 parts by weight or less. The reaction inhibitor is optionally added as necessary to control the catalytic activity of a platinum catalyst or the like and to prevent the adhesive composition from thickening or gelling before heat curing. .

  The viscosity modifier can be added for the purpose of adjusting the viscosity of the addition-curable silicone resin in order to reduce the variation in the thickness of the sheet when the adhesive sheet is produced. Any conventionally known viscosity modifier can be used as the viscosity modifier, and is not particularly limited. Examples of the viscosity modifier include fumed silica, fumed silica, colloidal silica, fumed alumina, fumed alumina, and colloidal alumina. The viscosity modifier is more preferably fumed silica or fumed alumina. In addition, the said viscosity modifier can be used individually by 1 type or in combination of 2 or more types. The surface of the viscosity modifier may be subjected to a hydrophobic treatment (surface treatment) or the like. The amount of the viscosity modifier to be added is 0.05 to 10 parts by weight based on 100 parts by weight of the silicone resin. If the amount is less than 0.05 part by weight, the effect of adjusting the viscosity tends not to be obtained. On the other hand, when the addition amount exceeds 10 parts by weight, the viscosity tends to increase too much, the fluidity decreases, and the variation in sheet thickness tends to increase. The addition amount of the viscosity modifier is more preferably 0.1 part by weight or more and 5 parts by weight or less, further preferably 0.5 part by weight or more and 2 parts by weight or less.

A-2-2. Physical properties of the bonding member 30:
Next, physical properties of the adhesive member 30 and the adhesive composition will be described.

  In the present embodiment, the ratio of the rubber hardness of the adhesive member after heating after further heating the adhesive member 30 at 240 ° C. for 2000 hours (hereinafter, simply referred to as “the ratio of the rubber hardness of the adhesive member” to the rubber hardness of the adhesive member 30 or "Ratio of rubber hardness") is 1.2 or less. If the rubber hardness ratio of the bonding member exceeds 1.2, the degree of curing deterioration of the bonding member 30 due to long-time use of the electrostatic chuck 100 at a high temperature becomes high, and it becomes difficult to maintain flexibility. Tend. On the other hand, if the ratio of the rubber hardness of the adhesive member is 1.2 or less, the degree of curing deterioration of the adhesive member 30 due to long-time use of the electrostatic chuck 100 at a high temperature becomes high, and the flexibility becomes poor. It tends to be easier to maintain. The ratio of the rubber hardness of the adhesive member is more preferably 1.1 or less, and further preferably 1.0 or less.

  In the present embodiment, the ratio of the shear bond strain of the adhesive member after heating after further heating the adhesive member 30 at 240 ° C. for 2,000 hours to the shear bond distortion of the adhesive member 30 (hereinafter simply referred to as “shear bond distortion of the adhesive member”) Ratio "or" ratio of shear bond strain ") is greater than or equal to 0.8. If the ratio of the shear bond strain of the bonding member is less than 0.8, the degree of curing deterioration of the bonding member 30 due to long-time use of the electrostatic chuck 100 at a high temperature increases, and it is difficult to maintain flexibility. It tends to be. On the other hand, if the ratio of the shear bond strain of the bonding member is 0.8 or more, the degree of curing deterioration of the bonding member 30 due to long-time use of the electrostatic chuck 100 at a high temperature is reduced, and flexibility is reduced. Tends to be easily maintained. The ratio of the shear bond strain of the bonding member is more preferably 0.85 or more, and even more preferably 0.9 or more.

In the present embodiment, the ratio of the paste viscosity of the adhesive composition at a shear rate of 1 s ^{-1 to} the paste viscosity of the adhesive composition at a shear rate of 10 s ^-1 constituting the adhesive member 30 is 2.4 or less. When the ratio of the paste viscosity of the adhesive composition exceeds 2.4, the thixotropy of the resin is large, the fluidity of the resin is deteriorated, and the adhesive member 30 caused by using the electrostatic chuck 100 at a high temperature for a long time is reduced. It tends to be difficult to maintain flexibility. On the other hand, if the ratio of the paste viscosity of the adhesive composition is 2.4 or less, the thixotropy of the resin is small and the fluidity of the resin is good, so that the electrostatic chuck 100 is used at a high temperature for a long time. As a result, the flexibility of the adhesive member 30 tends to be easily maintained. In addition, since the thixotropy of the resin is small, when producing an adhesive sheet from the adhesive composition, it is easy to reduce the variation in the sheet thickness (reduction in variation in the sheet thickness), and the adhesive sheet is produced from the adhesive composition. When the adhesive paste is applied to the ceramic member 10 and the base member 20, it becomes easier to apply the adhesive paste more uniformly (reduction in application unevenness). By facilitating the reduction in the variation in the sheet thickness and the reduction in the uneven coating, the heat transfer becomes uniform throughout the adhesive member 30, and the temperature distribution of the ceramic member 10 becomes uniform. The paste viscosity ratio of the adhesive composition is more preferably 2.2 or less, and even more preferably 2.0 or less.

A-3. Manufacturing method of the electrostatic chuck 100:
Next, a method for manufacturing the electrostatic chuck 100 according to the present embodiment will be described. First, a plate-shaped ceramic member 10 in which a conductive material layer such as the chuck electrode 40 and the heater electrode 50 is disposed is manufactured. The production of the ceramic member 10 can be performed by, for example, a known sheet laminating method or a press molding method.

  An example of a method for manufacturing the ceramic member 10 by the sheet lamination method is as follows. First, a plurality of ceramic green sheets are prepared by mixing an alumina raw material, a butyral resin, a plasticizer, and a solvent, and forming the resulting mixture into a sheet by a doctor blade method. Further, necessary processing such as formation of through holes, filling of via ink, and application of electrode ink for forming the chuck electrode 40 and the heater electrode 50 is performed on a predetermined ceramic green sheet. The portion where the electrode ink is applied becomes a conductive material layer. As the via ink and the electrode ink, a metallized ink that is made into a slurry by mixing a conductive material such as tungsten or molybdenum, an alumina raw material, an Ethocel (registered trademark) resin, and a solvent is used. Then, a plurality of ceramic green sheets are laminated, thermocompression-bonded, and processed into a predetermined size to obtain a ceramic molded body.

  After the obtained ceramic molded body is degreased in nitrogen, it is fired at a predetermined temperature (for example, 1500 ° C. to 1600 ° C.) in a humidified hydrogen nitrogen atmosphere at normal pressure to produce a plate-shaped ceramic member 10.

  Next, the ceramic member 10 and the base member 20 are joined via the adhesive member 30. Specifically, in addition to the ceramic member 10, an adhesive (adhesive sheet) formed by sheeting the base member 20 and the adhesive composition is prepared. The base member 20 is formed of, for example, an aluminum alloy. The adhesive is an adhesive composition containing an addition-curable silicone resin (addition-curable silicone resin composition). The adhesive sheet is made into an adhesive paste by stirring the adhesive composition under vacuum, and the formed adhesive paste is formed into a sheet shape using a roll coater or the like, if necessary, for a predetermined time. It is manufactured by heating at a predetermined temperature and semi-curing. An adhesive is arranged between the ceramic member 10 and the base member 20, and they are bonded together in a vacuum and heated as they are. Thereby, the adhesive is cured to form the adhesive member 30, and the ceramic member 10 and the base member 20 are bonded by the adhesive member 30. Thereafter, post-processing (polishing of outer periphery, formation of terminals, etc.) is performed as necessary. With the above manufacturing method, the electrostatic chuck 100 having the above-described configuration is manufactured.

A-4. Performance evaluation:
The performance evaluation described below was performed on an adhesive (adhesive paste, adhesive sheet) composed of the adhesive composition used in the above-described production method. 3 and 4 are explanatory diagrams showing the results of the performance evaluation.

A-4-1. For each sample:
As shown in FIGS. 3 and 4, test pieces of samples S1 to S10 were used in the performance evaluation. For each test piece, an adhesive composition was prepared in a blending amount determined for each sample, and an adhesive composed of each adhesive composition was used.

(Production method of adhesive paste)
The method for producing the adhesive paste for each sample is as follows. To the addition-curable silicone resin, carbon black of the type and the amount of carbon powder added as described in Samples S1 to S10 is added. Thereby, an adhesive paste is produced. The curing speed of the adhesive paste can also be adjusted by the type and amount of the filler, and when the same type of filler is used, the curing speed tends to decrease as the amount of addition increases. Alumina (Al ₂ O ₃ ) particles are used as a filler for controlling thermal conductivity and strength.

Specifically, samples S1 to S10 are an adhesive composition (addition-curable silicone resin composition) containing the following materials.
100 parts by weight of addition-curable silicone resin (including 0.003 parts by weight of platinum catalyst, 2 parts by weight of silane coupling agent, and 3 parts by weight of crosslinking agent)
-Carbon black (X) parts by weight-Alumina particles (300-X) parts by weight

The carbon blacks A1 to A5 used in the samples S1 to S5 and S7 to S10 are as follows.
-A1: SeatTA (trade name) manufactured by Tokai Carbon Co., Ltd.
・ A2: Asahi # 35 (trade name) manufactured by Asahi Carbon Co., Ltd.
・ A3: HTC # SL (trade name) manufactured by Shin Nikka Carbon Co., Ltd.
・ A4: # 4000B (trade name) manufactured by Mitsubishi Chemical Corporation
A5: Denka Black (trade name) manufactured by Denka Corporation

(Method of manufacturing adhesive sheet)
The method for producing the adhesive sheet of each sample (the method for semi-curing (sheeting) the adhesive paste) is as follows. The adhesive paste prepared as described above is spread on a polyethylene terephthalate (PET) film. A known method can be used as a method for spreading the coating. In this performance evaluation, a doctor blade is used. Next, the adhesive paste spread on the PET film is cut into a predetermined size, and then, the cut adhesive paste with the PET film is heated at a predetermined temperature for a predetermined time by a dryer to obtain an adhesive paste. Is semi-cured. Thereby, an adhesive sheet with a PET film is formed. During the heating, each adhesive paste may be covered with a cover film as necessary, for example, to prevent adhesion of dust.

A-4-2. Evaluation method:
(Paste viscosity)
The paste viscosity of the adhesive composition was measured using a known viscosity measuring device (for example, a cone plate type viscometer TVE-22H type manufactured by Toki Sangyo Co., Ltd.). Specifically, the shear rates 1s- ¹ , 2s- ¹ , 5s- ¹ , 10s- ¹ , 20s- ¹ , 10s- ¹ , 5s- ¹ , 2s- ¹ using the adhesive paste prepared as described above. , 1s ^-1 in order. 3 and 4, “1 s ⁻¹ (a)” represents the paste viscosity at the first shear rate 1 s ⁻¹ . 3 and 4, “10 s ⁻¹ (b)” represents the paste viscosity at the initial shear rate of 10 s ⁻¹ . The paste viscosity ratio “(a) / (b)” represents the ratio of the value of “1 s ⁻¹ (a)” to the value of “10 s ⁻¹ (b)”. The larger the value of “(a) / (b)”, the higher the thixotropy and the lower the flexibility of the adhesive composition.

(Rubber hardness)
Using a known rubber hardness measurement device (type A durometer specified in JIS K 6253), the rubber hardness (a) of the adhesive composition and the adhesive composition after heating after heating at 240 ° C. for 2000 hours. The rubber hardness (b) was measured. In the measurement of the rubber hardness, the rubber hardness (a) of the adhesive composition is a rubber hardness immediately after the adhesive composition is cured by the following method. The rubber hardness ratio “(b) / (a)” was determined based on the rubber hardnesses (a) and (b). In FIG. 3 and FIG. 4, the rubber hardness “initial (a)” is specifically specified as follows. First, the adhesive paste prepared as described above is placed in a container having an inner diameter of 18 mm and a length of 17 mm, for example, heated at 100 ° C. for 10 hours, and further heated at 150 ° C. for 50 hours to cure the adhesive paste. Thus, a cured product (adhesive composition) was obtained. The curing conditions for obtaining the cured body from the adhesive paste may be any conditions under which the adhesive paste is cured, and may be different depending on the material constituting the adhesive paste. The rubber hardness on the upper and lower surfaces of the obtained cured product was measured, and the average of the measured values was specified as the rubber hardness “initial (a)”. On the other hand, in FIGS. 3 and 4, the rubber hardness “240 ° C. and 2,000 h (b)” was specified as follows. The cured product (adhesive composition) obtained above was further heated at 240 ° C. for 2000 hours, and the rubber hardness on the upper and lower surfaces of the cured product (adhesive composition after heating) was measured. It was specified as “240 ° C. 2000 h (b)”. 3 and 4, “(b) / (a)” represents the ratio of the value of “240 ° C. and 2000 h (b)” to the value of “initial (a)”. The larger the value of “(b) / (a)”, the harder the material is due to heating, which means that the material is more easily cured and deteriorated.

  In addition, the rubber hardness of the adhesive composition that has been bonded to the adherend (that is, cured) can be measured by the following method. First, the adhesive composition is scraped off from the adherend using a knife or the like. At this time, it is preferable to remove the adhesive composition so that the thickness of the adhesive composition that has been removed is as large as possible. The adhesive composition that has been stripped off is laminated, and the rubber hardness of the adhesive composition can be measured using the above-mentioned rubber hardness measuring machine. When laminating the stripped adhesive composition, the adhesive composition is placed when the thickness of the laminated adhesive composition is measured by pressing the indenter (indenter) with the rubber hardness measuring machine. It is preferable to laminate the layers so that the thickness of the layers does not affect the hardness of the underlying substrate. It is preferable that the thickness of the laminated adhesive composition is, for example, 6 mm or more. The rubber hardness measured in the adhesive composition immediately after being stripped is referred to as “initial (a)”, and the adhesive after heating after heating the stripped adhesive composition at 240 ° C. for 2000 hours. It is possible to calculate the rubber hardness ratio “(b) / (a)” by setting the rubber hardness measured in the composition to “240 ° C. and 2000 h (b)”.

(Shear adhesion distortion)
Using a known tensile tester (for example, Autograph (AG-IS) manufactured by Shimadzu Corporation), the shear adhesion strain (amount of strain) of the adhesive composition in the tensile test (a) and heating at 240 ° C. for 2000 hours After the heating, the adhesive composition was measured for shear adhesion strain (b). Based on the shear bond strains (a) and (b), a shear bond strain ratio “(b) / (a)” was determined. In the measurement of the shear bond strain, the shear bond strain (a) of the adhesive composition is the shear bond strain immediately after the adhesive composition is cured by the following method. 3 and 4, the shear bond strain “initial (a)” was specifically identified as follows. FIG. 6 is an explanatory diagram schematically showing a calculation method of the shear bond strain. First, the test piece for the measurement is, specifically, an adhesive sheet prepared as described above, which is obtained by bonding the 12.5 mm ends of two aluminum plates 201 and 202 having a width of 12.5 mm × a length of 100 mm × a thickness of 1 mm. Attach to each of the x12.5mm parts, attach the two aluminum plates in a direction that can be pulled in opposite directions, heat at 100 ° C for 10 hours, and further heat at 150 ° C for 50 hours to bond It produced by doing. As a result, as shown in columns A and B of FIG. 6, the two adhesive sheets respectively attached to the two aluminum plates 201 and 202 are joined to each other, and the adhesive to be subjected to the calculation of the shear adhesive strain is performed. Composition SA is constituted. The total thickness t of the adhesive compositions attached to the two aluminum plates 201 and 202 was 0.7 mm in FIGS. 3 and 4. Next, the two aluminum plates 201 and 202 were relatively moved so that a shear force acts on the adhesive composition SA. For example, using a tensile tester, while moving one aluminum plate 201 in one direction parallel to the bonding surface (for example, the upward direction in column C of FIG. 6) at a tensile speed of 2 mm / min, the load and the moving distance And measure. The shear adhesive stress was calculated by dividing the load by the adhesive area (12.5 mm × 12.5 mm) of the adhesive composition before moving. The relative movement of the two aluminum plates 201 and 202 is continued until the adhesive composition SA breaks, and the distance ΔL when the shear adhesive stress is maximized is measured. Finally, as shown in the following equation (1), by dividing the distance ΔL by the total thickness t of the adhesive composition SA before the movement, the shear bond distortion in the “initial (a)” of the adhesive composition SA is obtained. (%) Was calculated. On the other hand, in FIGS. 3 and 4, the shear bond strain “240 ° C. and 2,000 h (b)” was specified as follows. Using a test piece obtained by further heating the test piece prepared by the above method at 240 ° C. for 2,000 hours, the adhesive composition after heating was heated to “240 ° C. 2,000 h (b)” in the same manner as described above. Was calculated. 3 and 4, "initial (a)" represents the shear bond distortion of the adhesive composition immediately after the preparation of the test piece. In addition, in FIG. 3 and FIG. 4, “240 ° C., 2000 h (b)” represents the shear bond strain of the adhesive composition after heating at 240 ° C. for 2000 hours. 3 and 4, “(b) / (a)” represents the ratio of the value of “240 ° C. and 2000 h (b)” to the value of “initial (a)”. A smaller value of “(b) / (a)” indicates that the material becomes harder by heating, which means that the material is more easily cured and deteriorated.
Shear adhesion strain (%) = (ΔL / t) × 100 (1)

  In addition, the shear adhesive distortion of the adhesive composition already adhered to the adherend can be measured by the following method. First, the adhesive composition is cut out together with the adherend by laser cutting or the like. The size and shape of the test piece to be cut out can be held by a jig of a tensile tester, and the two adherends bonded by the adhesive composition are inverted with respect to each other as shown in FIG. Any size and shape that can be pulled in the direction may be used. In addition, since the thickness of the adhesive composition is not particularly limited, it is also possible to use the cut-out adhesive composition with an adherend as it is for measurement. Before performing the tensile test, the adhesive area of the adhesive composition in the cut test piece and the thickness of the adhesive composition are measured. Thereafter, a tensile test is performed in the same manner as described above, and the distance ΔL at which the shear adhesive stress is maximized is divided by the total thickness t of the adhesive composition before movement, thereby obtaining a shear adhesive strain (% ) Is calculated.

(Adhesion evaluation)
A 350 mm aluminum-glass joined body obtained by joining an aluminum plate and a glass plate with the adhesive sheet (thickness: 700 μm) prepared as described above was heated at 230 ° C. for 1000 hours. The joined body obtained as a result was visually observed from the glass surface and confirmed by using an ultrasonic deep scratching apparatus (SAT). When there was no crack or peeling in the glass, the evaluation of the adhesiveness was evaluated as “O”.

(Density unevenness evaluation)
The φ350 mm aluminum-glass joined body produced as described above was heated at 230 ° C. for 1000 hours. The density unevenness of the joined body obtained as a result was observed by using an ultrasonic deep scratch device (SAT). When density unevenness was not observed, the density unevenness evaluation was rated as “○”.

A-4-3. Evaluation results:
FIG. 3 shows the measurement results of the paste viscosity, the rubber hardness, and the shear bond strain for the samples S1 to S6. FIG. 3 further shows the results of the evaluation of adhesion and the evaluation of density unevenness. The rubber hardness ratio of sample S6 was 2.04, a value exceeding 1.2, and the shear bond distortion ratio was 0.35, a value less than 0.8. This was considered to be because the flexibility of the adhesive composition could not be maintained because no carbon black was added to the adhesive composition. Specifically, radicals generated at a high temperature of 230 ° C. are not trapped, and the trapped radicals cause oxidative degradation of the addition-curable silicone resin in a chain, and as a result of the accelerated oxidative degradation, an addition-curable This was considered to be because the crosslinking density of the silicone resin was increased (that is, the addition-curable silicone resin was hardened), and the flexibility of the adhesive composition could not be maintained. On the other hand, the ratio of the paste viscosity of Sample S6 to which carbon black was not added was 1.7, a value of 2.4 or less. This was considered to be because no carbon black was added to the adhesive composition, so that the fluidity of the addition-curable silicone resin was not inhibited.

Sample S4 in which the BET specific surface area of carbon black is 89.3 m ² / g, and the average primary particle diameter of the primary particles constituting the carbon black (hereinafter, also simply referred to as “average primary particle diameter of carbon black”) is 43 nm. And a sample S5 having a carbon black BET specific surface area of 69.7 m ² / g and an average primary particle diameter of carbon black of 57 nm have rubber hardness ratios of 1.41 and 1.27, respectively. , 1.2, and the ratio of shear bond strain was 0.67, 0.72, which was less than 0.8. This is because although the carbon black is added to the adhesive composition, the BET specific surface area of the carbon black is large (the average primary particle diameter of the carbon black is small), so that the flexibility of the adhesive composition is maintained. It was thought that it was not possible. Specifically, since the BET specific surface area of the carbon black is large (the average primary particle size of the carbon black is small), the amount of the addition-curable silicone resin that coats the surface of the carbon black is large, and the carbon black in the entire adhesive member 30 is reduced. It was considered that this was because the amount of the addition-curable silicone resin capable of flowing between the resin and the carbon black was small, so that the flexibility of the resin could not be maintained. Further, the ratios of the paste viscosities of the samples S4 and S5 were both 2.8 and more than 2.4. Also, because the BET specific surface area of the carbon black is large (the average primary particle diameter of the carbon black is small), the amount of the addition-curable silicone resin covering the surface of the carbon black is large, It was considered that as a result of the small amount of the addition-curable silicone resin capable of flowing between the carbon black and the resin, the paste viscosity of the resin was increased.

The ratios of the rubber hardnesses of the samples S1 to S3 are 1.10, 0.99, 0.96 and 1.2 or less, respectively, with respect to the samples S4 to S6. , 1.00, 0.85, 0.81 and 0.8 or more. This is because the BET specific surface area of the carbon black added to the adhesive composition was 40 m ² / g or less, and the average primary particle diameter of the carbon black was 80 nm or more. It was thought that it was because sex could be maintained. Specifically, the carbon black can sufficiently capture radicals generated at a high temperature of 230 ° C., and the oxidation deterioration of the addition-curable silicone resin is suppressed. As a result, the crosslinking density of the addition-curable silicone resin becomes too high. (Ie, the addition-curable silicone resin did not become too hard), and it was considered that the flexibility of the adhesive composition could be maintained. The paste viscosity ratios of Samples S1 to S3 were 2.0, 1.9, 1.8, and 2.4 or less, respectively. This was considered because the BET specific surface area of the carbon black added to the adhesive composition was 40 m ² / g or less, and the average primary particle diameter of the carbon black was 80 nm or more. Specifically, since the BET specific surface area of the carbon black is small (the average primary particle diameter of the carbon black is large), the amount of the addition-curable silicone resin coating the surface of the carbon black is small, and the carbon black in the entire adhesive member 30 is reduced. It was considered that the paste viscosity of the resin was lowered by increasing the amount of the addition-curable silicone resin that could flow between the resin and the carbon black.

Among the samples S1 to S6, the samples having evaluation results of “「 ”in both the evaluation of the adhesiveness and the evaluation of the density unevenness were the samples S1 to S3. This is because in samples S1 to S3, the BET specific surface area of the carbon black added to the adhesive composition was 40 m ² / g or less, and the average primary particle diameter of the carbon black was 80 nm or more. As described above, this was considered to be because the flexibility of the adhesive composition could be maintained. On the other hand, in the samples S4 to S6, the evaluation of the adhesiveness was “x”, as described above, because the flexibility of the adhesive composition could not be maintained, and in the φ350 mm aluminum-glass joined body, It was considered that peeling occurred because the difference in thermal expansion between the aluminum plate and the glass plate could not be reduced. In addition, the density unevenness evaluation of the sample S6 was “x” because the addition of carbon black to the adhesive composition accelerated the curing deterioration of the addition-curable silicone resin due to radicals, It is considered that the components in the composition changed.

FIG. 4 shows the measurement results of the paste viscosity, the rubber hardness, and the shear bond strain for the samples S1 and S6 to S10. In samples S7 to S10, carbon black of carbon black type A1 was used. The result of sample S6 to which no carbon black was added is as described above. In sample S7 in which the addition amount of carbon black was 1 part by weight with respect to 100 parts by weight of the addition-curable silicone resin, the ratio of shear bond strain was 0.86, which was 0.8 or more, but the ratio of rubber hardness was Was 1.35, a value exceeding 1.2. The paste viscosity ratio of Sample S7 was 1.7 and 2.4 or less. On the other hand, in samples S1 and S8 to S10 in which the addition amount of carbon black is 2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the addition-curable silicone resin, the rubber hardness ratio is 1.00 to 1 .18 and a value of 1.2 or less, the ratio of shear bond strain is 0.94 to 1.07 and a value of 0.8 or more, and both the ratio of rubber hardness and the ratio of shear bond strain are It was a good value. This is because the BET specific surface area of the carbon black added to the adhesive composition is 40 m ² / g or less, the average primary particle diameter of the carbon black is 80 nm or more, and the amount of the carbon black added is It was thought that the reason for this was that the flexibility of the adhesive composition could be maintained when the amount was 2 to 20 parts by weight based on 100 parts by weight of the addition-curable silicone resin. Specifically, the carbon black can sufficiently capture the radicals generated at a high temperature of 230 ° C., and the oxidative deterioration of the addition-curable silicone resin is suppressed, so that the flexibility of the adhesive composition can be maintained. It was thought that it was possible. The ratio of the paste viscosities of Samples S1, S8 and S9 was 1.9, 2.0, 2.0 and 2.4 or less. That is, in the adhesive composition in which the addition amount of carbon black is 2 parts by weight to 10 parts by weight with respect to 100 parts by weight of the addition-curable silicone resin, in addition to the rubber hardness ratio and the shear bond distortion ratio, the paste viscosity Good results were also obtained for

A-5. Effects of this embodiment:
As described above, the electrostatic chuck 100 according to the present embodiment includes the ceramic member 10, the base member 20, and the base member 20 having a coefficient of thermal expansion different from that of the ceramic member 10 and the ceramic member. And an adhesive member 30 that is disposed on the ceramic member 10 and joins the ceramic member 10 and the base member 20. The adhesive member 30 (adhesive composition) contains an addition-curable silicone resin and carbon black having a BET specific surface area of 40 m ² / g or less.

  As described above, in the electrostatic chuck 100 of the present embodiment, the adhesive member 30 includes the addition-curable silicone resin. Addition-curable silicone resins have good flexibility. Therefore, good flexibility of the adhesive member 30 can be maintained. Further, since the addition-curable silicone resin is a type of resin that is cured by addition polymerization, there is no generation of by-products that occur when the condensation-curable silicone resin is cured. Therefore, no bubbles are generated due to the by-products, and no bubbles remain in the cured adhesive member 30. Therefore, since the adhesion between the bonding member 30 and the ceramic member 10 and the base member 20 is not hindered by air bubbles, good adhesion between the bonding member 30 and the ceramic member 10 and the base member 20 is maintained. Can be.

  Further, in the electrostatic chuck 100 of the present embodiment, the adhesive member 30 contains carbon black. Since carbon black has a radical capturing ability, it can capture radicals generated when the electrostatic chuck 100 is used at a high temperature of about 200 ° C. For this reason, chain degradation of the addition-curable silicone resin due to radicals can be suppressed, and the good flexibility of the adhesive member 30 can be maintained.

In addition, the BET specific surface area of the carbon black included in the adhesive member 30 of the electrostatic chuck 100 according to the present embodiment is 40 m ² / g or less. With such a configuration, the amount of the addition-curable silicone resin that coats the surface of the carbon black is smaller than in the case where the BET specific surface area of the carbon black exceeds 40 m ² / g, and the carbon black in the entire adhesive member 30 is reduced. The amount of addition-curable silicone resin that can flow between carbon black is large. Thereby, in the electrostatic chuck 100 of the present embodiment, the increase in the viscosity of the addition-curable silicone resin is suppressed, and the excellent flexibility of the adhesive member 30 can be maintained.

  Thus, according to the electrostatic chuck 100 of the present embodiment, since the bonding member 30 has good flexibility, the ceramic member 10 when the electrostatic chuck 100 is used at a high temperature of about 200 ° C. Stress caused by a difference in the coefficient of thermal expansion between the base member 20 and the base member 20 is reduced. Consequently, according to the electrostatic chuck 100 of the present embodiment, the controllability of the temperature distribution of the wafer W is improved, and the flatness of the ceramic member 10 is reduced due to the occurrence of warpage or the like in the ceramic member 10. Can be suppressed. Further, according to the electrostatic chuck 100 of the present embodiment, since the adhesive member 30 has good adhesiveness, it is possible to suppress the adhesive member 30 from being peeled off from the ceramic member 10 or the base member 20, As a result, the controllability of the temperature distribution of the wafer W can be improved.

  The bonding member 30 of the electrostatic chuck 100 according to the present embodiment contains carbon black having an average primary particle diameter of 80 nm or more. The average primary particle diameter of carbon black contained in the adhesive member 30 of the electrostatic chuck 100 of the present embodiment is 80 nm or more. With such a configuration, the amount of the addition-curable silicone resin that coats the surface of the carbon black is smaller than when the average primary particle diameter of the carbon black is less than 80 nm, and the carbon black and carbon in the entire adhesive member 30 are reduced. The amount of the addition-curable silicone resin that can flow between black is large. Thereby, in the electrostatic chuck 100 of the present embodiment, the increase in the viscosity of the addition-curable silicone resin is suppressed, and the excellent flexibility of the adhesive member 30 can be maintained.

  Thus, according to the electrostatic chuck 100 of the present embodiment, since the bonding member 30 has good flexibility, the ceramic member 10 when the electrostatic chuck 100 is used at a high temperature of about 200 ° C. Stress caused by a difference in the coefficient of thermal expansion between the base member 20 and the base member 20 is reduced. As a result, according to the electrostatic chuck 100 of the present embodiment, the controllability of the temperature distribution of the wafer W can be improved, and the flatness of the ceramic member 10 can be prevented from lowering. Further, according to the electrostatic chuck 100 of the present embodiment, since the adhesive member 30 has good adhesiveness, it is possible to suppress the adhesive member 30 from being peeled off from the ceramic member 10 or the base member 20, As a result, the controllability of the temperature distribution of the wafer W can be improved.

  The carbon powder contained in the adhesive member 30 of the electrostatic chuck 100 according to the present embodiment is carbon black. Thereby, radicals generated when the electrostatic chuck 100 is used at a high temperature of about 200 ° C. can be effectively captured. For this reason, chain degradation of the addition-curable silicone resin due to radicals can be suppressed, and the good flexibility of the adhesive member 30 can be maintained. Also, carbon black is easily available on the market.

  The amount of carbon black contained in the adhesive member 30 of the electrostatic chuck 100 of the present embodiment is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin. If the amount of carbon black added to the electrostatic chuck 100 is less than 2 parts by weight, the degree of increase in rubber hardness after use at high temperatures is high, and the degree of decrease in shear bond distortion after use at high temperatures. Becomes larger. When the amount of carbon black added to the electrostatic chuck 100 exceeds 20 parts by weight, the amount of the addition-curable silicone resin coating the surface of the carbon black is large, and the amount of carbon black and carbon black in the entire adhesive member 30 is large. Since the amount of the flowable addition-curable silicone resin is small, the viscosity of the addition-curable silicone resin is increased, and the flexibility is lowered at the time of curing, that is, before use at a high temperature. In addition, the degree of increase in rubber hardness after use at high temperatures increases. In the electrostatic chuck 100 of the present embodiment, the amount of carbon black added to the adhesive member 30 is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin. In addition to exhibiting paste viscosity, it can exhibit good rubber hardness and good shear bond distortion even after use at high temperatures. In the electrostatic chuck 100 of the present embodiment, since the adhesive member 30 having such characteristics is used, it is possible to effectively maintain good flexibility even after being used at a high temperature.

  In the electrostatic chuck 100 according to the present embodiment, the ratio of the rubber hardness of the heated adhesive member after the adhesive member 30 is further heated at 240 ° C. for 2,000 hours to the rubber hardness of the adhesive member 30 is 1.2 or less. That is, in the electrostatic chuck 100 of the present embodiment, the degree of curing deterioration of the adhesive member 30 due to long-time use of the electrostatic chuck 100 at a high temperature is low. Therefore, the adhesive member 30 of the electrostatic chuck 100 of the present embodiment can maintain good flexibility before long-time use at high temperature even after long-time use at high temperature.

  In the electrostatic chuck 100 of the present embodiment, the ratio of the shear bond distortion of the adhesive member after heating after the adhesive member 30 is further heated at 240 ° C. for 2000 hours to the shear bond distortion of the adhesive member 30 is 0.8 or more. is there. That is, in the electrostatic chuck 100 of the present embodiment, the degree of curing deterioration of the adhesive member 30 due to long-time use of the electrostatic chuck 100 at a high temperature is low. Therefore, the adhesive member 30 of the electrostatic chuck 100 of the present embodiment can maintain good flexibility before long-time use at high temperature even after long-time use at high temperature.

In the adhesive composition of the present embodiment, the ratio of the paste viscosity (a) at a shear rate of 1 s ^-1 of the adhesive composition to the paste viscosity (b) at a shear rate of 10 s ^-1 of the adhesive composition "(a)". / (B) "is 2.4 or less. That is, in the adhesive composition of the present embodiment, since the thixotropy is small and the flowability is good, in the composition to which carbon black is similarly added, at 240 ° C. for 2,000 hours, even after being sufficiently heated. A flexible cured product is obtained. In the electrostatic chuck 100 of the present embodiment, since the adhesive composition having such characteristics is used as the adhesive member 30, good flexibility can be effectively achieved even after use at a high temperature. Can be maintained.

B. Modification:
The technology disclosed in the present specification is not limited to the above-described embodiment, and can be modified into various forms without departing from the gist thereof. For example, the following modifications are also possible.

  The configuration of the adhesive composition in the above embodiment can be variously modified. Further, the type of the addition-curable silicone resin, the type of the carbon powder, the added amount of the carbon powder, and the added amount of other materials contained in the adhesive composition are limited to those described in the above embodiment. is not. Further, each material constituting the adhesive composition is merely an example, and other materials may be included as necessary.

In the above embodiment, as the carbon powder added to the adhesive composition, a carbon powder having a BET specific surface area of 40 m ² / g or less and an average particle diameter of primary particles constituting the carbon powder of 80 nm or more was used. , But is not limited to this. That is, the carbon powder added to the adhesive composition may have a BET specific surface area of 40 m ² / g or less, or an average primary particle diameter of the carbon powder of 80 nm or more.

  In the above embodiment, carbon black is used as the carbon powder added to the adhesive composition, but is not limited thereto. That is, the carbon powder added to the adhesive composition may be carbon fiber, carbon nanotube, or graphene. Further, two or more kinds of carbon powders can be used in combination.

  In the above-described embodiment, the configuration in which the ceramic member 10 and the base member 20 are directly joined to the adhesive member 30 is adopted, but the present invention is not limited to this. For example, another material (for example, a polyimide resin or the like) may exist between the ceramic member 10 and the adhesive member 30. Further, in the configuration in which the adhesive member 30 is composed of a plurality of layers, the other material may constitute at least one of the plurality of layers.

  In addition, the present invention is not limited to the electrostatic chuck 100 including the adhesive member 30, and may be another holding device such as a vacuum chuck including the above adhesive member, or a semiconductor manufacturing device component such as a shower head including the above adhesive member. Can be applied to the composite member.

10: Ceramic member 20: Base member 21: Refrigerant channel 30: Adhesive member 40: Chuck electrode 50: Heater electrode 60: Driver electrode 100: Electrostatic chuck W: Wafer

Claims (9)

A ceramic member, a base member having a coefficient of thermal expansion different from the coefficient of thermal expansion of the ceramic member, and an adhesive member disposed between the ceramic member and the base member to join the ceramic member and the base member. A composite member comprising:
The adhesive member includes an addition-curable silicone resin and a carbon powder,
The carbon powder has a BET specific surface area of 40 m ² / g or less.
A composite member characterized by the above-mentioned. A ceramic member, a base member having a coefficient of thermal expansion different from the coefficient of thermal expansion of the ceramic member, and an adhesive member disposed between the ceramic member and the base member to join the ceramic member and the base member. A composite member comprising:
The adhesive member includes an addition-curable silicone resin and a carbon powder,
The average particle diameter of the primary particles constituting the carbon powder is 80 nm or more,
A composite member characterized by the above-mentioned. In the composite member according to claim 1 or 2,
The carbon powder is at least one selected from the group consisting of carbon black, carbon fiber, carbon nanotube, and graphene.
A composite member characterized by the above-mentioned. The composite member according to claim 3,
The carbon powder is carbon black,
The addition amount of the carbon black in the adhesive member is 2 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the addition-curable silicone resin.
A composite member characterized by the above-mentioned. In the composite member according to any one of claims 1 to 4,
The ratio of the rubber hardness of the heated adhesive member after heating the adhesive member at 240 ° C. for 2000 hours to the rubber hardness of the adhesive member is 1.2 or less.
A composite member characterized by the above-mentioned. In the composite member according to any one of claims 1 to 5,
The ratio of the shear bond distortion of the adhesive member after heating after the adhesive member was further heated at 240 ° C. for 2000 hours to the shear bond distortion in the adhesive member is 0.8 or more.
A composite member characterized by the above-mentioned. In an adhesive composition containing an addition-curable silicone resin and carbon powder,
The carbon powder has a BET specific surface area of 40 m ² / g or less.
An adhesive composition comprising: In an adhesive composition containing an addition-curable silicone resin and carbon powder,
The average particle diameter of the primary particles constituting the carbon powder is 80 nm or more,
An adhesive composition comprising: The adhesive composition according to claim 7 or 8,
The ratio of the paste viscosity of the shear rate 1 s ^-1 of the adhesive composition to the paste viscosity of the shear rate 10 s ^-1 of the adhesive composition is 2.4 or less.
An adhesive composition comprising:

Images