WO2019107271A1 - Plasma-resistant resin composition and electrostatic chucking device employing same - Google Patents

Abstract

[Problem] To provide: a resin composition in which plasma resistance is considerably enhanced regardless of the type of a matrix resin; and an electrostatic chucking device employing the same. [Solution] The present invention provides: a resin composition that is used in an environment in which said resin composition is directly or indirectly exposed to plasma and that is characterized by comprising a resin, which serves as a matrix, and a filler comprising a layer-like inorganic compound that is dispersed in the resin, which serves as the matrix, and that possesses ion exchanging property, wherein the resin and the layer-like inorganic compound are blended at 1-90% by volume; and an electrostatic chucking device employing said resin composition.

Description

Resin composition having plasma resistance, and electrostatic chuck device using the same

The present invention relates to a resin composition having high plasma resistance, and an electrostatic chuck device using the same.

The plasma processing apparatus plasmas a predetermined gas with a high frequency power source or the like to generate reactive chemical species having high reaction activity such as radicals, ions, and electrons. The plasma processing apparatus utilizes physical impact force or chemical reactivity of the reactive chemical species, for example, CVD (chemical vapor deposition) in the manufacturing process of semiconductor, liquid crystal panel, solar cell, LED, etc. It is used as an apparatus, sputtering apparatus, plasma etching apparatus, plasma ashing apparatus and the like. In addition to these, it has a wide range of applications in general industries such as surface modification and dry cleaning.
The plasma processing apparatus is mainly made of metal, quartz or the like, but a resin member is used in part. For example, a packing or an O-ring is used as a sealing material of a vacuum system (gas supply unit, plasma source, plasma processing chamber, exhaust pipe, etc.) in reduced pressure plasma. The resin members used in the plasma source portion, the plasma processing chamber, and the exhaust pipe are exposed to reactive chemical species with high reactivity directly or indirectly, and are degraded by decomposition or deterioration. For this reason, the degree of vacuum decreases, particles and contamination occur, and periodical replacement is required. It is a problem that the production stop at that time causes cost increase and productivity decrease.
In particular, since the electrostatic chuck device is installed in the plasma processing chamber and directly exposed to reactive chemical species, deterioration of the resin member is remarkable. Conventionally, although the chucking part (wafer installation part) of the electrostatic chuck apparatus was comprised with the polyimide resin, it is changed into the ceramic for the said deterioration. Although the electrostatic chuck apparatus (FIG. 1) in which ceramics were used is used combining an aluminum member and a ceramic member, those joining is performed using an adhesive agent. For example, in the case of the etching apparatus, the wafer is heated and cooled through the electrostatic chuck apparatus depending on the process conditions. Therefore, the aluminum member and the ceramic member may be distorted (displaced) due to the difference between their thermal expansion coefficients, which may lead to breakage. The adhesive is also used to absorb the strain due to the difference in the thermal expansion coefficient. However, the adhesive has the problem of deterioration due to the plasma, the maintenance frequency is increased, and the cost increase and the decrease in production efficiency become problems.

As a resin composition of a molded member having improved plasma resistance, in Patent Document 1, various fillers can be added to the fluorine-containing elastomer composition having high plasma resistance in order to reinforce the elastomer, increase the amount, and improve the processability. The invention in which is used is disclosed. Further, Patent Document 2 discloses that a vulcanized product having excellent compression set resistance characteristics and plasma resistance can be obtained by combining the fluororubber composition and the spherical composite cured melamine resin particles, and therefore, for a semiconductor manufacturing apparatus. There is disclosed an invention which can be effectively used as a vulcanized molding material of a sealing material.
As a resin composition of the adhesive agent which improved plasma resistance, it is disclosed by patent document 3 that the adhesive sheet containing acrylic rubber and a thermosetting resin has high plasma resistance.
Furthermore, as a method of preventing the deterioration of the adhesive used for the electrostatic chuck, it has been proposed to cover the surface of the adhesive with a material having high plasma resistance so that the adhesive is not exposed to plasma (Patent Document 4) ).

JP, 2013-057057, A JP, 2014-118510, A JP, 2009-071023, A JP, 2017-041631, A

The inventions disclosed in Patent Documents 1 to 3 are characterized in that a matrix resin or a combination of a specific matrix resin and a specific filler exhibits high plasma resistance, and the effect thereof is as follows: Because it is limited to the resin, or the combination of the specific resin and the specific filler, the application and application have been limited. In addition, the plasma resistance was not sufficient.
As a protective material (edge seal) for preventing deterioration of the adhesive of the electrostatic chuck device disclosed in Patent Document 4, it is disclosed that only an elastomer is used, and a material having high plasma resistance is used. Even if there were, there was a possibility that the frequency of replacement would be high, and there was room for improvement.
Therefore, the present invention reduces the frequency of replacement by providing a resin composition that significantly improves the inherent plasma resistance of the resin regardless of the matrix resin, and an electrostatic chuck device using the resin composition. Reduce costs and improve production efficiency. Further, the resin composition can be a molded member or an adhesive.

The inventors of the present invention conducted intensive studies on the above problems, and found that when the filler of the layered inorganic compound having ion exchangeability is dispersed in the resin, it is possible to exhibit high plasma resistance. And completed the present invention.
That is,
The present invention (1) is
A resin composition used in an environment exposed directly or indirectly to plasma, comprising:
Matrix resin,
And a filler of a layered inorganic compound having ion exchangeability dispersed in the matrix resin,
The blending of the layered inorganic compound is characterized in that it is 1 to 90% by volume with respect to the sum of the volume of the matrix resin and the volume of the layered inorganic compound.
It is a resin composition.
The present invention (2) is
The resin composition according to the invention (1), wherein the ion exchangeability is anion exchangeability.
The present invention (3) is
The resin composition according to the invention (1) or (2), wherein the layered inorganic compound is represented by the following formula (1).
{A _1-x B _x (OH) ₂ } (D _{x / n} · mH ₂ O) (1)
In the formula, A is a divalent metal ion, B is a trivalent metal ion, D is an n-valent anion, x is a real number in the range of more than 0 and 0.4 or less, and m is a real number greater than 0 It is.
The present invention (4) is
The resin composition according to the invention (3), wherein the layered inorganic compound is a layered inorganic compound represented by the following formulas (2) and (3).
{Mg _1-x Al _x (OH) ₂ } (CO ₃ ) _{x / 2} · mH ₂ O (2)
1.5 <(1-x) / x <4 (3)
The present invention (5) is
The resin composition according to the invention (4) or (5), wherein the layered inorganic compound is a hydrotalcite represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O .
The present invention (6) is
The resin composition according to any one of the inventions (1) to (5), wherein the adhesive contains a silicone resin.
The present invention (7) is
The resin composition according to any one of the inventions (1) to (6), wherein the adhesive is included in a plasma etching apparatus.
The present invention (8) is
The resin composition according to any one of the inventions (1) to (7), wherein the resin composition is an adhesive.
The present invention (9) is
The resin composition according to any one of the inventions (1) to (7), wherein the resin composition is used as a resin molded member obtained by curing the resin composition.
The present invention (10) is
The resin composition according to the invention (9), wherein the resin molded member is any one of a belt, a band, a packing, an O-ring, and a sheet.
The present invention (11) is
The resin molded member is used as a protective material that covers the surface of an adhesive exposed portion used in an electrostatic chuck device provided in a plasma etching apparatus, and isolates the adhesive surface from plasma. It is a resin composition of the invention (9) or (10).
The present invention (12) is
An electrostatic chuck device comprising the resin composition described in the inventions (1) to (11).

According to the present invention, it is possible to provide a resin composition having significantly improved plasma resistance regardless of the type of matrix resin. The obtained resin composition can be used in a wide range of applications as an adhesive or a molded member, and can be effective in improving maintenance costs and production efficiency of a plasma device.

It is the top view and sectional drawing of the electrostatic chuck apparatus contained in a plasma etching apparatus. It is a scanning microscope surface photograph before and behind plasma treatment of the resin composition of Example 1 and Comparative Example 1.

1. Resin composition used in an environment directly or indirectly exposed to plasma The resin composition of the present invention is a resin composition in which a layered inorganic compound having ion exchange properties is dispersed in a resin which is a matrix. It is used in an environment exposed to plasma directly or indirectly. The resin composition according to the present invention is excellent in plasma resistance, and can be used as a molded member such as an adhesive of an electrostatic chuck device or a sealing material of a plasma device. The adhesive is not limited to a liquid or paste adhesive, and may be a sheet or tape adhesive. In addition, as in the case of an adhesive, it includes, in the form of a liquid or paste, cured by heat treatment or the like.
Moreover, it can also be used as a protective material by using it as a cover which covers sealing materials, such as packing and O-ring, and a member with low plasma resistance as a use of a shaping | molding member.

Here, "exposed directly or indirectly to the plasma" is not limited to the case where the resin composition according to the present invention is in direct contact with the plasma, but contacts with electrons, ions and radicals generated from the plasma. Including the case. For example, in the reduced pressure plasma processing apparatus, the resin composition according to the present invention is not limited to the case where it is used in the plasma generation part of the plasma chamber, and used in the inside or connection part of plasma source, plasma chamber, exhaust piping etc. Including the case where

Moreover, "dispersed" here is not limited to the case where the inorganic compound is present in a uniform state in the matrix resin, and may be unevenly distributed. For example, depending on the mode (shape and arrangement) to be used, the plasma resistance can be efficiently improved by making a large number of localized near the surface exposed to plasma.

Furthermore, "plasma resistance" is durability with respect to plasma here, and is evaluated by the change in mass and surface observation before and after plasma exposure. The mass change before and after the plasma exposure can be measured by weighing the mass before and after the plasma exposure using a direct reading balance or the like. The surface observation before and after the plasma can be evaluated by observing generation of a crack or the like by observation with an optical microscope, a scanning electron microscope or the like.

1-1. Composition of resin composition 1-1-1. Matrix Resin The resin contained in the resin composition according to the present invention is not particularly limited, as long as the layered inorganic compound can be dispersed. For example, acrylic resin, polyolefin resin, polyurethane resin, fluorine resin, ethylene-vinyl acetate resin, epoxy resin, polyvinyl chloride resin, polyvinyl acetate resin, silicone resin, phenol resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl alcohol Resin, polyvinyl pyrrolidone resin, polyvinyl butyral resin, polymethacrylate resin, melanin resin, urea resin, melamine resin, polyester resin, alkyd resin, fluoro resin, ABS resin, AS resin, nylon resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin , Polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polybenzimidazole resin, Cyanoacrylate resin, an aqueous polymer - isocyanate resin, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, nitrocellulose, resorcinol, ether cellulose, and the like, can be selected depending on the application or the like. The said resin can be used in mixture of plurality.
Depending on the case where it is used as an adhesive or when it is used as a molded member, a resin exhibiting preferable performance can be selected, but from the viewpoint of plasma resistance, a molded resin is also used as a silicone resin or fluorine resin having high plasma resistance. Is also preferable.

1-1-2. Layered Inorganic Compound Filler Having Ion Exchangeability In the resin composition according to the present invention, a layered inorganic compound filler having ion exchangeability is dispersed. The layered inorganic compound filler is not particularly limited, as long as it can be dispersed in the matrix resin. For example, smectite group montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, steven site; vermiculite group di. Vermiculite, tri. Vermiculite; mica group muscovite, paragonite, illite, phlogopite, biotite, flash mica, lepidolite; margarite group of the brittle mica group, clintonite; pyrophyllite group of the pyrophyllite group, talc, kaolinite group Some kaolinite, dickite, nacrite, halloysite, chrysotile, lizardite, antigorite, layered perovskite, hydrotalcite group, having anion exchange properties, and zirconium phosphate; transition metal oxyacid salt; alkali silicate And those having cation exchangeability of These layered inorganic compound fillers may be used in combination of two or more.
Moreover, among these, in order to improve plasma resistance, the layered inorganic compound filler which has anion exchange property is preferable, and a hydrotalcite is more preferable.

The hydrotalcite is a type of layered inorganic compound represented by the following formula (1). The layered inorganic compound represented by the following formula (1) is also referred to as a hydrotalcite-like compound.
{A _1-x B _x (OH) ₂ } (D _{x / n} · mH ₂ O) (1)
In the formula, A is a divalent metal ion, B is a trivalent metal ion, D is an n-valent anion, x is a real number in the range of more than 0 and 0.4 or less, and m is a real number greater than 0 And it is a real number that changes depending on the degree of dehydration.
Among these layered inorganic compounds, compounds represented by the following formulas (2) and (3) are more preferable because of their high anion exchangeability.
_{{Mg 1-x Al x (} OH) 2} CO3 · mH 2 O (2)
1.5 <(1-x) / x <4 (3)
Among them, hydrotalcite represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O is particularly preferable because it has an ability to exchange ions with various anions.

Although hypothesized, the action mechanism for improving the plasma resistance of the layered inorganic compound will be described below.
The plasma processing apparatus plasmifies the source gas. That is, electrons, radicals derived from gas, and ions derived from gas exist in plasma. When the source gas is oxygen gas, electrons, oxygen ions, and oxygen radicals are generated. In order to improve the plasma resistance of the resin member, it is necessary to cause these reactive chemical species to survive without reacting with the resin member. In particular, in the case of radicals, it is easy to cause the radicals to react with each other and be activated, and for electrons and ions, it is easy to react and react with ions or substances having opposite charges.
Here, the case of a layered inorganic compound filler having anion exchangeability is considered. Because of the large surface area of layered inorganic compound fillers, there are many opportunities for contact with reactive species. For this reason, a reaction is likely to occur between the layered inorganic compound filler and the reactive species. That is, the reactive species incorporated into the layer collide with (react with) other substances in a narrow space and die. For example, in the case of (1) radicals, the radicals react with one another to be activated, (2) the electron with negative charge is reacted with the oxygen ion with positive charge to be activated, (3) negative The oxygen ion having the following charge has a mode in which it is ion-exchanged with an anion present in the layer to be dead and the like. In the case of the hydrotalcite represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, it is considered that the carbonate ion present in the layer and the oxygen ion having a negative charge are ion exchanged.
On the other hand, when a layered inorganic compound filler having cation exchangeability is used, an embodiment in which an oxygen ion having a positive charge is ion-exchanged with a cation existing in an interlayer to be dead is listed instead of the above-described embodiment (3). Be

In general, reactive species generated by plasma depend on the source gas (type or combination of one or more types of gases) and plasma processing conditions (gas flow rate, plasma chamber pressure, etc.), the type, concentration, charge valence Since the radical reactivity and the like change, the type and amount of the layered inorganic compound filler added to the resin composition can be adjusted.

The average thickness of the layered inorganic compound filler is not limited as long as the effects of the present invention are exhibited, but it is preferably 0.005 μm to 0.1 μm.
Here, the value of the average thickness is a value obtained by observing and measuring the thickness of at least 100 fillers of the layered inorganic compound filler with a scanning electron microscope, and determining the average value.

The size of the layered inorganic compound filler is not particularly limited, and for example, the average plate surface diameter is 0.008 μm to 1.0 μm. The thickness is preferably 0.02 μm to 0.8 μm, and more preferably 0.02 μm to 0.7 μm. When the average plate surface diameter is in such a range, the dispersibility of the layered inorganic compound filler in the resin is sufficient, and it becomes easy to industrially produce.
Here, the value of the average plate surface diameter is a value obtained by observing and measuring at least 100 fillers of the layered inorganic compound filler with a scanning electron microscope, and determining the average value thereof. More specifically, the “average plate surface diameter” is the diameter of a circle having the same area as the area of the plate-like surface of the filler imaged by scanning microscope observation (for example, in known software) The average value of the area diameter derived by calculating

The BET specific surface area of the layered inorganic compound filler is preferably 5 m ² / g to 150 m ² / g. More preferably, it is 7 m ² / g to 125 m ² / g, and still more preferably 8 m ² / g to 100 m ² / g. When the BET specific surface area is in such a range, the layered inorganic compound filler can obtain sufficient ion exchange ability, aggregation of the particles is difficult to occur, and the particles can be uniformly dispersed in the resin.
Here, the BET specific surface area can be measured in accordance with JIS Z 8830: 2013 “Method of measuring specific surface area of powder (solid) by gas adsorption”.

In the layered inorganic compound filler, if necessary, the particle surface is coated with at least one surface treatment agent selected from higher fatty acids, anionic surfactants, higher fatty acid phosphate esters, coupling agents and polyhydric alcohol esters. Also good. By coating with a surface coating, the dispersibility of the layered inorganic compound filler in the resin is improved, and further functionalization and stabilization of the resin are possible.

The blending amount of the layered inorganic compound filler is 1% by volume to 90% by volume, preferably 1% by volume to 50% by volume, and more preferably 1% by volume to 35% by volume, with respect to the matrix resin. . When the amount of the layered inorganic compound filler is in such a range, sufficient adhesiveness can be obtained when used as an adhesive, and when used as a molded member, sufficient fluidity is obtained. As it is obtained, the formability can be enhanced.

1-1-3. Other Additives The resin composition according to the present invention may further contain additives depending on the application. For example, a crosslinking agent, a curing catalyst, an inorganic filler (excluding the layered inorganic compound), an organic filler, an adhesive imparting component, a water repellent, an oil repellent, an ultraviolet absorber, an antibacterial agent, an antistatic agent, a paint fixing agent Anti-wrinkle agents, antioxidants, surfactants, coupling agents, coloring agents, solvents, etc. can be mentioned. Among them, the inorganic filler is added for the purpose of reducing the thermal expansion coefficient of the molded body and improving the elastic modulus of the molded body, and crushed, spherical, subspherical, fibrous and phosphorus pen-like materials are used. In particular, spherical or subspherical fillers having an average particle diameter of 10 μm or less are preferable in consideration of surface smoothness. Moreover, a fibrous thing can also be used aiming at the reinforcing effect of crack resistance. The inorganic filler can be used in a range in which the total of the layered inorganic compound and the inorganic filler is 1% by volume to 90% by volume with respect to the volume of the resin component of the resin composition. When it is in the range related to the compounding amount of the layered inorganic compound and the inorganic filler, the thermal expansion coefficient of the cured product is suppressed, the thermal shock resistance is sufficient, and further, the resin composition is sufficiently fluid, Workability is high, and generation of voids can be suppressed.
An organic filler such as a thermal thermoplastic resin, a rubber component, or various oligomers may be added to the resin composition for the purpose of improving the crack resistance and reducing the elastic modulus of the molded product. The organic filler can be used in such a range that the total amount of the layered inorganic compound filler and the organic filler is 1% by volume to 90% by volume with respect to the volume of the resin component of the resin composition.

1-1-4. Base Material and Release Sheet The resin composition according to the present invention may be a sheet-like or tape-like thin film adhesive. In that case, the resin composition can be laminated on a substrate, and a release film is provided on the surface of the laminated resin composition layer opposite to the substrate, and the resin composition until used It can be a layer protective material. Moreover, the said base material can also use a peeling film.

The said base material is not specifically limited, For example, a polypropylene film, a fluororesin film, a polyethylene film, a polyethylene terephthalate film, and paper are mentioned.

Moreover, a peeling film is not specifically limited, A polypropylene film, a fluorine resin film, a polyethylene film, a polyethylene terephthalate film, and paper are mentioned. The peeling film can use what gave peelability with silicone resins, such as a polydimethylsiloxane, on the surface which contact | connects the said resin composition layer.

The thickness of the substrate and the peelable film is preferably 1 μm to 200 μm, and more preferably 10 μm to 100 μm. The release film preferably has a 90 ° peel strength to the adhesive sheet in the range of 0.01 g / cm to 10.0 g / cm. When the 90 ° peel strength is within the above range, the peelable film does not easily peel off during processing of the adhesive sheet with a protective film, and the peelable film peels off from the adhesive layer cleanly during attachment processing, resulting in good workability. Become. The 90 ° peel strength can be measured by a known method, and can be based on, for example, JIS Z0237: 2009 “adhesive tape / adhesive sheet test method”.
When the peelable film is laminated on both sides of the adhesive sheet, it is preferable that the peelability of the peelable film laminated on one side be different from the peelability of the peelable film laminated on the other side.

1-2. Physical Properties, etc. of Resin Composition The physical properties, etc. of the resin composition according to the present invention are not particularly limited, and can be determined depending on the application, etc.

1-2-1. Physical Properties in the Case of Using as an Adhesive, etc. An example of using as an adhesive used in an electrostatic chuck apparatus, which is a preferred example of the present resin composition, will be described below. The physical properties and the like are merely examples and do not limit the present invention.

1-2-1-1. Viscosity before curing of adhesive for electrostatic chuck device The viscosity before curing of the resin composition according to the present invention can be, for example, 100 mPa · s to 5000 Pa · s, and 1 Pa · s to 5000 Pa · s is more Preferably, 5 Pa · s to 5000 Pa · s is more preferable. When the viscosity before curing of the resin composition is in such a range, if it is lower than 100 mPa · s, it has appropriate fluidity and film formation is easy. The high viscosity side, that is, the upper limit of the viscosity, is not particularly limited as long as it can flow by pressure or heating.
The viscosity can be measured by a known method, for example, according to JIS K7117-1: 1999 "Plastic-liquid, emulsion or dispersion resin-measurement method of apparent viscosity with Brookfield type rotational viscometer". It can be measured in compliance.

1-2-1-2. Viscoelastic property etc. after curing of adhesive for electrostatic chuck device The loss tangent at a predetermined temperature of the adhesive after curing of the resin composition according to the present invention can be 0.008 to 5, 0.03 -3 is more preferable. When the loss tangent is in such a range, it is appropriately elastic and viscous, and can absorb the strain due to the difference in the thermal expansion of the material of the bonded part of the electrostatic chuck device, and the adhesive layer is broken In addition to the above, it is possible to prevent deformation due to viscous flow and the like. If viscous flow occurs, it may not return to the original layer shape when heated and cooled, and then returned to the original temperature (for example, the temperature in the room), and the electrostatic chuck device may form accurate wiring. In the case of using as a stage of an etching apparatus or the like to be performed, there is a possibility that the wiring processing accuracy of the apparatus may be deteriorated, such as deviation of the stage parallelism.
Here, the predetermined temperature is a temperature at which the electrostatic chuck device is used, and is a temperature determined according to the application and process conditions.
The measurement of the loss tangent can be performed by a known method, and can be measured, for example, by a method according to JIS K7244-4. The ratio (G ′ ′ / G ′) of the complex loss elastic modulus (referred to as G ′ ′) and the complex storage elastic modulus (referred to as G ′) measured by this measurement can be a loss tangent.

The storage elastic modulus of the adhesive after curing of the resin composition according to the present invention at 30 ° C. is preferably 5 × 10 ⁴ Pa to 5 × 10 ⁸ Pa, and more preferably 1 × 10 ⁵ Pa to 1 × 10 ⁸ Pa.
The storage elastic modulus at 100 ° C. is preferably 1 × 10 ⁴ Pa to 1 × 10 ⁸ Pa, and more preferably 5 × 10 ⁴ Pa to 5 × 10 ⁷ Pa. Furthermore, the storage elastic modulus at 150 ° C. is preferably 1 × 10 ⁴ Pa to 1 × 10 ⁷ Pa.

The elastic modulus of the adhesive after curing of the resin composition according to the present invention preferably has a small change in the heat deterioration test and the heat cycle test. For example, in the case where the electrostatic chuck device is used as a stage of an etching device or the like that performs accurate wiring formation, heating and cooling are repeated when the stage unit is used. Therefore, if the change in elastic modulus after the heat deterioration test or heat cycle test is large, the amount of distortion of the adhesive after curing of the resin composition is not stable, the stage position is not stable, and the wiring processing accuracy of the device is lowered. There is a risk of
The elastic modulus can be measured by a known method, and can be measured, for example, in accordance with JIS K 6254: 2010 "Vulcanized rubber and thermoplastic rubber-Determination of stress / strain characteristics".
The thermal deterioration test can be conducted by a known method, but can be conducted, for example, according to JIS K 6257: 2010 "Vulcanized rubber and thermoplastic rubber-Determination of heat aging characteristics". For example, when a test is carried out on a post-cure adhesive of a resin composition under a thermal degradation condition of 150 ° C. × 250 h, the change in elastic modulus after the test is preferably in the range of 30% to 500% .
The heat cycle test can be conducted by a known method, and can be conducted, for example, by a method according to JIS K 6270: 2001 "Vulcanized rubber and thermoplastic rubber-Determination of tensile fatigue characteristics-Constant strain method". . For example, when the test is performed with heat cycle conditions of -20 ° C. to 125 ° C. for 100 cycles for the adhesive after curing of the resin composition, the change in elastic modulus after the test is in the range of 50% to 300%. Is preferred.

1-2-1-3. Adhesive strength after curing of adhesive for electrostatic chuck device The adhesive strength after curing of the resin composition according to the present invention can be 0.1 N / mm ² to 100 N / mm ² and can be 0.5 N / mm ² to 80 N / mm ² is more preferable, and 1 N / mm ² to 50 N / mm ² is more preferable. The adhesive strength at 150 ° C. can be 0.05 N / mm ² to 100 N / mm ^2, and more preferably 0.1 N / mm ² to 50 N / mm ² .
Furthermore, when the heat cycle conditions of the adhesive after curing of the resin composition are tested as −20 ° C. to 125 ° C. and 100 cycles, the change in elastic modulus after the test is in the range of 50% to 300%. Is preferred. When the adhesive strength is in such a range, it is possible to prevent the decrease in the adhesive force due to the repeated application of the thermal stress due to the heating and cooling cycles of the electrostatic chuck device.

1-2-2. Physical Properties, etc. When Using as a Resin Molding Member When using as a resin molding member, the physical properties can be freely determined according to the molding method and application.
Here, the method for molding the resin molded member is not particularly limited, and a known molding method can be used. For example, injection molding, injection compression molding, extrusion molding, compression molding, blow molding, press molding and the like can be mentioned. It can be selected in consideration of the nature of the matrix resin to be used and the use of the resin molded member.
In addition, a base material can be manufactured by the above-described forming method or the like, and cutting and the like can be additionally performed.
Below, the case where an elastomer is used as matrix resin and others are divided and demonstrated.

1-2-2-1. When a matrix resin is used as an elastomer The following will explain an example where the matrix resin is used as an elastomer in a resin molded member used in an electrostatic chuck apparatus, which is a preferred example of the present resin composition. Here, the elastomer in the present specification refers to a resin exhibiting rubber elasticity at 23 ° C. For example, it is used as a belt or a band-like resin molding member. The physical properties and the like are merely examples and do not limit the present invention.

1-2-2-1-1. Viscosity before curing The viscosity of the resin composition according to the present invention before curing is too high in flowability when the viscosity is low, making it difficult to control the shape. Particularly in the case of a sheet-like shape or the like, it becomes difficult to control the thickness. In addition, when the viscosity is too high, the fluidity is insufficient and the molding becomes difficult.
The viscosity can be measured by a known method, for example, according to JIS K7117-1: 1999 "Plastic-liquid, emulsion or dispersion resin-measurement method of apparent viscosity with Brookfield type rotational viscometer". It can be measured in compliance.

1-2-2-1-2. Hardness after curing The hardness after curing of the resin composition according to the present invention is not particularly limited, and can be determined according to the application. For example, when used as a protective material for protecting the adhesive surface of the electrostatic chuck device, the Shore A hardness after curing is preferably 10 to 100, and more preferably 20 to 90. The Shore A hardness can be measured using a durometer (spring-type rubber hardness meter) that presses and deforms an indenter on the surface of an object to be measured, measures the amount of deformation (indentation depth), and digitizes it. When the Shore A is in such a range, it has appropriate rigidity, and can be fixed to the adhesive surface of the electrostatic chuck device as a protective material without looseness (without any gap). Moreover, it becomes possible to follow the shape of the adhesive surface, and it becomes possible to fix the surface without a gap. When a gap is present between the adhesive surface and the protective material, the reactive chemical species described above penetrate from the gap, resulting in incomplete protection of the adhesive.

1-2-2-1-3. Elongation after curing The elongation after curing of the resin composition according to the present invention is not particularly limited, and can be determined according to the application. For example, when used as a protective material for protecting the adhesive surface of the electrostatic chuck device, the elongation after curing is preferably 1% to 1000%, and more preferably 3% to 500%. When the elongation rate is in such a range, it becomes a flexible protective material, and the operability at the time of fixing on the adhesive surface of the electrostatic chuck device becomes easy, and the working efficiency of the attachment can be increased. In addition, the glass transition temperature (Tg), which is a parameter related to the elongation, is sufficiently high, and can be used in a heating environment. The elongation can be measured by a known method, and can be measured, for example, in accordance with JIS K-6251: 2010 "Vulcanized rubber and thermoplastic rubber-How to determine tensile properties".

1-2-2-1-4. Tensile Strength after Curing The tensile strength after curing of the resin composition according to the present invention is not particularly limited, and can be determined according to the application. For example, when used as a protective material for protecting the adhesive surface of the electrostatic chuck device, the tensile strength after curing is preferably 0.1 N / mm ² to 100 N / mm ² , and 0.1 N / mm ² to 80 N / mm ² is more preferable. When the tensile strength is in such a range, it has sufficient strength and is not easily broken. The upper limit of the tensile strength is not particularly limited, but when the tensile strength is high, the hardness and the elongation increase, and the above-mentioned problems occur. The tensile strength can be measured by a known method, and can be measured, for example, in accordance with JIS K-6251: 2010 "Vulcanized rubber and thermoplastic rubber-Determination of tensile properties".

1-2-2-2. When matrix resin is resin (hard resin) other than elastomer (plastic resin) used for the electrostatic chuck apparatus which is a suitable example of the present resin composition which is a preferable example of the present resin composition An example of the case is described. That is, when the matrix resin of the said shaping | molding member is resin which shows glass elasticity at 23 degreeC, it is used as a resin-molding member of the structure of a hard resin. When the matrix resin is used as an elastomer, there are advantages such as ease of operation, but the structure is weak, and there is a limit in matching with the complicated structure of the other to be fixed. On the other hand, in the case of using a hard resin as a matrix resin, it is necessary to use a device such as screwing to fix, but it can be processed according to the complicated structure of the other party to be fixed and is structurally strong. There is an advantage.
Moreover, a thermosetting resin and a thermoplastic resin can be used as a matrix resin in this invention. Therefore, it may be liquid or solid at normal temperature, as long as it exhibits properties suitable for the molding method at the time of molding. For example, in the method of molding by flowing into a mold, it is sufficient to have fluidity, that is, viscosity, to flow in the mold at the temperature at the time of molding. When a matrix resin and a layered inorganic compound filler are blended by a kneader or the like using a thermoplastic resin, the kneader may have elasticity and viscosity that can be molded by the kneader, that is, viscoelasticity.
The physical properties and the like are merely examples and do not limit the present invention.

1-2-2-2-1. Viscosity before curing of thermosetting resin or viscosity at melting of thermoplastic resin Viscosity before curing when matrix resin of resin composition according to the present invention is thermosetting resin, and matrix resin as thermoplastic resin The viscosity at the time of melting when it is used as a resin is not particularly limited. It is sufficient that the viscosity is suitable for the molding method of the resin molded member.

1-2-2-2-2. Tensile modulus of elasticity of the resin molded member The modulus of elasticity after curing of the resin composition according to the present invention is not particularly limited, and can be determined according to the application. For example, when used as a protective material for protecting the adhesive surface of the electrostatic chuck device, the tensile modulus after curing is preferably 0.2 GPa to 40 GPa, and more preferably 0.5 GPa to 30 GPa . In the case where the tensile elastic modulus is in such a range, it can be fixed using a screw or the like, and it can not be too hard and can have high processability.
The measurement of the tensile elastic modulus after curing can be performed by a known method, and can be measured, for example, in accordance with JIS K7161-1994 "Plastics-Test method of tensile properties".

1-2-2-2-3. Tensile Strength of Resin Molded Member The tensile strength after curing of the resin composition according to the present invention is not particularly limited, and can be determined according to the application. For example, when using as a protective material which protects the adhesive agent surface of the said electrostatic chuck apparatus, 50 kPa or more is preferable and, as for the tensile strength after the said hardening, 200 kPa or more is more preferable. When the tensile strength is in such a range, it has sufficient strength and is not easily broken. There is no particular upper limit of tensile strength, but if the tensile strength is high, it becomes too hard and processing becomes difficult. The tensile strength can be measured by a known method, and can be measured, for example, in accordance with JIS K7161-1994 "Plastics-Test method of tensile properties".

1-3. Method for Producing Resin Composition According to the Present Invention The method for producing the resin composition according to the present invention can be produced by a known method, and for example, the matrix resin, the layered inorganic compound filler and other components are measured in predetermined amounts. For example, it may be prepared by mixing with a bead mill.
Moreover, when using the said resin composition as a sheet-like adhesive agent or a tape-like adhesive agent, it can thin-film the prepared resin composition on a base material using a well-known method. As a method of forming a thin film, for example, a method using an applicator may be mentioned.
In the case of processing as a forming member, it can be formed by a known method, for example, a method of flowing the resin composition into a mold and applying pressure by a press machine for forming.

1-4. Applications of the Resin Composition According to the Present Invention The resin composition according to the present invention is used in an environment exposed to plasma directly or indirectly because of its high plasma resistance. Although it does not specifically limit as an aspect of use, It is preferable to use as molded members, such as an adhesive agent and a sealing material.

The plasma apparatus in which the resin composition according to the present invention is used is not limited to the general plasma used under reduced pressure (under vacuum), but also includes atmospheric pressure plasma (atmospheric pressure plasma) used under atmospheric pressure. The plasma processing apparatus is not particularly limited as long as it is an apparatus using plasma, such as a plasma etching apparatus, a plasma ashing apparatus, a CVD apparatus, a sputtering apparatus, a deposition apparatus, a dry cleaning apparatus, and a surface reforming apparatus.

The resin composition according to the present invention can be used in an electrostatic chuck device as a suitable application. For example, (1) a mode in which a metal base which is a conductive portion is bonded as an adhesive layer, and a suction portion which is an insulating member which sucks a silicon wafer etc., (2) the adhesive layer An adhesive surface protection material which isolates the surface of the adhesive layer not included in the invention from the plasma.

The electrostatic chuck apparatus which is a suitable example is explained in full detail below by making FIG. 1 into an example. FIG. 1 is a top view (FIG. 1a) and a sectional view (FIG. 1b) of an electrostatic chuck device used in a plasma processing apparatus.
The electrostatic chuck device 100 is configured by stacking the ceramic adsorption portion 10, which is an insulating member, the adhesive layer 20, the insulating layer 30, the electrically insulating elastic layer 40, the metal substrate 50, the conductive portion 60, and the electrode 70 in layers. be able to. Additionally, adhesive surface protectors 80 and 90 can be provided to isolate the adhesive from the plasma. The through holes provided in the electrostatic chuck device 100 are for receiving silicon wafer support pins of a lift rod that delivers the silicon wafer from the robot hand to the electrostatic chuck device. By moving the wafer delivery pin up and down, the silicon wafer can be detached from the electrostatic chuck device and delivered to the robot hand. It is preferable that a temperature control means, such as a heat medium passage (not shown) through which a heat medium for adjusting the wafer temperature is formed, be formed inside the metal base 50. The electrostatic chuck device 100 can apply a voltage to the electrode 70 to charge the adsorbing portion 10 and adsorb the silicon wafer by electrostatic force. Further, the adsorption can be released by removing the voltage.

By using the resin composition according to the present invention as an adhesive, it can be used for the adhesive layer 20, and it is possible to alleviate the strain caused by the difference in the thermal expansion coefficient between the ceramic member and the aluminum member, and further to plasma resistance It is possible to improve the When using for this application, it is preferable to use a sheet-like adhesive because the coating operation is simplified.
When the resin composition according to the present invention is used as a sheet-like adhesive, the thickness of the sheet-like adhesive can be designed according to the application and is not particularly limited. For example, it can be 5 μm to 500 μm, more preferably 10 μm to 200 μm, and still more preferably 20 μm to 150 μm.

Moreover, the resin composition by this invention can be used for adhesive surface protection materials 80 and 90 by setting it as a shaping | molding member. Adhesive surface protection materials 80 and 90 isolate the adhesive layer 20 from the plasma and can prolong the life of the adhesive layer.
The adhesive surface protection materials 80 and 90 can be used in the form of a band, for example, by using an elastomer as a matrix. In this case. The elastic force of the elastomer enables it to be attached and fixed to the electrostatic chuck device, and the replacement operation is simplified.
Further, the adhesive surface protection members 80 and 90 can be fixed to the electrostatic chuck device by screwing or the like by using the matrix as the cured resin, and the electrostatic chuck device having the complicated structure is also possible. It can be processed according to the shape, can be fixed without gaps, and can be structurally strong.
In addition, although the resin composition of the present invention exerts an effect even if it is used for either the adhesive layer 20 or the adhesive surface protective materials 80 and 90 described above, the use of both of them further enhances the effect. Can play. Since the adhesive surface protection material has high plasma resistance, in addition to a decrease in replacement frequency, it is easy to replace, so that the maintenance time can be significantly shortened. In the case of the electrostatic chuck device where only the conventional adhesive is used, it is necessary to take the electrostatic chuck device out of the plasma processing apparatus, send it to the manufacturer for maintenance, and there is a situation where production can not be performed for a certain period However, there is an effect that the necessity is lost.

Examples of applications as other molded members include sealing materials such as packings and O-rings; and belt-like, sheet-like or three-dimensional structures.
The packing and the O-ring can be used, for example, as a sealing material at a connecting portion of a vacuum system (gas supply portion, plasma source, plasma processing chamber, exhaust pipe, etc.) in reduced pressure plasma. The conventional sealing material with low plasma resistance, which is used in the plasma source portion, plasma processing chamber, and exhaust piping, needs to be replaced once every several months due to deterioration due to plasma. By using the material, it is possible to prolong the life.
In addition, as an application of the structure having a three-dimensional structure, silicon wafer support pins of elevating rods that deliver a silicon wafer from a robot hand to a plasma device when loading and installing a wafer in a plasma processing device that is a semiconductor manufacturing device. Can be used, etc.

<Production of Resin Composition>
Example 1
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4 H ₂ O, average plate surface diameter: 249 nm, BET specific surface area relative to a commercially available silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) 50 m ² / g} was blended so as to be 15% by volume, and mixed in a bead mill.
(Comparative example 1)
Only commercially available silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) was only stirred by a bead mill.

<Plasma resistance evaluation>
(Plasma treatment 1)
The adhesive prepared in Example 1 and Comparative Example 1 is formed into a film of 10 cm × 10 cm × 100 μm thick on a PET peeling film, and then heated at 120 ° C. for 5 minutes in a drying furnace. Dried. After drying, the release film was removed to obtain a sample for evaluation.
The prepared sample for evaluation was placed on a flat surface in a plasma device and subjected to plasma treatment for 24 hours. The processing conditions of the plasma are shown below.
Plasma processing system: Unity Me (made by Tokyo Electron Ltd.)
High frequency power output: 1000 W
High frequency power supply frequency: 13.56 MHz
Bias power output: None Vacuum degree: 133.33Pa
Oxygen gas flow rate: 450 sccm
Fluorine gas flow rate: 50 sccm
Stage temperature: 25 ° C
Plasma treatment time: 24 hours

(Example 2)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² relative to a silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) / G} was blended so as to be 1.5% by volume, and mixed and adjusted with a 3-roll mill.
(Example 3)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² relative to a silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) / G} was blended so as to be 3.5% by volume, and mixed and adjusted with a 3-roll mill.
(Example 4)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² relative to a silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) / G} was blended so as to be 8.0% by volume, and mixed and adjusted with a 3-roll mill.
(Example 5)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² relative to a silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) / G} was blended so as to be 17.5% by volume, and mixed and adjusted with a 3-roll mill.
(Example 6)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) with respect to silicone adhesive (Momentive Performance Materials TSE 3032, mixing ratio TSE 3032 (A): TSE 3032 (B) = 100 parts by weight: 10 parts by weight) ) ₁₆ CO ₃ · 4 H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² / g} was blended so as to be 8.0% by volume, and mixed and adjusted with a three-roll mill.
(Example 7)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) with respect to silicone adhesive (Momentive Performance Materials TSE 3032, mixing ratio TSE 3032 (A): TSE 3032 (B) = 100 parts by weight: 10 parts by weight) ) ₁₆ CO ₃ · 4 H ₂ O, average plate surface diameter: 249 nm, and BET specific surface area: 50 m ² / g} were blended so as to be 33.3% by volume, and were mixed and adjusted with three rolls.
(Example 8)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (with respect to silicone adhesive ((Momentive Performance Materials TSE 3032, mixing ratio TSE 3032 (A): TSE 3032 (B) = 100 parts by weight: 10 parts by weight) OH) ₁₆ CO ₃ .4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² / g} was blended so as to be 50.0% by volume, and mixed and adjusted with a three-roll mill.
(Comparative example 2)
Only commercially available silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) was only stirred by a bead mill.
(Comparative example 3)
Hydrotalcite {Composition formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, average plate surface diameter: 249 nm, BET specific surface area: 50 m ² relative to a silicone adhesive (KE-1820 manufactured by Shin-Etsu Silicone Co., Ltd.) / G} was blended so as to be 0.5% by volume, and mixed and adjusted with a 3-roll mill.
(Comparative example 4)
A silicone adhesive (Momentive Performance Materials TSE 3032, mixing ratio TSE 3032 (A): TSE 3032 (B) = 100 parts by weight: 10 parts by weight) was mixed and adjusted by a mixer.

<Plasma resistance evaluation>
(Plasma treatment 2)
The adhesive prepared in each of Examples 2 to 8 and Comparative Examples 2 to 4 is formed into a film of 30 mm × 30 mm × 1 mm thick on a PET peeling film, and then at 120 ° C. in a drying furnace. It was heated for 2 hours to dry and cure. After curing, the release film was released to obtain a sample for evaluation.
The prepared sample for evaluation was placed on a flat surface in a plasma device and subjected to plasma treatment for 4 hours. The processing conditions of the plasma are shown below.
Plasma processing system: RIE-10 NRT (manufactured by SUMCO)
High frequency power output: 250 W
Bias power output: None Vacuum degree: 100 Pa
Oxygen gas flow rate: 45 sccm
CF ₄ flow rate: 5 sccm
Stage temperature: 25 ° C
Plasma treatment time: 4 hours

(Mass decrease measurement)
The mass reduction evaluation was performed by weighing the mass of the evaluation sample before and after plasma treatment using a direct reading balance (Metler: MS104TS / 00) to calculate the mass reduction rate. The measured results are shown in Tables 1 to 3. In the measurement, each evaluation sample was processed in three samples, and the average value was taken as the measurement result.

(Surface state change observation)
<Plasma treatment 1>
The surface condition was observed using a scanning microscope (manufactured by Hitachi High-Technologies Corporation: SE-5000), and the surface condition of the evaluation sample before and after the plasma treatment of the resin composition of Example 1 and Comparative Example 1 was observed. The results are shown in FIG.
<Plasma treatment 2>
Using a digital microscope (manufactured by Keyence Corporation: VHX-6000), changes in appearance of the evaluation samples before and after plasma treatment of the resin compositions of Examples 2 to 8 and Comparative Examples 1 to 3 were observed at a magnification of 500 times. Evaluation criteria are as follows.
○: No change in appearance of resin composition before and after plasma treatment.
Fair: slight streaks are observed in the resin composition after plasma treatment.
X: A plurality of clear streaks are observed in the resin composition after plasma treatment.

(Evaluation)
The mass reduction rate of Example 1 was 0.28%, and a good result of 1/10 or less was obtained as compared with Comparative Example 1. Also in the surface observation, no large change was observed while the crack was generated on the surface in Comparative Example 1. From this, the effects of the present invention can be understood.
Further, in Examples 2 to 8 and Comparative Examples 2 to 4, even if conditions are changed using another plasma apparatus (etching apparatus), the mass reduction rate of each Example can be suppressed to a low level, and Also in surface observation, it is clear that it is excellent in plasma resistance, and the effect of the present invention can be understood.

 

 

DESCRIPTION OF SYMBOLS 100 Electrostatic chuck apparatus 10 Suction surface 20 Adhesive layer 30 Insulating layer 40 Electric-insulation elastic layer 50 Metal base 60 Conductive part 70 Electrode 80, 90 Adhesive surface protection material

Claims (12)

1. A resin composition used in an environment exposed directly or indirectly to plasma, comprising:
   Matrix resin,
   And a filler of a layered inorganic compound having ion exchangeability dispersed in the matrix resin,
   The blending of the layered inorganic compound is characterized in that it is 1 to 90% by volume with respect to the sum of the volume of the matrix resin and the volume of the layered inorganic compound.
   Resin composition.
2. The resin composition according to claim 1, wherein the ion exchangeability is anion exchangeability.
3. The resin composition according to claim 1, wherein the layered inorganic compound is represented by the following formula (1).
   _{{A 1-x B x (} OH) 2} (D x / n) · mH 2 O (1)
   In the formula, A is a divalent metal ion, B is a trivalent metal ion, D is an n-valent anion, x is greater than 0 and in the range of 0.4 or less, and m is a real number greater than 0. .
4. The resin composition according to claim 3, wherein the layered inorganic compound is a layered inorganic compound represented by the following formulas (2) and (3).
   {Mg _1-x Al _x (OH) ₂ } (CO ₃ ) _{x / 2} · mH ₂ O (2)
   1.5 <(1-x) / x <4 (3)
5. The layered inorganic _compound, characterized in that it is a hydrotalcite represented by _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O, the resin composition according to claim 4 or 5.
6. The resin composition according to any one of claims 1 to 5, wherein the resin composition contains a silicone resin.
7. The resin composition according to any one of claims 1 to 6, wherein the resin composition is contained in a plasma etching apparatus.
8. The resin composition according to any one of claims 1 to 7, wherein the resin composition is an adhesive.
9. The resin composition according to any one of claims 1 to 7, wherein the resin composition is used as a resin molded member obtained by curing the resin composition.
10. 10. The resin composition according to claim 9, wherein the resin molded member is any one of a belt, a band, a packing, an O-ring, and a sheet.
11. The resin molded member is used as a protective material that covers the surface of an adhesive exposed portion used in an electrostatic chuck device provided in a plasma etching apparatus, and is used as a protective material that isolates the adhesive surface from plasma. 11. The resin composition according to item 9 or 10.
12. An electrostatic chuck device comprising the resin composition according to any one of claims 1 to 11.

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