JP2003119087A - Composite coating material, laminated body, corrosion resistant member, halogen gas plasma resistant member and method for manufacturing composite coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite coating material which is to be applied on a ceramic member and which has high heat resistance and hardly causes brittle fracture and dropping of particles. SOLUTION: The composite coating material contains a ceramic porous body having open pores and a resin impregnating the pores. The ceramic porous body has an effect to keep certain heat resistance while the resin filling the pores suppress brittle fracture and prevents dropping of the particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite coating material, a laminate, a corrosion resistant member, a halogen gas plasma resistant member, and a method for producing a composite coating material.

[0002]

2. Description of the Related Art Semiconductors requiring a super clean state
In body manufacturing equipment, deposition gas and etching gas
Chlorine gas as a cleaning gas and
Halogen-based corrosive gas such as fluorine-based gas is used
There is. For example, semiconductor manufacturing equipment such as thermal CVD equipment
However, after deposition, ClF_Three, NF _Three  , C
F_FourHalogen-based corrosive gas such as HF, HF, and HCl
The semiconductor cleaning gas consisting of In addition,
WF at the position stage₆  , SiH_TwoCl_TwoSuch
The halogen-based corrosive gas of
It

A chamber or dome for semiconductor manufacturing equipment
It is known to be formed of alumina, aluminum nitride, or silicon carbide ceramics.

[0004]

The inventor of the present invention has studied the formation of such a member for semiconductor manufacturing equipment using yttrium-aluminum garnet. However, since yttrium-aluminum garnet is brittle, cracks easily occur, which makes it difficult to use as a bulk material. Therefore, the present inventor
It was studied to coat the surface of the alumina base material with yttrium-aluminum garnet (Japanese Patent Application No. 2001).
-110136 specification). This aims to utilize the heat resistance and corrosion resistance of yttrium-aluminum garnet and to reduce the possibility of contamination by aluminum element. At this time, the yttrium-aluminum garnet coating has been studied to be formed by a thermal spraying method from the viewpoint of manufacturing cost and the advantage that the film thickness can be increased.

However, since the yttrium-aluminum garnet film formed by the thermal spraying method is generally porous, it has low strength and may be broken by thermal stress, or particles may fall off when ion-etched. Further, particles are likely to be generated from the film, and it is difficult to clean and remove contamination. For example, when particles fall from a ceramic member onto a wafer, defects such as film formation defects, insulation defects, and conduction defects occur, which causes semiconductor defects.

An object of the present invention is to provide a composite coating material provided on a ceramic member, which is less likely to cause brittle fracture and less likely to be shredded.

[0007]

The present invention provides a composite coating material provided on a ceramic member, which comprises a ceramic porous body having open pores and a resin impregnated in the open pores. It relates to a composite coating material characterized.

The present invention also provides a laminate comprising a ceramic member and a coating provided on the surface of the ceramic member, wherein the coating is made of the composite coating material. It is related to.

Further, the present invention is a method for producing a composite coating material provided on a ceramic member, wherein a ceramic porous body having open pores is formed on the ceramic member, and then a resin liquid is applied to the surface of the ceramic porous body. Is applied to fill the open pores with the resin solution, and then the resin solution is cured to generate the resin, whereby the open pores are impregnated with the resin.

The composite coating material of the present invention comprises a ceramic porous body having open pores and a resin impregnated in the open pores. This ceramic porous body bears heat resistance. However, there is brittleness only with a ceramic porous body,
Moreover, shedding is likely to occur. In particular, this tendency is strongly observed in the ceramic porous body formed by the thermal spraying method.
Therefore, by impregnating the open pores with resin, brittle fracture of the ceramic porous body is less likely to occur. At the same time, the resin impregnated into the open pores makes it difficult for the ceramic particles to be shed from the vicinity of the surface of the ceramic porous body. This resulted in a composite coating material with heat resistance, brittleness resistance and shatter resistance.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The ceramic constituting the ceramic porous body is not limited, but preferably has high heat resistance, and more preferably has high corrosion resistance. The following are particularly preferable as such ceramics. (1) Ceramics containing a composite oxide of a rare earth element or an alkaline earth element and alumina. In particular, a composite oxide of yttria and alumina. (2) Aluminum-containing ceramics. For example, alumina, aluminum nitride, sialon. (3) Nitride ceramics. For example, aluminum nitride, silicon nitride, sialon, silicon carbide.

The following are examples of the composite oxide of yttria and alumina. _{(1) Y 3 Al 5 O} 12 (YAG: yttrium - aluminum garnet). Yttria and alumina 3:
It is contained in a ratio of 5 and has a garnet crystal structure. (2) YAlO ₃ (YAP). Perovskite crystal structure. (3) Y ₄ Al ₂ O ₉ (YAM). Monoclinic system.

When the composite coating material of the present invention is applied to applications where high purity is required, particularly semiconductor production equipment applications, the ceramic porous body may contain a small amount of alkali metal or transition metal. Preferably 10 in total
It is preferably 0 ppm or less, and more preferably 30 ppm or less. In addition, this content is measured by inductively coupled plasma (ICP) or quantitative analysis by GD-MS.

The content of resin in the composite coating material is not limited. However, when the content of the resin is 5% by volume or more, the effect of the present invention becomes more remarkable. From this viewpoint, it is more preferable that the content of the resin is 8% by volume or more. Further, when the content of the resin is 30% by volume or less, it is easy to maintain the heat resistance and the corrosion resistance of the composite coating material at a high level. From this viewpoint, the content of the resin is more preferably 20% by volume or less. The content of the resin in the composite coating material is measured by observing the difference in porosity before and after the resin impregnation and observing the cross section.

The resin is not particularly limited, but from the viewpoint of heat resistance and corrosion resistance, fluororesin, silicone resin and polyimide resin are preferable.

Although the material of the ceramic member is not limited,
The following materials are particularly preferable. (1) A dense sintered body or a porous porous sintered body of alumina, aluminum nitride, or silicon carbide. (2) A paste layer or a coating layer containing powder of alumina, aluminum nitride or silicon carbide is formed on another base material, and the paste layer or the coating layer is sintered by a subsequent heat treatment. , A film of aluminum nitride or silicon carbide is formed.

The shape of the ceramic member is not particularly limited,
It may be plate-shaped or film-shaped.

In the preferred embodiment, an intermediate layer is provided between the ceramic member and the composite coating.

The material of the intermediate layer is not limited, but an yttrium compound is preferable. As the yttrium compound,
The following can be illustrated. (1) Yttria. (2) Solid solution containing yttria (zirconia-yttria solid solution, rare earth oxide-yttria solid solution). (3) Composite oxide containing yttria (for example, the above-mentioned yttrium-aluminum garnet, Y ₄ Al ₂ O)
₉ , YAlO ₃ ) (4) Yttrium trifluoride (5) Y-Al- (O) -F (6) Y ₂ Zr ₂ O ₇

More preferably, the yttrium compound forming the intermediate layer contains at least yttria. This includes yttria, solid solutions containing yttria, and complex oxides containing yttria.

The thickness of the coating is preferably 10 μm or more in order to exert the effect of the present invention. Further, from the viewpoint of suppressing the peeling or shedding of the coating from the ceramic member, it is preferably 1000 μm or less.

The coating of the present invention may be present continuously on the surface of the ceramic member. However, it is not essential that the entire surface of the ceramic member is formed continuously. For example, the case where the members are discontinuously generated on the surface of the member and a plurality of island-shaped layered products are formed is also included. It also includes the case where the film is scattered or scattered on a predetermined surface of the member.

The laminate of the present invention can be used as a base material for a corrosion resistant member. A target for which the corrosion resistant member exhibits corrosion resistance is a semiconductor manufacturing apparatus such as a thermal CVD apparatus.
In such a semiconductor manufacturing apparatus, a semiconductor clean gas composed of a halogen-based corrosive gas is used. The laminate of the present invention has corrosion resistance not only in the halogen gas plasma but also in the plasma atmosphere of the gas in which the halogen gas and the oxygen gas are mixed.

The laminate of the present invention can be used as a base material for a halogen gas plasma resistant member exposed to plasma of halogen gas. As halogen gas, ClF
₃ , NF ₃ , CF ₄ , WF ₆ , Cl ₂ , BCl _{3 and the} like can be exemplified.

In producing the composite coating material of the present invention, preferably, a ceramic porous body having open pores is formed on a ceramic member by a thermal spraying method, and then a resin liquid is applied to the surface of the ceramic porous body, After filling the open pores with this resin solution, the resin solution is cured to generate the resin, thereby impregnating the open pores with the resin.
This process will be described.

First, a raw material powder for a ceramic porous body is sprayed on a ceramic member or its precursor to form a sprayed film.

The pressure at the time of thermal spraying is not particularly limited, and a normal pressure spraying method or a low pressure spraying method can be adopted. The open porosity of the ceramic porous body can be adjusted by adjusting the pressure.

After forming the sprayed film, the sprayed film can be heat treated. The heat treatment temperature at this time is not limited, but preferably 1300 ° C. or higher, or 1800 ° C.
The following is preferable.

The raw material powder of the ceramic porous body may be a powder composed of the desired ceramic porous body, or may be a mixed powder that forms the ceramic porous body after thermal spraying (and the above-mentioned heat treatment).

For example, when it is desired to form a ceramic porous body made of a composite oxide containing yttria, the following raw materials can be used. (1) Spraying a powder of a composite oxide of yttria and alumina. (2) Spray a mixture of yttria powder and alumina powder.

Further, the raw material for the intermediate layer can be sprayed before the raw material for the ceramic porous body is sprayed. Also in this case, the raw material powder for the intermediate layer may be a powder made of the desired ceramic, or may be a mixed powder that forms the intermediate layer after thermal spraying (and the above-mentioned heat treatment).

When spraying the mixed powder, the mixed powder may be directly sprayed. Alternatively, a binder and a solvent may be added to the mixed powder and granulated by a spray drying method, and the granulated powder may be sprayed.

When spraying a mixed powder of yttria powder and alumina powder, the 50% average particle diameter of the yttria powder is preferably 0.1 μm or more and 100 μm or less. Further, the 50% average particle diameter of the alumina powder is preferably 0.1 μm or more and 100 μm or less. However, both the yttria powder and the alumina powder have a 50% average particle diameter (D50) of 1 when secondary particles do not exist.
The particle size of the secondary particles, and if secondary particles are present, the particle size of the secondary particles.

The ratio of yttria powder to alumina powder is not particularly limited. However, when converted to the mol ratio of yttria and alumina (yttria / alumina),
It is preferably 2-1 and more preferably 0.5-0.7.

The mixed powder is yttria powder or
The powder of the third component other than the lumina powder may be included.
However, such a third component is a yttria-alumina compound.
Crystal phase of garnet phase and perovskite phase of composite oxide film
It is preferable that it does not adversely affect
Garnet phase and pero of yttria-alumina composite oxide
Place yttria or alumina in the skeleton phase
It is preferable that the component be replaced. These ingredients
The following can be given as examples. La_TwoO_Three, Pr
_TwoO_Three, Nd_TwoO_Three, Sm_TwoO_Three, Eu_TwoO_Three, Gd_Two
O_Three, Tb_TwoO_Three, Dy_TwoO_Three, Ho_TwoO_Three, Er_TwoO
_Three, Tm_TwoO_Three, Yb_TwoO_Three, La_TwoO_Three, MgO, C
aO, SrO, ZrO_Two, CeO_Two, SiO_Two, Fe _Two
O_Three, B_TwoO_Three

Next, the resin liquid is applied onto the ceramic porous body, impregnated in the ceramic porous body, and cured. The resin liquid is not particularly limited, but is preferably a room temperature curable type or a thermosetting type. The curing temperature is determined according to the curing temperature of the resin liquid used.

Preferably, the resin liquid is vacuum degassed before the curing. At this time, it is preferable to put the ceramic member in a vacuum container.

Further, it is preferable that the impregnation of the resin liquid into the open pores is promoted by increasing the pressure of the ambient atmosphere of the ceramic member before or during the curing. This pressure is preferably 1 atm or more, more preferably 5 atm or more. Further, the ceramic member can be pressurized by housing the ceramic member in a closed container such as an autoclave and heating it.

The composite coating material of the present invention comprises 190
It has heat resistance in a temperature range of ℃ or less, preferably 130 ℃ or less.

[0040]

Example 1 A mixed powder of yttria powder and alumina powder was prepared. Yttria powder with a 50% average particle size of 0.5 μm was spray-dried to 3
Granulated to 0 μm. The 50% average particle diameter of the alumina powder was set to 30 μm. Yttria particles and alumina particles were mixed in a weight ratio of 57.1: 42.9. The molar ratio of yttria to alumina is 3: 5. The yttria powder and the alumina powder were wet mixed using a ball mill.

A member made of a flat alumina plate having a size of 10 mm × 10 mm × thickness of 2 mm was prepared (alumina purity 99.7%). The surface of this member was ultrasonically cleaned, and the mixed powder was plasma sprayed onto the cleaned surface using a plasma spraying machine manufactured by Sruzer Metco. When spraying,
Argon was supplied at a flow rate of 40 liters / minute, and hydrogen was supplied at a rate of 12
Flowed at a flow rate of 1 / min. The spray output was 40 kW and the spray distance was 120 mm. 1 for the obtained laminated body
Heat treatment was performed at 500 ° C. to form a ceramic porous body film.

Next, a liquid fluororesin was applied onto the ceramic porous film, the laminate was then housed in a vacuum container and kept at room temperature, and the air in the resin liquid was degassed by vacuum. Then, the laminate was taken out from the vacuum container into the atmosphere and
The composite coating material of the present invention was obtained by heating and curing at ℃.

Next, the crystal phase in this composite coating material and the volume% (vol.%) Of the resin were measured by the following method, and the presence or absence of cracks and shedding were evaluated.

(Identification of crystal phase) The crystal phase was identified by an X-ray diffractometer. And YAL (420) / YAG (4
20) was calculated. The measurement conditions are as follows. CuKα, 50kV, 300mA, 2 θ = 20-70 ° Device used: Rotating anticathode type X-ray diffractometer "Rigaku Denki" R
“INT” ”(volume% of resin) The porosity of the porous body layer before impregnating the resin and the porosity of the composite coating layer after impregnating the resin are measured, and the difference is measured by the volume% (vol. %). (Presence or absence of cracks) The surface of the coating was observed with a scanning electron microscope at a magnification of 5000 times. (Evaluation of shedding) Scotch tape was adhered to the surface of each coating, and then the tape was peeled off. Then, a 1 mm × 1 mm field of view was observed with a scanning electron microscope on the adhesive surface of the peeled tape, and the number of particles having a size of 1.0 μm or more attached to the adhesive surface was counted.

As a result, an yttrium-aluminum garnet crystal phase was confirmed. The resin density was 10% by volume. No crack was found on the film surface. And the number of shredded particles was two.

Example 2 In Example 1, the resin was changed to a silicone resin. Also, cure 120
Performed at ° C. As a result, a yttrium-aluminum garnet crystal phase was confirmed. The resin density was 12% by volume. No crack was found on the film surface. And the number of shredded particles was 4.

(Example 3) In Example 1, the resin was changed to a polyimide resin. Also, cure 220
Performed at ° C. As a result, a yttrium-aluminum garnet crystal phase was confirmed. The resin density was 8% by volume. No crack was found on the film surface. Then, the number of shredded particles was 3.

Comparative Example 1 Under the same conditions as in Example 1, a porous material coating was formed on the alumina member. However, neither impregnation of the resin liquid nor curing was performed in this film. As a result, a yttrium-aluminum garnet crystal phase was confirmed. The porosity of this coating was measured by the Archimedes method and found to be 10%. The number of shed particles was 70.

[0049]

As described above, according to the present invention, it is possible to provide a composite coating material provided on a ceramic member, which is less likely to cause brittle fracture and less likely to be shed.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 4/18 C23C 4/18 F term (reference) 4F100 AA33B AD01A AD01B AK01C AT00D AT00E BA03 BA04 BA05 BA07 BA10A BA10C BA10E BA13 DD20B DJ00B EH462 EH56B EH562 EJ592 EJ82C EJ962 YY00C 4K031 AA08 AB02 AB03 AB11 CB09 CB14 CB42 CB43 CB45 CB46 CB47 FA01 FA09

Claims (14)

[Claims] 1. A composite coating material provided on a ceramic member, comprising: a ceramic porous body having open pores; and a resin impregnated in the open pores. . 2. The content of the resin in the composite coating material is 5 to 30% by volume,
The material according to claim 1. 3. The material according to claim 1, wherein the ceramic porous body is composed of at least one of yttria, alumina, and a composite oxide of yttria and alumina. 4. The material according to claim 1, wherein the ceramic porous body is formed by a thermal spraying method. 5. A laminated body comprising a ceramic member and a coating provided on the surface of the ceramic member, wherein the coating is a composite coating according to any one of claims 1 to 4. A laminate, which is made of a material. 6. An intermediate layer is provided between the ceramic member and the coating.
The laminate described. 7. The thickness of the coating is 10 μm or more,
It is 1000 micrometers or less, The laminated body of Claim 5 or 6 characterized by the above-mentioned. 8. A laminate comprising the laminate according to any one of claims 5 to 7 as a base material,
Corrosion resistant material. 9. A halogen gas plasma resistant member that is exposed to a plasma of a halogen gas, comprising the laminate according to any one of claims 5 to 7 as a base material. And a member for halogen gas plasma resistant. 10. A method for producing a composite coating material provided on a ceramic member, comprising forming a ceramic porous body having open pores on the ceramic member, and then applying a resin liquid to the surface of the ceramic porous body. A method for producing a composite coating material, comprising: filling the resin liquid into the open pores, and then curing the resin liquid to generate a resin, thereby impregnating the resin into the open pores. 11. The method according to claim 10, wherein the content of the resin in the composite coating material is 5 to 30% by volume. 12. The ceramic porous body is yttria,
The method according to claim 10 or 11, which comprises at least one of alumina and a composite oxide of yttria and alumina. 13. The method according to claim 12, wherein the ceramic porous body is formed into a film by a thermal spraying method. 14. The method according to claim 10, wherein the resin liquid is vacuum degassed in a state where the resin liquid is applied to the ceramic porous body.