JP5545792B2 - Corrosion resistant material - Google Patents

Description

  The present invention relates to a corrosion-resistant member used in an environment such as a halogen-based corrosive gas or a halogen-based gas plasma.

In a semiconductor manufacturing apparatus or a flat panel display manufacturing apparatus, since manufacturing is performed in an environment such as a halogen-based corrosive gas or a halogen-based gas plasma, a member having corrosion resistance is used. In recent years, the corrosion resistance of rare earth compounds has been confirmed, and among them, yttrium oxide has attracted attention. And the member which gave the corrosion-resistant film | membrane which contains a yttrium oxide on the base-material surface is proposed. (For example, see Patent Document 1)
JP 2001-164354 A

  However, in order to increase the accuracy of the device, it is necessary to have a lower particle property with respect to members used inside a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus or the like.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a corrosion-resistant member that reduces particles generated by use in an environment such as a halogen-based corrosive gas and a halogen-based gas plasma.

In order to achieve the above object, a corrosion-resistant member according to the present invention has, for example, the following configuration.
That is, a base material, a gadolinium oxide sol-gel film formed on the base material by a sol-gel method, and a thermal spray coating formed on the gadolinium oxide sol-gel film by a thermal spray method, the thermal spray coating is made of yttrium and gadolinium. The gadolinium oxide sol-gel film is made of an oxide containing any of the above, and has a thickness of 0.05 μm or more and 10 μm or less, and is heat-treated at 300 ° C. or more and 1200 ° C. or less to provide a corrosion-resistant member.

  In addition, for example, the corrosion-resistant member is used in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus. Or electrostatic chuck, heater, gas dispersion plate, baffle plate, baffle ring, shower plate, and chamber, bell jar, dome and their inner wall materials, and high-frequency transmission window, infrared transmission window, monitoring window, susceptor, clamp ring, It is a focus ring, a shadow ring, an insulating ring, a dummy wafer, a lift pin for supporting a semiconductor wafer, a bellows cover, a cooling plate, an upper electrode, or a lower electrode.

  ADVANTAGE OF THE INVENTION According to this invention, the corrosion-resistant member which further reduces the particle | grains which generate | occur | produce by use in environments, such as halogen-type corrosive gas and halogen-type gas plasma, can be provided.

  As a result of intensive studies, the present inventors have found that a gadolinium oxide sol-gel film exhibits excellent corrosion resistance when exposed to a halogen-based corrosive gas or a halogen-based gas plasma, and the generation of particles is reduced. It has also been found that the gas barrier property is high when exposed to halogen-based corrosive gas or halogen-based gas plasma.

(Configuration of corrosion resistant member)
Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.

  In the present embodiment, the material of the substrate is not particularly limited, but glass, quartz, metals such as aluminum and stainless steel, ceramics such as alumina, and the like can be used. Further, if necessary, the surface may be roughened by blasting.

  The thickness of the gadolinium oxide sol-gel film of this embodiment is preferably 0.05 μm or more and 10 μm or less. When the thickness is 0.05 μm or more, the effect of particle reduction can be expected. Moreover, when the thickness is 10 μm or less, the adhesion strength to the substrate can be maintained, and peeling and chipping can be prevented. In particular, it is preferably 0.05 μm or more and 1 μm or less.

  The method for forming the gadolinium oxide sol-gel film of this embodiment is not particularly limited, and a spray method, a dip method, an ink jet method, or the like can be used.

  The firing temperature of the gadolinium oxide sol-gel film of this embodiment is preferably 300 ° C. or higher and 1200 ° C. or lower. When the firing temperature is 300 ° C. or higher, the gadolinium interparticle bonding is sufficient, and the effect of particle reduction can be expected. In addition, when the firing temperature is 1200 ° C. or less, grain growth can be suppressed, and the effect of particle reduction can be expected. Moreover, peeling and cracks due to internal stress or thermal expansion can be suppressed by setting the firing temperature to 1200 ° C. or less.

  The gadolinium oxide sol-gel film having a firing temperature of 1200 ° C. or less is formed in close contact with the substrate with a strength of 20 MPa or more. By setting the adhesion strength between the gadolinium oxide sol-gel film and the substrate to 20 MPa or more, peeling of the gadolinium oxide sol-gel film during use or during cleaning can be prevented. When peeled off, particles are likely to be generated from the exposed portion of the substrate, but this can be prevented.

  The thickness of the thermal spray coating of the present embodiment is preferably 50 μm or more and 1000 μm or less. By setting the thickness to 50 μm or more, an effect of corrosion resistance can be expected even when exposed to halogen-based corrosive gas or halogen-based gas plasma. Further, by setting the thickness to 1000 μm or less, it is possible to suppress peeling and cracking due to internal stress and thermal expansion between the base material and the thermal spray coating.

The porosity of the thermal spray coating of the present embodiment is preferably 5% or more and 15% or less. By setting the porosity to 5% or more, it is possible to prevent the thermal spray coating from peeling or cracking. Further, by setting the porosity to 15% or less, sufficient strength can be maintained, cracking and peeling can be prevented, and permeation of halogen-based corrosive gas and halogen-based gas plasma can be suppressed.

  The formation method of the thermal spray coating of the present embodiment is not particularly limited, but can be formed by flame spraying, high-speed flame spraying (HVOF), plasma spraying, explosion spraying, cold spray, aerosol deposition method, or the like. Among these, it is preferable to form by plasma spraying which has a high spraying power and is suitable for spraying a high melting point material.

  The gas used for plasma generation during plasma spraying in this embodiment is not particularly limited, and argon gas, helium gas, nitrogen gas, hydrogen gas, oxygen gas, or the like can be used.

  The thermal spray powder used to form the thermal spray coating of this embodiment preferably has an average particle size of 20 μm or more and 60 μm or less. By setting the average particle size to 20 μm or more, the thermal spray powder can flow on the plasma flame without being blown off when being applied to the plasma flame, and can adhere to the member in a molten state.

  Further, by setting the average particle size to 60 μm or less, the sprayed powder does not pass through the plasma flame when it is introduced into the plasma flame, but can flow over the plasma flame and adhere to the member in a molten state. It is particularly preferable to use a thermal spray powder having an average particle size of 30 μm or more and 50 μm or less.

  The purity of the sprayed coating and the gadolinium oxide sol-gel film of this embodiment is preferably 99.9% or more. When the purity is 99.9% or more, the corrosion resistance is improved, and generation of particles can be suppressed even when exposed to halogen-based corrosive gas and halogen-based gas plasma.

  An embodiment according to the present invention will be described below. However, this invention is not limited at all by each Example demonstrated below.

  The average particle size of the thermal spray powder described below was measured using a laser diffraction / scattering particle size measuring machine.

  The number of particles in the examples described below is such that a gadolinium oxide sol-gel film or a sprayed coating is irradiated for 10 hours in CF4 plasma with an RIE apparatus, and then the number of particles of 0.5 μm or more is measured using a particle counter. Measurements were made.

  The etching rate described below is performed by masking a part of the gadolinium oxide sol-gel film or sprayed film with polyimide tape, irradiating it in CF4 plasma with an RIE apparatus for 10 hours, and then measuring the level difference in the presence or absence of masking. Determined by doing.

(Samples 1, 2)
Prepare a 100 × 100 × 5t (mm) aluminum substrate with a blasting treatment on the substrate surface, spray gadolinium oxide sol onto the substrate surface using a spray nozzle, and a firing temperature of 400 ° C. in an electric furnace. Heating was performed for 5 hours to form a 1 μm gadolinium oxide sol-gel film.

  Thereafter, a spray powder of gadolinium oxide and yttrium oxide having an average particle size of 30 μm to 40 μm and a purity of 99.9% was used using an ASP7100 plasma spraying machine manufactured by Aeroplasma Co., Ltd., voltage 275 V, current 110 A, argon gas flow rate 25 L / min, oxygen Under a spraying condition of a gas flow rate of 40 L / min, a sprayed coating of 200 μm to 300 μm was formed on the gadolinium oxide sol-gel film, and the number of particles and the etching rate were measured.

(Samples 3 and 4)
A sprayed powder of gadolinium oxide having an average particle size of 30 μm to 40 μm and a purity of 99.9%, a yttrium oxide spray powder, and an aluminum substrate of 100 × 100 × 5 t (mm) having a blasted surface were prepared. Then, using an ASP7100 plasma spraying machine manufactured by Aeroplasma Co., Ltd., a spray coating of 200 μm to 300 μm on the aluminum substrate under the spraying conditions of voltage 275 V, current 110 A, argon gas flow rate 25 L / min, oxygen gas flow rate 40 L / min. And the number of particles and the etching rate were measured.

FIG. 1 shows the measurement results of samples 1 to 4 manufactured in this way. Specifically, the measurement results of the number of particles and the etching rate with and without the gadolinium oxide sol-gel film are shown.
As is clear from FIG. 1, the samples 1 to 4 have no difference in the etching rate depending on the presence or absence of the gadolinium oxide sol-gel film, but the gadolinium oxide sol-gel film is formed by forming the gadolinium oxide sol-gel film as in samples 1 and 2. The number of particles is reduced to 1/3 to 1/4 compared to the samples 3 and 4 which are not formed.

In Samples 3 and 4, peeling occurred between the base material and the gadolinium oxide sprayed film. Therefore, it was found that by forming a gadolinium oxide sol-gel film, the halogen-based corrosive gas and the halogen-based gas plasma are blocked, and a reduction effect can be obtained with respect to the generation of particles from the substrate.

(Samples 5-9)
A 100 × 100 × 5 t (mm) aluminum oxide base material having a blasted surface is prepared, and gadolinium oxide sol is sprayed on the surface of the base material using a spray nozzle. A gadolinium oxide sol-gel film of 0.03 μm (sample 5), 0.05 μm (sample 6), 1 μm (sample 7), 10 μm (sample 8), and 20 μm (sample 9) was formed by heating at a temperature of 5 hours.

  Thereafter, a sprayed powder of gadolinium oxide having an average particle size of 30 μm to 40 μm and a purity of 99.9% was used using an ASP7100 plasma spraying machine manufactured by Aeroplasma Corporation, voltage 275 V, current 110 A, argon gas flow rate 25 L / min, oxygen gas flow rate 40 L. A sprayed coating of 200 μm to 300 μm was formed on the gadolinium oxide sol-gel film under the spraying condition of / min, and the number of particles was measured.

(Samples 10-14)
Prepare a 100x100x5t (mm) aluminum oxide base material that has been blasted on the surface of the base material, spray gadolinium oxide sol onto the surface of the base material using a spray nozzle, and firing temperature of 700 degrees in an electric furnace. Heated at C for 5 hours to form gadolinium oxide sol-gel films of 0.03 μm (sample 10), 0.05 μm (sample 11), 1 μm (sample 12), 10 μm (sample 13), and 20 μm (sample 14).

  Thereafter, a sprayed powder of gadolinium oxide having an average particle size of 30 μm to 40 μm and a purity of 99.9% was used using an ASP7100 plasma spraying machine manufactured by Aeroplasma Corporation, voltage 275 V, current 110 A, argon gas flow rate 25 L / min, oxygen gas flow rate 40 L. A sprayed coating of 200 μm to 300 μm was formed on the gadolinium oxide sol-gel film under the spraying condition of / min, and the number of particles was measured.

(Samples 15-19)
A 100 × 100 × 5 t (mm) aluminum oxide base material is prepared by blasting the base material surface, and gadolinium oxide sol is sprayed onto the base material surface using a spray nozzle, and the firing temperature is 1500 degrees in an electric furnace. Heated at C for 5 hours to form gadolinium oxide sol-gel films of 0.03 μm (sample 15), 0.05 μm (sample 16), 1 μm (sample 17), 10 μm (sample 18), and 20 μm (sample 19).

  Thereafter, a sprayed powder of gadolinium oxide having an average particle size of 30 μm to 40 μm and a purity of 99.9% was used using an ASP7100 plasma spraying machine manufactured by Aeroplasma Corporation, voltage 275 V, current 110 A, argon gas flow rate 25 L / min, oxygen gas flow rate 40 L. A sprayed coating of 200 μm to 300 μm was formed on the gadolinium oxide sol-gel film under the spraying condition of / min, and the number of particles was measured.

  FIG. 2 shows the measurement results of samples 5 to 19 manufactured in this way. Specifically, the number of particles depending on the thickness of the gadolinium oxide sol-gel film and the firing temperature is shown.

  Samples 5 to 9 having a baking temperature of 200 ° C. for the gadolinium oxide sol-gel film have a large number of particles, not limited to the thickness. In sample 9, peeling of the gadolinium oxide sol-gel film occurred.

  In samples 15 to 19 having a baking temperature of 1500 ° C. for the gadolinium oxide sol-gel film, peeling of the gadolinium oxide sol-gel film occurred due to internal stress or thermal expansion. Furthermore, the number of particles is large due to peeling of the gadolinium oxide sol-gel film.

  In the samples 10 to 14 where the baking temperature of the gadolinium oxide sol-gel film is 700 ° C., the samples 11 to 13 have a small number of particles and the gadolinium oxide sol-gel film does not peel off. Sample 10 and sample 14 had a large number of particles, and in sample 14, peeling of the gadolinium oxide sol-gel film occurred.

  From the above results, the gadolinium oxide sol-gel film is heat treated at a thickness of 0.05 μm or more and 10 μm or less at 300 ° C. or more and 1200 ° C. or less to block halogen-based corrosive gas and halogen-based gas plasma, and from the substrate. It was found that a reduction effect can be obtained against the generation of particles.

  Corrosion-resistant members in which a gadolinium oxide sol-gel film is formed on a base material and a thermal spray coating is formed on the gadolinium oxide sol-gel film have excellent corrosion resistance against halogen-based corrosive gas or halogen-based gas plasma. It is suitable for use in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus exposed to a gas or halogen-based gas plasma.

In addition, as a member used in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus, for example, an electrostatic chuck, a heater, or the like is used for a member having an electrostatic electrode or a resistance heating element. be able to.
Since a metal having low corrosion resistance is often used for the electrostatic electrode or the like, the corrosion resistance and gas barrier property can be greatly improved by forming them with the corrosion-resistant member of the present invention, thereby reducing particles.

The corrosion-resistant member of this embodiment can be used for a gas dispersion plate, a baffle plate, a baffle ring, a shower plate, etc. for introducing a halogen-based corrosive gas into the apparatus.
Furthermore, it can be applied to chambers, bell jars, domes and their inner wall materials, which are processing containers into which gas is introduced, and high-frequency transmission windows, infrared transmission windows and monitoring windows, and susceptors and clamp rings used in the containers. It is exposed to halogen-based corrosive gas and halogen-based gas plasma such as focus ring, shadow ring, insulation ring, dummy wafer, lift pin to support semiconductor wafer, bellows cover, cooling plate, upper electrode, lower electrode, etc. It can be applied to various required members.

(1) As described above, the corrosion-resistant member according to the present embodiment is formed of a base material, a gadolinium oxide sol-gel film formed on the base material by a sol-gel method, and a spray method on the gadolinium oxide sol-gel film. By providing the thermal sprayed coating, a sol-gel film formed of gadolinium oxide, which is a high plasma resistant material, is provided. As a result, particles can be reduced even when used in an environment such as halogen-based corrosive gas and halogen-based gas plasma.
Furthermore, the halogen-based corrosive gas and the halogen-based gas plasma can be shut off to suppress particles and peeling from the substrate.

(2) And, for example, the thermal spray coating of the present embodiment is characterized by being made of an oxide containing any one of yttrium, gadolinium, aluminum and zirconium. Thereby, even if the surface of the member is exposed to the halogen-based corrosive gas and the halogen-based gas plasma, the particles from the sprayed coating can be reduced because the member is formed with a highly corrosion-resistant coating.

(3) Further, for example, the corrosion-resistant member of this embodiment is characterized in that the gadolinium oxide sol-gel film is heat-treated at a temperature of not less than 0.05 μm and not more than 10 μm, and not less than 300 ° C. and not more than 1200 ° C. Thereby, a highly dense and highly corrosion-resistant sol-gel film can be obtained.

(4) Further, for example, the corrosion-resistant member of this embodiment is characterized in that it is used in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus. Alternatively, as described above, it has a high corrosion resistance, and is difficult to transmit halogen-based corrosive gas and halogen-based gas plasma. Suitable for use in halogen-based gas plasma environments.

(5) Further, the corrosion-resistant member of the embodiment of the present invention includes an electrostatic chuck, a heater, a gas dispersion plate, a baffle plate, a baffle ring, a shower plate, a chamber, a bell jar, a dome and their inner wall materials, and high-frequency transmission. Window, infrared transmission window, monitoring window, susceptor, clamp ring, focus ring, shadow ring, insulating ring, dummy wafer, lift pin to support semiconductor wafer, bellows cover, cooling plate, upper electrode, lower electrode Specifically, by using it as a member as described above, the generation of particles is reduced and the industrial effect is enhanced.

FIG. 1 is a table showing the number of particles and the etching rate depending on the presence or absence of a gadolinium oxide sol-gel film according to an embodiment of the present invention. FIG. 2 is a table showing the thickness of the gadolinium oxide sol-gel film in this example and the number of particles depending on the firing temperature.

Claims (3)

A substrate;
A gadolinium oxide sol-gel film formed on the substrate by a sol-gel method;
A thermal spray coating formed by a thermal spraying method on the gadolinium oxide sol-gel film ,
The thermal spray coating is made of an oxide containing any one of yttrium and gadolinium, and the gadolinium oxide sol-gel film is heat-treated at a temperature of not less than 0.05 μm and not more than 10 μm, and not less than 300 ° C. and not more than 1200 ° C. Corrosion resistant member. The corrosion-resistant member according to claim 1 , wherein the corrosion-resistant member is used in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus. Electrostatic chuck, heater, gas diffusion plate, baffle plate, baffle ring, shower plate, chamber, bell jar, dome and their inner wall materials, high frequency transmission window, infrared transmission window, monitoring window, susceptor, clamp ring, focus ring 3. The corrosion-resistant member according to claim 2 , wherein the member is any one of a lift ring, a bellows cover, a cooling plate, an upper electrode, and a lower electrode for supporting a shadow ring, an insulating ring, a dummy wafer, and a semiconductor wafer.

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