JP2000247726A - Member for semiconductor producing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a member for a semiconductor producing apparatus, having corrosion resistance sufficient to a corrosive gas atmosphere and slightly causing particles and a member for a semiconductor producing apparatus having strong thermal shock. SOLUTION: This member for a semiconductor producing apparatus is used for a semiconductor producing apparatus for carrying out a treatment using a corrosive gas and comprises a ceramic sintered compact having <=10% porosity and >=1 μm surface roughness Ra. The member is especially suitable in the case in which the member is used as a part or the whole of a semiconductor production treatment vessel for carrying out the treatment using a corrosive gas in the vessel. The preferable shape consists essentially of a spherical surface shape part composed of a first spherical surface part having >=300 mm radius of curvature R1 and a second spherical surface part continued to the end part of the first part and having >=10 mm radius of curvature R2. Either the first spherical part or the second spherical part is inscribed in the other and the thickness of the spherical surface shape part is 5-15 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor manufacturing apparatus for performing a predetermined process on a semiconductor wafer with a corrosive gas such as a plasma generated by a high frequency or microwave from a halogen-based gas or the like. The present invention relates to a member for a manufacturing apparatus.

[0002]

2. Description of the Related Art In recent years, in a semiconductor manufacturing process, use of corrosive gas such as plasma generated by introducing high frequency or microwave into an atmosphere such as a halogen-based gas has been increasing. Such a corrosive gas is highly reactive, and in a semiconductor manufacturing apparatus that performs a predetermined process using the corrosive gas, a part of the member exposed to the corrosive gas has a certain member life. High corrosion resistance is required.
Representative members requiring such high corrosion resistance include a processing container such as a bell jar, an electrostatic chuck, a susceptor, and a clamp ring.

On the other hand, in the semiconductor manufacturing process, there is another problem of particle contamination on the semiconductor wafer, and the members of the semiconductor manufacturing apparatus are required to have high corrosion resistance and to reduce the number of particles from the members. .

Conventionally, quartz or stainless steel has been used as such a member, but there is a problem that the life of the member is short due to insufficient corrosion resistance to the above-mentioned corrosive gas.

For this reason, ceramics sintered bodies such as alumina, aluminum nitride, yttrium-aluminum-garnet, and the like are being used as members having excellent corrosion resistance in place of quartz and stainless steel.

During operation of the semiconductor manufacturing apparatus, the surface of the member exposed to a corrosive gas such as a halogenated gas plasma reacts with the corrosive gas to form a halide. An oxide film is formed. Since the halide is stable against corrosive gas, it has a function of reducing the corrosion rate of the member.

When the member is quartz or the like, the halide formed on the surface has a low boiling point and volatilizes quickly, so that corrosion proceeds at a high speed. However, alumina, aluminum nitride, yttrium-aluminum In a ceramic sintered body such as garnet, the halide formed on the member surface has a high boiling point, and this film delays the progress of corrosion. Therefore, the film has higher corrosion resistance than quartz or the like.

As described above, the halide film on the member surface has low reactivity to corrosive gas, but the corrosion gradually progresses, is decomposed into volatile substances, and is removed from the surface. Then, the surface of the new member is exposed and reacts with the corrosive gas to form a halide film again. Of this series of corrosion mechanisms,
The rate-limiting step of the corrosion rate is the reaction rate between the halide and the corrosive gas. Therefore, a film having a low reactivity with a corrosive gas of a generated halide film has excellent corrosion resistance.

On the other hand, JP-A-10-45461, JP-A-10-45467, and JP-A-10-23687
No. 1 discloses that a sintered body of yttrium-aluminum-garnet has excellent corrosion resistance and has a porosity of 3% or less and a surface roughness Ra in order to obtain better corrosion resistance.
Is set to 1 μm or less.

It has been conventionally known that yttrium-aluminum-garnet has excellent corrosion resistance. However, in the above-mentioned technique, yttrium-aluminum-garnet or the like reduces porosity and surface roughness as described above. It is described that a material having high corrosion resistance to plasma of a fluoride-based gas is thereby obtained.

In the above publication, the reason for reducing the porosity and the surface roughness is that if the surface roughness Ra is large, the contact area exposed to the plasma increases, the plasma is concentrated on the projections of the irregularities, and the porosity decreases. The reason is that if the value is large, the corrosion resistance is lowered due to selective corrosion of the pores. For this reason, Japanese Patent Application Laid-Open Nos.
Japanese Patent Application Publication No. 0-236871 describes that even when Ra is within the range of 1 μm, a material whose Ra is remarkably reduced by a mirror surface treatment exhibits better corrosion resistance.

[0012]

However, during the operation of the semiconductor manufacturing apparatus, the surface portions of the members used in the semiconductor manufacturing apparatus are, as time passes, halides formed by reacting with the corrosive gas described above. And the precipitates formed by substances evaporated by the wafer etching process, etc. These halide films and precipitates tend to peel off when grown to a certain thickness, which has an adverse effect on semiconductor products. Causes generation of particles.
In particular, when the surface roughness Ra is small as described above, such peeling is likely to occur. For this reason, there is a demand for a member that has high corrosion resistance and generates less particles.

[0013] Originally, a ceramic sintered body is a material having a low thermal shock resistance, in which a crack is generated by a slight temperature difference, so that a temperature difference is generated as in a processing vessel in which a plasma atmosphere is formed. It is difficult to apply to.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a member for a semiconductor manufacturing apparatus which has sufficient corrosion resistance to a corrosive gas atmosphere and generates few particles. I do. Another object of the present invention is to provide a member for a semiconductor manufacturing apparatus that is resistant to thermal shock in addition to the above.

[0015]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have formed a member for a semiconductor manufacturing apparatus with a ceramic sintered body, and have set an allowable range of the porosity of the sintered body. It has been found that by increasing the surface roughness to some extent and increasing the surface roughness, particles are less likely to be generated while maintaining sufficient corrosion resistance against corrosive gases such as halogen-based gas plasma. It has been found that such an effect is remarkable among members for semiconductor manufacturing equipment, particularly when used as a part or all of a processing container for semiconductor manufacturing in which a process is performed using a corrosive gas. did.

Further, while maintaining such surface roughness, yttrium-aluminum-
It has been found that when garnet is used, the generation of such particles is reduced, and in particular, the particle suppression effect can be further enhanced by increasing the amount of SiO _{2 in} the sintered body to some extent.

Further, the ceramic sintered body generally has low thermal shock resistance, but by devising the shape of the member, the thermal stress generated in the member can be reduced. It has been found that sufficient thermal shock resistance can be obtained as a container member.

The present invention has been made based on such knowledge, and a first invention is a member for a semiconductor manufacturing apparatus used in a semiconductor manufacturing apparatus for performing processing using a corrosive gas, comprising Provided is a member for a semiconductor manufacturing apparatus, wherein the member is made of a ceramic sintered body having a ratio of 10% or less and a surface roughness Ra of more than 1 μm.

A second aspect of the present invention is a member for a semiconductor manufacturing apparatus used as a part or all of a processing chamber for semiconductor manufacturing in which a process is performed using a corrosive gas, wherein the porosity is 10% or less. And a member for a semiconductor manufacturing apparatus characterized by comprising a ceramic sintered body having a surface roughness Ra of at least 1 μm exposed to a corrosive gas.

According to a third aspect, in the second aspect, a first spherical portion having a radius of curvature R1 of 300 mm or more and a second spherical portion continuous to an end of the first portion and having a radius of curvature R2 of 10 mm or more are provided. Mainly a curved surface portion composed of a spherical portion, one of the first spherical portion and the second spherical portion is inscribed in the other, and the thickness of the curved portion is in the range of 5 to 15 mm. A member for a semiconductor manufacturing apparatus is provided.

A fourth aspect of the present invention is the member for a semiconductor manufacturing apparatus according to any one of the first to third aspects, wherein a main constituent phase of the ceramic sintered body is a yttrium-aluminum-garnet sintered body. I will provide a.

According to a fifth aspect of the present invention, there is provided a member for a semiconductor manufacturing apparatus used in a semiconductor manufacturing apparatus for performing processing using a corrosive gas, wherein the porosity is 10% or less and the surface roughness Ra is 1 μm.
m, a sintered body of yttrium-aluminum-garnet having a SiO ₂ content of 0.15% by weight
And 10% by weight or less.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The member for a semiconductor manufacturing apparatus of the present invention has a porosity of 1
It is made of a ceramic sintered body having a surface roughness Ra of 0% or less and having a surface roughness Ra of more than 1 μm, and is preferably used as a member for a semiconductor manufacturing apparatus that has less corrosion than conventional ones while maintaining excellent corrosion resistance. Has characteristics.

By making the surface roughness Ra of the ceramic sintered body larger than 1 μm as described above, the unevenness on the surface of the member brings about an anchor effect on a halide film or a precipitate formed on the surface. In addition, the precipitates are less likely to be separated, and the generation of particles is reduced. That is, when the surface roughness Ra is larger than 1 μm, the surface area increases, and the number of sites for holding the halogenated film and the precipitates increases. When Ra is less than 1 μm, the corrosion resistance is improved, but the anchor effect is small, and the adhesion of the film is weak, so that continuous production becomes difficult, which is unsuitable as a member for a processing container. R
The more preferable range of a is 3 to 500 μm. 500
If it exceeds μm, the anchor effect is sufficient, but the etching rate is increased and the corrosion resistance is slightly lowered, which is not preferable.

As a method for making Ra more than 1 μm, various processings such as blasting can be mentioned, but the most preferable method is to make Ra more than 1 μm on the surface of the sintered body after burning. If the thickness does not exceed 1 μm by annealing, perform processing at the stage of the molded body, and after sintering,
May be exceeded. The reason why the annealed surface is preferable is that when the surface of the sintered body is processed to have a thickness of more than 1 μm, microcracks are induced on the surface of the sintered body, and the electric field during the plasma treatment is concentrated on the cracks, thereby deteriorating corrosion resistance. That's why. Therefore, when trying to obtain Ra of more than 1 μm in the processing of the sintered body, it is preferable to perform a heat treatment such as heating the sintered body after processing to close or dull cracks.

Not only the surface roughness of the sintered body but also the pores on the surface of the ceramic sintered body constituting the member contribute to the anchor effect. That is, the presence of a large number of pores on the surface of the sintered body allows the halogenated film and the precipitate to be held in such a manner as to bite into the pores, making it difficult for them to peel off, thereby reducing the generation of particles. Thus, in order to contribute to the anchor effect, the porosity of the sintered body is preferably 3% or more.

Such an anchor effect increases as the porosity increases. However, when the porosity exceeds 10%, the connection between the particles at the neck becomes weaker, and the particles fall off due to the dropping of the particles. In addition, corrosion resistance is reduced. Therefore, the porosity of the sintered body is set to 10% or less.

In general, the corrosion resistance due to plasma etching is measured by irradiating plasma from above onto a small sample of which part of the surface has been masked with a polyimide tape, a Teflon tape or the like, removing the masking after etching, and forming a step or surface roughness. Is evaluated as an etching rate. In the case of such an evaluation, the surface roughness Ra
Is more than 1 μm, it is true that the corrosion resistance is slightly lower than that of a member having Ra of 1 μm or less, and it is also true that the corrosion resistance is slightly lowered by increasing the porosity. However, even if the surface roughness and the porosity are reduced in this way, the corrosion resistance does not decrease to such an extent as to be a problem in terms of the life of the member, and rather, the halide film or the precipitate which cannot be evaluated by such a test is evaluated. It is important to suppress the generation of particles due to peeling. The present invention is intended to solve such a large problem in the semiconductor manufacturing process that the generation of particles is reduced at the expense of the corrosion resistance to some extent, and has a great advantage as a whole.

As the ceramic sintered body constituting the member of the present invention, those usually used in this field can be applied, but they have high corrosion resistance to corrosive gas such as plasma such as halogen-based gas. Al ₂ O ₃ , AlN,
Preferred are Si ₃ N ₄ , SiC, yttrium-aluminum-garnet (YAG) and the like.

Among them, yttrium-aluminum-
Garnet is particularly preferred. This is because the yttrium-aluminum-garnet sintered body has less particles in particular than other ceramic sintered bodies. this is,
The halide formed by the reaction of yttrium-aluminum-garnet with the corrosive gas is more resistant to the corrosive gas compared to the halide formed in other ceramic sintered bodies, for example, alumina and aluminum nitride. This is because it is stable. That is, as described above, a series of cycles in which the surface is first covered with the halide film and the halide film is formed again on the exposed surface of the member which has been corroded is slow, and thus the halide is formed. This is because the speed at which the film is separated and particles are generated becomes slow.

The yttrium-aluminum-garnet sintered body is usually added with SiO ₂ or the like as a sintering aid,
Although the densification of the sintered body is intended, when the porosity of the sintered body is set slightly higher within the range of 10% or less as in the present invention, the sintering aid for the densification is not originally used. Not required. However, if the porosity is slightly increased within the range of 10% without adding any sintering aid, the bond at the neck portion between the particles is weak, and when used for a member for a semiconductor manufacturing apparatus, it is corrosive. When exposed to the gas, the neck portion is easily broken, and as a result, the generation of particles due to particle shedding increases.

On the other hand, 0.15% by weight of SiO ₂
If it is added in an amount exceeding 10% by weight and not more than 10% by weight, sintering proceeds by liquid phase sintering, and the sintered body particles are strongly bound to each other by the yttria-alumina-silica-based glass phase remaining at the grain boundary part. In addition, the generation of particles due to shedding is greatly reduced. Therefore, yttrium-
SiO ₂ in the aluminum-garnet sintered body is 0.1%.
It is preferable that the content be in the range of more than 15% by weight and 10% by weight or less.

[0033] Yttrium was added in such an SiO ₂ the range of 10 wt% greater than 0.15 wt% - aluminum - garnet sintered corrosion resistance than that of SiO ₂ and 0.15 wt% or less It is true that is slightly reduced. However, the yttria-alumina-silica-based glass, which is present at the grain boundary portion by adding SiO _2, has a relatively high corrosion resistance, though slightly inferior to the yttrium-aluminum-garnet particles, and therefore has a long service life. Corrosion resistance does not decrease to a point where it is problematic. Therefore, as described above, SiO ₂ is added at 0.
By adding in an amount of more than 15% by weight and not more than 10% by weight, it is possible to further reduce the generation of particles, which is a big problem in semiconductor manufacturing, while sacrificing some of the corrosion resistance in a range where no problem occurs. Becomes

On the other hand, when the addition amount of SiO _{2 in} the yttrium-aluminum-garnet sintered body is increased, the proportion of silica in the yttria-alumina-silica glass, which is the grain boundary phase, increases, and -The corrosion resistance of the silica-based glass is reduced,
The corrosion resistance of the member deteriorates, and the added amount of SiO ₂ is 10% by weight.
When it exceeds, it becomes difficult to satisfy the level of corrosion resistance required for a member of a semiconductor manufacturing apparatus. Therefore, S
When adding iO ₂ , the addition amount is set to 10% by weight or less.

Examples of the member for a semiconductor manufacturing apparatus to which the present invention can be applied include a processing container such as a bell jar, an electrostatic chuck, a susceptor, and a clamp ring.
The present invention is particularly suitable for a processing container.

That is, the porosity is 10% or less, and at least the surface roughness Ra of the surface exposed to the corrosive gas is 1%.
By constituting the processing vessel member with a ceramic sintered body larger than μm, the generation of particles due to the dropout of halides and precipitates from the inner surface of the processing vessel is suppressed, and the semiconductor manufacturing equipment is continuously operated for a long period of time. It is possible to do. In this case, the processing container member may constitute the entire processing container,
It may constitute a part of the processing container.

In the case of the processing vessel, since the inner surface is downward or vertical, the halide film or precipitate generated on the inner surface of the member by the halogen-based plasma always receives its own weight during the operation. Therefore, as compared with other members, how strongly the halide film or the precipitate adheres becomes a more important problem.

That is, when the processing vessel is made of a member having a small Ra as in the prior art, since the halide film and the precipitate do not adhere firmly, there is a danger that a large amount of particles are generated by dropping the film together during operation. Therefore, continuous operation is difficult, which causes a great decrease in productivity.

When the present invention is applied to a processing container member as described above, it is preferable that the present invention is mainly composed of a curved portion.
The reason is that, as described above, since the ceramic sintered body generally has low thermal shock resistance, for example, when the shape of the processing container member has a sharp edge, the thermal stress is concentrated on the edge portion, and This is because the possibility of destruction is high. In order to avoid such thermal stress destruction, the processing container member is mainly composed of a curved surface portion, and has a first shape having a radius of curvature of 300 mm or more (including a case where the radius of curvature is infinite, that is, a flat surface). And the radius of curvature is 1
It is preferable that the second spherical portion be made of 0 mm or more, and either one of the first spherical portion and the second spherical portion be inscribed in the other.

More specifically, as shown in FIG. 1, the radius of curvature R1 of the first spherical portion 2 of the processing vessel member 1 is set to 300.
mm or more (including infinity), the radius of curvature R2 of the second spherical portion 3 is preferably 10 mm or more, and one of the spherical portions 2 and 3 is desirably inscribed in the other.

The reason that R1 is set to 300 mm or more is that 300 mm or more.
If it is less than mm, stress concentration tends to occur easily, and the effect of forming a curved surface is reduced. Also, R2 is set to 1
The reason why the thickness is set to 0 mm or more is that stress concentration easily occurs when the thickness is less than 10 mm. The stress concentration that occurs when R2 is less than 10 mm is particularly remarkable when R1 is infinite. One of the first spherical portion and the second spherical portion is inscribed in the other because sharp edges do not occur in this manner.

The thickness of the curved portion is 5 to 15 mm.
It is preferred that If it is less than 5 mm, it is desirable from the viewpoint of thermal shock resistance, but the mechanical strength of the ceramic sintered body is not always large, so that there remains a problem in the structural integrity of the member. In particular, in the case of large processing vessel members, lack of a certain thickness causes insufficient strength, and the thermal expansion coefficient is relatively large, so that thermal stress at fixed parts caused by temperature differences is destroyed. This is because there is a great risk of causing the problem. On the other hand, if it exceeds 15 mm,
On the other hand, although the mechanical strength is sufficient, the thermal shock resistance is reduced as the thickness becomes thicker, and destruction due to thermal stress is liable to occur.

Next, an example of application as a member for a processing container will be described. FIG. 2 is a sectional view showing an inductively coupled plasma etching apparatus to which the member of the present invention is applied. Reference numeral 10 in the figure is a processing container member to which the present invention is applied. The processing container member 10 has a dome shape, and a metal lower chamber 11 is provided below the processing chamber member 10 so as to be in intimate contact with the processing container member 10. A support table 13 is disposed in an upper part of the lower chamber 11, and an electrostatic chuck 14 is provided thereon. A semiconductor wafer 15 is mounted on the electrostatic chuck 14. A DC power supply 16 is connected to the electrodes of the electrostatic chuck 14 so that the semiconductor wafer 15 is electrostatically attracted. The support table 13 has R
The F power supply 17 is connected. On the other hand, lower chamber 1
A vacuum pump 18 is connected to the bottom of 1 so that the inside of the chamber 11 can be evacuated. Further, a gas supply nozzle 19 for supplying an etching gas, for example, a CF ₄ gas, above the semiconductor wafer is provided above the lower chamber 11.
Is provided. An induction coil 20 is provided around the processing container member 10, and a high frequency of, for example, 400 kHz is applied to the induction coil 20 from an RF power supply 21.

In such an etching apparatus, the inside of the chamber 12 is evacuated to a predetermined degree of vacuum by a vacuum pump 18 and the semiconductor wafer 15 is electrostatically adsorbed by the electrostatic chuck 14. By supplying power to the coil 20 from the RF power supply 21 while supplying the _four gases, plasma of an etching gas is formed above the semiconductor wafer 15, and the semiconductor wafer 15 is etched into a predetermined pattern. In addition,
By supplying power to the support table 13 from the high-frequency power supply 17, the anisotropy of etching can be increased.

At the time of such an etching process, the inner surface of the processing container member 10 receives a plasma attack and a fluoride film or the like adheres. However, since the processing container member 10 is formed of the above-described member of the present invention, the processing container member 10 has high corrosion resistance to plasma and is hard to drop attached matter.

The processing container member of the present invention is not limited to the apparatus shown in FIG. 2, but can be applied to the etching apparatus shown in FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals, and description thereof will be omitted. Here, a ceramic sub-chamber 22 extending upward is provided at the center of the top wall of the processing container member 10. A gas introduction unit 25 is provided above the sub-chamber 22, and an etching gas is introduced from the gas introduction unit 23 into the sub-chamber 22. An induction coil 24 is wound around the sub-chamber 22, and an RF power supply 25
Supplies a high frequency. Therefore, the etching gas is introduced into the sub-chamber 22 from the gas introduction unit 23 and the high frequency is supplied to the induction coil 24, whereby the plasma of the etching gas is formed in the sub-chamber 22, and the plasma is supplied to the semiconductor wafer 15. And etched.

When the present invention is applied to a member for a processing container, the processing container is not limited to the above-mentioned processing container, but may be any one used for processing using a corrosive gas such as CVD film formation. Good.

[0048]

Embodiments of the present invention will be described below. (First Embodiment) Here, evaluation as a member for a semiconductor manufacturing apparatus was performed from the amount of particles generated during operation of the semiconductor manufacturing apparatus and the amount of corrosion caused by corrosive gas. Ion-exchanged water and a dispersant were added to a plurality of types of ceramic powders as raw materials, and mixed in a pot mill. The slurry thus formed was dried and granulated by a spray drier, and formed into a clamp-ring shaped body by CIP molding. This molded body is processed into a shape corresponding to the processing container,
It baked at 400-1700 degreeC, and was set as the clamp ring for a test. The manufactured clamp ring is parallel-plate type RIE.
A test operation was performed with the apparatus attached to an etching apparatus. In the test operation, CF ₄ and O ₂ were introduced into the chamber at a ratio of 4: 1 as an etching gas, and plasma as a corrosive gas was generated by high frequency. After 100 hours of continuous operation, the number of particles on the 6-inch wafer and the amount of corrosion of the clamp ring due to corrosive gas were examined to evaluate the member as a member for a semiconductor manufacturing apparatus. Table 1 shows the results.

In Examples 1, 2, and 3, yttrium-aluminum-garnet (YA) having a porosity of more than 3% and 10% or less and a surface roughness Ra of more than 1 μm was used.
G) A member whose main constituent phase is a sintered body. They are,
An appropriate surface roughness and the presence of surface pores exert an anchor effect, and the resulting halogenated film and precipitates are unlikely to peel off, so that there is little generation of particles, and the material has excellent properties as a member for semiconductor manufacturing equipment. Was confirmed. Further, due to the high corrosion resistance of the YAG sintered body, generation of particles was smaller than that of other materials, and it was confirmed that the YAG sintered body was particularly excellent as a member for a semiconductor manufacturing apparatus.

Examples 4, 5, and 6 are members whose main constituent phase is a 99.99% alumina sintered body having a porosity of more than 3% and 10% or less and a surface roughness Ra of more than 1 μm. is there. These are slightly inferior in corrosion resistance to Examples 1, 2 and 3, but exhibit an anchor effect due to the presence of moderate surface roughness and surface pores, resulting in a halogenated film formed.
Since the separation of the precipitate was hard to occur, the generation of particles was small.

Examples 7 and 8 are members having a 99.5% alumina sintered body having a porosity of more than 3% to 10% or less and a surface roughness Ra of more than 1 μm as a main constituent phase. These have corrosion resistance even worse than those of Examples 4, 5, and 6, but due to the appropriate surface roughness and the presence of surface pores, an anchor effect is exhibited, and the generated halogenated film and precipitates are less likely to peel off. The generation of particles was small, and in that respect, it was preferable as a member for a semiconductor manufacturing apparatus.

Comparative Examples 1, 2, 4, 5, 7, and 8 have a YAG sintered body and alumina 99.9 having a surface roughness of 1 μm or less.
This is a member having a 9% sintered body and a 99.5% alumina sintered body as main constituent phases. Because these have too small surface roughness,
Since the effective anchor effect was not exhibited and the generated halide film and precipitates were largely peeled off, the number of generated particles was large, which was shown to be unfavorable as a member of a semiconductor manufacturing apparatus.

Comparative Examples 3, 6, and 9 are members whose main constituent phases are a YAG sintered body, an alumina 99.99% sintered body, and an alumina 99.5% sintered body having a porosity exceeding 10%. is there. Since the porosity is too high, the particles are weakly linked to each other, remarkably shed, resulting in a large amount of particles and low corrosion resistance, and it has been confirmed that these are not preferable as semiconductor manufacturing equipment members.

As described above, the porosity is 10% or less,
In addition, it has been found that a member having a ceramic sintered body having a surface roughness Ra of greater than 1 μm as a main constituent phase has excellent characteristics as a member for a semiconductor manufacturing apparatus because the generation of particles is small. In addition, it was confirmed that a member whose main constituent phase was a YAG sintered body had particularly low generation of particles and high corrosion resistance, and was particularly excellent as a member for a semiconductor manufacturing apparatus.

[0055]

[Table 1]

(Second Embodiment) Y satisfying the condition that the porosity is 10% or less and the surface roughness Ra is larger than 1 μm.
When the amount of SiO ₂ in the AG sintered body was changed,
Evaluation as a member for a semiconductor manufacturing apparatus was performed by examining the number of particles on a 6-inch wafer and the amount of corrosion of the clamp ring by corrosive gas after 100 hours of continuous operation as in the first embodiment.

As in the first embodiment, a clamp ring composed of a YAG sintered body having a porosity of more than 3% and not more than 10% and a surface roughness Ra of more than 1 μm as a main constituent phase is used. Produced. Similarly, the produced clamp ring was attached to a parallel plate type RIE etching apparatus, and CF ₄ and O ₂ were used as an etching gas in a ratio of 4: 1.
By introducing plasma into the chamber at a rate of, and generating a plasma as a corrosive gas by high frequency, and after continuous operation for 100 hours, the number of particles on the 6-inch wafer and the amount of corrosion by the corrosive gas on the clamp ring are examined. Evaluation as a member for a semiconductor manufacturing apparatus was performed. Table 2 shows the results.

In Test Examples 1 and 2, the YAG sintered body was made of SiO ₂
Since the amount was 0.15% by weight or less, although the corrosion rate was low, the number of generated particles was slightly increased, and it was confirmed that the material was somewhat inferior as a member for a semiconductor manufacturing apparatus.

In Test Examples 3 to 7, the SiO 2 in the YAG sintered body was used.
_{Since the} amount ₂ is more than 0.15% and not more than 10% by weight, the particles of the sintered body are strongly bonded by the yttria-alumina-silica-based glass phase, the number of generated particles is small, and the corrosion rate is small. It has been confirmed that the material has extremely favorable characteristics as a member for a semiconductor manufacturing apparatus.

In Test Examples 8 to 11, although the number of particles was small since the amount of SiO ₂ was 10% by weight or more, the corrosion rate was high, and it was confirmed that they were somewhat inferior as members for semiconductor manufacturing equipment. Was.

[0061]

[Table 2]

As described above, the porosity is 10% or less,
And has a surface roughness Ra of more than 1 μm and SiO ₂
YAG having an amount of more than 0.15% by weight and not more than 10% by weight
A member having a sintered body as a main constituent phase, while maintaining a good anchoring effect, can prevent particle generation particularly effectively because particles do not easily fall off, and also has good corrosion resistance, It was confirmed that it was particularly effective as a member for a semiconductor manufacturing apparatus.

(Third Embodiment) Here, a member for a processing container as shown in FIG. 1 was manufactured as a member for a semiconductor manufacturing apparatus. 99.5% alumina, 9 alumina
9.99%, aluminum nitride and YAG were selected and evaluated for each.

In manufacturing the processing container member, first,
To each of the ceramic powders, 0.2% by weight of silicon oxide, ion-exchanged water, and a dispersant were added and mixed in a pot mill. The slurry thus formed was dried and granulated by a spray drier, and a molded body was produced by CIP molding. Next, the formed body was processed into a member shape for a processing container and then fired, and R1 = 300 mm and R2 = 20 m in FIG.
A member for a processing container with m and t = 7 mm was obtained. Each of these porosity was 10% or less. In producing such a processing container member, a processing container member having various inner surface roughnesses was manufactured by blasting after sintering at the stage of forming a molded body.

Using the apparatus shown in FIG. 2 incorporating these processing vessel members, CF ₄ and O ₂ were introduced into the chamber at a ratio of 4: 1 from the gas supply nozzle 19, A high frequency of 400 kHz is applied to form plasma, and an RF power source 1
The etching process was performed while applying a high frequency of 7 to 13.56 MHz, and the processing container member of the present invention was evaluated.

Table 3 shows the materials used, the surface roughness, and the evaluation results as processing container members. The evaluation as a processing container member was performed based on continuous operability. The evaluation criteria for continuous operation were those in which the film did not fall off for more than 500 hours.
(Good), and the film that did not fall for 500 hours and the film was dropped was evaluated as x (impossible).

As shown in Table 3, in Examples 9 to 20 where the surface roughness Ra of the portion corresponding to the inner surface of the container was larger than 1 μm.
In any of the materials, during the continuous operation, the film did not fall off before the elapse of 500 hours, and good continuous operation was exhibited.

On the other hand, in Comparative Examples 10 to 17 in which the surface roughness Ra was 1 μm or less, in any of the materials, the film fell off before the elapse of 500 hours during the test operation, and there was a problem in the continuous operability. confirmed.

As described above, the porosity is 10% or less,
It has been confirmed that a ceramic sintered body having a surface roughness Ra of more than 1 μm exposed to a corrosive gas has preferable characteristics as a member for a processing container as compared with a ceramic sintered body having a Ra of 1 μm or less.

[0070]

[Table 3]

(Fourth Embodiment) Here, the porosity is 10
% Or less, and the surface roughness R of the surface exposed to the corrosive gas
By changing the shape of the processing container member made of a ceramic sintered body having a larger than 1 μm, a processing container member was manufactured by the manufacturing method described above. Using the apparatus shown in FIG. 2 incorporating such a processing container member, CF ₄ and O ₂ are introduced into the chamber at a ratio of 4: 1 from the gas supply nozzle 19, and the induction coil 20 is supplied from the RF power supply 21.
To form a plasma by applying a high frequency of 400 kHz to
13.56 MHz from RF power supply 17 to support table 13
The etching treatment was performed while applying the high frequency as described above, and each processing container member was evaluated.

Table 4 shows the shape of the processing container member and the evaluation results as the processing container member. The evaluation as a member for a processing container was made based on the presence or absence of cracks (thermal shock resistance).

Test Examples 12 to 20 satisfy the conditions that R1 is 300 mm or more, R2 is 10 mm or more, and the wall thickness is 5 to 15 mm. It was confirmed that the shape of the container member was preferable.

In Test Examples 21, 24, 27 and 30, since R2 was 10 mm or less, thermal stress exceeding the strength of the member was concentrated on the R2 portion due to a rise in the temperature of the member during the test operation, and a crack was generated.

In Test Examples 23, 26, 29, and 32, since the wall thickness was smaller than 5 mm, they could not withstand the thermal stress due to the temperature rise of the members during the test operation, and cracks occurred.

In Test Examples 22, 25, 28 and 31, since the wall thickness exceeded 15 mm, cracks occurred due to thermal shock due to the temperature rise of the members during the test operation.

As described above, when the present invention is applied to a processing container member, the processing container member must have an R1 of 300 mm or more and an R1
It was confirmed that not only the generation of particles due to the falling off of the halide film and the precipitates but also the generation of cracks hardly occur when the shape 2 satisfies the conditions of 10 mm or more and the thickness of 5 to 15 mm. Was done.

[0078]

[Table 4]

[0079]

As described above, according to the present invention,
The member for a semiconductor manufacturing apparatus is made of a ceramic sintered body, and has a porosity of 10% or less and a surface roughness R
By setting a to a value larger than 1 μm, particles can be hardly generated while maintaining sufficient corrosion resistance against corrosive gas such as halogen-based gas plasma. Such an effect was remarkable when used as a part or the whole of a processing container for semiconductor manufacturing in which processing was performed using a corrosive gas among members for semiconductor manufacturing equipment.

While maintaining such surface roughness, yttrium-aluminum-
When garnet is used, the generation of such particles is reduced. In particular, the effect of suppressing particles is further enhanced by setting the amount of SiO _{2 in} the sintered body to more than 0.15% by weight and 10% by weight or less. be able to.

Further, although the ceramic sintered body generally has low thermal shock resistance, when applied as a member for a processing container, it has a first spherical portion having a radius of curvature R1 of 300 mm or more;
It is continuous with the end of the first portion and has a radius of curvature R2 of 1
The main component is a curved surface portion including a second spherical portion of 0 mm or more, and one of the first spherical portion and the second spherical portion is inscribed in the other, and the thickness of the curved portion is 5
By devising the shape of the member so as to be in the range of ~ 15 mm, it is possible to reduce the thermal stress generated in the member,
Sufficient thermal shock resistance can be obtained as a member for a semiconductor manufacturing apparatus, particularly a member for a processing container.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a processing container member to which the present invention is applied.

FIG. 2 is a diagram showing an example of a plasma etching apparatus using a processing vessel member to which the present invention is applied.

FIG. 3 is a diagram showing another example of a plasma etching apparatus using a processing container member to which the present invention is applied.

[Explanation of symbols]

 1, 10; processing container member 2: first spherical portion 3: second spherical portion 12; chamber 13, support table 14, electrostatic chuck 15, semiconductor wafer 19, gas supply nozzles 20, 24, induction coil 17 , 21, 25; High frequency power supply 23; Gas inlet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naomizu Odano 1-2-23 Kiyosumi, Koto-ku, Tokyo Inside the Pacific Cement Co., Ltd. (72) Inventor Eiji Fukuda 1-2-23 Kiyosumi, Koto-ku, Tokyo No. Pacific Research Institute of Cement Co., Ltd. (72) Inventor Chiharu Wada 1-2-23 Kiyosumi, Koto-ku, Tokyo, Japan Inventor of Pacific Cement Co., Ltd. (72) Inventor Atsushi Suzuki 3-chome, Akimichi, Izumi-ku, Sendai City, Miyagi Prefecture 5 Japan Co., Ltd. Japan Theratec Headquarters Factory (72) Inventor Hiromichi Otaki 3-chome, Izumi-ku, Sendai-shi, Miyagi 5th Japan Co., Ltd. Theratech Corporation Headquarters Factory (72) Inventor Yukio Kishi Izumi-ku, Sendai-shi, Miyagi F-term (reference) in Japan Ceratech headquarters factory No.5, Atsutsu 3-chome 4G030 AA12 AA36 AA37 BA23 BA33 HA25

Claims (5)

[Claims] 1. A member for a semiconductor manufacturing apparatus used in a semiconductor manufacturing apparatus for performing processing using a corrosive gas, wherein the ceramic sintered body has a porosity of 10% or less and a surface roughness Ra of more than 1 μm. A member for a semiconductor manufacturing apparatus, comprising a body. 2. A member for a semiconductor manufacturing apparatus used as a part or all of a processing container for semiconductor manufacturing in which a process is performed using a corrosive gas, wherein the porosity is 10% or less and at least A member for a semiconductor manufacturing apparatus, comprising a ceramic sintered body having a surface roughness Ra of more than 1 μm exposed to a corrosive gas. 3. A curved surface portion comprising: a first spherical portion having a radius of curvature R1 of 300 mm or more; and a second spherical portion continuous to an end of the first portion and having a radius of curvature R2 of 10 mm or more. Wherein one of the first spherical portion and the second spherical portion is inscribed in the other, and the thickness of the curved portion is in the range of 5 to 15 mm. 3. The member for a semiconductor manufacturing apparatus according to 2. 4. The ceramic sintered body according to claim 1, wherein the main constituent phase is a yttrium-aluminum-garnet sintered body.
A member for a semiconductor manufacturing apparatus according to the above item. 5. A member for a semiconductor manufacturing apparatus used in a semiconductor manufacturing apparatus for performing a process using a corrosive gas, wherein the yttrium-aluminum has a porosity of 10% or less and a surface roughness Ra of more than 1 μm. -A garnet sintered body, wherein the amount of SiO _{2 in} the member exceeds 0.15% by weight and
A member for a semiconductor manufacturing apparatus, wherein the content is 0% by weight or less.