JP4563966B2 - Semiconductor processing apparatus member and method for manufacturing the same - Google Patents

Description

  The present invention relates to a member for a semiconductor processing apparatus and a method for manufacturing the same, and in particular, a semiconductor that needs to be plasma-treated in an environment where halogen or a halogen compound is present, or fine particles generated by the plasma treatment need to be cleaned and removed. This is a proposal for an effective technique used in the field of processing equipment.

  In semiconductor manufacturing and processing processes, highly corrosive harmful gases such as fluorides and chlorides or aqueous solutions are used in each process, so the materials used in these processes have a problem of severe corrosion wear. It was.

  In particular, semiconductor devices are mainly composed of compound semiconductors whose materials are made of Si, Ga, As, P, etc. In the manufacturing process, processes such as film formation, impurity implantation, etching, ashing, and cleaning are performed. Most of the processes are performed by a so-called dry process in which processing is performed in a vacuum or reduced pressure.

  As an apparatus belonging to this dry process, an oxidation furnace, a CVD apparatus, an epitaxial growth apparatus, an ion implantation apparatus, and the like. There are members and parts such as diffusion furnaces, reactive ion etching apparatuses, plasma etching apparatuses and the like, piping, supply / exhaust fans, vacuum pumps, valves and the like attached to these apparatuses.

For these devices, it is known to use the following corrosive gas species. For example, fluorides such as BF ₃ , PF ₃ , PF ₆ , NF ₃ , WF ₃ , HF, BCl ₃ , PCl ₃ , PCl ₅ , POCl ₃ , AsCl ₃ , SnCl ₄ TiCl ₄ , SiH ₂ Cl ₂ , SiCl ₄ , HCl, Cl ₂ and other chlorides, HBr and other bromides, and NH ₃ and Cl ₃ F.

By the way, in the dry process using these halides, plasma (low temperature plasma) is used to activate the reaction. In such a plasma use environment, it becomes a highly corrosive atomic or ionized halide such as F, Cl, Br, I, etc. In addition, during plasma etching, SiO ₂ , Si ₃ N ₄ , Si Since fine powdery solids called particles such as W and W are produced, it is necessary to take measures against them.

For example, one of the countermeasures is a surface treatment with aluminum anodic oxide (alumite). In addition, Al ₂ O ₃ , Al ₂ O ₃ .TiO ₂ , Y ₂ O ₃ and other alkaline earth metals, Group IIIa metal oxides are coated on the surface of the member by spraying or vapor deposition, or sintered. There are techniques to do (Patent Documents 1 to 4).

Furthermore, recently, by re-melting the surface of the Y ₂ O ₃ the sprayed coating by laser irradiation or electron beam irradiation solution morphism coating technique for improving the corrosion resistance and resistance to plasma erosion resistance (Patent Document 5) also.

On the other hand, diamond-like carbon (DLC) suitable for adsorbing Si thin films for etching using the Johnson Rabeck force in electrostatic chucks that are not intended for anticorrosion but are used in environments containing halogen-based gases. ) Has also been proposed (see Patent Documents 6 to 10).
Japanese Examined Patent Publication No. 6-036583 JP-A-9-69554 JP 2001-164354 A Japanese Patent Laid-Open No. 11-80925 JP 2005-256098 A JP-A-5-144929 JP 2002-246455 A JP-A-10-158815 JP-A-10-64986 Japanese Patent Laid-Open No. 6-200377

  In the field of recent semiconductor processing technology, semiconductor processing equipment or its members and parts are often exposed to severe corrosive environments caused by various halogens and halogen compounds from the viewpoint of aiming for higher precision and high precision. In such an apparatus or the like, the use environment becomes more severe due to the presence of highly corrosive halogen ions generated during plasma etching. Furthermore, recent semiconductor processing apparatus members that require high-precision processing have been repelled even with environmental pollutants (particles).

  According to the research by the inventors, it is found that the main component of the environmental pollutant (particle) is a component of the member disposed in the semiconductor processing apparatus and the surface treatment film coated on the surface thereof. I came. Therefore, it is considered that further improvements are required for members and coatings that are currently used as halogen corrosion resistant members or plasma erosion resistant surface treatment coatings. In other words, in various semiconductor device processing apparatuses that have recently been studied, elements other than Si, metals, non-metallic compounds, etc. in thin film components are all considered to be pollutants.

  Therefore, various corrosion-resistant / plasma-erosion-resistant coatings as disclosed in Patent Documents 1 to 4, and oxides, silicides, nitrides and the like constituting electrostatic chuck members for absorption / desorption of Si thin films Films and sintered bodies are now considered as a source of contamination rather.

In addition, since the DLC mainly composed of carbon and hydrogen and the coating film disclosed in Patent Documents 6 to 10 are formed of a non-metallic material that does not include a metal component, they are sufficient for halogens and halogen compounds. Exhibits excellent corrosion resistance. However, this DLC and its coating were developed for the purpose of adsorbing and desorbing the Si thin film on the electrode surface of the electrostatic chuck, and are hard and have high electrical resistivity (10 ⁸ to 10 ¹³ Ωcm). Damage and peeling easily occur, and there are many problems in using this for each member for a semiconductor processing apparatus.

That is, the present invention proposes a technique developed for the purpose of solving the following problems of the prior art.
(1) DLC is very hard (especially having a high electrical resistivity of 10 ⁸ to 10 ¹³ Ωcm) and has low ductility. Therefore, in an environment where the substrate is heated, the DLC is between the substrate and the DLC. Large thermal stress is generated and easily peels off. In other words, it peels even when a slight thermal / mechanical impact or bending stress is applied, and sometimes peels due to a change in room temperature even if it is left in the room. In particular, DLC having a high electrical resistivity has a large residual stress in the film, so that it is difficult to make it thick, and there are many pinholes. Therefore, even if DLC itself is a material having excellent corrosiveness, the base material is easily corroded by the fact that only a thin film can be formed and the corrosive component entering from the pinhole.
(2) DLC itself is excellent in halogen corrosion resistance, but when subjected to plasma etching treatment, DLC itself is not only easily peeled off but also becomes a small round cylindrical piece under the influence of residual stress. This is a source of environmental pollution. The DLC peeled off due to such a cause is not corroded by acid, alkali, halogen or the like, nor is it vaporized, so it cannot be removed by the apparatus cleaning technique using a chemical such as HF or Cl ₃ F. This is a source of environmental pollution.
(3) In addition, in the conventional DLC forming method disclosed in the prior patent documents 6 to 10 and the like, it is difficult to form a thickness of 10 μm or more, and a DLC having a uniform thickness is formed on the surface of a member having a complicated shape. However, it is insufficient as a technique for forming on a substrate such as a ceramic sintered body having a sprayed coating or pores.

The present invention was developed for the purpose of solving the above-described problems, and an undercoat layer made of a porous sprayed coating is provided on the surface of a base material. The open pores of the thermal spray coating constituting the pores are sealed by intrusion filling of ultrafine solid particles having a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic% of 1 × 10 ⁻⁹ m or less. together comprising Te, solution morphism also the film surface, the carbon content of from 85 to 50 atomic%, ing from the deposition layer of 1 × ^{10 -9} m or less of the super-fine solid particles of the hydrogen content of 15 to 50 atomic% amorphous Jo carbon hydrogen solid layer is a member for a semiconductor processing device consisting of those coated form.

Among the above-mentioned member configurations according to the present invention, the amorphous carbon hydrogen solid layer is a layer having a thickness of 80 μm or less, hardness Hv: 500 to 2300, and electric resistivity of 10 ⁵ to 10 ⁸ Ωcm. It has the characteristics of less than . On the surface of the A Ndakoto layer, it is preferable that the surface is one having a secondary recrystallized layer produced by high-energy radiation treatment.

In addition, the present invention holds a substrate to be processed in which an undercoat layer made of a porous spray coating is formed on the surface in an exhausted reaction vessel and introduces a hydrocarbon-based gas to the substrate to generate a high-frequency wave. Electric power and high voltage pulse are superimposed and applied to generate plasma of the introduced hydrocarbon gas, and at the same time, by holding the substrate at a negative potential, the carbon content is 85 to 50 atomic%, the hydrogen content 15 to 50 atomic% of ultrafine solid particles of 1 × 10 ⁻⁹ m or less are vapor-deposited to enter and fill the open pores of the sprayed coating, and the carbon content of the sprayed coating is 85 to 50. atomic%, semiconductor processing, wherein that you cover forming an amorphous carbon hydrogen solid layer ing from the deposition layer of 1 × 10 -9 ^m or less of the super-fine solid particles of the hydrogen content of 15 to 50 atomic% Propose a manufacturing method for equipment members

In the production method of the present invention, the layer formed of the amorphous carbon hydrogen solid has a thickness of 80 μm or less, a hardness Hv: 500 to 2300, and an electric resistivity of 10 ⁵ to 10 ⁸ Ωcm. It has the characteristics of less than . On the surface of the A Ndakoto layer, it is preferable that the surface is to form a secondary recrystallized layer produced by high-energy radiation treatment.

(1) According to the present invention, fine solid particles mainly composed of amorphous carbon and hydrogen are formed on the surface portion of the substrate to be processed by a plasma CVD process in which high-frequency power and high voltage pulses are superimposed. In addition to covering the surface and infiltrating and filling the pores, the defects of the substrate to be treated can be repaired and the amorphous carbon hydrogen solid layer can be easily formed to a certain thickness. .
(2) According to the present invention, by applying a negative voltage to the substrate to be treated, fine solid particles mainly composed of positively charged ions and radical carbon and hydrogen are formed on any surface of the substrate. Since it can be adsorbed and grown evenly on the part, it is possible to form a uniform film on every part of the substrate having a complicated shape, especially on a hidden part, and even in minute pores. In addition to this, it is possible to enter the open pores and securely seal them.
(3) According to the present invention, the amorphous carbon hydrogen solid layer (film) coated on the surface of the substrate is dense and excellent in adhesion, and has a small residual stress at the time of film formation. Therefore, it is chemically stable without being affected by seawater, acids, alkalis and organic solvents, and the sealing of the base material and the corrosion-resistant coating can be realized at the same time.
(4) According to the present invention, since the hardness is relatively low and the electrical resistivity is less than 10 ⁸ Ωcm, it has ductility, so that it peels even if the substrate is subjected to thermal and mechanical bending deformation. There is nothing.
(5) According to the present invention, even if the amorphous carbon hydrogen solid film coated on the substrate surface is formed to a thickness of 80 μm or less (preferably 0.5 μm to 50 μm), the film is resistant to peeling. A film having excellent properties can be formed.
(6) According to the present invention, the amorphous carbon hydrogen solid layer has characteristics of hardness Hv: 500 to 2300 and electrical resistivity: less than 10 ⁸ Ωcm, but has excellent adhesion and ductility, and halogen. When decomposed by a plasma etching action in a gas atmosphere, especially when oxygen is contained, most of it is discharged as a gas body such as C _n H _m , CO ₂ , CO, H ₂ , and H ₂ O. Therefore, it does not become a particle generation source.
(7) According to the present invention, since the amorphous carbon hydrogen solid layer exhibits excellent corrosion resistance against chemical corrosion action by halogen gas or halogen compound, the generation of corrosion products serving as particle generation sources is prevented. Can be eradicated.

  Therefore, in the semiconductor processing apparatus according to the present invention having the above-described amorphous carbon hydrogen solid layer, since the inside of the reaction vessel is always maintained in a clean environment, high-precision and high-precision semiconductor processing can be efficiently performed over a long period of time. You can do well.

Semiconductor processing equipment member according to the present invention, as described above, the open pores in and a surface layer portion of that sprayed coating formed on the substrate surface (undercoat layer), fine solid composed mainly of carbon and hydrogen Amorphous carbon hydrogen solids layer, particularly hydrogen, in which particles (nano-order ultrafine particles having a size of about 1 × 10 ⁻⁹ m or less) are intruded or deposited by coating these fine solid particles. It is characterized by being covered with a solid having a large content (15 atomic% or more). What is important in the present invention is to form a film by attracting and adsorbing amorphous carbon hydrogen solids mainly composed of carbon and hydrogen in the open pores and on the surface of a member for a semiconductor processing apparatus.

The layer formed on the surface of the undercoat layer by the intrusion and deposition of the amorphous carbon hydrogen solid in the present invention, as will be described in detail later, under the generation of hydrocarbon gas plasma, By superimposing and applying a negative potential to the substrate that is the member to be treated, amorphous fine solid particles mainly composed of carbon and hydrogen deposited in a gas phase in this atmosphere are attracted and adsorbed on the surface of the substrate. It is formed by the method of making. In such a film-forming environment, the hydrocarbon-based gas as a film-forming material source is easily decomposed by plasma, and activated hydrocarbons and other ions and radicals of carbon and hydrogen are generated. In addition to intruding into the surface defect layer, the surface is covered with a certain thickness. For example, the amorphous solid fine particles enter the pores on the surface of the substrate or the minute pores of the undercoat (sprayed coating, etc.) and seal or deposit on the surface to form a film. Become.

  In the above-described plasma CVD method of the present invention, low molecular weight hydrocarbons decomposed and generated by the plasma of hydrocarbon-based gas, carbon and hydrogen ions and radicals remain in a gas phase state (in the form of clouds or mist). These amorphous materials are generated so as to cover the entire base material, and these are attracted and adsorbed to the surface of the base material or the undercoat such as a sprayed coating, and further enter and fill the open pores. As the treatment time elapses, the fine solid particles in the form of deposit on the surface of the coating other than the open pores, thereby covering the entire surface of the coating. According to the experiments by the inventors, it is possible to form the film up to about 80 μm.

Hereinafter, the plasma CVD process in which the high frequency voltage and the high voltage pulse are superimposed will be described with reference to the drawings. In this method, the substrate to be treated 2 having a sprayed coating on the surface is applied with a negative potential (negative voltage) in the reaction vessel 1, and therefore, a hydrocarbon gas excited positively by plasma and charged positively. Ions and radicals are generated in the form of clouds or mist so as to cover the entire surface of the substrate 2 to be treated under a negative voltage, and the surface of the substrate 2 is an amorphous minute component mainly composed of carbon and hydrogen. It is adsorbed by repeated discharge deposition of solid particles. Therefore, even if the shape of the base material 2 is complicated, there is a feature that sealing and covering are performed relatively evenly. For example, even for a T-shaped and S-shaped substrate as shown in FIG. 1, the amorphous carbon hydrogen solid is adsorbed only on the substrate portion, that is, only on the portion with the substrate ( The portion having no negative potential can be prevented from adsorbing). In this way, the substrate can be made to have a negative potential, and both the sealing and covering processes can be performed, and any part can be formed evenly. In this regard, when a plasma discharge of a hydrocarbon gas is simply performed without applying a negative potential, the thickness of the film made of the amorphous carbon hydrogen solid formed is not uniform. The reason is that, in the case of only plasma energy, the gas decomposition efficiency varies depending on the hydrocarbon gas concentration, and the gas concentration itself varies depending on the shape and position of the T and S-shaped samples described above.

Further, in the plasma CVD process in which the high-frequency voltage and the high-voltage pulse of the present invention are superimposed, a layer made of amorphous carbon hydrogen solid produced using a hydrocarbon-based gas as a film forming raw material is made hydrophobic. Can do. As a result, even if the base material may come into contact with the corrosive aqueous solution, the wettability with the aqueous solution is reduced, and the surface can be finished so that the corrosion reaction is not easily caused. On the other hand, when a film containing N ₂ or SiO ₂ is used in the atmosphere gas during or after the film formation of the lipophilic amorphous carbon hydrogen solid, it can be changed to hydrophilic. . Therefore, the film formed by the present invention can be appropriately changed according to the interface characteristics.

The layer of amorphous carbon hydrogen solids described above can control the carbon and hydrogen content of this layer by changing the type of hydrocarbon-based gas for film formation. For example, the larger the C / H ratio of the hydrocarbon gas component, the higher the carbon content in the formed amorphous carbon hydrogen solid layer. However, in this case, since the film has a high hardness and a high electrical resistivity, the wear resistance is improved, but the ductility is poor and the internal stress is large, and there is a problem that it is difficult to form a thick film. Many micropores are also easily generated. Therefore, although the film itself made of amorphous carbon hydrogen solids is excellent in corrosion resistance, there is a problem in that peeling of the film is promoted by the corrosive components of the environment entering through these pores and corroding the base material.
In order to overcome the above problem, in the present invention, the carbon content of the amorphous carbon-hydrogen solid layer is set to be less than 85 atomic%.

  On the other hand, in the present invention, the hydrogen content of the amorphous carbon hydrogen solid is 15 atomic% or more. The reason for this is that a thick film can be formed by reducing the residual stress of the amorphous carbon-hydrogen solid layer, and therefore, from the viewpoint of improving resistance to bending deformation and corrosion resistance, a higher hydrogen content is preferable. Because it is advantageous. However, when the hydrogen content exceeds 50 atomic%, it is not preferable because it is difficult to form a film.

That is, in the present invention, the C / H ratio in the hydrocarbon-based gas for film formation is reduced (the hydrogen content ratio is increased to 15 atomic percent or more and less than 50 atomic percent), that is, amorphous carbon hydrogen solids By increasing the hydrogen content in the layer, the resistance to bending deformation of the base material is increased, and the generated film is less likely to be peeled off. As described above, the amorphous carbon hydrogen solid film having an increased hydrogen content exhibits the characteristics that the hardness Hv is 500 to 2300 and the electrical resistivity is less than 10 ⁸ Ωcm. It can be said that the physical property values are extremely low by comparison. In addition, since the internal stress value of the obtained film is small, it is possible to form an amorphous carbon hydrogen solid layer having a maximum film thickness of 80 μm.
For these reasons, the amorphous carbon hydrogen solid layer has a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic%. Preferably, the carbon content is 84 to 68 atomic% and the hydrogen content is 16 to 32 atomic%.

Hereinafter, the characteristics of the amorphous carbon-hydrogen solid layer, which is the most characteristic configuration in the present invention, are summarized as follows.
a. The main component of the amorphous carbon hydrogen solid is composed of carbon and hydrogen. Therefore, it is not affected by seawater, various acids, alkalis and organic solvents, and is chemically stable.
b. Aggregates of amorphous fine solid particles (nano-order ultrafine particles with a size of about 1 × 10 ⁻⁹ m or less) mainly composed of carbon and hydrogen, produced by plasma activated decomposition reaction of hydrocarbon-based gas Since each particle and the particle deposition layer are in an amorphous state, there is no grain boundary that is prone to defects, a dense and excellent adhesion, and no peeling from the substrate or the like.
c. Amorphous carbon hydrogen solid layer (film) is smooth (Ra: 0.5 μm or less) and has excellent wear resistance (friction coefficient μ: 0.11 to 0.2), so foreign matter is difficult to adhere. .
d. The amorphous carbon hydrogen solid layer is made lipophilic (hydrophobic) and hydrophilic by a method such as coexisting N ₂ or Si in a hydrocarbon gas during film formation and injecting Si into the surface after film formation. Therefore, it can be applied to industrial fields where interface characteristics are regarded as important.
e. It is known that the surface of a member for a semiconductor processing apparatus is destroyed when subjected to a plasma etching action in a halogen gas environment, but the amorphous carbon-hydrogen solid layer of the present invention, particularly the hydrogen content is 15 to Many layers of 50 atomic% often become gases such as C _m H _n , H ₂ , and H ₂ O at the time of decomposition, and particles of environmental pollution are less likely to be generated.

  Next, an apparatus for forming the amorphous carbon hydrogen solid layer will be described. FIG. 2 shows an apparatus for forming an amorphous carbon-hydrogen solid layer on the surface of the base material 2 that is a material to be treated. This apparatus mainly uses a reaction vessel 1 connected to a ground and a conductor 3 connected to a target object 2 disposed at a predetermined position in the reaction vessel 1 for film formation in the reaction vessel 1. A high voltage pulse generating power source 4 for applying a high voltage pulse is provided through an organic gas introducing device (not shown), a vacuum device (not shown) for evacuating the reaction vessel, and the like.

  In addition, the above apparatus is provided with a plasma generating power source 5 for generating a hydrocarbon-based gas plasma around the object to be processed 2, and a high voltage is applied to the conductor 3 and the object to be processed 2. In order to apply both the pulse and the high-frequency voltage simultaneously, a superimposing device 6 is interposed between the high voltage pulse generation power source 4 and the plasma generation power source 5. The gas introduction device and the vacuum device are connected to the reaction vessel 1 through valves 7a and 7b, respectively, and the conductor 3 is connected to the superposition device 6 through a high voltage introduction unit.

  In order to form an amorphous carbon hydrogen solid layer on the surface of the object to be processed using the above apparatus, the object to be processed 2 is placed at a predetermined position in the reaction vessel 1, and the reaction is performed by operating a vacuum apparatus. After the air in the container 1 is discharged and degassed, an organic hydrocarbon gas is introduced into the reaction container 1 by a gas introduction device. Next, high frequency power from the plasma generating power source 5 is applied to the object 2 to be processed. Since the reaction vessel 1 is in an electrically neutral state by the ground wire 8, the object to be processed has a relatively negative potential. For this reason, the positive ions in the plasma of the introduced gas generated by the application are generated along the shape of the object 2 to be negatively charged.

  Then, a high voltage pulse (negative high voltage pulse) from the high voltage pulse generating power source 4 is applied to the object to be processed 2, and positive ions in the hydrocarbon gas plasma are attracted and adsorbed on the surface of the object to be processed 2. By this treatment, the thick amorphous film can be uniformly formed on the surface of the workpiece 2. In the hydrocarbon-based gas plasma, the following phenomenon occurs, and finally, an amorphous carbon hydrogen solid containing carbon and hydrogen as main components is vapor-deposited to form a surface layer portion of the workpiece 2 -It is considered that the film penetrates into the pores or is formed so as to cover the surface to form a film.

In other words, it is presumed that the amorphous carbon hydrogen solid layer is formed according to the following processes (a) to (d).
(I) Ionization of the introduced hydrocarbon gas (there are active neutral particles called radicals)
(B) Ions and radicals that have changed from the hydrocarbon-based gas collide impactively with the surface of the object to which a negative voltage is applied,
(C) C—H having a low binding energy is cut by the energy at the time of collision, and then activated C and H are polymerized by repeating the polymerization reaction to form an amorphous state mainly composed of carbon and hydrogen. Vapor deposition of carbon hydrogen solids of
(D) Then, the above reaction (c) is the place in the pores of the object (A Ndakoto sprayed skin layer), in the gas holes are filled with fine solid particles of amorphous carbon hydrogen solid, whereas, If performed on the surface, an amorphous carbon hydrogen solid film is formed.

In this apparatus, by changing the output voltage of the high voltage pulse generating power source 4 as shown in the following (a) to (d), ion implantation including metal may be performed on the object 2 to be processed. it can.
(A) When ion implantation is focused on: 10 to 40 kV
(B) When performing both ion implantation and film formation: 5 to 20 kV
(C) When only film formation is performed: several hundred V to several kV
(D) When focused on sputtering, etc .: several hundred V to several kV

In the high voltage pulse generation power source 4,
Pulse width: 1 μsec to 10 msec,
Number of pulses: It is also possible to repeat one to a plurality of pulses.
Further, the output frequency of the high frequency power of the plasma generating power source 5 can be changed in the range of several tens of kHz to several GHz.

Examples of the film forming organic gas introduced into the reaction vessel 1 include an organic hydrocarbon gas composed of carbon and hydrogen, and those added with B, Si, O, Cl, or the like.
(I) Gas phase state at room temperature (18 ° C.) CH ₄ , CH ₂ CH ₂ , C ₂ H ₂ , CH ₃ CH ₂ CH ₃ , CH ₃ CH ₂ CH ₂ CH ₃
(B) Liquid phase at normal temperature C ₆ H ₅ CH ₃ , C ₆ H ₅ CH ₂ CH, C ₆ H ₄ (CH ₃ ) ₂ , CH ₃ (CH ₂ ) ₄ CH ₃ , C ₆ H ₁₂ , C ₆ H ₅ Cl
(C) Organic Si compound (liquid phase)
(C ₂ H ₅ O) ₄ Si, (CH ₃ O) ₄ Si, [(CH ₃ ) ₄ Si] ₂ O

  The gas introduced into the reaction vessel in the gas phase at normal temperature can be introduced into the reaction vessel 1 as it is, but the compound in the liquid phase is heated to gasify the gas. (Steam) is fed into the reaction vessel. When an amorphous solid film is formed using an organic Si compound, Si may be mixed into the film, but since Si is strongly bonded to carbon, the object of the present invention is not hindered. .

Examples of the base material and the surface treatment film (undercoat) suitable for the shape of the amorphous carbon hydrogen solid layer according to the present invention include the following.
(B) Metal substrate: Al, Ti, Ni, Cr, No, Ta, Nb, Si and their alloys (b) Non-metal substrate: Plastic, sintered material, quartz, glass (c) Surface treatment film (a) the thermal spray coating (including an alloy) metal, oxides, silicides, borides, nitrides, ceramics such as carbides and cermets sprayed coating or the like of these metals
(B) high energy irradiation treatment coating: by high energy irradiation treatment such as laser or electron beam the surface of said thermally sprayed skin layer, re-melting treatment of the surface layer (secondary recrystallization layer) the formed film or the like

In addition, as the thermal spraying method for surface treatment film formation, electric arc spraying method, flame spraying method, high-speed flame spraying method, atmospheric plasma spraying method, reduced pressure plasma spraying method, water plasma spraying method, explosion spraying method, cold spray method Although it can be applied to a coating formed by any spraying method such as, it is particularly suitable for a spraying coating formed by forming a ceramic material by various plasma spraying methods. This is because the ceramic sprayed coating is generally more porous than the metal-based or cermet-based coating, and thus the effects of the present invention are easily manifested .

The surface state of the front surface treatment film, as it is basically, for example, in the case of the thermal spray coating, while spraying (the as Sprayed), can be formed an amorphous carbon hydrogen solid layer as described above, this spraying The film may be formed by mechanically grinding / polishing the surface of the film, or performing electron beam irradiation treatment or laser irradiation treatment to remelt the surface film.

In the latter case, for example, a new layer, that is, a porous layer made of an oxide of the above-mentioned group IIIa element, is formed on the porous sprayed layer made of an oxide of the group IIIa element in such a manner that the portion of the outermost layer of the sprayed coating is altered. It is possible to form a secondary recrystallized layer obtained by secondary transformation of the material layer.
Generally, in the case of a metal oxide of a group IIIa element, for example, yttrium oxide (yttria: Y ₂ O ₃ ), the crystal structure is a cubic crystal belonging to the tetragonal system. When the yttrium oxide powder is plasma sprayed, when the molten particles collide and deposit on the surface of the substrate while being rapidly cooled while flying toward the substrate at high speed, the crystal structure becomes cubic ( A primary transformation is performed to a crystal form composed of a mixed crystal including monoclinic crystal in addition to Cubic. That is, the crystal type of the porous layer is composed of a crystal type composed of a mixed crystal including an orthorhombic system and a tetragonal system by performing a primary transformation by being super-cooled during thermal spraying. On the other hand, the secondary recrystallized layer is a layer in which the crystal type composed of the mixed crystal that has undergone primary transformation is secondarily transformed into a tetragonal crystal type.

  In this way, by subjecting the porous layer of the group IIIa oxide mainly composed of orthorhombic crystals that have undergone primary transformation to a high-energy irradiation treatment, at least the deposited sprayed particles of the porous layer are treated. By heating above the melting point, this layer is transformed again (secondary transformation), and its crystal structure is returned to a tetragonal structure to be crystallographically stabilized. In such a layer, during the primary transformation due to thermal spraying, the thermal strain and mechanical strain accumulated in the thermal spray particle deposition layer are released to stabilize the properties physically and chemically, and this layer accompanying melting. Also realizes densification and smoothing.

  In addition to the method described above, a metal ion or metal thin film having a strong chemical affinity with carbon such as Cr, Si, Ta, Nb, Ti, etc. is formed on the surface of the object 2 in advance. It is also possible to form a film in which the amorphous carbon hydrogen solid of the present invention is deposited.

( Reference Example 1)
In this example, the hydrogen content of the amorphous carbon hydrogen solid layer (film) formed on the surface of the Al base material, the resistance to bending deformation of the base material, and the subsequent change in corrosion resistance were investigated.
(1) Test base material and test piece The test base material is Al (JIS-H4000 stipulated 1085), and from this base material, a test piece of dimensions: width 15 mm × length 70 m × thickness 1.8 mm is used. Produced.
(2) Method for forming amorphous carbon hydrogen solid layer and its properties An amorphous carbon hydrogen solid film was formed to a thickness of 1.5 μm over the entire surface of the test piece. At this time, the hydrogen content in the amorphous carbon hydrogen solid film was controlled in the range of 5 atomic% to 50 atomic% (the balance was carbon).
(3) Test Method and Conditions The test piece on which the amorphous carbon hydrogen solid film was formed was subjected to bending deformation at 90 °, and the appearance of the amorphous carbon hydrogen solid film at the bent portion was enlarged 20 times. Observed with a mirror. Moreover, it used for the salt spray test prescribed | regulated to JIS-Z2371, and was exposed for 96 hours.
(4) Test results Table 1 shows the test results. As is clear from this test result, when the hydrogen content in the amorphous carbon hydrogen solid film is small and the carbon content (No. 1 to 3) is large, when the bending deformation of 90 ° is given, the film Peeling or peeling locally. On the other hand, when these peel test pieces were subjected to a salt spray test, it was found that Al was corroded on the substrate, a large amount of white rust was generated, and the corrosion resistance was completely lost. On the other hand, the amorphous carbon hydrogen solid film having a hydrogen content of 15 atomic% to 50 atomic% (No. 4 to 8) does not peel even by bending deformation, and well withstands the salt spray test, It was confirmed that it had excellent corrosion resistance.

(Example 1 )
In this example, an Al ₂ O ₃ sprayed coating was previously applied to an Al substrate, and then an amorphous carbon hydrogen solid film having a different hydrogen content as in Reference Example 1 was formed thereon. The bending deformability and salt spray resistance test performance were investigated.
(1) Test base material and test piece The same Al test piece as in Example 1 was used as the test base material, and the film thickness as an undercoat was formed by atmospheric plasma spraying prior to the formation of the amorphous carbon hydrogen solid film. An 80 μm Al ₂ O ₃ film was applied.
(2) Test method and conditions Same as Example 1.
(3) Test results Table 2 shows the test results. As is clear from these test results, even when an amorphous carbon-hydrogen solid layer is formed on the Al ₂ O ₃ sprayed coating, bending deformation resistance is not obtained in a film having a low hydrogen content (No. 1 to 3). Because it is small, it peeled easily. On the other hand, the amorphous carbon hydrogen solid layer (Nos. 4 to 8) containing a large amount of hydrogen has ductility, and even when subjected to bending deformation, the film does not peel off and is excellent in the salt spray test. It was confirmed that the corrosion resistance was maintained.

( Reference Example 2 )
In this reference example, in order to investigate the basic anticorrosion performance of the amorphous carbon hydrogen solid film according to the present invention, a highly versatile SS400 steel and Al are used as a base material, and the amorphous carbon hydrogen solid film is used for this. Was directly formed to a film thickness of 0.5 to 50 μm. In addition, corrosion resistance was investigated by exposing to an environment with different corrosion characteristics such as (a) high humidity, (b) salt spray, (c) 5% H ₂ SO ₄ , and (d) 5% NaOH as an anticorrosive environment. .

(1) Base material and test piece dimension Two types, SS400 steel and Al, were used as a base material, and a test piece having a width of 30 mm, a length of 50 m, and a thickness of 2 mm was produced from each.
(2) Amorphous carbon hydrogen solid film and its thickness Using the above-mentioned apparatus, an amorphous carbon hydrogen solid film formed to a thickness of 0.5 to 50 μm over the entire surface of the test piece was prepared (hydrogen-containing Amount 22-26 atomic%).
(3) Corrosion test conditions The following conditions were selected as the corrosion test conditions.
(I) High humidity atmosphere: Using a constant temperature and humidity chamber, the test piece was exposed to an atmosphere of 30 ° C. and 90% relative humidity for 1000 hours.
(B) Salt spray: A 96-hour test was conducted by the salt spray test method defined in JISZ2371.
(C) 5% H ₂ SO ₄ immersion: It was immersed in a 5% H ₂ SO ₄ aqueous solution (20 to 25 ° C.) for 100 hours.
(D) 5% NaOH immersion: immersed in a 5% NaOH aqueous solution (30 to 35 ° C.) for 100 hours.
(4) Evaluation method The evaluation of the corrosion test results was carried out by visual observation of changes in the surface of the test piece before and after the test and changes in the color tone in the aqueous solution of H ₂ SO ₄ and NaOH. In addition, as a test piece for comparison, untreated SS400 steel and Al were subjected to a corrosion test under the same conditions.
(5) Corrosion test results Table 3 shows the corrosion test results. As is apparent from the test results, the untreated SS400 steel test piece generates red rust or dissolves (No. 1) in all test atmospheres (No. 1, 3, 5) except 5% NaOH immersion. 5) Moreover, in the Al non-processed test piece (No. 2, 4, 6, 8), while generating white rust (No. 4) under conditions other than in a high-humidity atmosphere, an acid (No. 6), an alkali ( No. 8) also dissolved while generating hydrogen gas.
On the other hand, the test piece formed with the amorphous carbon hydrogen solid film exhibited excellent corrosion resistance regardless of the type of the base material, and showed sufficient corrosion resistance in all corrosive environments at a film thickness of 1 μm or more. . However, when the film thickness was 0.5 μm, the occurrence of red rust was suppressed in a high humidity atmosphere and an alkaline aqueous solution (5% NaOH) immersion, but slight red rust and white rust were observed in salt spray and sulfuric acid immersion.

  From the above results, it was found that the effective anticorrosive action of the amorphous carbon-hydrogen solid film was observed in the film thickness range of 0.5 to 50 μm, particularly in the range of 1 to 50 μm.

(Example 2 )
In this example, an oxide-based ceramic sprayed coating was directly formed on the surface of a test piece made of SS400 steel base material, and then the surface was coated with an amorphous carbon hydrogen solid film, and then subjected to a salt spray test. The corrosion resistance was investigated.
(1) Base material and specimen size SS400 steel (dimensions: width 50 mm × length 70 m × thickness 3.2 mm)
(2) Types of thermal spray coating and thermal spraying method The following oxide ceramic was directly formed on the surface of the test piece to a thickness of 70 μm by the atmospheric plasma spraying method. The reason why the ceramic sprayed coating was applied slightly thin is to determine the sealing / coating effect of the amorphous carbon-hydrogen solid film by a short test. (Numbers indicate mass)
(A) Al ₂ O ₃
(B) Cr ₂ O _{3
(C) 8% Y 2 O} 3 · 92% ZrO 2
(D) Al ₂ O ₃ .MgO swinel (e) 98% Al ₂ O ₃ .2% TiO ₂
(F) Y ₂ O ₃
(3) Formation and Thickness of Amorphous Carbon Hydrogen Solid Film Using the same apparatus as in Example 1, the film was formed to a film thickness of 5 μm (hydrogen content: 16 to 26 atomic%).
(4) Corrosion test conditions A 96-hour corrosion test was conducted by the salt water injection test method defined in JIS-Z2371.
(5) Evaluation method The evaluation of the corrosion test was determined by the presence or absence of red rust on the surface of the oxide ceramic before and after the test. For comparison, a sprayed coating that does not cover the amorphous carbon hydrogen solid film was tested under the same conditions.
(6) Corrosion test results Table 4 shows the corrosion test results. As is apparent from the test results, red rust was observed in all of the untreated sprayed coatings (No. 2, 4, 6, 8, 10, 12). That is, it is considered that salt water entered from the pores of the ceramic sprayed coating to corrode the base material of SS400 steel, and the eluted iron ions floated on the coating surface to generate red rust. On the other hand, the test pieces (No. 1, 3, 5, 7, 9, 11) coated with the amorphous carbon hydrogen solid film have good sealing property and covering performance for any ceramic film. The occurrence of red rust was not observed.

(Example 3 )
In this embodiment, when used in a corrosive atmosphere or an environment where an organic solvent is handled, the amorphous carbon hydrogen solid film on the oxide ceramic sprayed coating when a metallic undercoat is applied to an SS400 steel substrate is used. The anticorrosive effect was investigated.
(1) Base material and test piece dimensions The same as in Example 2 .
(2) Types of thermal spray coating and thermal spraying method (numbers are mass%)
(A) Undercoat: 80% Ni-20% Cr (atmospheric plasma spraying method)
(B) _{Topcoat: Al 2 O 3, Y 2} O 3, 8% Y 2 O 3 -92% ZrO 2 ( atmospheric plasma spraying)
The film thickness is 50 μm for the undercoat and 150 μm for the topcoat.
(3) Amorphous carbon hydrogen solid film forming method and film thickness
The film thickness was set to 5 μm by the same method as in Reference Example 1 (hydrogen content: 26 to 34 atomic%).
(4) Corrosion conditions (a) 5% HCl: A beaker containing a 5% HCl aqueous solution was maintained at 20 to 23 ° C., a test piece was immersed, and acid resistance was evaluated.
(B) 5% NaOH: A test piece was immersed in a beaker containing a 5% NaOH aqueous solution, and the alkali resistance was evaluated at a temperature of 20 to 23 ° C. for 24 hours.
(C) 95% toluene: The test piece was immersed in a 95% toluene solution for reagents (15 to 20 ° C.) for 24 hours to evaluate organic solvent resistance.
(5) Corrosion test results Table 5 shows the corrosion test results. As is clear from the test results, no red rust was produced in 5% NaOH and an organic solvent regardless of the presence of the undercoat and the amorphous carbon hydrogen solid film, and no change was observed in the appearance. On the other hand, in a 5% HCl aqueous solution, even if an undercoat is applied, the top coat is not applied to the film (No. 2, 4, 6, 8, 10, 12) that is not covered with the amorphous carbon hydrogen solid film. Regardless of the type, all were corroded, and the color of the HCl aqueous solution changed from yellow to light yellow, and dissolution of the SS400 steel and the undercoat component of the base material was estimated. On the other hand, the color tone of the aqueous HCl solution in which the film (No. 1, 3, 5, 7, 9, 11) coated with the amorphous carbon hydrogen solid layer is not changed, and the film maintains a healthy state. Was.

(Example 4 )
In this example, in consideration of utilization as a semiconductor processing apparatus member, an oxide ceramic sprayed coating was directly formed on an Al base material, and then the corrosion resistance in various halogen-based gases was investigated.
(1) Base material and test piece dimensions A test piece having dimensions of 20 mm in width, 30 m in length, and 2.3 mm in thickness was sampled using Al (JISH4000 regulation 1085) as a base material.
(2) spray coating type and thermal spraying the thermal spray coating _{types: Al 2 O 3, YAG (} Y 3 Al 5 O 12), Y 2 O 3
Each of them was formed to a thickness of 150 μm on an Al base by direct atmospheric plasma spraying.
(3) Amorphous carbon hydrogen solid film forming method and film thickness
The film thickness was 5 μm by the same method as in Reference Example 1 (hydrogen content 22 to 34 atom%).
(4) Corrosion test conditions (a) Active halogen gas test:
For this test, the apparatus shown in FIG. 3 was used, and the test piece 31 was left on an installation table 36 inside a stainless steel tube 33 provided at the center of the electric furnace 32, and then the corrosive gas 34 was left on the left side. Then, the quartz discharge tube 35 provided in the middle of the piping was loaded with a microwave having an output of 600 W to promote the activation of the corrosive gas. In a test using such an apparatus, the activated corrosive gas is introduced into the electric furnace, and after corroding the test piece 31, it is discharged out of the system from the right side. Using such a corrosion test apparatus, a 10-hour corrosion test was performed while flowing a test piece temperature of 180 ° C., 150 ml / min of corrosive gas CF ₄ , and 75 ml / min of O ₂ .
(B) 5% HCl immersion test: A beaker containing a 5% HCl aqueous solution was maintained at 20 to 23 ° C., a test piece was immersed, and acid resistance was evaluated.
(C) HCl vapor test:
A 30% HCl aqueous solution was placed at the bottom of a desiccator for chemical experiments, a glass porous plate was disposed thereon, and then a test piece was allowed to stand on the glass plate. In this environment (20 to 25 ° C.), HCl vapor having a high vapor pressure is generated, and the test piece is corroded by HCl vapor rising from the hole of the glass plate.
In addition, the untreated SS400 steel plate is such that red rust is generated on the entire surface by a one-hour test.
(D) HF steam test:
A test piece was allowed to stand in an autoclave made of SUS316 having a capacity of 3 L, and then 500 ppm of HF gas was injected from the outside, and a corrosion test was performed at 150 ° C. for 24 hours.
(5) Corrosion test results Table 6 shows the corrosion test results. As is apparent from this test result, in the test pieces (No. 2, 4, 6) that do not form the amorphous carbon hydrogen solid film, the ceramic sprayed coating itself exhibits relatively good corrosion resistance, but the pores of the film are not observed. As a result of the corrosion of the base material Al caused by the corrosive gas that penetrated into the interior and the loss of the bonding strength with the ceramic film, a peeling phenomenon was observed.
On the other hand, the test piece formed with an amorphous carbon hydrogen solid film showed sufficient corrosion resistance against all corrosive gases, and the film itself was dense, and no abnormality was observed in appearance. .

(Example 5 )
In this example, the surface of the oxide ceramic sprayed coating was irradiated with high energy such as an electron beam and a laser to investigate the anticorrosive effect of the amorphous carbon hydrogen solid film on the melted film-forming particles on the coating surface. did.
(1) Base material and test piece dimension The test piece of width 20mm * length 30m * thickness 3.2mm was extract | collected using SS400 steel.
(2) Types of thermal spray coating and types of thermal spray coating: Y ₂ O ₃
The film was formed to a thickness of 80 μm using an atmospheric plasma spraying method.
(3) Types and conditions of high energy irradiation (a) Electron beam irradiation: Using an electron beam irradiation apparatus having the following specifications, a film surface depth of 3 μm was remelted.
Irradiation atmosphere: 1 × 10 ^{−1 to} 5 × 10 ⁻³ MPa
Irradiation output: 10-30 KeV
Irradiation speed: 1 to 20 mm / s
(B) Laser irradiation: Using a laser irradiation apparatus having the following specifications, 10 μm was melted again from the surface of the film.
Laser power: 2-4kw
Beam area: 5-10 mm ²
Beam scanning speed: 5 to 20 mm / s
(4) Formation of amorphous carbon hydrogen solid film and film thickness
The film thickness was 3 μm by the same method as in Reference Example 1 (hydrogen content: 26 to 38 atomic%).
(5) Corrosion test conditions (a) Salt spray test: 96 hours test conducted according to JISZ-2371 (b) Active halogen gas test: conducted under the same conditions as in Example 4 (c) HCl vapor test: desiccator for chemical experiments After placing a 30% HCl aqueous solution at the bottom of the glass plate and placing a porous glass plate on top of it, place a test piece on the glass plate, and in this environment, a large amount of HCl vapor from an HCl solution with a high vapor pressure. And SS400 steel is red rusted on the entire surface by exposure for 1 h.
(6) Corrosion test results Table 7 shows the corrosion test results. As is apparent from this test result, even if the Y ₂ O ₃ sprayed coating is irradiated with a beam and a laser, the coating as it is (Nos. 2 and 6) does not cause local red rust in all corrosion tests. Recognized and cannot completely prevent internal entry of corrosive components. In order to elucidate the cause, when the surface of the sprayed coating irradiated with an electron beam and laser is observed with a magnifying glass, the pores peculiar to the sprayed coating have disappeared due to the melting phenomenon, but there are many small cracks. found. These cracks are irradiated with high energy, and compared with the fact that a lot of red rust is generated in all corrosion tests in the films (No. 4 and 8), the effect of high energy irradiation is recognized but sufficient countermeasures It is not.
On the other hand, in the film (No. 1, 3, 5, 7) coated with the amorphous carbon hydrogen solid film, the intrusion of the corrosive component is completely prevented regardless of the presence or absence of high energy irradiation, and red rust is not generated. It was not recognized at all.

  The technology of the present invention is used as a member for a semiconductor processing apparatus such as a deposition shield, a baffle plate, a focus ring, an insulator ring, a shield ring, a bellows cover, and an electrode. In addition, the present invention is also useful as a surface treatment technology for preventing wear of a conveying member such as a Si thin film or a processed product of the Si thin film and preventing wrinkles on the processed product, and a plasma processing container such as a liquid crystal device. The present invention can also be applied to inner members and parts.

It is an approximate line figure of the distribution situation of the amorphous carbon hydrogen solid film concerning the present invention formed with respect to the sprayed-coating test piece which carried out T and S character type. It is a basic diagram of the apparatus for depositing an amorphous carbon hydrogen solid. It is a basic diagram of the corrosion test apparatus using the gas containing a halogen compound.

Explanation of symbols

1 Reaction vessel 2 Object to be treated (base material)
3 Conductor 4 High voltage pulse generating power source 5 Plasma generating power source 6 Superimposing device 7 Valve 8 connected to a vacuum device for removing air in the reaction vessel 9 Ground wire 9 High voltage introducing portion 21 Steel substrate 22 Thermal spray coating 23 Amorphous carbon hydrogen solid film 31 Test piece 32 Electric furnace 33 Stainless steel tube 34 Corrosive gas 35 Quartz discharge tube 36 Test piece installation table

Claims (8)

An undercoat layer composed of a porous sprayed coating is provided on the surface of the substrate, and the undercoat layer has an open pore of the sprayed coating constituting the layer, a carbon content of 85 to 50 atomic%, and a hydrogen content. It is sealed by intrusion filling with ultrafine solid particles of 1 × 10 ⁻⁹ m or less in an amount of 15 to 50 atomic% , and the sprayed coating surface also has a carbon content of 85 to 50 atomic% and a hydrogen content. the amount 15 to 50 atomic% of 1 × 10 -9 ^m or less of ultrafine solid amorphous carbon hydrogen solid layer ing from the deposition layer of the particles consist of coated formed semiconductor processing equipment for members. 2. The member for a semiconductor processing apparatus according to claim 1, wherein the amorphous carbon-hydrogen solid layer is a layer having a thickness of 80 [ mu] m or less. 3. The semiconductor processing apparatus according to claim 1, wherein the amorphous carbon-hydrogen solid layer has characteristics of hardness Hv: 500 to 2300 and electrical resistivity of less than 10 ⁵ to 10 ⁸ Ωcm. Element. On the surface of the front Kia Ndakoto layer, the semiconductor processing equipment member according to any one of claims 1-3, characterized in that it comprises a secondary recrystallization layer whose surface is generated by high-energy radiation treatment . In the evacuated reaction vessel, a substrate to be treated having an undercoat layer made of a porous spray coating is held on the surface and a hydrocarbon-based gas is introduced, and high-frequency power and high-voltage pulses are introduced into the substrate. Is applied in a superimposed manner to generate plasma of the introduced hydrocarbon gas, and at the same time, by maintaining the substrate at a negative potential, the carbon content is 85 to 50 atomic% and the hydrogen content is 15 to 50 atomic%. Ultra-fine solid particles of 1 × 10 ⁻⁹ m or less are vapor deposited and intruded into the open pores of the sprayed coating, and the carbon content is 85 to 50 atomic% and the hydrogen content on the surface of the sprayed coating. method for producing a 15 to 50 atomic% of 1 × 10 -9 ^m or less of the semiconductor processing equipment for members characterized that you cover forming an amorphous carbon hydrogen solid layer ing from the deposition layer of ultra fine solid particles . 6. The method of manufacturing a member for a semiconductor processing apparatus according to claim 5 , wherein the layer formed of the amorphous carbon-hydrogen solid is a layer having a thickness of 80 [ mu] m or less. Layer formed by the amorphous carbon hydrogen solids hardness Hv: from 500 to 2300, the electrical resistivity of claim 5 or 6, characterized in that it has a characteristic of less than 10 ⁵ ~ 10 ⁸ Ωcm Manufacturing method of member for semiconductor processing equipment. Before the surface of the Kia Ndakoto layer, semiconductor processing apparatus according to any one of claims 5-7, characterized in that the surface to form a secondary recrystallization layer produced by high-energy radiation treatment Manufacturing method of member.

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