JP2009242951A - Member for semiconductor processing apparatus, and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that a member in a semiconductor processing container is subjected to corrosion damages in an early state when it is plasma-etching processed in the environment containing halogen gas, very fine particles are generated to pollute the inside of the processing container, and the semiconductor processing production capacity is considerably degraded. <P>SOLUTION: In the member for the semiconductor processing apparatus, super-fine solid particles mainly consisting of carbon and hydrogen are allowed to enter an undercoat layer in a surface of a base material having the undercoat layer composed of a plating film, a PVD film or the like, and a film consisting of the aggregate of the super-fine solid particles is formed to cover a surface of the undercoat layer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

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 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 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 inventors' research, it is found that the main component of the environmental pollutant (particle) is a constituent component of the member disposed in the semiconductor processing apparatus and the surface treatment film coated on the surface thereof. I came. Accordingly, it is considered that further improvements are required for members and coatings 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 is one or more selected from a plating film, a PVD film, a CVD film, an anodized film, and a remelted film. In addition to the base material having an undercoat layer consisting of ultrafine solid particles having a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic% intruded and filled in the undercoat layer, Semiconductor processing in which an amorphous carbon hydrogen solid layer composed of a deposited layer of ultrafine solid particles having a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic% is formed on the surface of the undercoat layer This is a device member.

Among the above-described member configurations according to the present invention, the amorphous carbon hydrogen solid layer on the surface of the undercoat layer is a layer having a thickness of 80 μm or less, hardness Hv: 500 to 2300, and electric resistivity of 10 ^5. It has a characteristic of -10 ⁸ Ωcm. The surface of the undercoat layer is preferably a secondary recrystallized layer that is generated by high energy irradiation treatment.

The present invention also provides an undercoat layer having at least one selected from a plating film, a PVD film, a CVD film, an anodized film, and a remelted film in the exhausted reaction vessel. While holding the treated substrate and introducing a hydrocarbon gas, a high frequency power and a high voltage pulse are superimposed and applied to the substrate to generate plasma of the introduced hydrocarbon gas, and at the same time, the substrate is negatively charged. By maintaining the potential of the undercoat layer, ultrafine solid particles of 1 × 10 ⁻⁹ m or less having a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic% are vapor-phase precipitated to form the undercoat layer. The undercoat layer surface is composed of aggregates of ultrafine solid particles of 1 × 10 ⁻⁹ m or less having a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 atomic%. Amorph The scan carbon hydrogen solid was deposited proposes a method for manufacturing a semiconductor processing device member, characterized in that the coated.

In the production method of the present invention, the layer formed of the amorphous carbon hydrogen solid on the surface of the undercoat layer has a thickness of 80 μm or less, hardness Hv: 500 to 2300, and electric resistivity of 10 ^5. It has a characteristic of -10 ⁸ Ωcm. It is preferable to form a secondary recrystallized layer formed on the surface of the undercoat layer by high energy irradiation 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 exhibits properties of hardness Hv: 500-2300 and electrical resistivity: 10 ⁵ to 10 ⁸ Ωcm, but has excellent adhesion and ductility. , when decomposed by plasma etching action in the halogen gas atmosphere, in particular a large part of oxygen is included _{C n H m, CO 2,} CO, and gas material such as H 2, _{H 2} O emissions Therefore, it does not become a source of particles.
(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 that are the source of particles 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.

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.

As described above, the member for a semiconductor processing apparatus according to the present invention is such that the surface layer portion of the substrate to be treated having the surface treatment layer (undercoat layer) is a fine solid particle (nano-order super particle) mainly composed of carbon and hydrogen. Amorphous carbon hydrogen solids layer formed by depositing fine particles (with a size of about 1 × 10 ⁻⁹ m or less), particularly coated with a solid with a high hydrogen content (more than 15 atomic%) It is characterized by being. What is important in the present invention is that an amorphous carbon-hydrogen solid containing carbon and hydrogen as main components is attracted and adsorbed onto the surface of a member for a semiconductor processing apparatus.

  The layer formed in and under the undercoat layer of the base material by the penetration and deposition of the amorphous carbon hydrogen solid material in the present invention is a high frequency in the generation of hydrocarbon-based gas plasma, as will be described in detail later. By applying a voltage and a high voltage pulse in a superimposed manner to make the substrate, which is a member to be processed, have a negative potential, amorphous fine solid particles mainly composed of carbon and hydrogen deposited in this atmosphere are vaporized. It is formed by the method of attracting and adsorbing to the substrate surface. 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 fine solid particles invade into minute open pores of the undercoat and seal or deposit on the surface to form a film.

  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 fine solid particles that are generated so as to cover the entire base material, and are attracted and adsorbed on the surface of the undercoat, penetrated, filled, and eventually vapor-deposited, with the passage of processing time. Thus, it also deposits on the surface of the undercoat layer to cover the entire surface. 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, a negative potential (negative voltage) is applied to the substrate 2 to be treated in the reaction vessel 1, and therefore, ions and radicals of hydrocarbon gas excited by plasma and positively charged are: An amorphous micro-solid formed mainly on carbon and hydrogen on the surface of the base material 2 which is generated in a cloud or mist form so as to cover the entire surface of the substrate 2 having an undercoat layer under a negative voltage. The particles are adsorbed by repeated discharge deposition. 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 undercoat layer of the base material may come into contact with a corrosive aqueous solution, the wettability with the aqueous solution can be reduced, and the surface can be finished where the corrosion reaction is difficult to occur physically. It becomes like this. 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 surface-treated substrate 2. 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 surface treatment film of the substrate to be treated using the above apparatus, the object to be treated 2 is placed at a predetermined position in the reaction vessel 1, and a vacuum apparatus is used. After operating and exhausting the air in the reaction vessel 1 and degassing, an organic hydrocarbon gas is introduced into the reaction vessel 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 undercoat layer 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) When the reaction (c) occurs in the pores of the object to be treated (base material, undercoat sprayed coating, etc.), the pores are filled with fine solid particles of amorphous carbon hydrogen solids, On the other hand, if it is carried out 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.
(A) 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 room 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) undercoat layer (Surface treatment film)
(A) PVD, CVD film: metal (including alloy), oxide. Silicides, borides, nitrides, carbides, etc. (b) Metal plating films: Ni, Cr, Al, Fe, etc. (c) High energy irradiation treatment films: The surface of the PVD film or CVD film is a laser or electron beam. Film with surface layer remelted (secondary recrystallized layer) by high energy irradiation treatment

  The surface state of the surface treatment film on the substrate can basically form the amorphous carbon hydrogen solid layer as described above, but the surface of the undercoat layer can be mechanically ground and polished. The film may be formed after the surface film is remelted by electron beam irradiation or laser irradiation.

  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 reference 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, the presence or absence of the formation of the amorphous carbon hydrogen solid material layer of the present invention on various base materials and undercoat layers (surface treatment films) used in semiconductor processing apparatus was investigated.
(1) Test substrate and surface treatment film (a) Quartz (b) Soda glass (c) Sintered material (SiO ₂ , Al ₂ O ₃ , AlN)
(D) Polycarbonate (organic polymer material)
(E) PVD method (Al ₂ O ₃ , TiN, TiC thickness 1.5 μm)
(F) CVD method (Al ₂ O ₃ , TiC thickness 1.8 μm)
(G) Anodized aluminum (Al ₂ O ₃ , 8 μm)
(2) Method for Forming Amorphous Carbon Hydrogen Solid Film and Film Thickness The method for forming the amorphous carbon hydrogen solid film is the same as in Reference Example 1. However, the hydrogen content of the amorphous carbon-hydrogen solid film was 22 atomic%, and the film thickness was 5 μm.
(3) Test results Table 2 shows the test results. As is apparent from the test results, the amorphous carbon hydrogen solid film according to the present invention is not limited to non-metallic materials such as quartz, glass, and polycarbonate, but also to sintered bodies, PVD, CVD, anodized films, and the like. In addition, it was confirmed that the film exhibited good adhesion, and it was confirmed that it was advantageous as a protective film for these substrates.

(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, the acid (No. 6), 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.

(Reference Example 3)
In this reference example, the surface of an oxide ceramic sprayed coating is 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 in accordance with JISZ-2371 (b) Active halogen gas test: In this test, the test piece 31 was replaced with an electric furnace. After standing on the installation base 36 inside the stainless steel tube 33 provided at the center of 32, a corrosive gas 34 is allowed to flow from the left side, and a micro discharge with an output of 600 W is supplied to the quartz discharge tube 35 provided in the middle of the piping. Waves were loaded to promote activation of corrosive gases. 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 .
(C) HCl vapor test: A 30% HCl aqueous solution is placed at the bottom of a chemical experiment desiccator, a porous glass plate is placed on the top, and a test piece is placed on the glass plate. A large amount of HCl vapor is generated from an HCl solution having a high vapor pressure, and SS400 steel undergoes red rust on the entire surface when exposed to 1 h.
(6) Corrosion test results Table 4 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 the corrosion tests in the coatings (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.

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 connected to a vacuum device for removing air in the reaction vessel 8 Ground wire 9 High-voltage introduction part

Claims (8)

Carbon content 85 in the undercoat layer with respect to a substrate having an undercoat layer composed of any one or more selected from a plating film, a PVD film, a CVD film, an anodized film and a remelted film Intruded and filled with ultrafine solid particles having a hydrogen content of 15 to 50 atomic% and a carbon content of 85 to 50 atomic% and a hydrogen content of 15 to 50 on the surface of the undercoat layer. A member for a semiconductor processing apparatus, in which an amorphous carbon-hydrogen solid layer composed of a deposition layer of ultrafine solid particles of atomic% is formed. 2. The member for a semiconductor processing apparatus according to claim 1, wherein the amorphous carbon hydrogen solid layer on the surface of the undercoat layer is a layer having a thickness of 80 μm or less. 3. The member for a 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 10 ⁵ to 10 ⁸ Ωcm. . 4. The member for a semiconductor processing apparatus according to claim 1, wherein the surface of the undercoat layer is a secondary recrystallized layer generated by a high energy irradiation process. 5. A substrate to be treated having an undercoat layer made of any one or more selected from a plating film, a PVD film, a CVD film, an anodized film, and a remelted film is held in the exhausted reaction vessel. In addition, a hydrocarbon gas is introduced, and a plasma of the introduced hydrocarbon gas is generated by superimposing and applying high frequency power and a high voltage pulse to the base material, and at the same time holding the base material at a negative potential By vapor deposition 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 and intruding and filling the undercoat layer. , carbon content in the undercoat layer surface 85-50 atomic%, the amorphous carbon hydrogen solid comprising an aggregate of 1 × ^{10 -9} m or less of the super-fine solid particles of the hydrogen content of 15 to 50 atomic% The method of manufacturing a semiconductor processing device member, characterized in that the coating is deposited things. 6. The method for manufacturing a member for a semiconductor processing apparatus according to claim 5, wherein the layer formed of the amorphous carbon hydrogen solid on the surface of the undercoat layer is a layer having a thickness of 80 [mu] m or less. 7. The semiconductor according to claim 5, wherein the layer formed of the amorphous carbon-hydrogen solid has characteristics of hardness Hv: 500 to 2300 and electric resistivity of 10 ⁵ to 10 ⁸ Ωcm. Manufacturing method of member for processing apparatus. 8. The member for a semiconductor processing apparatus according to claim 5, wherein a secondary recrystallized layer formed on the surface of the undercoat layer by high energy irradiation treatment is formed on the surface of the undercoat layer. Production method.

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