JP2011047052A - Method of manufacturing member for semiconductor machining device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that, when a semiconductor machining treated vessel member is subjected to plasma etching working in an environment including a halogen gas, it receives corrosive damage at the initial stage, further, micro environmental contamination particles are generated to remarkably reduce the working production capacity of a semiconductor. <P>SOLUTION: In the method for producing a member for a semiconductor machining device, the base material to be treated is held in a reaction vessel, hydrocarbon based gas plasma is generated from the gas of an organometallic compound introduced into the vessel, thus the fine particles of an amorphous carbon-hydrogen solid matter comprising 15 to 40 at.% hydrogen are vapor-phase precipitated, and simultaneously, the hyperfine particles of a metal are co-precipitated so as to form a vapor-deposited film of a metal grain-containing amorphous carbon hydrogen solid matter, and thereafter, the film is subjected to oxidation treatment so as to produce metal oxide part grains. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a member for a semiconductor processing apparatus, and more particularly, to a semiconductor processing apparatus that requires cleaning and removing fine particles generated during plasma processing in an environment where halogen or a halogen compound is present. It is a proposal about a technique which is effective as various constituent members.

  Various devices used in semiconductor manufacturing and processing processes use highly corrosive harmful gases such as fluorides and chlorides or aqueous solutions in each process, so the components of these devices are subject to corrosion wear. It is known to be intense.

  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 recent semiconductor processing technology field, 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-level and high-precision processing. 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. In addition, recent semiconductor processing apparatus members that require high precision processing have been repelled even with minute 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. That is, in various semiconductor device processing apparatuses that have been recently studied, elements other than Si, metals, nonmetallic compounds, etc. in the 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 rather a source of contamination.

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). However, damage and peeling are likely to occur due to abrupt temperature change and accompanying deformation, and there are many problems in using this for each member for a semiconductor processing apparatus.

The present invention is a technology developed for the purpose of solving the following problems, for example, which the conventional technology has.
(1) Since DLC containing carbon as a main component is very hard (particularly for those having a high electrical resistivity of 10 ⁸ to 10 ¹³ Ωcm), it is poor in ductility. A large thermal stress is generated between the DLC and the DLC, so that they are easily separated. 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 generates a large residual stress during film formation, and thus cannot be made thick, and also has many pinholes. Therefore, even if DLC itself is a material excellent in 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) Although DLC itself is excellent in halogen corrosion resistance, it is not only peeled off easily by plasma etching treatment or halogen ions excited by plasma, but DLC is also affected by residual stress. It becomes a small round cylindrical piece and scatters around, which becomes 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 film forming method disclosed in the prior patent documents 6 to 10 and the like, it is difficult to form a film having a thickness of 10 μm or more, and a uniform thickness is formed on the surface of the member having a complicated shape. DLC cannot be formed, and 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 has been developed for the purpose of solving the above-described problems, and holds a substrate to be treated in a reaction vessel, introduces a gas of an organometallic compound into the vessel, and By applying superimposed high-frequency power and high-voltage pulse to the base material and generating hydrocarbon-based gas plasma from the introduced organometallic compound-based gas, amorphous carbon containing 15 to 40 at% hydrogen At the same time as vapor deposition of hydrogen solid particles, metal ultra-fine particles are co-deposited and adsorbed on the surface of the substrate, thereby vapor deposition deposition film of amorphous carbon / hydrogen solids containing metal particles And a method for producing a member for a semiconductor processing apparatus, wherein an oxidation treatment is performed to change a part or all of the ultrafine metal particles contained in the vapor deposition film to oxide ultrafine particles. To draft.

In the above production method of the present invention,
a. The amorphous carbon / hydrogen solid phase vapor deposition film comprises a deposited layer of fine solid particles having a carbon content of 85 to 60 at% and a hydrogen content of 15 to 40 at%, and in this film, Si, Y , Mg, Al and a thin film layer having a thickness of 80 μm or less, containing 3 to 30 at% of ultrafine particles of 1 × 10 ⁻⁹ m or less selected from Mg, Al and Group IIIA lanthanum series metals Being
b. The oxidation treatment performed after forming the vapor deposition film of amorphous carbon / hydrogen solids is performed by irradiating the vapor deposition film with oxygen gas plasma or in an environment containing oxygen at 100 ° C. to 500 ° C. By performing a heat oxidation treatment at ℃,
c. The base material is a base material made of a metal material or a non-metal material, or a ceramic sintered body, a thermal spray coating, a plating coating, a PVD coating, a CVD coating, an anodic oxidation coating, and a remelt treatment coating formed on the surface of these base materials. It is comprised by the 1 or more types of undercoat layer chosen from d. The substrate or the undercoat layer has a secondary recrystallized layer formed on the surface thereof by high energy irradiation treatment,
e. The vapor deposition film is a film obtained by any method such as PVD treatment, ion plating treatment, sputtering treatment, metal organic chemical vapor deposition, in addition to plasma CVD treatment,
Gives a more preferred solution.

(1) According to the present invention, the surface portion of the substrate to be treated is composed of carbon and hydrogen containing ultrafine metal oxide particles by a vapor deposition method in which high-frequency power and high voltage pulses are superimposed. In addition to forming a layer by coating amorphous fine solid particles, this layer is also infiltrated and filled into the pores of the substrate to be treated, particularly in the case of a sprayed coating, so that In addition to repairing defects, it is possible to easily form a vapor deposition film of amorphous carbon / hydrogen solid containing ultrafine metal oxide particles with a certain thickness.
(2) According to the present invention, by applying a negative voltage to the substrate to be treated, fine solid particles composed of positively charged metal ions and radical carbon and hydrogen are evenly distributed on all surface portions of the substrate. Because it is adsorbed and deposited on the substrate, it can infiltrate every part of the base material with a complicated shape, especially hidden parts, and even inside the microscopic pores, so that a uniform film can be formed. Thus, the open pores can be reliably sealed.
(3) According to the present invention, the amorphous carbon / hydrogen solid layer (vapor deposition deposition film) containing metal oxide fine particles coated on the substrate surface is dense and excellent in adhesion, Residual stress during film formation is small and chemically stable, so it is chemically stable without being affected by seawater, acids, alkalis, and organic solvents. it can.
(4) According to the present invention, a film made of an amorphous carbon / hydrogen solid material as a bulk material containing nano-order grades of metal or metal oxide has a relatively low hardness (Hv: 500 to 2300). Since it has ductility and its electrical resistivity is less than 10 ⁸ Ωcm, it does not peel even if the substrate is subjected to thermal and mechanical bending deformation.
(5) According to the present invention, an amorphous carbon / hydrogen solid phase vapor deposition film containing ultrafine metal oxide particles coated on the substrate surface is 80 μm or less, preferably 0.5 μm to 50 μm thick. Even when the film is formed, a film having excellent peeling resistance can be formed on the substrate surface.
(6) According to the present invention, the vapor deposition deposition film of amorphous carbon / hydrogen solid containing ultrafine particles of the metal oxide is excellent in adhesion and ductility, and depending on the kind of environmental halogen compound, the metal By selecting and using the type of oxide particles, the functions of metal oxides can be exhibited as they are while taking advantage of the properties of vapor-deposition deposited films of amorphous carbon and hydrogen solids. The generation of corrosion products can be eradicated.

  Accordingly, the semiconductor processing apparatus member coated with the above-described amorphous carbon / hydrogen solid phase vapor deposition film is highly sophisticated because, for example, the reaction container member is always maintained in a clean environment. High-precision semiconductor processing can be efficiently performed over a long period of time.

It is a basic diagram of a plasma CVD processing apparatus. It is a cross-sectional example of a DLC film in which SiO ₂ oxide particles produced by the method of the present invention are co-deposited. (Electron micrograph) It is an example of the section structure of the coat manufactured by the method of the present invention. It is an example of a cross-sectional micro sketch of a ceramic sprayed coating irradiated with an electron beam. It is a basic diagram of the corrosion test apparatus which activated the gas containing a halogen compound.

  First, a vapor deposition deposition film (hereinafter, simply referred to as “DLC film”) made of amorphous carbon / hydrogen solids, which plays an important role in the present invention, and a DLC film (hereinafter simply referred to as “DLC film”) containing ultrafine particles of metal oxide. A vapor deposition deposition apparatus for forming an “oxide particle-containing DLC film”) will be described. FIG. 1 shows an apparatus for forming a DLC film on the surface of a substrate (hereinafter, an example of a “plasma CVD apparatus” is shown). The plasma CVD processing apparatus includes a grounded reaction vessel 1, a conductor 3 connected to a substrate 2 to be processed disposed at a predetermined position in the reaction vessel 1, and a film formation in the reaction vessel 1. For applying a high voltage pulse through a device for introducing a hydrocarbon gas and an organic metal compound gas (not shown) or a vacuum device (not shown) for evacuating the reaction vessel 1 A voltage pulse generating power source 4 is provided. In this apparatus, a plasma generating power source 5 for generating a hydrocarbon-based gas plasma is disposed around the substrate 2 to be processed, and the conductor 3 and the substrate 2 to be processed are also provided. In order to apply both the high voltage pulse and the high frequency voltage at the same time, a superimposing device 6 is disposed between the high voltage pulse generating power source 4 and the plasma generating power source 5. The gas introduction device and the vacuum device are connected to the reaction vessel 1 via valves 7 a and 7 b, respectively, and the conductor 3 is connected to the superposition device 6 via a high voltage introduction unit 9.

  Using the above device. In order to form amorphous carbon / hydrogen solids on the surface of the electrically conductive substrate 2 to form these deposited layers, the substrate 2 is placed at a predetermined position in the reaction vessel 1. Then, after operating the vacuum device to discharge the air in the reaction vessel 1 and degassing it, an organic 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 substrate 2 to be processed. Then, since the reaction vessel 1 is in an electrically neutral state by the ground wire 8, the substrate 2 to be treated has a relatively negative potential. For this reason, the positive ions in the plasma of the organic gas generated by the application are generated around the negatively charged substrate 2 to be processed.

  In this state, when a high voltage pulse (negative high voltage pulse) from the high voltage pulse generation power source 4 is applied to the substrate 2 to be treated, an amorphous material having the property of positive ions in the organic (hydrocarbon) gas plasma. The fine particles of the solid carbon / hydrogen solid matter are attracted and adsorbed on the surface of the substrate 2 to be treated, and deposit and deposit, and grow into a film shape with the passage of time to form a film. That is, in the reaction vessel 1, finally, amorphous carbon / hydrogen solid particles composed of carbon and hydrogen are vapor-deposited around the substrate 2 to be treated, and then over the entire surface of the substrate. It is considered that a DLC film is formed.

That is, the process of forming a vapor deposition film of amorphous carbon / hydrogen solids on the thermal spray coating by such a plasma CVD processing apparatus (method) is formed through the following (a) to (c). It is considered to be done.
(A) ionization of the introduced carbon-hydrogen gas (active neutral particles called radicals also exist) occurs,
(B) Ions and radicals changed from the hydrocarbon-based gas collide impactively with the surface of the object to be treated, 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 material mainly composed of carbon and hydrogen. The solid carbon / hydrogen solid is vapor-deposited on the surface of the base material or in the pores of the sprayed coating.

In the above apparatus, by changing the output voltage of the high-voltage pulse generating power source 4 as shown in the following (a) to (d), ions of metal or the like can be implanted into the processing object 2. In particular, it is preferable to implant ions such as Si, C, and Ta into the surface of the base material or the undercoat because the adhesion of the DLC film is improved.
(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

  The high voltage pulse generating power source 4 can repeatedly generate one or more pulses with a pulse width of 1 μsec to 10 msec. 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.

As the organic gas for forming the DLC film introduced into the reaction vessel 1 of this apparatus, a hydrocarbon gas composed of carbon and hydrogen is suitable. For example, the following is used.
(I) Gas phase state at normal 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) Those in 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
In addition, a DLC film can be formed in a liquid phase at room temperature if it is performed with a gas generated by heating.

Next, a method for forming a DLC film containing ultrafine metal particles and a method for converting the ultrafine metal particles into an oxide will be described.
(1) Method for Forming DLC Film Containing Ultrafine Metal Particles A DLC film containing ultrafine metal particles can be formed by using an organometallic compound in which a metal element is bonded to the hydrocarbon-based material. Most of the organometallic compounds often show a liquid phase at room temperature. Therefore, after heating the liquid-phase organometallic compound into a gaseous state and then introducing it into the reaction vessel 1 and applying a voltage, the solid surface amorphous carbon film mainly composed of carbon and hydrogen is formed on the substrate surface. Metal ultrafine particles co-deposit. The size of the ultrafine particles of metal eutectoid in the DLC film is all on the nano order (1 × 10 ⁻⁹ m or less), so that it is difficult to discriminate not only in the optical microscope but also in the electron microscope.

Examples of the organometallic compound used for this purpose include (C ₂ H ₅ O) ₄ Si, (CH ₃ O) ₄ Si, (CH ₃ O) ₄ Si, [( CH ₃ ) ₃ Si] ₂ O and the like are suitable, and in order to co-deposit other metals, Al, Y, Mg and a lanthanum group element of Group IIIA of the periodic table were added to the Si position of the organic compound. It is possible by using things. For example, the precipitation of lanthanum series metals can be obtained by using an organometallic compound in which a lanthanum metal is bonded to a (C ₁₁ H ₁₉ O ₂ ) or (C ₁₂ H ₂₁ O ₂ ) group (for example, Sm ( _{C 11 H 19 O 2) 3} , Yb (C 11 H 19 O 2) 3, Sm (C 12 H 21 O 2) 3, Gd ( such as _{C 12 H 21 O 2) 3} ). Moreover, when co-depositing an alloy and 2 or more types of metal particles, it obtains by introduce | transducing the gas (vapor) of each organometallic compound in a processing container.

  The amount of collapsing of the ultrafine metal particles in the DLC film obtained by the method of the present invention is preferably 3 to 30 at% for the purpose of the present invention when Si is taken as an example. If the amount of eutectoid is 30 at% or more, quality control is difficult, and even if the concentration is increased further, the improvement of the effect cannot be obtained. This is because an oxide film cannot be formed. In the case of Y, Mg, Al and lanthanum series metals, the eutectoid rate in the same range as above is appropriate.

(2) About the metal contained in a DLC film Although the method of making a metal oxide fine particle coexist in a DLC film is mentioned later, the following are suitable as a metal particle suitable for the objective of this invention.

  Si, Y, Mg, Al, and lanthanum series elements having atomic numbers 51 to 71 belonging to Group IIIA of the periodic table are suitable. Specifically, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, eurobium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lb, lutetium Lu 15 elements.

  These lanthanum series metals are easily oxidized, easily react with moisture to generate hydrogen gas, and also react with hydrogen, nitrogen, and halogen. Therefore, the corrosion resistance of the metal itself is very low. However, when these metals are changed to oxides, the corrosion resistance is remarkably improved, and particularly when oxides of metals such as Si, Y, Mg, and Al are mixed, it is excellent compared to the conventional DLC film alone. It has the characteristics of exhibiting high halogen resistance and plasma erosion resistance.

Note that a DLC film that does not contain metal oxide fine particles exhibits the following characteristics.
(1) Although a general DLC film is excellent in high electrical resistance and chemical stability, it is easily damaged and destroyed when it is bombarded with excited halogen-based plasma ions. .
(2) Since the DLC film has a large residual stress at the time of film formation, it is easily broken by thermal shock or the plasma ions.
(3) When the DLC film is broken, the DLC film is rounded and scattered like a cylinder, and falls on the Si wafer, causing a product defect.
(4) When a DLC film is used alone, corrosion may be accelerated by pinholes often present in the film, and there is a tendency for reliability to be lacking.

In contrast, an oxide particle-containing DLC film containing metal oxide particles that are nano-order ultrafine particles exhibits the following characteristics and operational effects.
(1) This oxide particle-containing DLC film has a small residual stress and an electrical resistivity of less than 10 ⁸ cm. Therefore, even if this layer is formed, it has a great effect on the Johnson Rabeck action of a normal DLC film below. It does not affect and does not peel off due to thermal shock.
(2) It is resistant to the impact of halogen ions excited by plasma and exhibits high plasma erosion properties.
(3) DLC film containing oxide particles such as SiO ₂ even in an environment where all the semiconductor materials other than Si of the wafer material are considered to be environmental pollutants in the current semiconductor processing apparatus that has been highly accurate and highly cleaned. If so, even if plasma etched, it will not be a source of contaminants.

(3) Method for oxidizing metal ultrafine particles contained in DLC film The metal ultrafine particles contained in the DLC film can be changed to oxide by adopting the following method.
a. Heating in an atmosphere containing oxygen gas When a DLC film containing ultrafine metal particles is heated in air or an environment such as an atmospheric furnace containing oxygen gas, the ultrafine metal particles contained in the DLC film are Oxidizes and changes to oxide. Specifically, it changes to a chemically stable oxide such as Si → SiO ₂ , Al—Al ₂ O ₃ , Y → Y ₂ O ₃ , and exhibits corrosion resistance and plasma erosion resistance. The upper limit of the heating temperature in this case is 500 ° C. The heating time is determined according to the change rate of the oxide of the metal fine particles contained in the DLC film, and is, for example, about 0.1 to 1.0 h. If all the ultrafine metal particles contained in the DLC film are changed to oxides, the DLC film itself may be thermally deteriorated if the heating time is further increased.

  When the heating temperature is set to 500 ° C. or higher, the DLC film is deteriorated, chemical stability is lowered, physical properties are also lowered, and cracks may be generated in the film in some cases. On the other hand, at a temperature of 100 ° C. or lower, the oxidation rate of the ultrafine metal particles is slow and not productive.

b. Oxidation by oxygen gas plasma For example, a substrate having a DLC film containing ultrafine metal particles by introducing the oxygen gas or a gas containing oxygen gas into Ar, He or the like as an atmospheric gas using the plasma CVD apparatus of FIG. Is negatively charged to generate plasma, the ultrafine metal particles contained in the DLC film are bombarded with excited oxygen ions and gradually change from the surface to oxides. This method can be carried out directly after the formation of the DLC film, and since the DLC film is not likely to be overheated, the quality is stable and the productivity is improved as compared with the heating oxidation method. is there.

FIG. 2 shows that after an insulating DLC film is formed as an intermediate layer on the surface of a substrate, a DLC film containing ultrafine particles of Si oxide is coated thereon, and this is oxidized by an oxygen gas plasma irradiation method. 2 shows a cross section of the DLC film. The junction part of the normal DLC film which is an intermediate layer and the oxide particle-containing DLC film containing SiO ₂ fine particles is in close contact with each other so that it can hardly be confirmed. Further, the size of the SiO ₂ particles is so fine that it is not apparent even when observed with a high-magnification electron microscope (theoretical value is 3.57 × 10 ⁻¹⁰ m in diameter), and these particles are assembled in an infinite number of layers. It can be seen that the corrosion resistance is exhibited.

FIG. 3A to FIG. 3D show structural examples of DLC films containing metal oxide fine particles produced by applying the method of the present invention.
FIG. 3A shows a basic structure in the case where an oxide particle-containing DLC film 32 containing ultrafine particles of metal oxide is laminated directly on the surface of a metal or non-metal substrate 31.
FIG. 3B shows an oxide particle-containing DLC containing ultrafine particles of a metal oxide on a normal DLC film 33 not containing a metal oxide formed as an intermediate layer on the surface of the substrate. This is an example in which a film is coated.
FIG. 3 (c) shows the formation of an undercoat 34 such as a sprayed coating, a plating coating, a PVD coating, a CVD coating, an anodic oxide coating, and a remelted coating on the surface of the substrate, and then a metal oxide thereon. This is an example in which an oxide particle-containing DLC film containing ultrafine particles is coated and applied as an anticorrosion film for various members disposed in a semiconductor processing apparatus in which a film is formed by current technology. .
FIG. 3D shows an ordinary DLC film formed on the surface of the base material after an undercoat such as a sprayed film, a plated film, a PVD film, a CVD film, an anodized film and a remelted film is formed on the surface. 33 is formed, and an oxide-containing DLC film containing metal oxide fine particles is coated thereon as an outermost layer film.

In the member for a semiconductor processing apparatus manufactured by applying the method of the present invention, since an adhesion improving function as shown below is added, a member that exhibits excellent thermal shock resistance in addition to corrosion resistance is obtained. That is, the DLC film formed by plasma CVD or the like has a nano-order size in which the vapor (gas) of the organometallic compound is decomposed and excited by the plasma energy regardless of the presence or absence of ultrafine metal particles. It is characterized in that it becomes particles (1 × 10 ⁻⁹ m or less) and metal ions and adheres to the negatively charged substrate or undercoat surface by electrical impact. For this reason, even if pinholes, minute cracks, and the like are present on the surface of the base material or the undercoat, they exhibit a microscopic repairing action that penetrates into these defects and fills and seals them. Such a sealing action contributes extremely effectively as an anchoring effect (throwing effect) of the metal particle-containing DLC film laminated thereon, and thus is considered to be a cause of exhibiting excellent adhesion. .

Example 1
In this example, the hydrogen content of the amorphous carbon / hydrogen solid layer (DLC 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) DLC film formation method and properties The DLC film was formed to a thickness of 1.5 μm over the entire surface of the test piece. At this time, the DLC film whose hydrogen content was controlled in the range of 5 at% to 50 at% (the balance was carbon) was used.
(3) Test Method and Conditions The test piece on which the DLC film was formed was subjected to bending deformation at 90 °, and the appearance of the DLC film at the bent part was observed with a 20 × magnifier. 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 DLC film is low and the carbon content is high (No. 1 to 3), if the film is subjected to 90 ° bending deformation, the film is peeled off or locally. It peeled. 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. In contrast, DLC membranes with a hydrogen content of 15 at% to 50 at% (No. 4 to 8) do not peel off even by bending deformation, well withstand salt spray tests, and maintain excellent corrosion resistance. It was confirmed that

(Example 2)
In this example, the relationship between the DLC film thickness and the corrosion resistance of the oxide particle-containing DLC film containing ultrafine metal oxide particles was investigated.
(1) Test substrate and coating a. As a test substrate, SS400 steel (dimensions: width 30 mm × length 5 mm × thickness 3.2 mm) that easily causes red rust due to corrosive action was used.
b. DLC film: DLC film formed to a thickness of 0.5 μm, 1.0 μm, 3.0 μm, 8.0 μm, 15.0 μm on the entire surface of the base material using the apparatus shown in FIG. Two types of test films were prepared: an oxide particle-containing DLC film containing 22 at% of SiO ₂ oxide particles formed in the same film thickness on this DLC film. The SiO ₂ oxide was prepared by oxygen gas plasma irradiation.

(2) Corrosion test conditions a. The change in the DLC film was investigated by leaving it in an atmosphere of a constant temperature bath (30 ° C.) with a humidity of 95% for 800 hours.
b. The salt spray test prescribed in JIS Z2371 was conducted for 800 hours to investigate the general corrosion resistance of the DLC film.
c. The DLC film was immersed in a 3 mass% HCl aqueous solution for 48 hours to investigate the acid resistance of the DLC film. In the above tests, untreated SS400 steel specimens were tested under the same conditions as comparative examples.
(3) Test results The test results were summarized and shown in Table 2. As is clear from this result, the untreated SS400 steel test piece generates red rust even in 95% humidity, and the red rust turns black after the salt spray test, and the corrosion progresses in 3% HCl aqueous solution. It can be seen that the corrosion resistance is extremely poor. On the other hand, when the DLC film was formed to a thickness of 3 μm or more, it was confirmed that the DLC film exhibited sufficient corrosion resistance even against a highly corrosive 3% HCl aqueous solution. Also, under these test conditions, among the DLC films, those containing SiO ₂ oxide particles contained in this film exhibit excellent corrosion resistance and are compared with the corrosion resistance of DLC films not containing oxide particles. And it turned out to be inferior.

(Example 3)
In this example, the formation of the oxide fine particle-containing DLC film on the base material and the surface treatment film of various apparatuses used in the 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) Formation Method of DLC Film Containing Oxide Particles Using the plasma CVD apparatus shown in FIG. 1, the hydrogen content in the DLC film in which the surface of the test film is coated with an organosilicon compound as a film forming material to a thickness of 5 μm is used. The amount is 18 at% and the SiO ₂ content is 21.2 at%. The method of the oxide SiO ₂ is using oxygen gas plasma method.
(3) Test results Table 3 shows the test results. As is clear from the test results, the DLC film containing SiO ₂ fine particles has good adhesion to sintered materials, PVD, CVD, anodic oxide films, as well as metal materials such as quartz, glass, and polycarbonate. It was confirmed that it was advantageous as a protective film for these substrates.

In addition, as the metal oxide, an amorphous solid film containing fine particles such as Y ₂ O ₃ , Al ₂ O ₃ , MgO, CeO ₂ , and Yb ₂ O ₃ also exhibits good adhesion to the test substrate. It was.

Example 4
In this embodiment, after applying an undercoat such as aluminum oxide or aluminum nitride on the surface of the substrate, directly or after forming a DLC film not containing oxide fine particles, The thermal shock resistance of the coated oxide particle-containing DLC film was investigated.
(1) Test substrate and coating a. As test base materials, test pieces (dimensions: width 30 mm × length 50 mm × thickness) were prepared from Al alloy (JIS H400 standard 6061 alloy) Ti alloy (JIS H4600 standard 60 type alloy) Mg alloy (JIS H4201 standard type 1 alloy). 2.0 mm).
b. As an undercoat, Al ₂ O ₃ (sprayed coating 50 μm) AlN (PVD method 5 μm) was formed on the surface of the test substrate, and then the entire surface of these undercoats was formed on the DLC film and A film test piece coated with an oxide particle-containing DLC film was prepared.

(2) Thermal shock test conditions (i) As a thermal shock test, after each film test piece was heated in the air and then put into tap water at 20 ° C. for 10 cycles, the surface of the film was Observation was performed using a magnifying glass.
Test conditions (a) 200 ° C. × 15 minutes heating → 20 ° C. tap water injection (b) 350 ° C. × 10 minutes heating → 20 ° C. tap water injection (3) Test results Table 4 summarizes the thermal shock test results. . As is apparent from this result, the conventional DLC film (DLC films not including metal oxide particles: No. 1, 3, 5, 7, 9, 11) has a relatively low heating temperature of 200 ° C. → water cooling. Under the conditions, a healthy state was maintained, but when the heating temperature was increased to 350 ° C., cracks occurred in a part of the DLC film, and a tendency to peel locally was observed.
On the other hand, the oxide particle-containing DLC film containing SiO ₂ peculiar to the present invention maintained a healthy state even under the condition of 350 ° C. → water cooling, and neither peeling nor cracking was observed in the film.
Such a result shows that a normal DLC film has a large residual stress in a film formation state, and thus is easily cracked by a thermal shock load, whereas an oxide particle-containing DLC film containing SiO ₂ particles has a residual stress. It can be seen that it is small and hardly affected by physical changes in the base material and undercoat including thermal shock.

(Example 5)
In this example, an oxide-based ceramic sprayed coating was directly formed on the surface of a test piece made of an SS400 steel base material, and then an oxide particle-containing DLC film containing 15 at% Y ₂ O ₃ fine particles was formed on the surface. After coating, it was subjected to a salt spray test to investigate its corrosion resistance.
(1) Basic and test piece dimensions SS400 steel (dimensions: width 50 mm x length 70 mm x thickness 3.2 mm)
(2) Types of thermal spray coating and thermal spraying method The following oxide ceramics were formed directly 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 thinner is to determine the sealing / coating effect of the DLC film by a short test.
(A) Al ₂ O ₃
(B) Cr ₂ O _{3
(C) 8mass% Y 2 O} 3 · 92mass% ZrO 2
(D) 98 mass% Al ₂ O ₃ .MgO spinel (e) 98 mass% Al ₂ O ₃ .2 mass% TiO ₂
(F) Y ₂ O ₃
(3) Formation and Thickness of Oxide Particle-Containing DLC Film Using the same apparatus as in Example 1, it was formed to a film thickness of 5 μm (hydrogen content: 16 to 26 at%).
(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 not coated with the oxide particle-containing DLC film was tested under the same conditions.
(6) Corrosion test results Table 5 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 oxide particle-containing DLC film have good sealing performance and covering performance for any ceramic film. Demonstrated and no red rust was observed.

(Example 6)
In this example, an oxide particle-containing DLC film having a different amount of SiO ₂ particles was directly formed on the surface of a SUS316 base material, and then a test piece that was subjected to bending deformation was produced. Then, the corrosion test in the halogen gas atmosphere activated using this test piece was done, and the corrosion resistance of a DLC film and an oxide particle containing DLC film was investigated.
(1) Test substrate and coating a. As the test substrate, SUS316 steel (dimensions: width 10 mm × length 60 mm × thickness 2.0 mm) was used.
b. With the apparatus shown in FIG. 1, the DLC film containing the oxide particle-containing DLC film having a SiO ₂ content in the range of 1 to 32 at% with respect to the entire surface of the substrate was coated.
(2) Test method and conditions (i) Bending test: The central part of the test piece coated with the DLC film is bent at 90 °, and the presence or absence of damage to the film at the bent part is measured using a magnifying glass (× 5). And observed.
(Ii) Active halogen gas test: The apparatus shown in FIG. 5 was used for this test. In this test, the test piece 51 was allowed to stand on an installation table 56 inside a stainless steel tube 53 provided at the center of the electric furnace 52, and then a corrosive gas 54 was flowed from the left side. A microwave having an output of 600 W was added to the quartz discharge tube 45 provided in the middle of the piping to promote the activation of the corrosive gas. The activated corrosive gas was introduced into the electric furnace, and after the test piece 51 was corroded, it was discharged out of the system from the right side.
Further, in this test, a 30-hour corrosion test was performed while flowing a test piece temperature of 200 ° C., corrosive gas HCl of 300 ppm, NF _{3 of} 15 ppm, O _{2 of} 100 ppm, and remaining Ar of 75 ml / min.
(3) Test results The test results are summarized in Table 6. As is apparent from this result, in the bending test, no cracks were observed in the coating regardless of the presence or absence of metal oxide particles. However, when the DLC film after the bending test is subjected to a corrosion test, the surface of the film containing no SiO ₂ oxide particles (No. 1) and the film having a SiO ₂ content of 1 at% (No. 2) has a diameter of 1 to 1. Round peeling phenomenon of about 3 mm occurred in several places. This is probably because the corrosive gas penetrates into the inside through a small pinhole that cannot be found with a magnifying glass and corrodes the substrate, thereby lowering the adhesion of the DLC film. On the other hand, in the DLC film (No. 3-6, 9-12) containing 3 to 30 at% of SiO ₂ oxide particles, no abnormality was observed even after the test, and the sound state was maintained. However, in the DLC film (Nos. 7 and 13) containing 32 at% of SiO ₂ oxide particles, a slight amount of red rust was observed on the surface, indicating the presence of pinholes or cracks reaching the substrate surface in the film. This is probably because the coating tends to become brittle due to bending deformation when the SiO ₂ oxide particle content increases.

(Example 7)
In this embodiment, a DLC film containing various metal oxides is directly formed on an Al alloy base, and a DLC film not containing metal oxide particles is formed as an intermediate layer, and then the present invention is applied to the DLC film. The corrosion resistance of the laminated DLC film containing various metal oxide particles was investigated.
(1) Test substrate and coating a. As a test substrate, a test piece (size: width 30 mm × length 50 mm × thickness 2 mm) of an Al alloy (JIS H4000 regulation 6061) was used.
b. As a test film, a DLC film containing SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , Yb ₂ O ₃ , and CeO ₂ is directly formed on a substrate to a thickness of 5 μm, and an oxide particle as an intermediate layer After forming a DLC film that does not contain 5 μm, a test piece in which an oxide particle-containing DLC film was formed was prepared.
(2) Test conditions The following three types of tests were performed as corrosion test conditions.
a. Active halogen test: conducted in the same manner as in Example b. HCl vapor test: Corrosion test was conducted at 60 ° C. for 100 hours in air containing 300 ppm of HCl. (3) Test results Table 7 summarizes the test results. As is clear from this result, in the test pieces (No. 1 and 7) that do not contain oxide particles in the DLC film, the base material is corroded by the corrosive components that have penetrated into the inside through the pinholes, and a part of the film is removed. It peeled.
On the other hand, all the test pieces (No. 2-6, 8-12) laminated | stacked directly on the base material or on the intermediate | middle layer of the DLC film show the excellent corrosion resistance, as for the oxide particle containing DLC film, No abnormalities were found. From these results, the oxide particle-containing DLC film expands its volume due to oxidation of the metal fine particles, thereby sealing the pinholes existing in the DLC film, while the metal oxide itself has excellent corrosion resistance. it is conceivable that.

(Example 8)
In this example, the thermal shock resistance and halogen corrosion resistance of an oxide particle-containing DLC film containing a plurality of oxide particles were investigated.
(1) Test substrate and coating a. A commercially available graphite plate (size: width 30 mm × length 50 mm × thickness 5 mm) was used as a test substrate.
b. The structure and thickness of the test film are the same as in Example 5. However, a plurality of metal oxide particles are included in the DLC film, and the mixture ratio is 0.4 to 0.5 / 0.6 to 0.5 at%.
Combination of metal oxides: SiO ₂ / Al ₂ O ₃ , Al ₂ O ₃ / Y ₂ O ₃ , Y ₂ O ₃ / CeO ₂
(2) Test method and conditions a. Thermal shock test: After heating in air at 350 ° C. for 10 minutes, the operation of throwing it into tap water at 20 ° C. was repeated 10 times.
b. Active halogen gas corrosion: performed under the same conditions as in Example 5.
(3) Test results The test results are summarized in Table 8. As is clear from this result, even if an oxide particle-containing DLC film containing a plurality of metal oxide particles is laminated on a graphite substrate directly or on an intermediate layer of a DLC film not containing oxide particles, It has been confirmed that it can withstand thermal shock tests and exhibits excellent corrosion resistance against activated halogen compound gases.

Example 9
In this example, in consideration of the case where it is used in a corrosive atmosphere or an environment where an organic solvent is handled, oxide ceramic spraying is performed when a metal-based undercoat is applied to the surface of an SS400 steel substrate having poor corrosion resistance. The anticorrosion effect of the DLC film containing oxide particles (Al ₂ O ₃ ) on the film was investigated.
(1) Substrate: An SS400 steel plate having the same dimensions as in Example 2 was used.
(2) Types of thermal spray coating and thermal spraying method (numbers are mass%)
(A) Undercoat: 80 mass% Ni-20 mass% Cr (atmospheric plasma spraying method)
(B) _{Topcoat: Al 2 O 3, Y 2} O 3, 8mass% Y 2 O 3 -92mass% ZrO 2 ( atmospheric plasma spraying)
The film thickness is 50 μm for the undercoat and 150 μm for the topcoat.
(3) Formation method and film thickness of oxide particle-containing DLC film The film thickness was 5 μm by the same method as in Example 3 (hydrogen content: 26 to 34 at%).
(4) Corrosion conditions (ii) 5% HCl: A peaker containing a 5% HCl aqueous solution was maintained at 20 to 23 ° C., a test piece was immersed, and acid resistance was evaluated.
(B) 2% NaOH: A test piece was immersed in a beaker containing a 2% 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 9 shows the corrosion test results. As is clear from this test result, there is no occurrence of red rust in 5% NaOH and an organic solvent regardless of the presence of an undercoat and a DLC film containing oxide particles containing Al ₂ O _3. I was not able to admit. On the other hand, in the 5% HCl aqueous solution, even when the undercoat is applied, the coating (No. 2, 4, 6, 8, 10, 12) in which the oxide particle-containing DLC film is not coated is used. Regardless of the type, all were corroded, 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 HCl aqueous solution in which the DLC film (No. 1, 3, 5, 7, 9, 11) was immersed did not change, and the film maintained a healthy state.

(Example 10)
In this example, the anticorrosion effect of the DLC film containing fine metal oxide particles on the surface of the oxide ceramic sprayed coating irradiated with high energy such as an electron beam and a laser to melt the film forming particles on the coating surface. investigated.
(1) Base material and test piece dimension The test piece of width 20mm * length 30mm * thickness 3.2mm was extract | collected using SS400 steel.
(2) Types of thermal spray coating and thermal spraying method Thermal spray coating type: Y ₂ O ₃
The film was formed to a thickness of 100 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: 1-20mm / 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 and thickness of metal oxide particle-containing DLC film A DLC film containing ultrafine particles of each metal oxide of Y ₂ O ₃ , Al ₂ O ₃ , and CeO ₂ is formed to a thickness of 5 μm in the same manner as in Example 2. Formed. The carbon in the DLC film is 72 at% and hydrogen is 28 at%.
(5) Corrosion test conditions (a) Salt spray test: 96 hours test conducted according to JIS Z2371 (b) Active halogen gas test: conducted under the same conditions as in Example 4 (c) HCl vapor test: chemical test desicche After placing a 30% HCl aqueous solution at the bottom of the evening and disposing a porous glass plate on top of it, a test piece was allowed to stand on the glass plate. HCl vapor is generated, and SS400 steel is a corrosive environment that causes red rust on the whole surface by exposure for 1 h.
(6) Corrosion test results Table 10 shows the anticorrosive effect of the oxide particle-containing DLC film on the test piece irradiated with the undercoat Y ₂ O ₃ sprayed film by electron beam, and Table 11 shows the anticorrosive effect on the laser irradiated surface. . As is apparent from the results of this corrosion test, even when the Y ₂ O ₃ sprayed coating is irradiated with an electron beam and a laser, the coatings in the same state (Nos. 1 and 5) are found to have red rust in all corrosion tests. Therefore, the intrusion of corrosive components cannot be completely prevented.

In order to elucidate the cause, when the surface and cross section of the thermal spray coating irradiated with an electron beam and laser were observed with a magnifying glass, the pores peculiar to the ceramic thermal spray coating disappeared due to the melting phenomenon, but many small cracks occurred. Turned out to be. FIG. 4 is a sketch of a cross-sectional microstructure of a Y ₂ O ₃ sprayed coating after electron beam irradiation as a typical example. In the sprayed coating irradiated with the electron beam, only the vicinity of the surface layer was melted and densified, while it was found that minute cracks occurred when solidified by cooling. In addition, since the porous property at the time of thermal spraying film formation remains in the non-irradiated part inside the film, the cause of red rust is caused by the corrosion component that penetrates from the minute cracked part into the SS400 steel of the base material. It is thought that it was corroded, and the sealing treatment of the ceramic sprayed coating by electron beam and laser irradiation is not sufficient.

On the other hand, when the oxide particle-containing DLC film was coated on the irradiated surface of the thermal spray coating, it was confirmed that the corrosive environment was blocked and the occurrence of red rust was completely prevented.
In addition, the Y ₂ O ₃ , Al ₂ O ₃ , and CeO ₂ oxide particles themselves contained in the film are resistant to various halogen-based gases and have a very small particle size (nano-order class 1 × 10 ⁻⁹ m or less). Therefore, even if it exists in the DLC film, the wettability with the carbon hydrogen amorphous solid in the matrix is good, and both characteristics of the oxide solid and the amorphous solid mainly composed of carbon / hydrogen are combined. It is thought that it is demonstrating.

  The technology of the present invention is used as a member for a semiconductor processing apparatus such as an electrostatic chuck, 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 suitable as a surface treatment for a conveying member such as a Si thin film or a processed product of the Si thin film, and can also be applied to plasma processing container inner members and parts such as a liquid crystal device. Further, the present invention is effective as a technique for a mirror-coated thermal spray coating product, specifically, a printing roll, a film roll, a photosensitive paper roll, a liquid feed pump, a vacuum pump, and a blower. It can also be applied to impellers and casings.

DESCRIPTION OF SYMBOLS 1 Reaction container 2 Electrostatic chuck base material 3 Conductor 4 High voltage pulse generation power source 5 Plasma generation power source 6 Superimposing device 7a, 7b Valve 8 Ground 9 High voltage introduction part 31 Base material 32 Oxide particle containing DLC film 33 Oxide DLC film 34 containing no fine particles 34 Undercoat 41 Substrate 42 Ceramic sprayed coating 43 Through-holes 44 Open pores 45 DLC film 46 containing metal oxide fine particles Void 51 Test piece 52 Electric furnace 53 Stainless steel tube 54 Corrosive gas 55 Quartz discharge tube 56

Claims (5)

A substrate to be treated is held in a reaction vessel, and an organometallic compound gas is introduced into the vessel, and a high-frequency power and a high voltage pulse are superimposed and applied to the substrate to introduce the introduced organometallic compound system. By generating a hydrocarbon-based gas plasma from the gas of the above, vapor deposition of amorphous carbon / hydrogen solid particles containing 15 to 40 at% hydrogen, and at the same time, eutectoid ultrafine metal particles, Is adsorbed on the surface of the base material to form a vapor deposition film of amorphous carbon / hydrogen solid containing metal particles, and a part or all of the ultrafine metal particles contained in the vapor deposition film The manufacturing method of the member for semiconductor processing apparatuses characterized by performing the oxidation process which changes to an ultrafine particle of an oxide. The amorphous carbon / hydrogen solid phase vapor deposition film comprises a deposited layer of fine solid particles having a carbon content of 85 to 60 at% and a hydrogen content of 15 to 40 at%, and in this film, Si, Y , Mg, Al and a thin film layer having a thickness of 80 μm or less, containing 3 to 30 at% of ultrafine particles of 1 × 10 ⁻⁹ m or less selected from Mg, Al and Group IIIA lanthanum series metals The method for manufacturing a member for a semiconductor processing apparatus according to claim 1, wherein: The oxidation treatment performed after forming the vapor deposition film of amorphous carbon / hydrogen solids is performed by irradiating the vapor deposition film with oxygen gas plasma or in an environment containing oxygen at 100 ° C. to 500 ° C. The method for producing a member for a semiconductor processing apparatus according to claim 1, wherein the method is performed by performing a heat oxidation treatment at a temperature of 0 ° C. The base material is a base material made of a metal material or a non-metal material, or a ceramic sintered body, a thermal spray coating, a plating coating, a PVD coating, a CVD coating, an anodic oxidation coating, and a remelt treatment coating formed on the surface of these base materials. The method for producing a member for a semiconductor processing apparatus according to any one of claims 1 to 3, wherein the member comprises at least one undercoat layer selected from among them. The semiconductor according to any one of claims 1 to 4, wherein the base material or the undercoat layer has a secondary recrystallized layer formed on the surface thereof by high energy irradiation treatment. Manufacturing method of member for processing apparatus.

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