TWI351444B - - Google Patents

Description

1351444 IX. EMBODIMENT OF THE INVENTION The present invention relates to a ceramic covering member for a semiconductor processing apparatus, and is particularly preferably used as a member or a part disposed in a semiconductor processing container for plasma etching processing or the like. Covering components such as. [Prior Art]

Devices used in the field of semiconductors or liquid crystals are usually processed using a plasma of a highly corrosive halogen-based etching gas during the processing. For example, the fine wiring pattern formed by the semiconductor processing apparatus is in a highly corrosive gas atmosphere such as a fluorine-based or chlorine-based gas, or a plasma is generated in a mixed gas atmosphere of such a gas and an inert gas, and is excited at the time. The strong reactivity of ions or electrons is finely processed (uranium engraved) and formed thereby. In the case of such a processing technique, at least a part of the wall surface of the reaction vessel or a member or a component (a receiver, an electrostatic chuck, an electrode, or the like) disposed inside the reactor is susceptible to corrosion by plasma energy, and thus is used. Materials that are resistant to plasma corrosion are important. As materials that can meet such requirements, metals (including alloys) or inorganic materials such as quartz and aluminum oxide have been used. For example, Japanese Laid-Open Patent Publication No. H10-4083 discloses that the surface of the inner member of the reaction container is covered with an inorganic material by a PVD method or a CVD method, or an oxide of a mb group element in the periodic table is formed. The quality film, or a method of covering γ2〇3 single crystal. Further, Japanese Laid-Open Patent Publication No. 2001-161643 discloses that an oxide belonging to the group Ilb in the periodic table, that is, γ2〇3, is coated on the surface of the member by melt-blown coating 1351444, thereby improving plasma corrosion resistance. Sexual technology. However, the prior method of covering the oxides of the Illb group and the like has become more stringent in the field of semiconductor processing technology in recent years, and requires higher precision processing and environmental quietness in a corrosive gas atmosphere, and cannot be a sufficient countermeasure.

Also disclosed in 'Patent Document 2' is a member covered with a Y203 melt-blown film, because of the recent processing of semiconductor components, in addition to the further high-output plasma uranium engraving, the processing atmosphere is alternately used repeatedly with fluorine-based gas and hydrocarbon. Gas, if this harsh condition is considered, further improvement is required.

For example, the fluorine-containing gas atmosphere generates a fluoride having a high vapor pressure by a strong corrosion reaction specific to a halogen gas, and on the other hand, in a hydrogen-containing hydrogen atmosphere, the decomposition of a fluorine compound generated in the fluorine-containing gas is promoted. Or, by converting a part of the film component into a carbide, the reaction to fluoride is further enhanced. Moreover, in the plasma environment in a fluorine-containing gas environment, the above reaction is promoted, so that it becomes a very harsh corrosive environment. Further, in such an environment, corrosive products, i.e., fine particles, are generated, which may fall and adhere to the surface of the integrated circuit of the semiconductor article, which may cause damage to the device. SUMMARY OF THE INVENTION Problems to be Solved by the Invention A main object of the present invention is to provide a ceramic covering member which is used as a member disposed in a semiconductor processing container for plasma etching processing in a corrosive gas atmosphere or Components. -6- 1351444 Another object of the present invention is to provide a member which is excellent in resistance to plasma corrosion in a corrosive gas atmosphere, suppresses generation of contaminants (fine particles), and reduces maintenance load on the apparatus. Means for Solving the Problem As a means for achieving the above object, the present invention proposes a ceramic covering member for a semiconductor processing apparatus which is oxidized by a substrate of a nib group on the surface of the substrate a porous layer composed of the material; and a secondary recrystallized layer of the oxide provided on the porous layer. A preferred solution of the present invention is a structure having an undercoat layer between the substrate and the porous layer.

The preferred solution of the present invention is that the substrate is (1) aluminum and its alloys 'titanium and its alloys, stainless steel and other special steels, nickel-based alloys, other metals or alloys thereof; (2) quartz, glass, or a ceramic composed of an oxide or carbide 'boride, a telluride, a nitride, and the like; (3) a cermet composed of the above ceramic and the above metal: alloy: (4) plastic; (5) The surfaces of the materials (1) to (4) are subjected to metal plating (electroplating, sputtering, electroless plating) or a metal vapor deposited film. The preferred solution of the present invention is the above porous layer, which is a bismuth, bismuth or strontium-like element (镧, 铈, 鐯, 、, 钐, 钐, 铕, 釓, 铽, 镝, 鈥, bait, table, mirror) , 镏) of the oxide. In a preferred solution of the present invention, the porous layer is composed of a melt blown film 1351444 having a layer thickness of about 50 to 2000 μm and a porosity of about 5 to 20%. Preferably, the secondary recrystallization layer is a high-energy irradiation treatment layer formed by subjecting the secondary recrystallized layer of the porous layer to a secondary metamorphosis by high-energy irradiation treatment. The preferred resolving means of the present invention is that the secondary recrystallized layer is a porous layer containing orthorhombic crystals, which is subjected to high-energy irradiation treatment to become a tetragonal structure and become a tetragonal crystal structure. a layer with a porosity of less than 5%

The preferred solution of the present invention is that the secondary recrystallized layer is a cerium oxide meltblown film which is formed by a cubic crystal and a monoclinic crystal, and is subjected to high-energy irradiation treatment to be subjected to secondary metamorphism. A layer of cubic crystals. Preferably, the secondary recrystallization layer has a maximum roughness (Ry) of about 6 to 16 μm; an average roughness (Ra) of about 3 to 6 μm; and a 10-point average roughness (Rz) of 8 ~24μηι or so. Preferably, the secondary recrystallization layer of the present invention has a layer thickness of about ΙΟΟμπι or less. φ The preferred solution of the present invention is that the undercoat layer is any one selected from the group consisting of nickel, aluminum, tungsten, molybdenum, titanium, and the like, alloys, oxides, nitrides, borides and carbides. And a coating film having a thickness of about 50 to 500 μηι selected from any one of the above-mentioned metal alloy and the cermet composed of the above ceramics. The ceramic covering member for a semiconductor processing apparatus of the present invention having the above structure In the atmosphere of a halogen-containing compound gas and/or an atmosphere containing a hydrocarbon-based gas, especially in the corrosive environment in which the two atmospheres are alternately repeated - 8 - 1351444, the corrosion effect on the plasma can be exerted for a long time. Resistance and durability. Further, in the ceramic covering member of the present invention, fine particles composed of a film constituent component or the like which is generated during plasma etching in the above-mentioned corrosive environment are less likely to cause environmental pollution. Therefore, high-quality semiconductor elements and the like can be produced with high efficiency. Further, according to the present invention, since the contamination by the fine particles is small, the cleaning operation of the semiconductor processing apparatus or the like is reduced, and the productivity is improved. Further, according to the present invention, by obtaining the above-described effects, the plasma output can be improved to improve the etching effect and speed. Therefore, the size of the device can be reduced or reduced, and the overall effect of the semiconductor production system can be improved. [Embodiment] The ceramic covering member for a semiconductor processing apparatus of the present invention is most effective when it is used for plasma etching in a corrosive gas atmosphere and is used as a member or a part for exposing the environment to the environment. working. The term "such environment" refers to the intense corrosion of components, etc., especially the presence of such components in a fluorine- or fluorine-containing gas (hereinafter referred to as "fluorine-containing gas") atmosphere, for example, containing SF6, CF4, CHF3, C1F3. The atmosphere of a gas such as HF, or the atmosphere of a hydrocarbon-based gas such as C2H2 or CH4 (hereinafter referred to as "hydrocarbon-containing gas"), or an atmosphere in which these two atmospheres alternately overlap. The above fluorine-containing gas atmosphere mainly contains fluorine or fluoride, or contains oxygen (〇2). Fluorine is particularly reactive (corrosive) in halogens and is characterized by the reaction with oxides or carbides in addition to metals to produce corrosion products having a higher vapor pressure of -9 - 1351444. Therefore, a metal or an oxide, a carbide or the like in the fluorine-containing gas atmosphere does not form a protective film for suppressing the corrosion reaction on the surface, and the corrosion reaction is carried out without limitation. However, as will be described later, even in such an environment, the elements belonging to the mb group of the periodic table, that is, the elements of yttrium, lanthanum or atomic sequence 5 7-71 and the oxides thereof, will still perform better. Corrosion resistance.

On the other hand, in the atmosphere containing hydrogen sulfide, the carbonized hydrogen itself is not highly corrosive, but has a characteristic of performing an oxidation reaction under a fluorine-containing gas atmosphere and performing a completely opposite reduction reaction. Therefore, a metal or a metal compound exhibiting a relatively stable corrosion resistance in a fluorine-containing gas atmosphere is weakened when exposed to such a hydrogen sulfide-containing atmosphere. Then, the portion containing the carbonized hydrogen gas is contacted, and if it is again exposed to the fluorine-containing gas atmosphere, the film of the compound which is initially stabilized is chemically destroyed, and it is conceivable that the corrosion reaction proceeds in the end.

In particular, in addition to the externalization of the above-mentioned atmosphere gas, in the environment where plasma is generated, both fluorine and hydrocarbon are ionized to generate a highly reactive atomic fluorine 'hydrocarbon, so corrosion and reduction are more intense. It is more prone to produce corrosion-producing substances. The corrosion products thus produced will vaporize in the plasma environment or become fine particles, which will obviously pollute the interior of the plasma processing vessel. Therefore, in the present invention, it is particularly effective as a countermeasure against corrosion in an environment in which a fluorine-containing gas/hydrogen-containing hydrogen atmosphere is alternately repeated, which not only prevents the generation of corrosion products but also suppresses the generation of particles. Secondly, the inventors first reviewed the fluorine-containing gas or carbon-containing hydrogen gas -10- 1351444

In the atmosphere of the body, it also exhibits good resistance to uranium and environmental pollution. As a result, as the material used for covering the surface of the substrate, it is effective in the present invention to obtain an oxide using an element belonging to the group Illb of the periodic table. Specifically, it is a ruthenium, osmium or anthracene element such as 镧, 铈, 镨, 铵, 、, 钐, 铕, 釓, 铽, 镝, 鈥, 饵, 饵, 、, 、, 饵, 饵, 、, 、, 馏Oxides; among them, rare earth oxides such as ruthenium, osmium, iridium, osmium, and mirror are preferred for the ruthenium-like element. In the present invention, these oxides may be used singly or in a mixture of two or more kinds, a complex oxide, a eutectic or the like. The reason why the present invention focuses on the above metal oxides is better than the halogen-resistance uranium resistance and the resistance to electric hunger of other oxides. The ceramic covering member of the present invention can be used as a substrate (1) aluminum and its alloys, titanium and its alloys, stainless steel and other special steels, nickel-based alloys, other metals or alloys thereof; (2) quartz, glass, Or a ceramic composed of a mixture of oxides or carbides, borides, tellurides, nitrides and the like (3) cermets composed of the above ceramics and the above metals and alloys (4) plastics (5) in the above materials (1)~(4) The surface is subjected to metal plating (electrical ore plating, electroless plating, electroless plating) or a metal vapor deposited film. As described above, the present invention is characterized in that the surface of the substrate is covered with an oxide of a mb group element in the periodic table having excellent corrosion resistance, environmental pollution resistance and the like in a corrosive environment. As the means for covering, the present invention employs the method described below. That is, in the present invention, as a method of forming a porous film of a specific thickness of -11 - 1351444 on the surface of a substrate, a melt blow method is used as an ideal example. Therefore, in the present invention, the oxide of the nib group element is first formed into a meltblown material powder by pulverization or the like to form a powder particle having a particle diameter of 5 to 80 μm, and the meltblown material powder is melt-sprayed to the surface of the substrate by a specific method. Further, a porous layer composed of a porous melt blown film having a thickness of 50 to 200 μm is formed.

Further, as the method of melt-spraying the oxide powder, it is preferable to use the atmospheric plasma melt-blown method or the reduced-pressure plasma melt-blown method, but the hydro-electric slurry melt-blown method or the burst melt-blown method may be applied depending on the use conditions. When the melt blown film (porous layer) obtained by melt-blown the oxide powder of the group Illb element has a thickness of less than 5 μm, the performance of the film under the above-mentioned corrosive environment is insufficient; on the other hand, the layer is insufficient. If the thickness exceeds 2000 μm, the coupling force of the melt-blown particles is weak, and the force generated during film formation (which may be considered as the main cause of volume shrinkage caused by rapid cooling of the particles) is also large, and the film is easily broken. .

Further, the porous layer (melt-blown film) is formed by directly forming a base material or by forming a primer beforehand, and then forming a melt-blown film of the oxide on the primer. The above-mentioned primer coating forms nickel and its alloys, cobalt and alloys thereof, aluminum and alloys thereof, titanium and alloys thereof, molybdenum and alloys thereof, tungsten and alloys thereof, chromium and the like by melt-blowing or vapor deposition. A metal film such as an alloy is preferred, and the thickness thereof is preferably about 50 to 500 μm. The task of this primer coating is to isolate the surface of the substrate from the corrosive environment to improve the uranium resistance and to achieve adhesion between the substrate and the porous layer. Therefore, when the film thickness of the primer coating is less than 50 μm, not only the sufficient corrosion resistance cannot be obtained, but also it is difficult to form an average film of -12-1351444. On the other hand, if the film thickness is thicker than 500 μm, the corrosion resistance will be saturated. The melt blown film composed of the oxide of the element belonging to the Illb group has an average porosity of about 5 to 20%. The porosity is different depending on the type of melt blowing method, such as a reduced pressure plasma melt blow method, an atmospheric plasma melt blow method, etc., and the type of melt blown method used may vary. Ideally, the average porosity is in the range of 5 to 10%. When the porosity is less than 5%, the relaxation of the 4P thermal force accumulated in the film is weakened, and the thermal shock resistance is deteriorated. On the other hand, when it exceeds 10%, especially when it exceeds 20%, corrosion resistance or plasma corrosion resistance is obtained. ' Will deteriorate. The surface of the porous (melt-blown film) has an average roughness (Ra) of about 3 to 6 μm when applied to the atmospheric plasma melt-blown method; the maximum roughness (Ry) is about 16 to 32 μm; and the 10-point average roughness (RZ) is about 8~24μηι. In the present invention, the porous layer is used as a melt blown film, and in addition to the excellent thermal shock resistance of the film, a coating layer having a specific film thickness can be obtained in a short time and at a low cost. Moreover, the film is further provided with a fine secondary recrystallized layer in the upper layer to alleviate the thermal shock, so that the entire film is relieved of the buffering effect of the thermal shock. In this sense, a composite film in which a secondary recrystallized layer is formed on the lower layer of the meltblown film is disposed in the lower layer, and the two are multiplied to produce an effect of improving the durability of the film. Then, the most characteristic structure of the present invention is to form a type on the porous layer which is formed on the porous meltblown film composed of the oxide of the group Ilb element oxide to deteriorate the outermost layer portion of the melt blown film. In the new layer, the porous layer composed of the oxide of the above-mentioned Illb element is subjected to a secondary-13-1351444 metamorphosis to provide a secondary recrystallization layer.

In general, in the case of a metal oxide of an Illb group element such as yttrium oxide (Y2〇3), the crystal structure is a cubic crystal belonging to a tetragonal system. When the cerium oxide (hereinafter referred to as cerium oxide) powder is subjected to plasma melt-blown, the molten particles are super-cooled while flying toward the substrate at a high speed, and collide against the surface of the substrate to form a crystal structure. In addition to the cubic crystal cubics (Cubic), it also contains orthorhombic mono cl ini C, and the primary metamorphosis is a crystalline form composed of such mixed crystals. In other words, the crystal form of the porous layer is formed by a super-fast cooling at the time of melt-blown, and is transformed into a crystal form comprising a mixed crystal of a tetragonal system and an orthorhombic system. The secondary recrystallization layer is a layer in which a crystal form composed of the above-described mixed crystals after primary transformation is subjected to a secondary transformation into a tetragonal crystal type.

In the present invention, the above-mentioned group Illb oxide porous layer composed mainly of a mixed crystal structure containing orthorhombic crystals after primary transformation is melted by high-energy irradiation treatment to melt the porous layer. The sprayed particles are heated to a temperature above the melting point at a minimum to cause the layer to be metamorphosed again (quadratic metamorphism), and the crystal structure is returned to the tetragonal structure and the crystallized layer is stabilized. At the same time, the present invention liberates the thermal distortion or mechanical distortion accumulated in the deposited layer of the sprayed spray particles in the first metamorphosis caused by the melt blown, so that the properties are physically and chemically stable, and the melting can also be accompanied by melting. Realize the refinement and smoothing of this layer. As a result, the = secondary recrystallized layer of the metal oxide of the Ilb group is finer than the layer which maintains the meltblown layer and has a smooth layer of -14 - 1351444. Therefore, the secondary recrystallized layer becomes a fine layer having a porosity of less than 5% and less than 2%, and the surface average roughness is about 0.8 to 3_0 μϊη; the maximum roughness (Ry) is about 6 to 16 μmη; (Rz) is about 3 to 14 μm, and is a layer which is clear compared to the porous layer. In addition, the control of the maximum roughness (Ry) is determined from the viewpoint of environmental resistance. The reason for this is that the granules generated by the pulverization of the Φ slurry ions in the etched atmosphere will cause the particles to be easily affected by the maximum roughness (Ry) of the surface, and the chances of occurrence of the particles. It is bigger. Next, a method of performing the amount of irradiation for forming the above secondary recrystallized layer will be described. The method used in the present invention is preferably an electron beam treatment or a laser irradiation treatment such as 02 or YAG. As a condition of the electron beam irradiation treatment, it is recommended to introduce an inert gas such as argon gas in the empty irradiation chamber. It is treated by, for example, the following. Irradiation atmosphere: 10~0.0005Pa

Beam irradiation output: 0. l~8 kW Processing speed: l~30 m/s Of course, these conditions are not limited to the above range, and are not limited to these conditions as long as the specific effects can be obtained. The oxide of the Iiib element which has been subjected to electron beam irradiation treatment rises from the surface and finally reaches the melting point or more to become a molten state, and the electron beam irradiation output is increased, or the irradiation time is preferably (Ra) is 10 points. Under the condition of different polluting hair, the higher the energy of the sputum, the condition after the gas is irradiated to the hair, temperature. This solution, or -15 - 1351444 extended exposure time, will gradually advance into the interior of the film, so the depth of the irradiated layer can be controlled by changing these irradiation conditions. If it is 1 ΟΟμηη or less, the practically fused depth of Ιμιη to 50 μm, it becomes a secondary recrystallization layer suitable for the above object of the present invention. As the laser beam irradiation, a YAG laser using YAG crystallization may be used, or a C02 gas laser may be used when the medium is a gas. For the laser beam irradiation treatment, the conditions shown below are recommended.

Laser output: 0.1~10kW Laser beam area: 0.0 1 ~ 2 5 0 0mm2 Processing speed: 5~1 000mm/s

The layer treated by the electron beam irradiation treatment or the laser beam irradiation treatment may be subjected to secondary recrystallization upon cooling at a high temperature and then changed to a physicochemically stable crystal form, so that the modification of the film is The Y2〇3 film formed by the atmospheric plasma melt-blown method, for example, as described above, is a mixed crystal containing orthorhombic crystals in a molten state, and almost becomes a cubic crystal after irradiation with an electron beam. . In the following, if the secondary recrystallized layer composed of the oxide of the group Illb element of the periodic table after the high-energy irradiation treatment is integrated, the secondary recrystallized layer produced by the high-energy irradiation treatment is as follows. The secondary layer of the lower layer, that is, the porous layer composed of metal oxide or the like, is subjected to secondary metamorphism: or the oxide particles of the lower layer are heated above the melting point to eliminate at least a part of the pores to be fine. When the secondary recrystallized layer produced by the high-energy irradiation treatment is a layer obtained by subjecting the porous layer composed of the metal oxide of the lower-16-1351444 layer to a secondary metamorphism, When the melt blown film formed by the melt blow method is used, the unmelted particles at the time of melt blown are completely melted, and the surface is mirror-finished, so that the projections which are easily etched by the plasma can be eliminated. In the case of the porous layer, the maximum roughness (Ry) is 16 to 32 μm, but the maximum roughness (Ry) of the secondary recrystallized layer after the treatment is 6 to 16 μm, which is obviously smoother. The layer can suppress the generation of micro-φ particles which are a cause of contamination during plasma etching. c. The effect of the above a and b is that the porous layer is subjected to high-energy irradiation treatment of the secondary recrystallization layer, so that the through pores are clogged and no corrosive gas enters the inside through the through pores. (Substrate) improves the corrosion resistance of the substrate, and at the same time, because it is refined, it exerts strong resistance to plasma etching and exhibits excellent corrosion resistance and plasma corrosion resistance over a long period of time. ' d. The above secondary recrystallized layer has a porous layer underneath, so that the porous layer can work as a layer excellent in thermal shock resistance, and at the same time acts as a buffer region to alleviate the application of the upper layer to be refined. The thermal shock resistance of the secondary recrystallization layer, through this efficiency, produces an effect of alleviating the thermal shock of the entire film formed on the surface. In particular, when the porous layer and the secondary recrystallized layer are laminated as a composite layer, the effect is compounded and multiplied. Further, it is preferable that the secondary recrystallized layer produced by the high-energy irradiation treatment has a thickness of from 表面μηι to 50 μm or less from the surface. The reason is that if it is less than ιμιη, there is no film-forming effect. On the other hand, if it exceeds 5 Ομηι, the burden of high-energy irradiation treatment becomes large, and the film-forming effect is also saturated with -17-1351444. (Example 1)

In the present embodiment, the state of the melt-blown film formation by the oxide of the group Illb element and the state of the layer formed by the electron beam irradiation and the irradiation of the laser beam are obtained. In addition, 11 lb group oxides used in the test are 7 kinds of oxide powders such as Sc2〇3, Y2〇3, La2〇3, Ce〇2, Eu2〇3, Dy2〇3 and Yb2〇3 (average particle diameter: I〇~5〇μηι). Then, these powders are directly subjected to atmospheric plasma melt blowing (APS) or reduced pressure plasma melt blowing (LPPS) on one side of the original test piece (size: width 50 mm x length 60 mm x thickness 8 mm) to form a melt blown of thickness ΙΟΟμπι. Membrane. Thereafter, the surface of the film is subjected to electron beam irradiation treatment and laser beam irradiation treatment. The first table is the one who integrated the results of this experiment.

In addition, the melt-blown method of the Illb group element was tested because the actual melt-blown data for the lanthanum-based metal oxide such as atomic sequence 5 7 to 71 has not been reported so far to confirm whether it is suitable for the purpose of the present invention. The formation of the film, and the effect of the presence or absence of electron beam irradiation. According to the experimental results, it is known that the experimental oxide is as shown in the melting point of the first table (2300 to 2600 ° C), that is, the gas plasma can be sufficiently melted without the pores unique to the oxide melt blown film, and Become a better film. Further, the surface of the film is irradiated with an electron beam or a laser beam, and the protrusion of the film disappears due to the melting phenomenon, and it is confirmed that the entire surface becomes a fine and smooth surface. -18- 1351444 Table 1

No. Oxygen> i 成 film formation method surface chemical fused after high energy irradiation APS LPPS electron beam laser beam 1 S〇2〇3 2423 〇〇 smooth and smooth smooth · fine 2 Υ 2 〇 3 2435 〇〇 smooth · Fine smoothness and meticulousness 3 La2〇3 2300 〇〇 Smooth, smooth and delicate · Fine 4 Ce02 2600 〇〇 Smooth, fine and smooth · Fine 5 Eu2〇3 2330 〇〇 Smooth, fine and smooth · Detailed 6 Dy2〇3 2931 〇〇 Smooth and detailed Smooth and detailed 7 Yb203 2437 〇〇 Smooth, fine and smooth · Detailed

Remarks (1) The melting point of oxides varies according to the literature, so it indicates the highest temperature (2) Film formation method: APS atmospheric plasma melt blowing method, LPPS vacuum plasma melting method (Experimental Example 2) For example, in the test piece after the high-energy irradiation treatment prepared in the above experiment 1, the melt-blown film of Y203 was observed by an optical microscope, and the profile of the melt-blown film before and after the electron beam irradiation treatment was observed by an optical microscope, and then the observation was high. The microstructural changes of the membrane caused by energy irradiation treatment. Fig. 1 is a view showing a micro-tissue change near the surface of a Υ2〇3 melt-blown film (porous film), and a film obtained by subjecting the film to electron beam irradiation, and a composite film having an undercoat layer. By. In the non-irradiated test piece shown in Fig. 1(a), it was found that the melt-blown particle systems constituting the film were independently present and the surface roughness was large. On the other hand, as shown in Fig. 1(b), a new layer different from the microstructure is formed on the melt blown film by the electron beam irradiation treatment. This layer causes the meltblown particles to fuse with each other to form a fine layer of -19-1351444 with less voids. In addition, the figure (c) shows an example of having an undercoat layer (Experimental Example 3).

In the present experimental example, the secondary recrystallization shown in Fig. 1(b) produced by the electron beam irradiation treatment of the Y203 spray-dissolving film of Fig. 1(a) and the following conditions were used. The layer was measured by XRD and was investigated in order to investigate the crystal structure of each layer. Fig. 2 shows the result, and shows the XRD pattern before the electron beam irradiation treatment. Then, Fig. 3 is an X-ray diffraction chart of the vertical axis before the amplification process, and Fig. 4 is an X-ray diffraction chart of the vertical axis after the amplification process. As can be seen from Figure 3, in the sample before processing, especially at 30. In the range of ~3 5°, a peak representing a monoclinic crystal is observed, and a pattern in which a cubic crystal is mixed with a monoclinic crystal is known. In contrast, as shown in FIG. 4, the secondary recrystallized layer after the electron beam irradiation treatment indicates that the peak of the Y2〇3 particle becomes sharp, and the peak of the monoclinic crystal is attenuated, and the surface index cannot be confirmed (202). ), (3 1 0), etc., and confirmed that only cubic crystals. In addition, this experiment was carried out by a RINT 1 5 00 X-ray diffraction device manufactured by Zhoukou Benedict Electric Machinery Co., Ltd. X-ray diffraction conditions

Output 40kV scanning speed 20/min In the first figure, the symbol 1 is the substrate, 2 is the porous layer (melt-blown particle deposition layer), 3 is the pore (void), 4 is the particle interface, 5 is the through-hole, 6 is The secondary recrystallized layer produced by the electron beam irradiation treatment is then 7-coated. Further, even if the laser beam irradiation treatment was performed, the result of observation of -20 to 1351444 using an optical microscope confirmed the same microstructural change as that of the electron beam irradiation surface. (Example 1) This example was applied to a surface of a wrong substrate (size: 50 mm x 50 mm x 5 mm) by an atmospheric plasma melt blow method to apply a bottom coating (melt-blown film) of 80 mass% Ni-20 mass% Cr. The powder of Y2〇3 and Ce02 was used for the formation of a porous film by atmospheric plasma melt blowing. After that, the surface of the meltblown film is subjected to two kinds of high-energy irradiation treatments such as electron beam irradiation and laser beam irradiation. Next, the surface of the experimental material thus obtained was subjected to plasma etching treatment under the following conditions. Then, the number of particles of the film component particles scattered by the etching process was measured, and the plasma corrosion resistance and environmental pollution characteristics were examined. The particles were placed in a 8 直径 diameter wafer placed in the container, and the number of particles having a particle size of 〇. 2 μm or more adhered to the surface was measured for 30 or more times to compare. Φ (1) Ambient gas and flow conditions as fluorine-containing gas 〇1^3/〇2/eight^8 0/1 00/1 60 (flow rate per minute cm3) as hydrocarbon-containing gas (: 21€ 2/8^ 80/1 00 (flow rate per 1 minute cm3) (2) Plasma irradiation output high frequency power: 1 300W Pressure: 4Pa -21 - 1351444

Temperature: 60 ° C (3) Plasma uranium engraving experiment a. Perform in a fluorine-containing gas atmosphere b. Perform in a hydrocarbon-containing gas atmosphere c. In a fluorine-containing gas atmosphere for 1 hour - a hydrocarbon-containing gas atmosphere for 1 hour Implementation in an interactive and repetitive atmosphere

Table 2 shows the experimental results of these. As can be seen from the results shown in the table, the amount of particles generated by the corrosion of the test film is higher in the fluorine-containing gas atmosphere than in the hydrocarbon-containing gas atmosphere, and the number of particles reaches 30. The time is also shorter. However, when the gas interaction between the two parties is repeated to form a plasma uranium engraving environment, the amount of particulate generation will increase significantly. The reason is that the fluorination (oxidation) reaction of the particles on the surface of the film in the fluorine-containing gas and the reaction of the reduction reaction in the atmosphere containing the hydrocarbon gas may damage the chemical stability of the particles on the surface of the film, and as a result, the mutual coupling force of the particles may be lowered. On the other hand, it is also thought that the fluoride of the film component is stable and can be easily scattered due to the etching action of the plasma. On the other hand, in the case of the test film obtained by the electron beam irradiation or the laser beam irradiation treatment, even if the fluorine-containing gas and the hydrocarbon-containing gas are alternately overlapped, the amount of scattering of the particles is extremely small, and it is confirmed that the film is exhibited. Excellent resistance to plasma corrosion. In addition, the main component of the fine particles attached to the surface of the tantalum wafer is ruthenium, fluorine, and carbon as it is, but the film is irradiated with electron beams or a laser beam. In the case of the second recrystallized layer of -22- 1351444, almost no component of the film was confirmed in the generated particles, and only fluorine and carbon β were present.

No. Film-forming material film formation method The amount of microparticles generated exceeds the time allowed for straightening (h) a After the electron beam irradiation in the state of the film formation: the fluorine-containing gas containing the hydrocarbon gas after the laser beam irradiation Reversal of the hydrogen fluoride gas and the hydrocarbon-containing gas 1 Y2〇3 Melt blown 70 or less 100 or more 35 100 or more 100 or more 2 Ce02 Melt blown 70 or less 100 or more 32 100 or more 100 or more Remarks

(1) The melt-blown system is formed by the atmospheric plasma melt-blown method (8 0Ni-20Cr), the film thickness is 80 μm, and the top coated oxide is 150 μm. (2) Fluorine-containing gas composition: CHF3/ O2/Ar= 80/1 00/160 (flow rate per 1 minute cm3) (3) Composition containing hydrocarbon gas: C2H2/Ar= 80/100 (flow per minute)

(4) The thickness of the layer containing one recrystallization: electron beam irradiation treatment: 2 to 3 μm, laser beam irradiation treatment: 5 to 10 μm (Example 2) This example is a surface of a substrate of 50 mm x 100 mm x 5 mm thick. The film forming material shown in Table 3 is melt blown to form a film. Then, the electron beam irradiation treatment for forming a secondary recrystallized layer suitable for the present invention is carried out for a portion. Then, a test piece having a size of 20 mm×20 mm×5 mni was cut out from the obtained experimental material, and other portions were covered by exposing the range of -23 to 1351444 lOmm×10 mm in the surface of the film after the irradiation treatment, and then the plasma was irradiated under the following conditions to an electron microscope. Wait for the amount of damage caused by plasma corrosion. (1) Gas atmosphere and flow conditions CF4/Ar/02 = 10 0/1000/10ml (flow per 1 minute)

(2) Plasma irradiation output Local frequency radio wave: 1300W Pressure: 1 33.3Pa The third table system integrates the above results. From the results shown in the table, the anodic oxide film (No. 8), the B4C melt blown film (No. 9), and the quartz (no process No. 10) in the comparative examples can be known to cause loss due to plasma corrosion. The amount is too large and not practical.

In contrast, the film having the secondary recrystallization layer in the outermost layer (No. 1 to 7) exhibits a certain degree even by maintaining the melt blown state by using the Π-lb group element as a film forming material. Corrosion resistance: Especially after the electron beam irradiation treatment, the resistance will be greatly improved, and the plasma corrosion damage can be reduced by 10~30%. -24- 1351444 Table 3

No, Film forming material film forming method Plasma uranium damage amount (min m) Remarks Depending on the film formation after electron beam irradiation 1 Sc2〇3 Meltblown 8.2 0.1 or less Inventive Example 2 γ20. Solution spray 5.1 0.2 or less 3 La2〇3 Meltblown 7.1 0.2 or less 4 Ce〇7 Dissolved spray 10.5 0.3 or less 5 Eu2〇i Meltblown 9.1 0.3 or less 6 Dy2〇3 Meltblown 8.8 0.3 or less 7 Yb20, melt blown 11.1 0.4 or less 8 ALCh Anodizing 40 „ Comparative Example 9 b4c Meltblown 28 _· 10 Quartz — 39 ··

Remarks (1) Melt-blowing method is the atmospheric plasma melt-blown method (2) The thickness of the melt-blown film is 130μπι (3) The anodized film is formed according to the ΑΑ25 specified in JISH8 60 1

(4) The thickness of the secondary recrystallization-containing layer by electron beam irradiation is 3 to 5 μm (Example 3) In this example, the film was formed by the method of Example 2, and the film was formed before and after the electron beam irradiation treatment. Resistance to plasma corrosion. As the test material, the mixed oxide shown below was directly applied to an aluminum substrate to form a thickness of 20 μm by atmospheric plasma melt blowing. (1) 95% Y2〇3 - 5% Sc203 (2)9 0%Υ2〇3 - 10%Ce2〇3 -25- 1351444 (3)90%Υ2〇3- 10%Eu2〇3 In addition, after film formation The electron beam irradiation, the gas atmosphere component, the plasma melt blowing conditions, and the like are the same as in the second embodiment.

In the fourth table, the above results are integrated into the plasma etching damage amount. From the results shown in the table, it is understood that, under the conditions suitable for the present invention, the film of the oxide of Group lb of the Periodic Table II exists, and even if these oxides are used in a mixed state, the plasma corrosion resistance is higher than that of the first layer. The ai2o3 (anodized) and B4C films of the comparative example shown in Fig. 3 are better. In particular, when the film is subjected to electron beam irradiation treatment, the performance is further improved, and excellent plasma corrosion resistance can be exhibited. Table 4

No. Film formation material film formation method Plasma corrosion main injury amount (#m) Film formation state After electron beam irradiation 1 95% Y2〇3-5% Sc2〇3 Meltblown 5.5 0.3 or less 2 90%Υ2〇3- 10% Ce2O3 Meltblown 8.5 0.2 or less 3 90% Υ2〇3- 10%Eu2〇3 Meltblown 7.6 0.3 Note

(1) The number of the film-forming material column indicates mass% (2) The melt-blown method is the atmospheric plasma melt-blowing method. (3) The thickness of the secondary recrystallization layer caused by electron beam irradiation is 3 - 5 μηι. Utilizing the technology of the present invention, compared to the conventional semiconductor processing apparatus

1351444 pieces, parts, etc. are used for surface treatment techniques of components and parts used in precision and high-slurry processing apparatuses. The present invention uses the fluorine-containing gas and the apparatus containing hydrogen-carbon gas, respectively. It is suitable for surface treatment of components such as stacking shields, buffer plates, poly top/bottom isolation rings, shielding rings, telescopic covers, electrodes, solids, etc. in plasma processing equipment in the harsh atmosphere of gas. technology. Further, the present invention is a surface treatment technique of a member for a liquid crystal device manufacturing apparatus. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A part (a) of a member having a previous melt blown film (a) a member (b) in which a layer is formed with a secondary recrystallized layer, and a partial sectional view having a primer (c) [Fig. 2] X-ray diffraction pattern of the secondary recrystallized layer produced by the melt-blown film (porous layer) as an electron beam irradiation [Fig. 3] γ2〇3 melt-blown film before electron beam irradiation treatment Photographing [Fig. 4] Secondary recrystallized layer after electron beam irradiation treatment: Photographing [Description of main components] 1 : Substrate 2 · Porous layer 3: Porosity (void). In particular, the semi-conductive ring and the dielectric are suitable for the outermost fabric, X-ray winding <wire winding -27- 1351444 4: particle interface 5: through-hole 6: secondary recrystallization layer 7: base coating

-28-

Claims (1)

1351444 X. Patent Application No. 1. A ceramic covering member for a semiconductor processing apparatus, characterized by a substrate; and a porous layer composed of an oxide of a group Ilb on the periodic surface of the substrate, and On the porous layer, high-energy irradiation by electron beam irradiation treatment in which the oxide porous layer which is once transformed into a cubic crystal and a monoclinic crystal by melt blowing is output by electron beam irradiation to φ 0·1 to 8 kw The second secondary recrystallized layer composed of cubic crystals is formed by secondary metamorphosis; the oxide secondary recrystallized layer has a maximum roughness (Ry) of 6 to 16 μm 〇2. The ceramic covering member for a semiconductor processing apparatus according to the first aspect of the invention, wherein the substrate and the porous layer have an undercoat layer 〇3. The semiconductor according to claim 1 or 2 Processing ® ceramic cover member for the device, wherein the substrate is (1) aluminum and its alloy, titanium and its alloy, stainless steel and other special steel, nickel-based alloy; (2) quartz, glass, or oxide or carbonization a ceramic composed of a mixture of boride, telluride, nitride and the like; (3) a cermet composed of the above ceramic and the above metal/alloy; (4) a plastic; (5) in the above material (1)~ (4) The surface is subjected to metal ore (electroplating, fusion plating, electroless plating) or a metal vapor deposited film. 4. The ceramic covering member for a semiconductor processing apparatus according to the first or second aspect of the invention, wherein the porous layer is made of yttrium, yttrium A -29- 1351444 or atomic sequence 5 7 to 7 1 It is composed of layers of cerium-like elements (镧, 铈, 镨, ammonium, giant, 钐, 铕, 釓, 铽'镝'鈥, bait, watch, gun, 镏). 5. The ceramic covering member for a semiconductor processing apparatus according to the invention of claim 2, wherein the porous layer has a layer thickness of about 50 to 2000 μm and a porosity of about 5 to 20%. It is composed of a melt blown film. 6. The ceramic covering member for a semiconductor processing apparatus according to the first or second aspect of the invention, wherein the secondary recrystallized layer is a porous layer containing orthorhombic crystals, by high energy Irradiation treatment, a layer which becomes a secondary transformation and becomes a tetragonal structure and has a porosity of less than 5%. 7. The ceramic covering member for a semiconductor processing apparatus according to the first or second aspect of the invention, wherein the secondary recrystallized layer has an average roughness (Ra) of 0.8 to 3.0 μm. 8. The ceramic covering member for a semiconductor processing apparatus according to the first or second aspect of the invention, wherein the secondary recrystallized layer has a 10 point average roughness (Rz) of about 3 to 14 μm. 9. The ceramic covering member for a semiconductor processing apparatus according to the first or second aspect of the invention, wherein the secondary recrystallized layer has a layer thickness of about ΙΟΟμηι or less. The ceramic covering member for a semiconductor processing device according to the second aspect of the invention, wherein the undercoat layer is nickel, aluminum, tungsten, molybdenum, titanium, and the like, an alloy, an oxide or a nitride. Any one or more selected from the group consisting of a boride and a carbide, and a cermet selected from the above metal alloy and the ternary alloy of the above -30-1351444 ceramic, formed to a thickness of about 50 to 500 μm The film. -31 -