TWI374492B - - Google Patents

Description

1374492 (1) Description of the Invention [Technical Field] The present invention relates to a plasma processing apparatus and a plasma processing method used in the field of semiconductor processing technology. In particular, a gas containing a halogen gas, an inert gas, oxygen or hydrogen, or a fluorine-containing or fluorine-containing compound (hereinafter referred to as "F-containing gas") and a hydrocarbon gas (hereinafter referred to as "CH-containing gas" An environment in which the atmosphere or the like is formed, or a plasma processing apparatus or a plasma processing method for performing plasma etching processing on a semiconductor element or the like in an environment in which the atmospheres are alternately formed alternately. [Prior Art]

When a device used in the field of semiconductors or liquid crystals is processed, the plasma energy of a highly corrosive halogen-based corrosive gas is utilized. For example, in a plasma etching treatment (processing) apparatus which is one of semiconductor processing apparatuses, it is based on a corrosive gas atmosphere of a chlorine-based or fluorine-based atmosphere, or a mixed gas atmosphere of such a gas and an inert gas. Violet generation uses the strong reactivity of ions or electrons excited at this time to etch the semiconductor element. In the case of such a processing technique, at least a portion of the wall surface of the reaction vessel, or a member or part (reliant, electrostatic chuck, electrode, etc.) disposed inside the reactor vessel is susceptible to acid etching due to plasma energy. (erosion), so it is important to use materials that are excellent in plasma resistance. In response to this demand, inorganic materials such as metals (including alloys) and quartz 'alumina, which have good corrosion resistance, have been used. For example, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 1374492 No. 4 083 discloses that the materials are coated on the surface of the inner member of the reaction vessel by the Pvd method or the CVD method, or formed by the Ilia of the periodic table. A dense film composed of an oxide of an element or a technique of coating a Y2〇3 single crystal. Further, in Japanese Laid-Open Patent Publication No. 2001-164354 or JP-A-2003-264169, it is disclosed that an oxide of an element belonging to the group Ilia of the periodic table is coated on the surface of the member by a spray method. A technology to improve plasma resistance.

However, the technique disclosed in Japanese Laid-Open Patent Publication No. Hei 10- 4083, which is a metal oxide of the Ilia group of the periodic table, can exhibit a relatively good resistance to plasma etching. However, the actual situation is that it is more severe. Among the corrosive atmospheres, in the field of semiconductor processing technology that requires high-precision processing and environmental cleanliness in recent years, it is not a sufficient measure. Further, the member coated with the Y203 spray film disclosed in Japanese Laid-Open Patent Publication No. 2001-164354 and Japanese Patent Application Laid-Open No. Publication No. No. No. 2003-264 No. In addition to the plasma etching action of higher output, the processing of the semiconductor member is under extremely harsh conditions in which the processing atmosphere is alternately used in which the highly corrosive fluorine-based gas and the hydrocarbon-based gas are alternately used. Therefore, it is desired to further Improvement. In particular, when the F-containing gas and the CH-containing gas are alternately used in an alternating manner, in the atmosphere containing the F gas, a strong corrosion reaction peculiar to the halogen causes generation of a fluoride having a high vapor pressure, and on the other hand, In the CH gas atmosphere, the decomposition of the fluoride formed in the F-containing gas is promoted, or a part of the membrane component of the skin 5-(3) 1374492 is turned into a carbide to further increase the reaction to the fluorination. Moreover, in a plasma environment, this reaction is promoted, which can become a very harsh corrosive environment. In particular, when etching is performed at a high plasma output, the potential difference between the plasma and the inner wall of the plasma processing vessel (processing chamber) becomes large, and the Υ2〇3 molten film coated on the inner wall surface is corroded. Therefore, the particles of the corrosion product generated in such an environment fall off the surface of the integrated circuit attached to the semiconductor article, which is a cause of damage to the device. SUMMARY OF THE INVENTION An object of the present invention is to expose a portion of a plasma atmosphere of a processing chamber itself used in a plasma etching process, members, and parts (hereinafter simply referred to as "members, etc.") in a corrosive gas atmosphere. Increased durability. Another object of the present invention is to improve the plasma corrosion resistance of a film formed on a surface of a member or the like in a corrosive gas atmosphere.

Still another object of the present invention is to provide a plasma processing method which can prevent the generation of particles of a corrosion product even at a high plasma output. In view of the means for achieving the above object, the present invention proposes a plasma processing apparatus which is a processing chamber for containing a processed object processed by etching a gas plasma; and a plasma generated by exposure to the processing chamber itself a portion of the atmosphere, a member or a component disposed in the processing chamber, and a porous layer including a metal oxide on one or more surfaces of the portion, the member, or the member. The composite layer of the secondary recrystallized layer of the metal oxide formed on the porous layer is formed by -6-(4) 1374492. Such a plasma processing apparatus of the present invention can adopt the following constitution. 1. Under the above porous layer, an undercoat layer made of a metal alloy, ceramic or ceramal is provided.

2. The etching treatment is performed by treating a fluorine-containing gas plasma, treating a gas mixture of a fluorine-containing gas and a hydrocarbon-containing gas, or repeatedly introducing the fluorine-containing gas and the hydrocarbon-containing gas alternately. Any way of processing. 3. The fluorine-containing gas system uses one or more selected from the group consisting of a CxFy gas such as CF4 or C4F8, a CHF-based gas, an HF-based gas, an SF-based gas, and a mixed gas of such a gas and 〇2. 4. The hydrocarbon-containing gas system is selected from the group consisting of CxHy gas such as CH4 and C2H2, helium-containing gas such as NH3, and a mixed gas of CxHy gas and 02 such as CH4 and 〇2, CH3F and 02, CH2F2 and 02. More than one type of gas. 5. The above metal oxide is a metal oxide containing an Ilia group element such as Sc, Y or a thorium-like element. 6. The secondary recrystallization layer is formed by subjecting a metal oxide which is once metamorphic to the porous layer to a secondary metamorphosis by high energy irradiation treatment. 7. The secondary recrystallized layer is a layer comprising a rhombohedral crystal layer which is subjected to secondary metamorphosis by a high-energy irradiation treatment to form a tetragonal crystal structure. 8_ The above high-energy irradiation treatment is an electron beam irradiation treatment or a laser beam (5) 1374492 irradiation treatment. 9. The potential difference between the surface of the plasma atmosphere exposed to the processing chamber, the surface of the member or the component, and the plasma is set to 120 V or more and 550 V or less. 10. The potential difference is controlled by high frequency power applied to a mounting table of the object to be processed provided in the processing chamber.

Further, the present invention proposes a plasma processing method in which the surface of the object to be processed contained in the processing chamber is subjected to plasma treatment by etching the plasma of the processing gas, and the following steps are performed: first, after exposure to a portion of the plasma atmosphere of the processing chamber itself, a surface of a member or a component disposed in the processing chamber, and a porous layer including a metal oxide and the metal oxide formed on the porous layer a step of coating the composite layer of the secondary recrystallization layer; and a step of inducing the first plasma to be treated when the first gas including the fluorine-containing gas is introduced into the processing chamber. Further, the present invention proposes a plasma processing method in which, when plasma is processed by etching plasma of a processing gas contained in a surface of a workpiece to be processed in a processing chamber, the following steps are performed: first, after exposure to a portion of the plasma atmosphere of the processing chamber itself, a surface of a member or a component disposed in the processing chamber, and a porous layer including a metal oxide and the metal oxide formed on the porous layer a step of coating a composite layer of a secondary recrystallized layer: a step of inducing a first gas including a fluorine-containing gas into the processing chamber to generate a first plasma; and a step of including a hydrocarbon gas When the second gas is introduced into the processing chamber (6) 1374492, the second plasma is excited to generate a second plasma for processing. Further, the above plasma treatment method of the present invention can adopt the following constitution. 1. The fluorine-containing gas system uses one or more selected from the group consisting of CxFy gas such as CF4 and C4F8, CHF-based gas 'HF-based gas, SF-based gas, and a mixed gas of these gases and 〇2.

2. The carbon-containing ammonia gas system uses a CxHy gas such as CH4 or C2H2, a helium-containing gas such as NH3, and a mixed gas of CxHy gas and 02 such as CH4 and 〇2, CH3F and 〇2, CH2F2 and 〇2. More than one gas selected. 3. The above metal oxide is a metal oxide of an Ilia group element containing Sc, Y, and a thorium-like element. 4. The secondary recrystallization layer is formed by subjecting a metal oxide which is once metamorphic to the porous layer to a secondary metamorphosis by high-energy irradiation treatment. 5. The secondary recrystallized layer is a porous layer containing an orthorhombic crystal, and is subjected to a high-energy irradiation treatment to perform a secondary transformation to form a layer of a tetragonal structure. 6. The above high energy irradiation treatment is an electron beam irradiation treatment or a laser beam irradiation treatment. 7. The potential difference between the portion of the plasma atmosphere exposed to the processing chamber, the surface of the member or the component, and the plasma is set to be 120 V or more and 550 V or less. 8. The potential difference is controlled by high frequency power applied to a mounting table of the (S)-9-(7) 1374492 processing body provided in the processing chamber. According to the invention having the above configuration, when the semiconductor component or the liquid crystal component is subjected to plasma etching, a halogen or the like which is formed alternately in a plasma atmosphere, particularly in an atmosphere containing F gas or an atmosphere containing F gas and an atmosphere containing CH gas, The plasma etching of the indoor components and the like in a corrosive gas atmosphere can impart durability for a long period of time. Further, according to the present invention, particles or the like of the corrosion product generated by the potential difference between the plasma etching treatment or the components in the processing chamber and the plasma are remarkably small, and high-quality semiconductor parts and the like can be produced with good efficiency. Furthermore, according to the present invention, since a characteristic film is formed on the surface of a member or the like, the output of the plasma can be raised to about 50 V, and the etching speed or the etching effect can be improved, thereby achieving plasma treatment. The device is compact and lightweight. [Embodiment]

Hereinafter, the details of the embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a partial cross-sectional view showing a processing chamber of a plasma processing apparatus to which the present invention is applied. Further, the plasma processing apparatus of the present invention is not limited to the configuration shown in Fig. 1. In Fig. 1, reference numeral 1 denotes a processing chamber for etching treatment. The processing chamber 1 is, for example, an aluminum cylindrical processing chamber having an anodized film (aluminum-resistant treatment) on its surface, and has a structure in which the etching processing chamber can be hermetically held. -10- (8) 1374492, in the inside of the processing chamber 1, the lower electrode 2, the electrostatic chuck 3 disposed on the upper surface of the object to be processed, such as the semiconductor wafer W by Coulomb force, and the electrostatic chuck 3, and The upper electrode 4 and the like are disposed above the electrostatic chuck 3 at a predetermined interval. In addition, the electrostatic chuck 3 has a configuration in which an electrostatic chuck electrode is provided between an insulating film made of a polyimide resin or the like, and the upper and lower electrodes 2 and 4 are the same as the processing chamber 1 The material is formed as well.

Further, a lower high-frequency power source (RF power source) 7' is connected to the mounting table 5 including the lower electrode 2 and the electrostatic chuck 3 via the lower integrator 6, and a predetermined frequency can be supplied from the lower high-frequency power source 7. Frequency power. Further, an upper high-frequency power source (RF power source) 9 is connected to the upper electrode 4 via the upper integrator 8. Further, on the upper electrode 4, a plurality of gas discharge holes 10 are provided on the lower surface thereof, and on the other hand, a gas supply portion 11 is provided at the top. In the processing chamber 1, although not shown in Fig. 1, an exhaust device is connected via a pipe, and the inside of the processing chamber 1 can be adjusted to an internal pressure of, for example, about 1.33 Pa to 133 Pa by the exhaust device. Further, from the gas introduction portion 11, the predetermined plasma processing gas can be introduced into the processing chamber 1 by, for example, an etching gas composed of an F-containing gas. Further, in this state, a predetermined high-frequency power having a relatively low frequency, for example, a high-frequency power having a frequency of several MHz or less is supplied from the lower high-frequency power source 7, and a predetermined high-frequency power having a relatively high frequency is supplied from the high-frequency power source 9'. For example, a high frequency power having a frequency of from a few tens of MHz to a tens of tens of MHz, whereby a plasma can be generated between the upper electrode 4 and the lower electrode 2, and the semiconductor wafer can be performed by the plasma -11 - 1374492 (9) Etching processing of the surface of the object to be processed. Further, the high-frequency power supplied from the upper high-frequency power source 9 to the upper electrode 4 is a user for generating plasma, and the high-frequency power supplied from the lower high-frequency power source 7 to the mounting table 5 is used to generate DC bias and suppress the energy of ions striking the semiconductor wafer W by the user"

In the processing chamber 1, as shown in Fig. 1, in addition to the mounting table 5 composed of the upper electrode 4, the lower electrode 2, or the electrostatic chuck 3, a shield ring 12 and a focus ring are disposed ( Focus ring 13 , a deposition shield 14 , an upper insulator 15 , a lower insulator 16 and a baffle plate 17 and the like. The shadow ring 12 and the focus ring 13 are formed of a substantially annular shape formed of, for example, tantalum carbide or niobium, and are disposed so as to surround the outer circumferences of the upper electrode 4 and the lower electrode 2, and the upper electrode 4 and the upper electrode 4 are The plasma generated between the lower electrodes 2 is configured to be bundled on the semiconductor wafer W.

The anti-deposition baffle 14 is provided to protect the inner wall of the processing chamber 1, and the upper insulator 15 and the lower insulator 16 are provided to maintain the atmosphere in the processing chamber 1, and the baffle 17 of the lower insulator 16 is The generated plasma is sealed without being discharged from the exhaust port 18 located below the plasma processing apparatus. The components and the like disposed in the processing chamber 1 are exposed to the above-mentioned F-containing gas atmosphere or the plasma-excited environment in which the F-containing gas and the CH-containing gas are alternately introduced in a strong corrosive environment during plasma etching. Atmosphere. In general, the above-mentioned F-containing gas atmosphere mainly contains fluorine and fluorinated -12- (10) (10)

1374492, or contains oxygen (〇2). Fluorine is particularly specific among halogen elements (corrosive), and of course, it is characteristic of a corrosion product having a high vapor pressure when reacting with an oxide. If the member or the like in the processing chamber 1 is exposed to the above-mentioned F-containing In the case of a plasma in a gas-erosting atmosphere, it is of course unnecessary to say that a metal or a carbide does not form a protective film for suppressing corrosion on the surface, and the corrosion reaction proceeds without limitation. With regard to the findings of the inventors of this case, it is known that in such an environment, an oxide belonging to a periodic element, i.e., an element of Sc or Y, atomic sequence 57 to 71, exhibits good corrosion resistance. On the other hand, in the atmosphere containing the above-mentioned CH gas, although the gas itself is not strongly corrosive, the reduction reaction which constitutes the opposite reaction of the oxidation reaction in the gas atmosphere is relatively stable if it is displayed in the atmosphere containing F gas. The corrosion-resistant gold) or the metal compound tends to weaken in chemical contact with the CH-containing gas atmosphere. Therefore, when the portion containing the CH gas is again exposed to the atmosphere containing the F gas, the initial stabilization is chemically destroyed, and finally the corrosion reaction continues, in particular, in addition to the change in the type of the atmosphere gas, in the environment of the sample production. Both F and CH are ionized to produce highly reactive F' C and hydrazine, so corrosion or reduction is accelerated, and 1 (plasma erosion) becomes more intense, and it is easy to generate corrosion products from the surface. The corrosion product formed in this way will be rich in reaction or carbide in the ring. Therefore, even if the oxygen atmosphere is carried out, the body atmosphere and the like are carried out according to the Ilia group and the like; in the atmosphere containing the F, the metal (in the case of a film which is in contact with the body will be a phenomenon) The atomic shape. The vapor in the environment of the acid-etching component, etc.-13- (11) (11)

1374492, or become fine particles, and obviously contaminate the inside of the processing chamber. In this regard, the plasma processing apparatus of the present invention is used to carry out the method, and in the above-mentioned F-containing gas atmosphere, the atmosphere containing F gas and the atmosphere containing CH gas, or the atmosphere containing the atmosphere of F and the atmosphere containing CH gas, the corrosion environment can be Effectively as a countermeasure against corrosion and acid etching, it prevents the generation of corrosion products, especially the generation of particles. Here, in the present invention, the above-mentioned member surface exposed to the plasma while being disposed in the processing chamber and subjected to plasma treatment is provided with a porous metal oxide containing an element belonging to the Ilia group. The layer and the composite film formed by forming a secondary recrystallized layer obtained by oxidizing the metal on the porous layer, that is, a corrosion reaction of the member or the like. The composite film may be formed on all of the members and the like, or may be selectively formed only in a portion where the electric power is high and the damage is large. In addition, the F-containing gas is a CHF-based gas such as CHF3, CH2F2, and CH3F, HF-based SF6, etc., in addition to the gas represented by the general formula CxFy, such as F2, CF4, (4:6, and C5F8). It is preferable that the SF-based gas is one or more selected from the group consisting of CFOs such as CF20 and the mixed gas of 〇2. Further, the CH-containing gas includes H2, CH4, CH3F, CH2F2, CHF3, and the like. In addition to the CxHy gas, the ruthenium-containing gas used or the like, or the mixture of the CH-containing gas or the ytterbium-containing gas and the <plasma treatment is repeated, and the composition of the surface which is effectively treated or the like can be suppressed twice. It is preferable to use a gas, a fluorine gas C2H2, a gas or a fluorine gas C2H2, and a gas selected from a mixed gas of nh3 〇2 - (12) 1374492. The inventor, etc. The material for forming the composite film formed on the surface of a member or the like in the processing chamber, in particular, a material exhibiting excellent uranium resistance or environmental pollution resistance in an environment containing F gas or CH-containing gas is reviewed.

As a result, it is found that the metal oxide which is an element of the Group IIU of the periodic table is excellent in resistance to uranium in the uranium environment as compared with other oxides. Halogen corrosion resistance, plasma corrosion resistance (corrosion resistance due to particles of corrosion products). In addition, it is also known that the metal oxide of the nia group refers to a lanthanum element such as Sc, Y and an atomic order of 57 to 71 (La, Ce, Pr, Nb, Pm, Sm, Eu, Gd, Tb, Dy, Ho, The oxides of Er, Tm, Yb, and Lu) are particularly suitable for the rare earth oxides of La, Ce, Eu, Dy, and Yb. In the present invention, these metal oxides may be used alone or in a mixture of two or more, a complex oxide, or a eutectic. In the present invention, a method in which the porous layer composed of the above metal oxide is coated on the surface of the member or the like with a predetermined thickness is used, and a suitable method is a spray method. Therefore, when performing the spray processing, first, the metal oxide of the Ilia group element is pulverized into a powder of a powder material having an average particle diameter of 50 to 80 μm, and the solution material powder is sprayed in a predetermined manner. On the surface of the member or the like, a porous layer composed of a molten film having a thickness of 50 to 2000 μm (a porosity of about 5 to 20%) is formed. When the thickness of the porous layer is less than 5 Oum, the function of the film of -15-(13) 1374492 in the above corrosive environment may not be sufficiently exerted, and on the other hand, if the thickness of the layer exceeds 2 G00um, the spray is performed. The mutual bonding force of the particles is weakened, and the stress generated during film formation (the contraction reaction and accumulation due to the rapid cooling of the particles is considered to be the cause) becomes large, and the film is easily broken.

In the method of forming a molten film composed of such a porous layer, an atmospheric plasma spray method or a reduced pressure plasma spray method is suitable, but a water plasma spray method or an explosion spray method is also used. It can be applied according to the conditions of use. Further, before the formation of the porous layer, an undercoat made of any one of a metal alloy, a ceramic, or a ceramic ceramal may be formed in advance on the surface of the member or the like. By the formation of the undercoat, the adhesion strength between the porous layer and the substrate becomes high, and at the same time, the corrosive gas is prevented from contacting the substrate. The above primer coating is preferably a metal film of Ni and its alloy, Co and its alloy, A1 and its alloy, Ti and its alloy, Mo and its alloy, W and its alloy, Cr and its alloy, and the like. The thickness is preferably about 50 to 200 um. The function of the undercoating is to block the surface of the member or the like from the corrosive environment to improve the corrosion resistance and to improve the adhesion between the substrate and the porous layer. Therefore, when the film thickness of the undercoat layer is less than 50 μm, not only the corrosion resistance is insufficient, but also uniform film formation is difficult, and even when the film thickness is thicker than 200 μm, the effect of corrosion resistance is saturated. As the ceramic to be applied to the primer, an oxide, a boride, a nitride, a telluride or the like is suitable, and a ceramic such as the above may be used as the above gold-16- (14). 1374492 A film of cermet composed of alloys. In addition to the atmospheric plasma spray method and the reduced pressure plasma spray method, the method of forming the primer coating may be a spray method such as a water plasma spray method or an explosion spray method, and It can also be formed by a vapor deposition method or the like.

In the plasma processing apparatus of the present invention, materials such as members for processing indoor members and the like, metals other than aluminum and its alloys, titanium and alloys thereof, stainless steel, other special steels, and nickel-based alloys (hereinafter, including alloys) In addition to the term "metal", quartz, glass, carbide, boride, telluride, nitride, and mixtures of these, ceramics, ceramics, and the like may be used. Inorganic materials such as ceramics, plastics, etc. Further, on the surface of the substrate composed of these materials, metal plating (electric plating, melt plating, chemical shovel) or a structure for forming a metal deposited film can be used. In the present invention, the most characteristic configuration is the presence of the secondary recrystallization layer on the surface of a portion, a member or the like which is directly exposed to the plasma treatment atmosphere. The secondary recrystallized layer is formed on the porous layer (that is, on the porous molten film) by, for example, subjecting the outermost layer portion of the porous layer composed of the Ilia group metal oxide to secondary metamorphism. And the layer formed. In general, when it is a metal oxide of an Ilia group element such as cerium oxide (antimony trioxide: Y2 〇 3 ), the crystal structure is a cubic crystal belonging to a tetragonal crystal. When the powder of the cerium oxide (hereinafter referred to as "antimony trioxide") is plasma-sprayed, the molten particles are deposited while colliding with the surface of the substrate while being rapidly cooled while flying toward the substrate at a high speed. In addition to the cubic crystal (Cublic), the crystal structure will also be transformed into a monoclinic crystal body at one time -17- (15) (15)

1374492 (monoclinic) mixed crystal structure. This is a metal porous layer. In addition, the above-mentioned secondary crystal layer refers to the above-mentioned metal oxide porous layer containing a mixed crystal state of an orthorhombic crystal and a normal crystal by cooling once during the spraying, and is subjected to secondary metamorphism by a shot process. A layer of crystalline crystal form. Fig. 4 is a view schematically showing a Y2〇3 molten film (a microscopic change in the vicinity of the surface of the film after the electron beam irradiation treatment of the film and the surface of the composite film having the bottom composite film. Fig. 4 (a non-irradiation test piece, It is found that the molten particles constituting the film are separated and the surface roughness is large. On the other hand, the same new layer can be formed on the molten film by the electron beam irradiation treatment shown in Fig. 4 . This layer is a dense layer in which the above-mentioned molten particles are fused to each other. Further, Fig. 4(c) shows a substrate. Further, the presence of a dense layer formed by electron beam irradiation is unique to the molten film. A film having a large number of pores and a heat-resistant layer. Fig. 5 is a graph showing a porous layer of a Y203 sprayed film and a secondary recrystallized layer formed by electron beam irradiation treatment, and Fig. 6 and Fig. 7 is a view showing XRD before and after electron beam irradiation of Υ203 (porous layer), Fig. 6 is an X enlarged by the vertical axis before processing; Table 7, Fig. 7 is a vertical axis after processing Enlarged X-ray diffraction Figure 6 is known, before processing On the 2〇3 molten film, the -18-oxide is mostly formed by the ultra-rapid crystal system and the molten film (the coating layer), and the micro-structure is not separated. Below the example of less coating, the strip XRD was used to measure the melt film pattern. Also line the graph chart. From the range of the peaks of the monoclinic (16) 1374492 crystal, especially the range of 30 to 35°, the cubic crystal is mixed with the monoclinic crystal. On the other hand, as shown in Fig. 7, it was found that the secondary recrystallized layer obtained by subjecting the Υ2〇3 molten film to electron beam irradiation treatment showed that the peak of the Y203 particle became sharp, and the peak of the monoclinic crystal was attenuated. , the surface index (202), (3 / 0), etc. become unrecognizable, only cubic crystal. Further, the XRD experiment was carried out using a RINT 1 5 00X line diffraction device manufactured by Rigaku Corporation. The X-ray diffraction conditions are shown below.

Output: 40 kV Scanning speed: 20/min Further, the symbol 41 shown in Fig. 4 is the substrate, 42 is the porous layer (the molten particle deposition layer), 43 is the pore (void), 44 is the particle interface, and 45 is The through pores 46 are secondary recrystallization layers formed by electron beam irradiation treatment, and 47 are bottom coating. Further, even in the case of using the laser beam irradiation treatment, the result of observation using an optical microscope can be seen as the same microstructural change as that of the electron beam irradiation surface. As described above, the present invention mainly discharges the porous layer of the Ilia group metal oxide composed of the crystal structure of the once-normal metamorphic orthorhombic body by high-energy irradiation treatment. The particles are at least heat treated to above the melting point and the layer is again metamorphosed (secondary metamorphosis), and the crystal structure is returned to the tetragonal structure to be crystallographically stabilized. At the same time, the present invention releases the thermal deformation or mechanical deformation stored in the deposited layer of the molten particles during the first metamorphosis caused by the spray, so that the properties are physically and chemically stable and can also be melted. The denseness of this layer is -19-(17) 1374492 and smoothed. As a result, the secondary recrystallized layer composed of the metal oxide of the Ilia group element can be a dense and smooth layer as compared with the layer which remains as it is.

Therefore, the secondary recrystallized layer has a porosity of less than 5%, preferably less than 2% of the densified layer, and the surface has an average roughness (Ra) of 0.8 to 3.0 um and a maximum thickness ( Ry) is a layer having a 6 to 16 um, 10 point average roughness (Rz) of about 3 to 14 um, and which is significantly different from the above porous phase. Further, the control of the maximum thickness (Ry) is determined by the viewpoint of environmental pollution resistance. The reason is that the surface of the inner member of the container is diced by using plasma ions or electrons excited in the etching processing atmosphere, and when the particles are generated, the influence is sufficiently exhibited on the maximum roughness (Ry) of the surface, when the 値When it becomes larger, the chance of particle generation increases. Next, a high-energy irradiation method for forming the secondary recrystallized layer will be described. The method used in the present invention can suitably use laser irradiation treatment such as electron beam irradiation treatment, CO 2 laser, and YAG laser, but , not only limited to these methods. (1) Electron beam irradiation treatment: In the irradiation chamber in which the air is discharged, an inert gas such as an Ar gas is introduced, and for example, it is recommended to perform treatment under the irradiation conditions as follows. Irradiation atmosphere: 0~0_0005Pa (Ar gas)

Beam irradiation output: 0.1 to 8 kW Processing speed: 1 to 30 mm/s Of course, the conditions are not limited to the above range, and suitable conditions for obtaining a suitable secondary recrystallization layer can be exemplified as long as the present invention can be obtained - The predetermined effect of 20- (18) 1374492 is not limited to these conditions.

The metal oxide containing the Ilia group element treated by electron beam irradiation rises from the surface and finally reaches the melting point and becomes molten. Since the melting phenomenon can be performed by increasing the electron beam irradiation output, increasing the number of irradiations, and increasing the irradiation time, and then expanding the inside of the film, the depth of the irradiation of the molten layer can be changed by changing the depth. Irradiation conditions to control. Practically, as long as there is a melting depth of lum 50 um, it becomes a secondary recrystallization layer suitable for the above object of the present invention. (2) In the case of a laser beam, in the case of a YAG laser or a medium using YAG crystallization, a CO 2 gas laser or the like can be used. For the irradiation treatment of the laser beam, the conditions of the second can be recommended. Laser output: 0.1~10kW Laser beam area: 0.01~2500mm2 Processing speed: 5~1000mm / s The layer treated by the above electron beam irradiation treatment or laser beam irradiation is subjected to high temperature metamorphism as described above while cooling The secondary recrystallization is precipitated and changes to a physicochemically stable crystal form, so the modification of the film is performed in units of the degree of crystallization. For example, as described above, the Y2〇3 film formed by the atmospheric plasma spraying method becomes a trapezoidal crystal body in a molten state, and changes almost to form a square crystal after electron beam irradiation. Hereinafter, the characteristics of the secondary recrystallized layer composed of the metal oxide of the Ilia group element of the periodic table subjected to the high energy irradiation treatment are collected. a. The secondary recrystallized layer formed by the high-energy irradiation treatment is such that the porous layer composed of the metal oxide or the like as the lower-order metamorphic layer is subjected to a secondary metamorphosis of the step -21 - (19) 1374492, or Since the oxide particles of the lower layer are heated above the melting point, at least a part of the pores disappear and are densified. b. a secondary recrystallized layer formed by high-energy irradiation treatment, particularly a layer obtained by further secondary metamorphism of a porous layer composed of a lower metal oxide, and particularly by a spray method In the formed molten film, the unmelted particles at the time of the melt are completely melted, and the surface is in a mirror-like state, so that the projections which are easily etched by the plasma disappear.

c. According to the effects of the above a and b, since the porous layer is a secondary recrystallized layer formed by high-energy irradiation treatment, the through pores are plugged, and penetrate the pores to penetrate the inside (substrate) The corrosive gas disappears, the corrosion resistance is improved, and the densification is achieved at the same time. Therefore, the plasma etching action can also exert a strong resistance, and the excellent corrosion resistance and plasma etching resistance can be exhibited for a long time. d. Since the above secondary recrystallized layer is a physicochemically stable crystal, the modification can be achieved by the degree of crystallization. Further, at this time, the thermal deformation introduced during the spraying can be simultaneously released to become a stable layer. e. The thickness of the secondary crystal layer formed by the high-energy irradiation treatment is preferably a thickness of about 1 to 50 μm from the surface. The reason is that when the lum is less than lum, there is no effect of film formation, and on the other hand, when it is thicker than 50 um, the burden of the high-energy irradiation treatment is increased, and the effect of film formation is saturated. Further, the lower layer of the porous layer is present as a layer excellent in thermal shock resistance. However, the layer has a function of buffering the upper layer. That is, by mitigating the heat of the dense secondary crystal layer applied to the upper layer

-22- C S (20) 1374492 The effect of the shock has the effect of mitigating the thermal shock of the entire membrane. This means that in the case where the lower layer has the porous layer composed of a molten film and the upper layer is composed of a composite film composed of a secondary recrystallized layer, a composite phase of the two layers can produce a phase. Multiply the effect to enhance the durability of the film.

Further, as described above, when etching is performed at a high plasma output, the potential difference between the member and the like in the processing chamber and the plasma is increased, and the molten film such as γ2〇3 coated on the member or the like is corroded, thereby generating. The particles of the corrosion product may fall and adhere to the surface of the object to be processed, thus causing a defect in the device. However, in the plasma processing apparatus of the present invention, when the acid corrosion resistance of the film formed on the surface of the member or the like is improved, even if the plasma output is increased until the potential difference between the member and the plasma is about 50 to 50 V, It also inhibits the generation of particles. Further, the potential difference between the member and the plasma can be controlled by the electric power applied to the mounting table 5 from the high-frequency power source 7 of Fig. 1, preferably 5 50 V or less, more preferably 120 V or more and 550 V or less. EXAMPLES (Example 1) In the surface of the interior wall member (aluminum baffle plate) of the plasma processing apparatus shown in Fig. 1, Y2〇3 (purity of 95 mass% or more) was sprayed to form a film formation ( Comparative Example B); and when Y203 is sprayed for film formation, an electron beam is irradiated on the surface thereof to be subjected to secondary metamorphism to form a layer having a secondary crystal layer (Inventive Example A), which is a Group 111 metal oxide. Example -23- (21) 1374492. In the respective processing chambers, the F-containing gas and the CH-containing gas are alternately introduced in reverse to perform plasma processing. After the Y2〇3 molten film is weakened, the semiconductor wafer as the plasma processed body is controlled. The amount of application of the high-frequency power of the mounting table is such that the potential difference between the potential of the processing chamber wall and the plasma changes to 200 V to 300 V, and the amount of dust (particles) generated on the semiconductor wafer by each potential difference is measured. The result is shown in Fig. 2. As a result, in the comparative example, as the potential difference increases, dust generated by the film (钇) is generated in addition to the dust generated by the semiconductor wafer, and in contrast, in the invention example, observation is possible. Due to the dust generated by the semiconductor wafer, the generation of particles due to the film composition (钇) is not seen at all, or only a little. (Example 2)

In order to investigate the limit of the potential difference between the inner wall member (a low insulator made of aluminum, the baffle plate, the anti-deposition baffle) and the plasma (the range of dust generation due to the film (钇) can be suppressed), Therefore, in the same manner as in the first embodiment, the surface of the inner wall member of the processing container is prepared by spraying Y203 to form a film (comparative example): when the crucible 203 is sprayed to form a film, the surface is further subjected to electrons. The beam irradiation treatment causes the secondary transformation to form a secondary crystal layer (Inventive Example A). In each of the processing chambers, the F-containing gas and the CH-containing gas are alternately introduced in reverse to perform plasma treatment, and after the Υ2〇3 film is weakened, the amount of application of the high-frequency power to the lower electrode is controlled to cause the member or the like. The potential difference from the plasma changes, and the amount of dust (particles) on the semiconductor wafer is measured for each potential difference -24 - (22) 1374492. The result is shown in Fig. 3. As a result, in Comparative Example B, as the potential difference increased, the amount of dust generated by the enthalpy increased in proportion to the enthalpy. In the case of the invention example A, even at the time of 5 50 V, no sputum was observed. The generation of dust. Therefore, it is understood that the electric paddle processing apparatus of the present invention can suppress the generation of dust due to enthalpy even when the potential difference is increased to a maximum of 55 QV.

[Possibility of industrial use]

The technique of the present invention is of course not necessary for the members, components, and the like used in a general semiconductor processing apparatus, and may be used as a surface treatment technique for a member for an electric paddle processing apparatus which is more recently required to be more precise and highly processed. In particular, the present invention is suitable as an anti-deposition barrier for a semiconductor processing apparatus that performs plasma treatment in a severe atmosphere in which a device containing F gas or a gas containing CH alone or a gas is alternately used repeatedly. Baffle plate, focus ring, upper lower insulator ring, shield ring, bellows cover, electrode, solid body, etc. Surface treatment technology for components, parts, etc. Further, the present invention is applicable to a surface treatment technique as a member for a liquid crystal device manufacturing apparatus. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a schematic configuration of a plasma processing apparatus according to an embodiment of the present invention. Fig. 2 is a graph showing the relationship between the potential applied to the chamber member and the like and the amount of dust (particles) generated by -25-(23)(23)1374492 Y2〇3. Fig. 3 is a view showing the relationship between the potential applied to the inside of the processing chamber and the like and the amount of dust (particles) generated by Y2〇3. Figure 4 is a cross-sectional view (a) of a film formed by a method of the prior art, a member (b) formed by forming a secondary recrystallized layer on the outermost layer by the method of the present invention, and a primer coated layer. Partial sectional view of member (c). Fig. 5 is an X-ray diffraction pattern of a Y203 molten film (porous layer) and a secondary recrystallized layer formed by electron beam irradiation treatment. Fig. 6 is a X-ray diffraction diagram of the state of the Υ203 molten film (porous layer) before the electron beam irradiation treatment. Fig. 7 is an X-ray diffraction diagram of the state of the Υ2〇3 molten film (porous layer) after electron beam irradiation treatment. [Main component comparison table] 1 ·Processing chamber 2 : Lower electrode 3 : Electrostatic clamp 4 : Upper electrode 5 : Mounting table 6 : Lower integrator 7 : Lower high frequency power supply 8 : Upper integrator 9 : Upper high frequency power supply

-26- C S (24)1374492 10 : Gas discharge port 11 : Gas introduction part 12 : Shadow ring 1 3 : Focus ring 14 : Deposition shield 15 : Upper insulator 16 : Lower insulator

17 : baffle 1 8 : exhaust port 41 : base material 42 : porous layer 43 : air hole 44 : particle interface 45 : through hole

46: Electron beam irradiation treatment 47: Bottom coating -27-

Claims (1)

1374492 Patent Application No. 096,108,643, Patent Application, Revision of the Patent Application, Revision of the Patent Application, October 6, 2010, Patent Application Range 1. A plasma processing apparatus, characterized by: venting by etching plasma gas a processing chamber of the processed object; and a portion exposed to the plasma generating atmosphere of the processing chamber itself, or a member or a component disposed in the processing chamber; A porous layer composed of a metal oxide formed by plasma spraying and a metal oxide formed on the porous layer are provided on one or more surfaces of the above-mentioned portion, the member, or the member. The composite layer of the secondary recrystallized layer of the material is formed. 2. The plasma processing apparatus according to claim 1, wherein the porous layer has an undercoat layer composed of a metal alloy, a ceramic or a ceramal. 3. The plasma processing apparatus of claim 1, wherein the etching treatment is a treatment of a fluorine-containing gas plasma, a treatment of a mixed gas plasma of a fluorine-containing gas and a hydrocarbon-containing gas, or a fluorine-containing treatment. The gas is alternately introduced in reverse with the hydrocarbon-containing gas for processing. 4. The plasma processing apparatus of claim 3, wherein the fluorine-containing gas system is selected from the group consisting of a CxFy gas, a CHF-based gas, an HF-based gas, an SF-based gas, and a mixed gas of the gas and the cerium 2; More than one type of gas. 5. The plasma processing apparatus according to claim 3, wherein the hydrocarbon-containing gas system is one or more selected from the group consisting of CxHy gas, helium-containing gas, and a mixed gas of CxHy gas 1374492 and helium-2. 6. The plasma processing apparatus according to claim 2, wherein the metal oxide is a metal oxide containing an nIa group element. 7. The plasma processing apparatus according to claim 1 or 2, wherein the second secondary recrystallization layer causes the metal oxide contained in the primary layer of the porous layer to be subjected to high energy irradiation treatment twice. Metamorphosis and formation. 8. The plasma processing apparatus according to claim 1 or 2, wherein the above-mentioned secondary recrystallized layer is a porous layer containing an orthorhombic crystal, which is subjected to secondary metamorphism by high-energy irradiation treatment. The layer of the organization of the tetragonal system. 9. The plasma processing apparatus of claim 7, wherein the high energy irradiation treatment is an electron beam irradiation treatment or a laser beam irradiation treatment. 10. The plasma processing apparatus of claim 8, wherein the high energy irradiation treatment is an electron beam irradiation treatment or a laser beam irradiation treatment. 11. The plasma processing apparatus according to claim 1, wherein the surface of the plasma atmosphere exposed to the processing chamber itself, the surface of the member or the component, and the plasma have a temperature of 120 V or more and 5 50 V or less. Potential difference. 12. The plasma processing apparatus according to claim 11, wherein the potential difference is controlled by high frequency power applied to a mounting table of the object to be processed provided in the processing chamber. 13. A plasma processing method, characterized in that: 1374492, when the surface of the object to be processed contained in the processing chamber is treated by plasma etching the plasma of the processing gas, the following steps are performed: First, A porous layer composed of a metal oxide formed by plasma spraying is formed in advance on a surface of a member or a component disposed in the processing chamber and exposed to a plasma atmosphere of the processing chamber itself. a step of coating a composite layer of the secondary recrystallized layer of the above metal oxide on the porous layer; and When the first gas including the fluorine-containing gas is introduced into the processing chamber, the gas is excited to generate a first plasma for processing. A plasma processing method, characterized in that: when the surface of the object to be processed contained in the processing chamber is processed by plasma for etching the plasma of the processing gas, the following steps are performed: First, exposure a porous layer composed of a metal oxide formed by plasma spraying and a porous layer formed on the surface of the processing chamber or the surface of the member or component disposed in the processing chamber a step of coating a composite layer of the secondary recrystallized layer of the metal oxide on the layer; and introducing the first gas including the fluorine-containing gas into the processing chamber, and exciting the first plasma to generate the first plasma And a step of introducing a second gas including a hydrocarbon gas into the processing chamber and exciting it to generate a second plasma for processing. 15. The plasma processing method according to claim 13 or 14, wherein the fluorine-containing gas system is from a CxFy gas, a CHF-based gas, an HF-based gas, an SF-based gas, and a mixed gas containing the gas and 02; Select one or more of -3- 1374492. A plasma treatment method, a metal oxide of a CxHy gas, a plasma treatment method containing more than one type of gas. The plasma processing method, the plasma metamorphism method in which the primary metamorphism of the pore layer is subjected to the secondary metamorphosis, and the porous crystal of the crystal layer is processed into a tetragonal system, wherein the laser beam irradiation treatment method is Wherein, or the laser beam irradiation portion. 16. In the scope of claim 13 or 14, wherein the gas system containing the above hydrocarbon is selected from the gas and the mixed gas of CxHy gas and 02. The invention relates to the above-mentioned metal oxide containing the Ilia group element 18. The above-mentioned secondary recrystallization layer is included in the above-mentioned metal oxide system. Many metal oxides are processed by high-energy irradiation. In the above-mentioned secondary recrystallized layer, an orthorhombic layer is provided, and a layer of the secondary metamorphosis is subjected to high energy irradiation treatment. 2〇. The plasma of the 18th application patent range The above-mentioned high-energy irradiation treatment is an electron beam irradiation treatment. 21_ The plasma of the 19th application patent range is the electron beam irradiation treatment. 22. The plasma processing method according to claim 13 or 14, wherein in the above-mentioned processing chamber, the surface of the portion exposed to the plasma atmosphere, the surface of the member or the part, and the plasma are such that the potential difference has a temperature difference of 1 20 V or more. 1374492 5 Potential difference below 50V. The plasma processing method according to claim 22, wherein the potential difference is controlled by high frequency power applied to a mounting table of the object to be processed provided in the processing chamber. -5-