Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/18—After-treatment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
  • H01L21/3065—Plasma etching; Reactive-ion etching
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
  • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
  • C23C4/11—Oxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
  • H01J37/32—Gas-filled discharge tubes
  • H01J37/32431—Constructional details of the reactor
  • H01J37/32458—Vessel
  • H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
  • H01J37/32495—Means for protecting the vessel against plasma

Definitions

• the present invention relates to a plasma processing apparatus and a plasma processing method used in the field of semiconductor processing technology, and in particular, an atmosphere such as a halogen gas, an inert gas, oxygen or hydrogen, or a gas containing fluorine and a fluorine compound (hereinafter referred to as “a gas”).
• a gas a gas containing fluorine and a fluorine compound
• Plasma etching on semiconductor devices, etc. in an environment composed of an atmosphere of hydrocarbon gas (hereinafter referred to as “CH-containing gas”) or an environment in which these atmospheres are alternately formed.
• CH-containing gas an atmosphere of hydrocarbon gas
• Devices used in the semiconductor and liquid crystal fields are often processed using the plasma energy of highly corrosive halogen-based corrosive gases.
• a chlorine-based fluorine-based corrosive gas atmosphere or these gases can be used to form a fine wiring pattern.
• Plasma is generated in a mixed gas atmosphere with an inert gas, and the semiconductor elements are etched using the strong reactivity of ions and electrons excited at that time to form wiring patterns.
• the wall surface of the reaction vessel used for such processing and the components (susceptors, electrostatic chucks, electrodes, etc.) placed inside it are susceptible to the erosion effect of plasma energy, so they are resistant to plasma. It is necessary to use materials with excellent erosion properties.
• materials such as metals (including alloys), quartz, and alumina that have good corrosion resistance have been used in such processing apparatuses.
• the material is coated on the surface of the reaction vessel inner material with a metal having good corrosion resistance by the PVD method or the CVD method, or in the periodic table. III or forming a film of oxides such a group element, or Y 2 0 3 technology that covers the single crystal is disclosed.
• Y 2 0 3 which is an oxide of an element belonging to Group IIIa of the Periodic Table III, is coated on the surface of a member by a thermal spraying method. Plasma erosion resistance ⁇ Technology to improve life is disclosed.
• the Y 2 O 3 sprayed coating is useful for improving the plasma erosion resistance
• the recent processing of semiconductor components has a higher plasma etching effect, and the processing atmosphere is corrosive. Under the harsh conditions of repeated use of a strong fluorine-based gas and hydrocarbon-based gas, further improvement is required.
• the F-containing gas atmosphere when an F-containing gas and a CH-containing gas are used alternately and repeatedly, the F-containing gas atmosphere generates fluoride with a high vapor pressure due to the strong corrosion reaction unique to halogen gas.
• the CH-containing gas atmosphere decomposition of the fluorine compound generated in the F-containing gas is promoted, or a part of the film component is changed to carbide to enhance the reaction to fluoride.
• the plasma environment in which these gases are used becomes a more severe corrosive environment because the above-described reaction is promoted.
• the present invention is abbreviated as “parts”, “parts” and “parts” (hereinafter simply referred to as “members”) that are exposed to the plasma atmosphere in a chamber used for plasma etching in a corrosive gas atmosphere. ) Propose a technology that improves durability.
• This paper also describes the plasma erosion resistance of coatings formed on the surfaces of materials, etc. in corrosive gas atmospheres, especially in the atmosphere where F-containing gas and CH-containing gas are used alternately.
• the present invention also proposes a plasma processing method capable of preventing the generation of corrosion product particles even under high plasma power.
• a plasma processing apparatus that processes the surface of an object to be processed accommodated in a chamber with an etching gas plasma, a portion exposed to the plasma generation atmosphere in the chamber,
• the surface force of the installation member or component is at least covered with a porous layer made of a metal oxide and a secondary recrystallized layer of the metal oxide formed on the porous layer. It is a plasma processing device.
• the plasma processing apparatus of the present invention can employ the following configuration.
• an undercoat layer made of metal / alloy, ceramics or cermet is provided.
• the etching treatment is treatment with fluorine-containing gas plasma, treatment with mixed gas plasma of fluorine-containing gas and hydrocarbon-containing gas, or treatment by alternately introducing fluorine-containing gas and hydrocarbon-containing gas repeatedly. Use either method.
• the fluorine-containing gas, CF 4, Ji 4? ⁇ 31 gas 8 such, CHF-based gas, HF-based gas, SF-based gas and one selected from among the mixed gas of the these gases 0 2
• the above gas is used.
• the hydrocarbon-containing gas includes C x Hy gas such as CH 4 and C 2 H 2 , H-containing gas such as NH 3 and CH 4 and 0 2 , CH 3 F and 0 2 , and CH 2 F 2 using one or more gases selected from among C x H y gas and mixed gas of 0 2 ⁇ 2.
• the metal oxide is a metal oxide containing Group IIIa elements such as Sc, Y and lanthanoids.
• the secondary recrystallized layer is formed by secondarily transforming a metal oxide that has undergone primary transformation contained in the porous layer by high energy irradiation treatment.
• the secondary recrystallized layer is a layer in which a porous layer containing orthorhombic crystals is transformed into a tetragonal structure by secondary transformation by high energy irradiation treatment.
• the high energy irradiation process is an electron beam irradiation process or a laser beam irradiation process.
• Table of parts, members or parts exposed to plasma atmosphere in the chamber The surface and the plasma have a potential difference of 120 V or more and 550 V or less.
• the potential difference is controlled by a high-frequency power applied to a mounting table for an object to be processed provided in the chamber.
• the present invention relates to a plasma processing method for processing a surface of an object to be processed accommodated in a chamber with an etching gas plasma, a part exposed to the plasma atmosphere in the chamber prior to the processing, A composite layer including a porous layer made of a metal oxide and a secondary recrystallized layer of the metal oxide formed on the porous layer is coated on the surface of the member or component disposed in the chamber. Then, a plasma processing method is proposed in which a first gas containing a fluorine-containing gas is introduced into the chamber, and the gas is excited to generate a first plasma for processing. .
• the present invention provides a plasma processing method for processing a surface of an object to be processed accommodated in a chamber with a plasma of an etching process gas.
• the surface Prior to this process, the surface is first exposed to a plasma atmosphere in the chamber.
• a composite material including a porous layer made of a metal oxide and a secondary recrystallized layer of the metal oxide formed on the porous layer on the surface of the member or part disposed in the chamber.
• a first gas containing a fluorine-containing gas is introduced into the chamber and then excited to generate a first plasma, and then a second gas containing a hydrocarbon gas is contained in the chamber.
• a plasma processing method characterized in that after gas is introduced, it is excited to generate a second plasma for processing.
• the fluorine-containing gas is selected from among CF 4, C 4 C x F y gas such as F 8, CHF-based gas, HF-based gas, SF-based gas and these gases and a gas mixture of 0 2 Use one or more gases.
• the hydrocarbon-containing gas includes C x Hy gas such as CH 4 and C 2 H 2 , H-containing gas such as NH 3 and CH 4 and 0 2 , CH 3 F and 0 2 , and CH 2 F 2 0 using one or more gases selected C x H y gas 2 such as from among the mixed gas of 0 2.
• the metal oxide is a metal oxide containing Group IIIa elements such as Sc, Y and lanthanoids.
• the secondary recrystallized layer is composed of a high-energy metal oxide that is primarily transformed in the porous layer. It was formed by secondary transformation by Nolegie irradiation treatment.
• the secondary recrystallized layer is a layer in which a porous layer containing orthorhombic crystals undergoes a secondary transformation by high energy irradiation treatment to form a tetragonal structure.
• the high energy irradiation process is an electron beam irradiation process or a laser beam irradiation process.
• the surface of the part, member or part exposed to the plasma atmosphere in the chamber and the plasma has a potential difference of 120 V or more and 550 V or less.
• the potential difference is controlled by high-frequency power applied to a mounting table for an object to be processed provided in the chamber.
• a plasma atmosphere particularly, a halogen or the like in which an F-containing gas atmosphere or an F-containing gas atmosphere and a CH-containing gas atmosphere are alternately and repeatedly formed.
• plasma etching is performed in a corrosive gas atmosphere, durability against plasma erosion of chamber internal members and the like can be improved over a long period of time.
• the present invention particles of corrosion products generated due to a plasma etching process or a potential difference between a member in a chamber and a plasma and the plasma are remarkably reduced, so that high-quality semiconductor parts can be efficiently used. It is possible to produce well. Furthermore, according to the present invention, since a characteristic film is formed on the surface of a member or the like, the plasma output can be increased to about 550 V, and the etching speed and the etching effect are improved. As a result, the plasma processing apparatus can be made smaller and lighter.
• FIG. 1 is a diagram showing a schematic configuration of a plasma processing apparatus according to an embodiment of the present invention.
• FIG. 2 is a diagram showing the relationship between the potential applied to the internal members of the processing chamber and the amount of dust (partite) generated due to Y 2 0 3 .
• the potential applied to the processing chamber within the member or the like is a diagram showing the relationship between Upsilon 2 0 3 due to dust (Pate Ikunore) emissions.
• FIG. 4 is a cross-sectional view (a) having a film formed by a method according to the prior art, a member (b) having a secondary recrystallized layer formed on the outermost layer by the method of the present invention, It is a fragmentary sectional view of the member (C) which has a groove.
• FIG. 5 is an X-ray diffraction pattern of a secondary recrystallized layer formed by Y 2 0 3 sprayed coating (porous layer) and electron beam irradiation treatment.
• Figure 6 is an X-ray diffraction pattern of the electron beam irradiation treatment prior to the state of Upsilon 2 0 3 sprayed coating (porous layer).
• Figure 7 is an X-ray diffraction diagram of the state after the electron beam irradiation treatment of Upsilon 2 0 3 sprayed coating (porous layer). ⁇ Best mode for carrying out the invention
• FIG. 1 is a partial cross-sectional view of a chamber of a plasma processing apparatus to which the present invention is applied.
• the plasma processing apparatus of the present invention is not limited to the configuration shown in FIG.
• reference numeral 1 denotes an etching chamber.
• This chamber 1 is, for example, a cylindrical chamber made of anoremi-um having an anodic oxide coating (alumite treatment) on the surface, and has a structure that can keep the etching treatment chamber airtight.
• the chamber 1 includes a lower electrode 2 and an electrostatic chuck 3 disposed on the upper surface of the lower electrode 2 for holding an object to be processed such as a semiconductor wafer W by Coulomb force.
• An upper electrode 4 and the like arranged at a predetermined interval are disposed above the electrostatic chuck 3.
• the electrostatic chuck 3 has a configuration in which, for example, an electrostatic chuck electrode is provided between insulating films made of polyimide resin or the like.
• the upper and lower electrodes 2 and 4 are the same as the chamber 1 respectively. It is preferable to be formed by the material.
• the lower electrode 2 and the electrostatic chuck 3 constitute a mounting table 5 on which the wafer W is mounted.
• a lower high-frequency power source (RF power source) 7 is connected to the mounting table 5 via a lower matching unit 6.
• the lower high-frequency power source 7 can supply high frequency power of a predetermined frequency. Yes.
• an upper high frequency power source (RF power source) 9 is connected to the upper electrode 4 via an upper matching unit 8.
• the upper electrode 4 is provided with a large number of gas discharge holes 10 on its lower surface, while the gas supply is on the top.
• Supply unit 1 1 is provided.
• an exhaust device is connected to the chamber 11 through a pipe.
• the inside of the chamber 1 is adjusted by an air device so that the internal pressure becomes, for example, about 1.3 3 Pa to 1 3 3 Pa.
• an etching gas made of a predetermined plasma processing gas for example, an F-containing gas, is introduced into the chamber 11 from the gas introduction section 11.
• the lower high frequency power supply 7 supplies a relatively low frequency, a predetermined high frequency power, for example, a high frequency power having a frequency of several MHz or less, and the upper high frequency power supply 9 supplies a relatively high frequency.
• a predetermined high-frequency power having a high frequency for example, a high-frequency power having a frequency of tens of MHz to hundreds of MHZ
• plasma can be generated between the upper electrode 4 and the lower electrode 2.
• the surface of the object to be processed such as the semiconductor wafer W can be etched by this plasma.
• the high-frequency power supplied from the upper high-frequency power source 9 to the upper electrode 4 is used to generate plasma, while the high-frequency power supplied from the lower high-frequency power source 7 to the mounting table 5 is It is used to generate a DC bias and control the energy of ions that collide with the semiconductor wafer W.
• the processing chamber 1 in addition to the mounting table 5 including the upper electrode 4, the lower electrode 2 or the electrostatic chuck 3, the shield ring 1 2, the focus ring 1 3, and the deposition chamber 1 Members such as NORED 14, UPPER INSULATOR 15, LOWER INSULATOR 1 6, and baffle plate 17 are disposed.
• the SINORED ring 1 2 and the focus ring 13 are made of, for example, silicon carbide Is formed in a ring shape and is arranged so as to surround the outer periphery of each of the upper electrode 4 and the lower electrode 2, and the plasma generated between the upper electrode 4 and the lower electrode 2 is generated by the semiconductor wafer W It is configured to converge.
• the depot shield 14 is provided to protect the inner wall of the chamber 1, and the upper insulator 15 and the lower insulator 16 are used to maintain the atmosphere in the chamber 1.
• the baffle plate 17 below the lower insulator 16 is provided to contain the generated plasma so that it does not flow out from the exhaust port 18 located below the plasma processing apparatus.
• the members placed in the chamber 1 are processed by plasma etching. At this time, the substrate is exposed to the above-mentioned F-containing gas atmosphere or a plasma-excited atmosphere in a strong corrosive environment where F-containing gas and CH-containing gas are alternately introduced.
• the F-containing gas atmosphere mainly contains fluorine or a fluorine compound, or may further contain oxygen (0 2 ).
• Fluorine is particularly reactive among halogen elements (strongly corrosive) and has the feature that it reacts with metals and oxides and carbides to produce corrosion products with high vapor pressure. Therefore, if the members in the chamber 11 are exposed to plasma in a highly corrosive atmosphere such as the F-containing gas atmosphere, even if they are oxides and carbides as well as metals. A protective film for suppressing the progress of the corrosion reaction is not generated on the surface, and the corrosion reaction proceeds infinitely.
• the inventor has found that, even in such an environment, elements belonging to group a in the periodic table III, that is, elements of Sc and Y, atomic numbers 5 7 to 71, and their oxides. As for, it was found that it shows good corrosion resistance.
• the CH itself is not strongly corrosive. However, since it constitutes a reduction reaction atmosphere that is completely opposite to the oxidation reaction that proceeds in the F-containing gas atmosphere, it is relatively stable in the F-containing gas. Corrosion resistant metals (alloys) and metal compounds are also included
• both F and CH are ionized to generate highly reactive atomic F, C, and H, which is corrosive and reducible. Acceleration accelerates the plasma erosion action and makes it easier for corrosion products to form from the surface of members.
• the corrosion products generated in this way are vaporized in this environment, or become fine particles that significantly contaminate the inside of the plasma processing vessel such as the chamber.
• the F-containing gas atmosphere, the mixed gas atmosphere of the F-containing gas and the CH-containing gas, or the F-containing gas atmosphere and the CH-containing gas atmosphere It is effective as a countermeasure against corrosion and erosion in a harsh and corrosive environment that is repeated alternately, and is also effective in preventing the generation of corrosion products and in particular suppressing the generation of particles. Therefore, in the present invention, the surface of the member or the like that is disposed in the chamber and is subjected to plasma at the same time when the skin treatment body is subjected to plasma treatment is made of a metal oxide containing an element belonging to group IIIa.
• this composite film formed by forming a secondary recrystallized layer obtained by secondary transformation of the metal oxyhydride on the porous layer.
• this composite film may be formed on all the members in the chamber or the like, and it may be formed by selecting only a part having a particularly high plasma density and a large damage.
• F-containing gas examples include F 2 , CF 4 , C 4 F S , C 4 F 6, C 5 F 8, and other gases represented by the general formula C x F y , CHF 3 , CH 2 F 2 And one or more gases selected from a mixed gas of fluorine gas and O 2 , such as CH F gas such as CH 3 F, HF gas, SF gas such as SF 6 and CFO gas such as CF 20 Is preferably used.
• H 2 , CH 4 , C 2 H 2 , CH 3 F, CH 2 F 2 , CHF 3 and the like C x Hy gas, NH 3 and other H-containing gas, walk-containing CH gas is good preferable to use at least one gas selected from a gas mixture of H-containing gas and 0 2.
• the inventor has good corrosion resistance and environmental pollution resistance even in the atmosphere of the composite film forming material formed on the surface of the member or the like disposed in the chamber, particularly in an atmosphere containing F gas or CH gas.
• the materials shown were examined.
• the metal oxide for forming the porous layer As a result, as the metal oxide for forming the porous layer, the metal oxide power of an element belonging to the Ilia group of the periodic table is superior in halogen corrosion resistance in a corrosive environment as compared with other oxides. It has been shown that it exhibits plasma erosion resistance (contamination resistance due to particles of corrosion products).
• Group a element metal oxides are Sc, Y and lanthanides with atomic numbers 57-71 (La, Ce, Pr, Nb, Pm, Sra, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), especially for lanthanoids, the rare earth oxides of La, Ce, Eu, Dy, and Yb are suitable.
• these metal oxides can be used singly or as a mixture of two or more, a double oxide, or a eutectic.
• a thermal spraying method is used as a preferred example. That is, III First, the metal oxide of group a element is first pulverized to form a thermal spray material powder consisting of particles having an average particle size of 5 to 80 ⁇ m, and this thermal spray material powder is sprayed onto the surface of a member or the like by a predetermined method. Thus, a porous layer composed of a thermal sprayed coating having a thickness of 50 to 2000 ⁇ (porosity of about 5 to 20%) is formed.
• the thickness of the porous layer is less than 50 ⁇ , the performance as a film in the corrosive environment is not sufficient. On the other hand, if the thickness of the layer exceeds 2000 m, the thermal spray particles are interconnected. In addition to weakening of the resultant force, the stress generated during film formation (probably due to volume shrinkage and accumulation due to rapid cooling of the particles) increases, and the film tends to be damaged.
• an air plasma spraying method or a low pressure plasma spraying method is suitable, but a water plasma spraying method or an explosion spraying method can also be applied depending on use conditions. is there.
• an undercoat made of any one of a metal, an alloy, ceramics, and cermet that is a composite material thereof may be formed in advance on the surface of a member or the like.
• this undercoat By forming this undercoat, the adhesion strength between the porous layer and the base material is increased, and the contact of the corrosive gas with the base material can be prevented.
• the undercoat is made of metal such as Ni and its alloys, Co and its alloys, A1 and its alloys, Ti and its alloys, Mo and its alloys, W and its alloys, Cr and its alloys, etc.
• the film thickness is preferably about 50 to 200 / m.
• the role of the undercoat is to improve the corrosion resistance by blocking the surface of the member or the like from the corrosive environment and to improve the adhesion between the substrate and the porous layer. Therefore, if the film thickness of this undercoat is less than 50 ⁇ m, not only the corrosion resistance is sufficient, but also uniform film formation is difficult.On the other hand, even if it is thicker than 200 m, the corrosion resistance effect is saturated. To do.
• the ceramic used for this undercoat oxide borides, nitrides, silicides and the like are suitable, and a film using a cermet made of these ceramics and the above metal-alloy may be used.
• a thermal spraying method such as an air plasma spraying method or a low pressure plasma spraying method, a water plasma spraying method or an explosion spraying method, or a vapor deposition method
• the material such as the inner member of the processing chamber of the plasma processing apparatus according to the present invention include metals such as aluminum and its alloys, titanium and its alloys, stainless steel, other special steels, and nickel-based alloys
• metals such as aluminum and its alloys, titanium and its alloys, stainless steel, other special steels, and nickel-based alloys
• ceramics composed of quartz, vitrified materials, carbides, borides, silicides, nitrides and mixtures thereof, and cermets composed of these ceramics and the above metals, etc.
• Inorganic materials and plastics can be used.
• the most characteristic configuration is the presence of the secondary recrystallized layer provided on the surface of a part, member or the like that is directly exposed to the plasma processing atmosphere.
• the secondary recrystallized layer is formed on the porous layer, that is, a porous sprayed coating, and for example, the outermost layer portion of the porous layer made of a group IIIa metal oxide is subjected to secondary transformation. It is a layer formed.
• the crystal structure is a cubic crystal belonging to a tetragonal crystal.
• yttria the powder of the yttrium oxide
• the molten particles collide with the surface of the substrate and accumulate while being rapidly cooled while flying toward the substrate at high speed.
• the crystal structure undergoes a primary transformation to a mixed crystal type crystal structure including monoclinic (monoc 1 inic) in addition to cubic (cubic). This is a metal oxide porous layer.
• the secondary crystal layer refers to the metal oxide that has undergone a primary transformation by being ultra-rapidly cooled during thermal spraying to form a mixed crystal state including orthorhombic crystals and tetragonal crystals.
• the porous material layer is a layer that has been secondarily transformed into a tetragonal crystal type by a second thermal spraying process.
• Fig. 4 schematically shows the change in the structure of the mouth of the vicinity of the surface of the Y 2 0 3 sprayed coating (porous film), the coating after the electron beam irradiation treatment, and the composite coating with an undercoat layer. It is.
• the spray particles constituting the coating exist independently, and the surface roughness is large.
• a new layer having a different microstructure is formed on the sprayed coating by the electron beam irradiation treatment shown in FIG. 4 (b). This layer is a dense layer with a small number of voids formed by the spraying of the spray particles.
• Figure 4 (c) An example having a dark coat is shown.
• FIG. 5 is an XRD measurement chart of a porous layer that is a Y 2 0 3 sprayed coating and a secondary recrystallized layer formed by electron beam irradiation treatment under the following conditions.
• the Upsilon 2 0 3 sprayed coating shows the XRD pattern before and after electron beam irradiation treatment. That is, FIG. 6 is an X-ray diffraction chart with the vertical axis expanded before processing, and FIG. 7 is an X-ray diffraction chart with the vertical axis expanded after processing.
• FIG. 6 is an X-ray diffraction chart with the vertical axis expanded before processing
• FIG. 7 is an X-ray diffraction chart with the vertical axis expanded after processing.
• the peak of monoclinic crystal is observed in the range of 30 ° to 35 °, and cubic and monoclinic crystals are mixed in the ⁇ 20 3 sprayed coating before processing.
• the secondary recrystallized layer obtained by electron beam irradiation treatment of this ⁇ 2 0 3 sprayed coating has a sharp peak showing 2 3 3 particles.
• the monoclinic peak is attenuated, and the plane indices (202) and (310) cannot be confirmed, indicating that it is only cubic.
• This XRD test was measured using a RINT 1 500 X-ray diffractometer manufactured by Rigaku Corporation.
• the X-ray diffraction conditions are as follows.
• reference numeral 41 is a base material
• 42 is a porous layer (sprayed particle deposition layer)
• 43 is a pore (void)
• 44 is a particle interface
• 45 is a through-hole
• 46 is an electron beam irradiation treatment.
• the resulting secondary recrystallized layer, and 47 is an undercoat.
• the porous layer of the group IIIa metal oxide mainly composed of the primary transformed orthorhombic crystal structure is subjected to high-energy irradiation treatment to thereby obtain the porous layer.
• Heat treatment of at least the melting point of the volume sprayed particles, and this layer is transformed again (secondary transformation), and its crystal structure is returned to the tetragonal weave to stabilize crystallographically. It was.
• the thermal strain and mechanical strain accumulated in the thermal spray particle deposition layer are released, and the properties are physically and chemically stabilized. It was decided to realize the densification and smoothing of this layer accompanying the powerful melting. As a result, the secondary recrystallized layer made of the metal oxide of the group ⁇ a element becomes a dense and smooth layer as compared with the thermally sprayed layer.
• this secondary recrystallized layer becomes a densified layer having a porosity of less than 5%, preferably less than 2%, and the surface has an average roughness (Ra) of 0.8 to 3.0 m, with a maximum roughness.
• the thickness (R y) is 6 to 16 ⁇ , and the 10-point average roughness (Rz) is about 3 to 14 ⁇ m, so that the layer is significantly different from the porous layer.
• the control of this maximum roughness (Ry) is determined from the viewpoint of environmental pollution resistance. The reason for this is that when the surface of the container member is scraped off by the plasma ions and electrons excited in the etching atmosphere and particles are generated, the effect is most apparent in the value of the maximum surface roughness (Ry).
• the laser irradiation process such as C0 2 laser and YAG laser is preferably used, but the invention is not limited to these methods.
• Electron beam irradiation treatment As a condition for this treatment, an inert gas such as Ar gas is introduced into the irradiation chamber where the air is exhausted, and the treatment is performed under the following irradiation conditions, for example. Recommended.
• an inert gas such as Ar gas is introduced into the irradiation chamber where the air is exhausted, and the treatment is performed under the following irradiation conditions, for example. Recommended.
• Beam irradiation output 0.1 to 8kW
• the metal oxide containing an Ilia group element that has been subjected to electron beam irradiation rises in temperature from the surface and eventually reaches the melting point or higher and becomes a molten state.
• This melting phenomenon gradually reaches the inside of the film by increasing the electron beam irradiation output, increasing the number of times of irradiation, and increasing the irradiation time. It can be controlled by changing the irradiation conditions. Practically, if the ilr depth is 1 / ⁇ to 50 ⁇ , a secondary recrystallized layer suitable for the above object of the present invention can be obtained.
• the layer subjected to the electron beam irradiation treatment or the laser beam irradiation treatment is transformed into a crystal form which is transformed into a physicochemically stable crystal by transforming to a high temperature and precipitating secondary recrystallization upon cooling. Modification proceeds in units of crystal level.
• the ⁇ 2 ⁇ 3 coating formed by the atmospheric plasma spraying method is mainly orthorhombic in the sprayed state as described above, but almost changes to cubic after electron beam irradiation.
• the characteristics of the secondary recrystallized layer composed of metal oxides of the Ilia group elements of the periodic table subjected to high energy irradiation are summarized below.
• the secondary recrystallized layer produced by the high energy irradiation treatment is obtained by further secondary transformation of a porous layer made of a metal oxide or the like which is the lower primary transformation layer, or the lower oxide particles are Due to the heating force above the melting point, at least part of the pores disappear and become dense.
• the secondary recrystallized layer produced by the high energy irradiation treatment is a layer obtained by further secondary transformation of a porous layer made of a metal oxide, particularly, it is formed by thermal spraying.
• a sprayed coating the unmelted particles at the time of spraying are completely melted and the surface is in a mirror state, so that projections that are easily plasma-etched disappear.
• the porous layer is a secondary recrystallized layer produced by high-energy irradiation treatment, so that the through-holes are blocked, and the internal (base) Corrosive gas that intrudes into the material is eliminated, corrosion resistance is improved, and since it is densified, it also has a strong resistance to plasma etching, and has excellent corrosion resistance and plasma erosion resistance over a long period of time. Demonstrate.
• the thickness of the secondary crystal layer produced by high-energy irradiation treatment it is preferable that the thickness of about 1 ⁇ 50 ⁇ ⁇ from the surface. The reason is that if the thickness is less than 50 m, there is no effect of film formation, while if it is thicker than 50 m, the burden of high-energy irradiation treatment is increased and the effect of film formation is saturated.
• the lower porous layer exists as a layer having excellent heat resistance, but this layer has a characteristic of acting as a buffer with the upper layer. That is, it has the effect of reducing the thermal shock applied to the entire film through the action of mitigating the thermal shock applied to the upper dense secondary crystal layer.
• the combined action of these two layers is synergistic. Effect occurs and the durability of the coating is improved.
• the potential difference between the member in the chamber and the plasma increases, and the sprayed coating such as ⁇ 2 ⁇ 3 coated on the member is corroded. Particle corrosion of the generated corrosion products, and dropping and adhering to the surface of the object to be processed will cause device failure.
• the plasma processing apparatus of the present invention when the erosion resistance of the film formed on the surface of the member is improved, the plasma output is increased until the potential difference between the member and the plasma is about 550V. In this case, the generation of particles can be suppressed.
• the potential difference between the member or the like and the plasma is controlled by the power applied to the mounting table 5 from the high-frequency power source 7 in FIG. 1, and is preferably 550 V or less, more preferably 120 V or more and 550 V or less.
• ⁇ 2 0 3 (or more purity 95 mass%)
• Examples of III a metals oxides that sprayed with film-forming (Comparative and example B), ⁇ 2 0 3 'After sprayed with film forming, its surface is secondary transformation by irradiating an electron beam to form the shape as a (Inventive Alpha) with secondary crystal layer.
• the respective chambers in one, plasma treatment is introduced repeatedly to F-containing gas and containing CH gases alternately, after weakening the Upsilon 2 0 3 sprayed coating is to be bra Zuma processed semiconductor Control the amount of high frequency power applied to the wafer mounting table
• the potential difference between the chamber wall potential and plasma was measured from 200V to 300V. The result is shown in Fig.2.
• Example 1 to investigate the limit value of the potential difference between the plasma processing vessel inner wall member (aluminum lower insulator, baffle, and depot shield) and the plasma (the range in which the generation of dust caused by coating (ittrium) can be suppressed) similar to the surface of the processing container inner wall material, Y 2 0 3 that sprayed with film forming (Comparative example beta), After film formation by spraying the Upsilon 2 ⁇ 3, further the surface An electron beam irradiation treatment (secondary transformation) to form a secondary crystal layer (Invention Example IV) was prepared.
• the technology of the present invention is used as a surface treatment technology for members for plasma processing apparatuses that are required to be more precise and highly advanced in recent years, as well as members and parts used in general semiconductor processing apparatuses.
• the present invention relates to a deposition shield for a semiconductor processing apparatus that performs plasma processing in a harsh atmosphere in which an F-containing gas and a CH-containing gas are used individually or in an environment where these gases are used alternately and repeatedly, Baffle It is suitable as a surface treatment technology for parts, parts, etc. such as plates, focus rings, upper 'lower insulator rings, shield rings, bellows covers, electrodes and solid derivatives.
• the present invention can be applied as a surface treatment technique for a member for a liquid crystal device manufacturing apparatus.

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